for download - Leibniz-Institut für Polymerforschung Dresden eV

10 th European Symposium 

on Polymer Blends 

BOOK OF ABSTRACTS 

March 7 to 10, 2010 

Dresden, Germany

Monday, March 8, 2010 Tuesday, March 9, 2010 Wednesday, March 10, 2010 

Chair: M. Stamm 

09:00 Opening Room HS 4 Chair: U. Wagenknecht Chair: J. Pionteck 

09:30 P G. Oenbrink Room HS 4 09:00 K D. Becker Room HS 4 09:00 K I. Mondragon Room HS 4 

10:20 K N. Zafeiropoulos Room HS 4 09:35 K M. Müller Room HS 4 09:35 K C. W. Macosko Room HS 4 

10:55 Break 10:05 Break 10:05 Break 

Blend interfaces and 

interphases 

Processing, morphology 

control, and properties 

Theory, computational 

methods, and modelling 

Processing, morphology 

control, and properties 

Nano-structured and 

nano-filled blends and 

copolymers 

Processing, 

morphology control, 

and properties 

Room 403 

Room HS 4 

Room 403 

Room HS 4 

Room 403 

Room HS 4 

Chair: D. R. Paul Chair: G. Floudas Chair: T. Inoue Chair: G. Heinrich Chair: B. Schartel Chair: B. A. Wolf 

11:25 T. Inoue E. Piorkowska 10:30 B. Steinhoff D. R. Paul 10:30 Y. Yu P. Moldenaers 

11:45 P. I. Aguayo D. Pospiech 10:50 R. Cardinaels B. A. Wolf 10:50 W. S. Chow N. Vranjes 

12:05 E. V. Prut W. Li 11:10 H.-J. Radusch D. Berek 11:10 R. Schlegel P. J. R. O. Nóvoa 

12:25 L. Bardash R. Jeziórska 11:30 B. Schartel A. L. Svistkov 11:30 A. Youssef K. K. C. Ho 

12:45 S. Grosse N. Yousefi 11:50 P. Svoboda G. Floudas 11:50 M. Gültner S. Ü. Çelik 

13:05 Lunch 12:10 Lunch 12:10 Lunch 

Chair: P. Pötschke Chair: H.-J. Radusch Chair: J.-U. Sommer 

14:20 K P. Anderson Room HS 4 13:30 K I. Iliopoulos Room HS 4 13:30 K U. Steiner Room HS 4 

14:55 K M. Omastová Room HS 4 14:05 K T. Ougizawa Room HS 4 14:05 K K. Mecke Room HS 4 

15:30 Break 14:40 Break 14:40 P K. Binder Room HS 4 

15:30 Closing Room HS 4 

Blend interfaces and 

interphases 

Nano-structured and 

nano-filled blends and 

copolymers 

Room HS 4 

Bio-related and 

functional blends 

Room 403 

Room 403 

Processing, 

morphology control, 


Room HS 4 

Chair: M. Stephan Chair: R. Jeziórska Chair: C. W. Macosko Chair: P. Moldenaers 

16:00 H. Goosens P. Franciszczak 15:10 V. V. Zuev F. Böhme 

16:20 S. Ilisch D.G. Hristova-Bogaerds 15:30 S. Bose I. Aravind 

16:40 P. Russo I. Chodák 15:50 M. M. Demir S. Tencé-Girault 

17:00 Z. Starý M. Weber 16:10 C. Prisacariu Z. Safidine 

17:20 V. Thakur A. Göldel 16:30 Break 

17:40 Poster Discussion 16:45 Departure for Sightseeing & Dinner 

K…Keynote Lecture P…Plenary Lecture

CONTENTS 

Contents 

Page № 

Organization 3 

General information 4 

Social events 6 

Program 7 

List of poster contributions 12 

Abstracts of lectures 19 

Abstracts of posters 83

ORGANIZATION 

Local Organizing Committee 

Manfred Stamm (Chairman) 

Jürgen Pionteck 

Petra Pötschke 

Jens-Uwe Sommer 

Udo Wagenknecht 

Kerstin Wustrack (Technical Organization) 

Organization 

Organizing Institute 

Leibniz-Institut für Polymerforschung Dresden e. V. 

International Scientific Committee 

Ivan Chodák, Bratislava, Slovakia 

George Floudas, Ioannina, Greece 

Andrzej Galeski, Lodz, Poland 

Gabriel Groeninckx, Leuven, Belgium 

Regina Jeziórska, Warsaw, Poland 

Alexei Khoklov, Moscow, Russia 

Paolo La Mantia, Palermo, Italy 

Chris Macosko, Minneapolis, USA 

Libor Matějka, Prague, Czech Republic 

Mark Matson, Reading, United Kingdom 

Iñaki Mondragon, San Sebastián, Spain 

Jean-Pierre Pascault, Lyon, France 

Donald R. Paul, Austin, USA 

Hans-Joachim Radusch, Halle, Germany 

Hans Wolfgang Spiess, Mainz, Germany 

Sabu Thomas, Kottayam, India 

The organizers gratefully acknowledge the financial support by 

. 

- 3 -

tram 3 

Nürnberger Platz 

General information 

Main railway station 

tram 8 

Nürnberger Platz 

HSZ 

66 

trams 3, 8 and bus 66 

Reichenbachstraße 

bus 61 

Technische 

Universität 

bus 66 

Technische 

Universität 

HSZ: Hörsaalzentrum, conference venue 

- 4 -

GENERAL INFORMATION 

General information 

Registration/Conference office 

Hörsaalzentrum of the Technische Universität Dresden, 

Bergstraße 64, 01069 Dresden 

The conference office is located in room 301 near the lecture halls. 

Opening hours: 

Sun, March 7, 2010: from 17:00 to 19:30 

Mon, March 8, 2010 - Wed, March 10, 2010: from 8:00 - throughout all sessions 

Contact details of the organizing institution 


Hohe Straße 6, 01069 Dresden 

Phone: +49 351 4658-282; Fax: +49 351 4658-214 

E-Mail: polymerblends2010@ipfdd.de 

www.ipfdd.de/polymerblends2010 

Posters 

Posters should be mounted by the end of the lunch break on Monday at the latest 

and will be up during the entire duration of the meeting. Poster display boards allow a 

format up to 1 m (width) x 1.4 m (height). 

Poster awards, sponsored by Wiley-VCH, will be assigned to the three best poster 

presentations and will be handed over to the awardees in the closing session of the 

meeting on March 10, 2010. 

Coffee and lunch breaks 

Drinks and a lunch bufett are served close to the lecture halls as well as to the poster 

displays in room 304 and some other spots on the third floor of the Hörsaalzentrum. 

Internet 

WLAN access will be possible for participants during the meeting. 

Name of the wireless network: VPN/WEB 

Login: TUD@gast.tu-dresden.de 

Password: Dresden 

In addition, you may use an internet terminal at the conference office. 

- 5 -

SOCIAL EVENTS 

Social events 

Welcome mixer 

Sun, March 7, 2010, 18:30 to 20:30, Hörsaalzentrum, 304 

free of charge - registration is required 

Sightseeing 

Tue, March 8, 2010 at 16:45 

free of charge - but please register to have your seat reserved! 

Buses are leaving after the lectures at 16:45 in front of the conference venue for a 

sightseeing tour, concluding at about 18:45 nearby the restaurant where the 

dinner is held. The bus tour will give you a chance to see some nice places 

outside the city centre, where tourists or business travellers staying only a couple 

of days normally do not come along. 

Conference dinner 

Tue, March 8, 2010 at 18:45 

free of charge - but please register to have your seat reserved! 

Café-Restaurant Luisenhof 

Bergbahnstraße 8 

01324 Dresden 

Tel.: (0351) 2 14 99 60 

The restaurant "Luisenhof" is located on the hills nearby the river Elbe and the 

famous bridge Blaues Wunder. 

A buffet is planned. The dinner will take place in an informal and relaxing 

atmosphere – no special dressing code. 

At about 22:30 the transfer by a shuttle bus back to the city centre is provided. 

- 6 -

PROGRAM 

Monday, March 8, 2010 

09:00 Opening 

Chair: M. Stamm 

Plenary Lecture 

Room HS 4 

09:30-10:20 G. Oenbrink 

Innovation in times of crisis - Polymer blends based on hyperbranched Nylons 

Keynote Lecture 

Room HS 4 

10:20-10:55 N. E. Zafeiropoulos 

Nanohybrid materials with block copolymers and nanoparticles 

10:55-11:25 Break 

Processing, morphology control, 


Room HS 4 Page 

Chair: D. R. Paul Chair: G. Floudas 

11:25-11:45 T. Inoue 

Structure-properties of a highperformance 

PLA alloy: toughening 

by the evolution of negative 

pressure 

11:45-12:05 P. I. Aguayo 

Relationships between processing, 

phase dispersion and mechanical 

performance in polypropylene filled 

compounds 

12:05-12:25 E. V. Prut 

Dynamic vulcanization of 

PP/EPDM thermoplastic elastomers 

containing PP of various molecular 

weight 

12:25-12:45 L. Bardash 

Thermostable porous polystyrene/polycyanurate 

IPNS via polymerization 

of high internal phase 

emulsions 

12:45-13:05 S. Grosse 

Recent state of the art in real time 

morphology analysis of flowing 

polymer blends and nanocomposites 

during extrusion processing 

by means of optical particle 

sensing 

13:05-14:20 Lunch 

- 7 - 

Page 

19 

Page 

Nano-structured and nano-filled 

blends and copolymers 

Room 403 Page 

37 E. Piorkowska 

Polymer nanoblends 

38 D. Pospiech 

In-situ synthesis of polyester nanocomposites 

with inorganic nanoobjects 

and their use to tailor properties 

of polymer blends 

39 W. Li 

The effect of silica nanoparticles on 

the phase behavior of polymer 

blends studied via a high-throughput 

experimentation approach 

40 R. Jeziórska 

Nano-structured composites - The 

potential of spherical nano-silica 

41 N. Yousefi 

Using HDPE/PA6 blend as a matrix 

for polymer/layered silicate nanocomposites: 

Morphology control 

and mechanical properties 

21 

66 

67 

68 

69 

70

Keynote Lectures 

Room HS 4 

Chair: P. Pötschke 

14:20-14:55 P. Anderson 

Confinement effects on clean and surfactant-laden drops 

14:55-15:30 M. Omastová 

Electrically conductive polymer blends 

15:30-16:00 Break 




Chair: M. Stephan Chair: R. Jeziórska 

16:00-16:20 H. Goosens 

Towards submicron thermoplastic 

vulcanizates: Synthesis, morphology 


16:20-16:40 S. Ilisch 

Effect of styrene and vinyl content 

of styrene butadiene rubber on 

dispersion and distribution of carbon 

black in SBR/NR blends 

16:40-17:00 P. Russo 

Processability and morphological 

analysis of thermoplastic polyurethane-carbon 

nanotube compounds 

17:00-17:20 Z. Starý 

Creep elongational experiments - 

new tool for investigations of morphology 

development in polymer 

blends 

17:20-17:40 V. Thakur 

Electron induced reactive processing 

of PP-EPDM thermoplastic 

vulcanizates 

17:40-19:45 Poster Discussion 

- 8 - 

Page 

Bio-related and functional 

blends 

Room 403 Page 

42 P. Franciszczak 

Morphology and physical properties 

of poly(butylene terephthalate)/polylactide 

reactive 

polymer blends 

43 D. G. Hristova-Bogaerds 

Biodegradable poly(3-hydroxybutyrate)/poly(butylene 

succinate) 

(PHB/PBS) blends: Effect of PBS 

on crystallization behavior and 

thermal stability of PHB 

44 I. Chodák 

Compatibilization of binary and 

ternary blends of biodegradable 

plastics 

45 M. Weber 

ABS/PA-alloys - influence of the 

compounding procedure on the 

materials performance 

46 A. Göldel 

Transfer mechanisms and localization 

of conductive nanofillers in 

different polar blend phases during 

melt mixing processes 

22 

23 

75 

76 

77 

78 

79

Tuesday, March 9, 2010 


Room HS 4 

Chair: U. Wagenknecht 

09:00-09:35 D. Becker 

Influence of the compounding process on phase morphology and mechanical 

properties of thermoplastic vulcanisates (TPV) 

09:35-10:05 M. Müller 

Modeling structure formation in diblock copolymer materials 

10:05-10:30 Break 




Chair: T. Inoue Chair: G. Heinrich 

10:30-10:50 B. Steinhoff 

In-line monitoring of blend morphology 

by small angle light scattering 

during extrusion: Influence of 

processing conditions 

10:50-11:10 R. Cardinaels 

Relaxation of droplets and fibrils in 

blends with one viscoelastic component: 

Bulk and confined conditions 

11:10-11:30 H.-J. Radusch 

Polymer blends on the basis of 

polypropylene for laser sinter 

technology 

11:30-11:50 B. Schartel 

Halogen-free flame retarded bisphenol 

A polycarbonate blends 

11:50-12:10 P. Svoboda 

Elastic properties of polypropylene/ethylene-octene 

copolymer 

blends 

12:10-13:30 Lunch 

Page 

Theory, computational methods, 

and modelling 

Room 403 Page 

47 D. R. Paul 

A new model for the effect of elastomer 

particle size on notched 

impact behaviour of polymer 

blends 

48 B. A. Wolf 

Polymer incompatibility caused by 

different molecular architectures 

49 D. Berek 

Separation of minor macromolecular 

constituents from multicomponent 

polymer blends by 

novel liquid chromatographic techniques 

50 A. L. Svistkov 

Modeling mechanical behavior of 

elastomeric nanocomposites based 

on styrene butadiene rubber 

51 G. Floudas 

Effect of pressure on the dynamic 

heterogeneity in miscible blends 


Room HS 4 

Chair: H.-J. Radusch 

13:30-14:05 I. Iliopoulos 

Ordered structures and nanostructured blends from polydisperse 

polymers 

14:05-14:40 T. Ougizawa 

Structure and adhesion in reactive interface between different polymers 

14:40-15:10 Break 

- 9 - 

Page 

24 

25 

32 

33 

34 

35 

36 

26 

27

Nano-structured and nano-filled 

blends and copolymers 


Chair: C. W. Macosko Chair: P. Moldenaers 

15:10-15:30 V. V. Zuev 

Polymer nanocomposites containing 

fulleroid nanofillers 

15:30-15:50 S. Bose 

Phase separation induced selective 

localization of multiwall carbon 

nanotubes in LCST-type blends: 

Effect on phase separation kinetics, 

viscoelastic behavior and 

electrical conductivity 

15:50-16:10 M. M. Demir 

Spontaneous emission of organophilic 

CdSe nanoparticles dispersed 

in segmented poly- 

(carbonate urethane) copolymer 

fibers by electrospinning 

16:10-16:30 C. Prisacariu 

Influence of the hydrogen bonding 

on the mechanical performance of 

segmented block copolyurethane 

elastomers 

16:30-16:45 Break 

16:45 Departure for Sightseeing & Dinner 

Wednesday, March 10, 2010 

Blend interfaces and interphases 

Room 403 Page 

71 F. Böhme 

From blends to block copolymers - 

Do coupling reactions in melt result 

in defined polymer structures? 

72 I. Aravind 

Reaction induced miscibility and 

phase behaviour of poly (trimethylene 

terephthalate)/ polycarbonate 

blends 

73 S. Tencé-Girault 

Co-continuous nanostructured 

blends by reactive blending: Synthesis, 

morphologies, structures 


74 Z. Safidine 

Establishment of TTT diagrams for 

the reinforced blends based on 

PP/PP-g-MAH/SGFR PA 66: Effect 

of compatibilizer 


Room HS 4 

Chair: J. Pionteck 

09:00.09:35 I. Mondragon 

Block copolymers as templates to develop nanostructures in thermoset matrices 

and composites 

09:35-10:05 C. W. Macosko 

Controlling the morphology of cocontinuous polymer blends via block copolymers 

10:05-10:30 Break 

- 10 - 

Page 

57 

58 

59 

60 

28 

29




Chair: B. Schartel Chair: B. A. Wolf 

10:30-10:50 Y. Yu 

Phase transitions of semifluorinated 

side-chain polyesters: 

Subnanometer free volumes from 

positron lifetime in comparison 

with pressure-volume-temperature 

experiments 

10:50-11:10 W. S. Chow 

Exfoliation-ability and processability 

of nanoclay in epoxy/glass 

fiber hybrid composites and polyamide/polypropylene 

blends 

11:10-11:30 R. Schlegel 

Characterization of the elastomeric 

behaviour of block-double graft 

copolymers with an energy based 

softening model 

11:30-11:50 A. Youssef 

Physical ageing of polyethylene 

oxide (PEO)/polyvinyl phenol 

(PVPh) blends 

11:50-12:10 M. Gültner 

Tuning the localization of functionalized 

MWNT in reactive PC/SAN 

blends 

12:10-13:30 Lunch 


Room HS 4 

Chair: J.-U. Sommer 

13:30-14:05 U. Steiner 

Block-copolymer derived photovoltaic devices 

- 11 - 


Room 403 Page 

52 P. Moldenaers 

Nanoparticles as interfacemodifiers 

in immiscible polymer 

blends: Effect of particle concentration, 

size and shape on coalescence 

and break-up 

53 N. Vranjes 

Morphology and properties of polypropylene/low 

density polyethylene 

blends compatibilized by ethylenepropylene-diene 

terpolymer 

54 P. J. R. O. Nóvoa 

Toughening of unsaturated polyester 

resins with solvent treated 

scrap tire rubber powders 

55 K. K. C. Ho 

Interface engineering of carbon 

fibre reinforced poly(vinylidene 

fluoride) 

14:05-14:40 K. Mecke 

Morphological measures for complex polymer geometries 


Room HS 4 

56 S. Ü. Çelik 

Proton conducting polymer electrolytes 

based on 1-vinyl-1,2,4triazole 

and vinylphosphonic acid 

14:40-15:30 K. Binder 

Phase behavior of polymer-containing systems: Recent advances by computer 

simulation 

15:30-15:50 Closing 

Page 

Page 

61 

62 

63 

64 

65 

30 

31 

20

List of poster contributions 

Poster № Page № 

Theory, computational methods, and modelling 

1 Modeling of branching and gelation in living 

copolymerization of monomer and divinyl cross-linker 

ATRP process - Study in frame of dynamic lattice liquid 

model (DLL) 

2 Foaming behavior of polystyrene containing dissolved 

CO2 during depressurisation 

3 Monte Carlo simulation of macromolecular reactions in 

heterogeneous polymer blends 

4 Evidence of microphase separation in random copolymer 

melts by dissipative particle dynamics simulation 

5 The microphase separation in melts of diblock-copolymer 

including linear and amphiphilic blocks (mathematical 

modelling) 

6 Modeling of the phase separation behavior of blends 

containing di- and triblock co-polymers 

Piotr Polanowski, 

Krzysztof Matyjaszewski 

Salah Al-Enezi, 

Meshal Al-Samhan 

Daria V. Guseva, 

Alexander V. Chertovich, 

Yaroslav V. Kudryavtsev, 

Arkadiy D. Litmanovich 

Alexei A. Gavrilov, 

Pavel G. Khalatur, 

Yaroslav V. Kudryavtsev, 

Alexander V. Chertovich 

A. A. Glagoleva, 

V. V. Vasilevskaya, 

A. R. Khokhlov 

Processing, morphology control, and properties 

7 Scale-up of an in-line process monitoring system to an 

industrial extruder for the production of nanocomposites 

8 Real time investigation of the nanostructuring process of 

PP nanocomposites in the melt along the extruder with 

NIR and Ultrasonic spectroscopy 

9 Preparation and sensing properties of novel 

polyurethane-carbon nanotube composite fibers 

10 Morphology and rheological property of PLA/PCL blend 

compatibilized by electron beam irradiation in the 

presence of functional monomer 

11 Proper use of rice straw in preparing of rubber 

composites with industrial applications 

12 Electrically stimulatable shape-memory materials based 

on carbon black filled ethylene-octene copolymer (EOC) 

and their blends 

13 Melt surface tension of miscible blends of poly(ethylene 

oxide) and poly(methyl acrylate) 

14 The temperature dependence of the subnanometre free 

volumes in semicrystalline polyethylene and polytetrafluoro 

ethylene: A positron lifetime and pressure-volume- 

temperature study 

15 Phase separation behavior in a rubber-modified epoxy 

system 

16 Incorporation of high molecular weight polymers in cocontinuous 

nanostructured blends by reactive blending 

17 Boron nitride filled SEBS/EVA blends: Processing and 

properties 

- 12 - 

Peter Friedel, Saija Ptacek, 

Doris Pospiech, Dieter Jehnichen 

Dieter Fischer, Jan Müller, 

Sven Kummer, Enrico Masarati 

Dieter Fischer, Sven Kummer, 

Jan Müller 

Qingqing Fan, Zongyi Qin, Long 

Chen, Jinghua Gong, Yue Tang, 

Meifang Zhu 

Boo Young Shin, 

Bong Shik Kim 

83 

84 

85 

86 

87 

88 

89 

90 

91 

92 

Galal A. M. Nawwar 93 

Hai Hong Le, Sybill Ilisch, 

Hans-Joachim Radusch 

D. Pfefferkorn, S. Sonntag, 

S. Kyeremateng, Z. Funke, 

H. W. Kammer, J. Kressler 

Yang Yu, G. Dlubek, J. Pionteck, 

R. Krause-Rehberg 

Raju Thomas, Jürgen Pionteck, 

Sabu Thomas 

Léa Gani, Sylvie Tencé-Girault, 

Michèle Milléquant, 

Stéphane Bizet, Ludwik Leibler 

Sebnem Kemaloglu, 

Gamze Karsli, A. Aytac, 

Guralp Ozkoc 

94 

95 

96 

97 

98 

99

18 The effects of carbon black content and structure on the Hamidreza Esfahany, 

performance of the natural rubber vulcanizates 

Payam Zahedi 

19 Permeability characterization of HDPE/PA-6/EVOH M. R. Saeb, M. Farahani, 

bottles: The effects of order of mixing and disperse 

phase content 

A. Kiani, S. Sarami, H. Garmabi 

20 Temperature dependency of permeability in HDPE and A. Kiani, M. R. Saeb, 

HDPE/PA-6/EVOH blow molded bottles against gasoline M. Farahani, H. Garmabi 

21 Electrically conducting blend based on epoxy resin with Abdolreza Mirmohseni, 

polyaniline/poly (butyl acrylate-vinyl acetate) composite Fahimeh Farshi Azhar 

22 Radiation curing of silicone blends A. Fainleib, V. Sakhno, 

D. Kolesnik 

23 Compatibilization of PP/TPU blends with different fillers Emi Govorĉin Bajsić, 

Vesna Rek, Ivana Pleić, 

Mirela Leskovac 

24 Blends of partly aromatic polyamides with hyperbranched Klaus Jähnichen, Brigitte Voit, 

aromatic polymers (polyesters and polyetheramides) - 

miscibility and properties 

Zhirong Fan, Phillippe Desbois 

25 Influence of chemical crosslinking on glass transition H. A. Khonakdar, 

temperature, crystallization and melting behavior of 

PE/EVA blends 

A. Haghighi-Asl 


26 Coating of surfaces by polyelectrolyte and surfactant 

mixtures 

27 Studies on transreaction kinetics in PET/PEN blends 

using rheological measurements 

28 Determination of surface anisotropy and viscoelastic 

response of cocontinuous blends 

29 Macro porosity in hybrid organic-inorganic polymer 

systems filled with inorganic particles 

30 Initial formation process of interface between dissimilar 

polymers by high-speed ellipsometry 

31 Effect of confinement and viscosity ratio on droplet 

coalescence in shear flow 

Saule Aidarova, Altynai 

Sharipova, Miras Issakhov, 

Kuanishbek Mussabekov, 

Victoria Dutschk, Reinhard Miller 

H. A. Khonakdar, M. A. Zolali, 

M. B. Teimouri, S. H. Jafari, 

U. Wagenknecht, B. Kretzschmar 

C. R. Lopez-Barron, 

C. W. Macosko 

Maksym Iurzhenko, Yevgen 

Mamunya, Gisele Boiteux, 

Eugene Lebedev 

Yuki Mishima, Rikki Honma, 

Seisuke Ata, Toshiaki Ougizawa 

Ruth Cardinaels, Pieter de 

Bruyn, Dongju Chen, Paula 

Moldenaers 

32 PCL/PA12 graft copolymers by coupling reactions in melt Lothar Jakisch, Andrea Gube, 

Frank Böhme 

33 Reactive and non-reactive polypyrroles as modifier for 

electrical conductive blends and composites 

34 Synthesis of defined PP-co-(PS macromonomers) and 

their application as compatibilizer in polymer blends 

J. Pionteck, J. Hegewald, 

M. Omastová 

Ulrich Schulze, Tamás Fónagy, 

Jürgen Pionteck, Béla Iván 

35 Janus particles in PS/PMMA polymer blends Thomas Ruhland, 

Andreas Walther, A. H. E. Müller 

Nano-structured and nano-filled blends and copolymers 

36 Elaboration and characterization of binary 

nanocomposites based on poly(n-butyl methacrylate-co- 

acrylic acid)/bentonite 

37 Effect of clay on the morphology and properties of high 

density polyethylene/polystyrene/clay nanocomposites 

prepared by melt mixing 

38 A novel compatibilization technique involving multiwall 

carbon nanotubes in polyamide6/acrylonitrile butadiene 

styrene blends 

- 13 - 

Hiba Chaouadi, Farid Metref, 

Said Djadoun 

Assia Siham Hadj Hamou, 

Farida Yahiaoui, Abderahmane 

Habi, Said Djadoun 

Bhagwan F. Jogi, 

Arup R. Bhattacharyya 

100 

101 

102 

103 

104 

105 

106 

107 

108 

109 

110 

111 

112 

113 

114 

115 

116 

117 

118 

119 

120

39 Phase morphology development in PA6/PP/ABS ternary 

polymer blends: Influence of compatibilizers and 

multiwall carbon nanotubes 

40 A new single-step synthesis method for hybrid polymer/ 

inorganic nanopartilce latexes 

41 Preparation of vinyl ester/nano alumina nanocomposites 

and study of their mechanical, physical and thermal 

properties 

42 Non-isothermal crystallization behavior of 

polypropylene/poly (trimethylene terephthalate) blends in 

presence of nanoclay particles 

43 Influence of enhanced transesterification on thermal 

degradation and rheological behavior of phenoxy/PTT 

blends in presence of nanoclay particles 

44 Study of elongational flow on mechanical properties and 

oxygen permeability of LLDPE/LDPE/OMMT 

nanocomposite blown films 

- 14 - 

Biswajit Panda, 

Arup R. Bhattacharyya, 

Ajit R. Kulkarni 

A. S. Pakdel, H. Eslami, 

S. Pourmahdian 

M. Esfandeh, H. Rahimi, 

M. Oroujzadeh 

Ali Kalati Vahid, Seyed-Hassan 

Jafari, Hossein Ali Khonakdar, 

Rüdiger Häßler, Dieter Jehnichen 

Javad Seyfi, 

Seyed-Hassan Jafari, 

Hossein Ali Khonakdar 

Hamidreza Esfahany, 

Hamid Garmabi 

45 Selective sequestering of CNTs in block copolymers Florian Wode, Martin Kirsten, 

Manfred Stamm, Apostolos 

46 Structural changes in thin films of supramolecular 

assemblies by blending with homopolymers 

47 Highly ordered arrays of Fe3O4 magnetic nanoparticles 

via block copolymer self assembly 

48 Comparison of nano composites based poly(acrylonitrilebutadiene-styrene) 

modified epoxy resin and TiO2 or 

MWCNT 

49 Modification of the electrical properties of polypropylene 

by modified expanded graphites (EGs) 

50 Nanocomposite blends: Multiwalled carbon nanotube 

filled polycarbonate melt mixed with montmorillonite filled 

polypropylene 

51 Nanoscaled molecularly imprinted polymers (MIPs) for 

specific recognition of amino acids via inverse 

miniemulsion polymerisation 

52 Optimization of electrical and mechanical properties of a 

PC/ABS blend by a hybrid filler system 

53 Novel titanium dioxide/polystyrene nanocomposites as 

precursor for advanced graphite electrode materials 

54 Natural rubber blended with polystyrene nanoparticles 

prepared by differential microemulsion polymerization 

55 Polymer blends of EVA/nano-sized PS filled with 

nanosilica 

56 Mechanical properties and morphology of XSBR/NR 

blends filled with PS nanoparticles 

57 Preparation and characterization of EVA/PS nanoparticles/MMT 

nanocomposites 

58 Synthesis and characterization of mixed proton and 

electron conducting polymer nanocomposites 

59 DSC and WAXS studies of cold crystallization of 

PLLA\montmorillonite nanocomposites 

Avgeropoulos, N. Zafeiropoulos 

Marcus Böhme, Bhanu Nandan, 

Manfred Stamm 

Andriy Horechyy, Nikolaos E. 

Zafeiropoulos, Peter Formanek, 

Anton Kiriy, Manfred Stamm 

P. Jyotishkumar, J. Pionteck, 

S. Thomas 

J. Pionteck, M. Kaiser, F. Piana, 

P. Pötschke, I. Krupa, 

M. Omastová 

Petra Pötschke, Bernd 

Kretzschmar, Liane Häussler, 

Mahmoud Abdel-Goad, 

Andreas Janke 

D. Wojciukiewicz, J. Riegler, 

T. Hirth, G. Tovar 

A. Kamper, S. Ilisch, H. H. Le, 

H.-J. Radusch 

Jan U. Wieneke, 

David Ruiz Abad, Gerd Brosig, 

Hartmut Wiggers, Christof 

Schulz, Mathias Ulbricht 

Saowaroj Chuayjuljit, 

Anyaporn Boonmahitthisud 


Nutnicha Piyawong 


Wasuthep Luecha 


Chutima Worawas 

Vijaykumar Ijeri, Stefano Bianco, 

Mauro Tortello, Lucandrea 

Cappelletto, Elena Tresso, 

Paolo Spinelli 

F. Ublekov, J. Baldrian, 

J. Kratochvil, E. Nedkov 

121 

122 

123 

124 

125 

126 

127 

128 

129 

130 

131 

132 

133 

134 

135 

136 

137 

138 

139 

140 

141

60 Novel CNTs/polystyrene composites by using in situ - 

polymerization and extrusion 

61 Phase behavior of binary blends of block copolymers 

with complementarily asymmetric compositions 

62 Nanocomposites of cellulose acetate, 

poly(epichlorohydrin) and organic-clay: Morphology and 

thermal behavior 

63 Chemical reactions at curing of polycyanurate ester 

resin/epoxy functionalized polyhedral oligomeric 

silsesquioxane blends 

64 Preparation and characterization of dental 

nanocomposite resin 

65 Novel polyurethane blends derived from polyetheric 

macrodiols 

66 Stress relaxation and residual strain of polyurethane 

elastomers and films based on dibenzyl monomers 

67 Synthesis and characterization of segmented 

polyurethane elastomers with an enhanced sequential 

ordering of the hard segments 

68 Tensile modulus and hysteresis behaviour of segmented 

polyesteric copolyurethanes based on single or mixtures 

of isocyanates 

Minna Annala, Jukka Seppälä 142 

Sang-Byung Park, 

Jeong-Kyu Lee, Jung-Guk Ha, 

Wang-Cheol Zin 

Juliana Aristéia de Lima, 

Maria Isabel Felisberti, 

Maria do Carmo Gonçalves 

A. Fainleib, O. Starostenko, 

O. Grigoryeva, B. Youssef, 

J.-M. Saiter, D. Grande 

Baolei Zhu, Mo Zhu, Ling Qi, 

Qinghong Zhang, Bing Sun, 

Meifang Zhu 

Cristina Prisacariu, 

Elena Scortanu 







69 The self-assembly of amphiphilic macromolecules Valentina Vasilevskaya 151 

Bio-related and functional blends 

70 Poly(lactic acid)/poly(3-hydroxybutyrate-co-3hydroxyvalerate) 

blends: Toughening effect of PHBV 

71 Ethylene vinyl acetate/cellulose composites: functional 

modification, morphology and phase interactions 

72 Investigation of physicochemical properties and microstructure 

of citric acid/glycerol blended corn starch 

73 Preparation and characterization of polymer electrolyte 

membranes based on poly(1-vinyl-1,2,4 triazole) and 

poly(styrene sulfonic acid) 

74 The non-isothermal crystallization kinetics of 

unplasticized and plasticized poly(lactic acid)/organoclay 

nanocomposite films 

75 Liquid sensing properties of melt-processed 

polypropylene and poly(e-caprolactone) blends with 

carbon nanotubes 

P. Ma, D. G. Hristova-Bogaerds, 

P. J. Lemstra, Sh. Wang, 

Y. Zhang 

Md. Minhaz-Ul Haque, 

Vera Alvarez, Mariano Pracella 

Ebru Uslu, Sevilay Atmaca, 

Sebnem Kemaloglu, 

Semin Ozge Ozkoc, 

Guralp Ozkoc 

Ayşe Aslan, Sevim Ünügür 

Çelik, Ünal Şen, Ayhan Bozkurt 

Serap Gumus, Guralp Ozkoc, 

Ayse Aytac 

Petra Pötschke, Kazufumi 

Kobashi, Tobias Villmow, Timo 

Andres, José António Covas, 

Maria Conceição Paiva 

76 Evaluation of PVA /Guar gum based polymer blend films A. P. Gupta, Gopal Arora 158 

77 Functional protein-polymer blends on the basis of 

polyacrylamide gel and gumic acids for sorption 

immobilization of enzymes 

Gulnara A. Bektenova 159 

- 15 - 

143 

144 

145 

146 

147 

148 

149 

150 

152 

153 

154 

155 

156 

157

ABSTRACTS 

OF 

LECTURES


INNOVATION IN TIMES OF CRISIS – POLYMER BLENDS 

BASED ON HYPERBRANCHED NYLONS 

Dr. Georg Oenbrink 

Evonik Degussa GmbH, High Performance Polymers 

georg.oenbrink@evonik.com 

In times of economic crisis and uncertain business developments open innovation along the 

value chain becomes one of the success factors for sustainable and profitable business development. 

Innovation management within Evonik Degussa Gmbh will be presented briefly. 

Based on high molecular, hyperbranched Nylons polymer blends with linear Nylons as well 

as other polymers have been evaluated regarding their physico-chemical and technical properties. 

Results obtained will be presented. 

- 19 -


PHASE BEHAVIOR OF POLYMER-CONTAINING SYSTEMS: 

RECENT ADVANCES BY COMPUTER SIMULATION 

Kurt Binder 

Johannes Gutenberg Universität, Institut für Physik, Staudinger Weg 7, 

55099 Mainz, Germany 

kurt.binder@uni-mainz.de 

Computer simulations dealing with the phase transitions and phase diagrams of polymer solutions, 

polymer mixtures, and polymers in heterogeneous environments are still a methodological 

challenge, since nontrivial structure occurs from the Angstrom-scale of covalent 

chemical bonds to the micrometer scale in the resulting multiphase materials. A brief review 

of the strategies that were developed to deal with these problems will be given, and a few 

highlights of recent results from the research group of the author will be described. 

For obtaining a qualitative understanding of phase behavior, often a drastically simplified 

model suffices. The extreme case is the Asakura-Oosawa model of polymer-colloid mixtures, 

which describes the interplay of liquid-vapor type phase separation and crystallization in these 

colloidal suspensions. Monte Carlo simulations give a lot of insight into these phenomena, 

including properties of the interfaces between coexisting phases. In this description, each 

polymer coil is coarse-grained to the level of a soft sphere, penetrable by other polymers. 

For studying the interplay of polymer conformation and phase behavior, more detailed models 

are required, such as the bond-fluctuation model on the lattice, or bead-spring off-lattice models. 

The latter have been used to study microphase separation in bottle-brush polymers in solution. 

Under bad solvent conditions, a transition from cylindrical structure to a pearlnecklace 

structure may occur. If two types (A, B) of side chains occur, the “peals” may form 

“Janus particles”. The possibility of “Janus cylinders” also is discussed. Using the bond fluctuation 

model, symmetrical binary blends in strictly d=2 dimensions were studied. The A-B 

interactions occur only across the fractal interface between dense space-filling segregated 

individual coils. Therefore in d=2 the critical temperature scales weaker than linear with the 

polymer chain length, in qualitative disagreement with Flory-Huggins theory, In d=3 dimensions, 

micelle formation in blends of asymmetric block copolymers and homopolymers has 

been studied, and shown that self-consistent field theory is still inaccurate for chain lengths of 

about N 100 coarse-grained monomers. Extending the study to include the effect of free surfaces, 

competition with polymer brush or surface micelle formation can be studied. 

Finally, the possibility of chemically specific predictions of phase diagram for polymer solutions 

is discussed, treating alkanes dissolved in carbon dioxide as an example. It is stressed 

that such problems cannot (yet?) be treated fully “ab initio”, but still require a little input from 

experiment. 

- 20 -


NANOHYBRID MATERIALS WITH BLOCK COPOLYMERS 

AND NANOPARTICLES 

A. Horechyy (1), N. E. Zafeiropoulos (1, 2), M. Stamm (1) 

(1) Leibniz-Institut für Polymerforschung Dresden e. V., Germany 

(2) University of Ioannina, Greece 

nzafirop@cc.uoi.gr 

Nanostructured materials have received considerable attention nowadays due to nanotechnological 

applications. Many of these applications require the manufacturing of densely 

packed systems, such as magnetic recording media, computing processors, multifunctional 

sensors, etc. To generate densely packed systems there have been two major routes; the first 

one being ‘scale down’ approaches (e.g. nanolithography, etc.); and the second being ‘bottom 

up’ approaches. The scale down approach is easier to employ but the amount of changes on a 

given surface is usually limited due to instrumentation restrictions (e.g in lithography the 

wavelength of the used radiation is the limiting factor). On the other hand, bottom up approaches 

are more difficult to use, but offer unlimited possibilities in terms of surface manipulation. 

The present work reports the generation of nanostructured surfaces based on a diblock 

copolymer and inorganic nanoparticles that have been selectively segregated in one of the 

polymer phases. 

- 21 -


CONFINEMENT EFFECTS ON CLEAN AND SURFACTANT- 

LADEN DROPS 

Patrick D. Anderson 

Eindhoven University of Technology, the Netherlands 

p.d.anderson@tue.nl 

Morphology development of blends in confined cases is relevant in many systems, for example 

in polymer processing, where the distance between the screw and barrel is small. Since 

surfactants are often added to blends to act as stabilisers and in this work we focus on their 

role on the deformation of confined drops. A boundary-integral method with modified Green's 

functions, which exactly satisfy the no-slip condition at the walls, is used to solve the flow 

equations. The resulting velocities are used in the convection-diffusion equation for the surfactant 

concentration which is handled with a finite volume method. The local surfactant concentration 

is coupled to the local surface tension via a Langmuir isotherm. 

Several examples of the influence of surfactants are shown: for drops in shear flow, the extreme 

cases of convection-dominated versus diffusion-dominated surfactant redistribution is 

shown. The strong shear field between the drop and the wall has a significant impact on the 

surfactant redistribution. For convection-dominated situations, this area is largely swept clear 

of the surfactant, leading to a local higher surface tension. In diffusion-dominated cases, the 

surfactant concentration remains uniform over the drop, but surface dilution, where the surface 

tension increases due to lower surfactant concentration, resulting in less deformation, 

becomes important. Migration of drops in pressure driven flows is also considered, where the 

influence of the surfactant coverage on migration velocity and transient drop shapes is shown. 

- 22 -


ELECTRICALLY CONDUCTIVE POLYMER BLENDS 

Mária Omastová 

Polymer Institute, Slovak Academy of Sciences, Dubravska cesta 9, 

842 36 Bratislava, Slovakia 

maria.omastova@savba.sk 

The preparation of polymeric blends became very important in the last decades. The main aim 

of blends production is creation of new materials combining synergistically the properties of 

the components of the blend. 

An extensive research has been done over the last 30 years concerning conducting polymers. 

Of these, polypyrrole, polythiophene and polyaniline have been studied most widely to date. 

Further research explores methods of combining intrinsically conductive polymers with other 

polymers, and applications in novel devices. Polyolefines can find new applications e. g. as 

antistatic plastic films or electromagnetic shielding by blending with polypyrrole [1], polyaniline 

or other conducting polymers [2]. The problem of surface static charge of poly(methyl 

methacrylate) can be also solved by blending with conductive polymers. In such blends the 

insulating polymer provides good mechanical properties and processability and the conducting 

polymer provides electrical conductivity. 

The contribution will provide evidence of a highly dynamical development of the new group 

of materials containing intrinsically conductive polypyrrole or polyaniline and insulating 

polymers. The fast increase in the number of preparation methods as well as in the variety of 

material combinations will be discussed. The variety of polypyrrole blends now include applications 

like antistatic materials, anti-corrosion coating, radiation shielding, electrochromic 

applications (displays, intelligent blinds) but also a new category of sensors and prothetic 

elements and other human medicine applications. Particularly the latter group of materials 

shows the highest growth of published results and therefore a rapid development of new applications 

in this area can be expected. 

Acknowledgements: This work was supported by project VEGA 2/0064/10. 

[1] Omastová M., Košina S., Pionteck J., Janke A., Pavlinec J.: Synth. Met., 1996, 81, 49–57. 

[2] Barthet Ch., Armes S.P., Chehimi M. M., Bilem C., Omastová M.: Langmuir, 14, 1998, 5032–5038. 

- 23 -


INFLUENCE OF THE COMPOUNDING PROCESS ON PHASE 

MORPHOLOGY AND MECHANICAL PROPERTIES OF 

THERMOPLASTIC VULCANISATES (TPV) 

Prof. Dr.-Ing. Bernd Poltersdorf (1), Dr.-Ing. Dietmar Becker (1), Prof. Dr.-Ing. Edmund 

Haberstroh (2), Dipl.-Ing. (FH) Fabian Kurzidim (3) 

(1) KraussMaffei Berstorff GmbH, Hannover, Germany 

(2) Rheinisch-Westfälische Technische Hochschule Aachen, Lehr- und Forschungsgebiet 

Kautschuktechnologie, Germany 

(3) Deutsches Institut für Kautschuktechnik, Hannover, Germany 

Dietmar.Becker@kraussmaffei.com 

From a morphological point of view Thermoplastic Vulcanisates (TPV) are dispersions of 

chemically crosslinked rubber particles in a matrix of a continuous thermoplastic phase. This 

is the most significant difference compared to other polymer blends made only of thermoplastic 

components. Because of this morphology, TPV show rubber-elastic behaviour at operation 

temperature. In contrast to rubber, the material melts at high temperatures and can be processed 

like a thermoplastic resin. 

The production process of TPV consists of two main steps. The first one is the mixing of the 

thermoplastic with the non-crosslinked rubber to achieve a co-continuous phase. The second 

one is the phase inversion with dynamic crosslinking of the rubber particles. The mechanical 

properties of TPV depend on the size of the rubber particles. The smaller they are, the better 

the properties. So for the production process, it is important to achieve the smallest possible 

size. 

TPV can be produced discontinuously in batch mixers or continuously on co-rotating twinscrew 

extruders. Because of its high efficiency, the continuous process is the most common 

one in industrial production. The standard parameters to design the process on a twin-screw 

are screw diameter, extruder length, screw configuration, output rate, screw speed and temperature 

profile. 

Since a co-rotating twin-screw is always running at an underfed mode, output ratio and screw 

speed can be varied. Fundamental investigations for a typical recipe based on PP and EPDM 

with peroxide cross-linking show the influence of screw speed and design on phase morphology 

and mechanical properties. 

In continuous mixing processes, the quality essentially depends on the accuracy of the material 

feeding. For TPV-compounding, the dosing of the rubber components via standard gravimetric 

feeders often leads to troubles. The normally used rubber pellets have irregular shape 

and tend to adhesion. An alternative is the feeding of rubber strips via rubber extruder and 

gear pump. Rough-cut strips from rubber bales are drawn in by the rubber extruder, plasticized 

and fed into the gear pump. The gear pump feeds the rubber material volumetrically into 

the twin-screw extruder. There are also advantages in process technology. The preplasticizing 

causes lower viscosity of the rubber. This in turn facilitates the mixing with thermoplastic 

resins. 

The new concept also offers new possibilities for the production of peroxide-crosslinked TPV, 

based on PP and EPDM. In an internal mixer, a rubber compound is produced which already 

includes the cross-linking system as well as further additives. In form of strips, this compound 

is fed via rubber extruder and gear pump into the compounding extruder. So the PP, which is 

separately fed into the twin-screw extruder, does not get in direct contact with the peroxide. 

Its degradation can be thus avoided. Experimental studies show a significant improvement of 

product quality. 

- 24 -


MODELING STRUCTURE FORMATION IN DIBLOCK CO- 

POLYMER MATERIALS 

Marcus Müller, Kostas Ch. Daoulas 

Institut für Theoretische Physik, Georg-August-Universität, Friedrich-Hund-Platz 1, 

37077 Göttingen, Germany 

mmueller@theorie.physik.uni-goettingen.de 

Diblock copolymers self-assemble into a variety of periodic nanostructures in the bulk. The 

length scale is dicated by the molecular extension. If the copolymer material is in contact with 

a patterned surface, the morphology of the diblock copolymer may either replicate the surface 

pattern without defects over large scales or a more complex reconstruction of the soft morphology 

at the patterned surface occurs depending on the mismatch between the symmetry 

and length scale of surface pattern and bulk morphology. Some irregular patterns, which do 

not have an analog in the bulk morphology, can be replicated in the copolymer material by the 

addition of "defectants". These are substances, e.g., homopolymers or nanoparticles, that enrich 

at locations, where the substrate pattern deviates from the bulk morphology, reduce the 

excess free-energy of these local morphologies and permit defect-free replication. The application 

of copolymer materials has attracted abiding interest for templating nanostructures in 

microelectronics and catalysis. 

Using soft, coarse-grained polymer models, we investigate the directed assembly of copolymer 

materials on various patterns. These models allow us to investigate large, threedimensional 

systems with an experimentally relevant degree of polymerization by computer 

simulations. Methods for computing free-energy differences of self-assembled morphologies 

and grain-boundaries will be discussed. We study the influence of the line-edge roughness of 

the substrate pattern on the polymer morphology and the kinetics of ordering. 

- 25 -


ORDERED STRUCTURES AND NANOSTRUCTURED 

BLENDS FROM POLYDISPERSE POLYMERS 

Séverin Dronet, Ilias Iliopoulos, Ludwik Leibler 

Matière Molle et Chimie, ESPCI-ParisTech and CNRS (UMR-7167), 10 rue Vauquelin, 

75231 Paris cedex 05, France 

ilias.iliopoulos@espci.fr 

Reactive blending is a very efficient and industrially relevant method for the preparation of 

polymer blends. The presence of reactive groups along the backbone or at the chain-end of the 

blended polymers allows for the in-situ formation of graft and block copolymers which stabilize 

the polymer/polymer interface, prevent coalescence and improve the blend homogeneity. 

We will show that reactive blending can be used as a tool for the synthesis of graft copolymers 

and preparation of nanostructured blends starting from polydisperse polymers. We focus 

on glassy-crystalline systems composed of polyamide-6 and methyl (or butyl) methacrylate 

copolymers. Molar mass, density and, most importantly, distribution of the reactive units 

along the methacrylic backbone are key parameters that control the efficiency of grafting and 

the morphology of the resulting blends. These materials exhibit unique properties such as 

transparency, creep resistance and solvent resistance. 

- 26 -


STRUCTURE AND ADHESION IN REACTIVE INTERFACE 

BETWEEN DIFFERENT POLYMERS 

Toshiaki Ougizawa, Hideko T. Oyama, Takashi Inoue 

Tokyo Institute of Technology, Japan 

tougizawa@op.titech.ac.jp 

The equilibrium interfacial thickness between immiscible polymer-polymer is quite small and 

the adhesion is too weak. Because the physical properties strongly depend on the interfacial 

structure and adhesion between different polymers, the control of interfacial structure is very 

important for polymer blend materials. One of them is to use the coupling reaction at the interface 

between different polymers, in which graft or block copolymers that consists of both 

polymers are formed. In this study, the structure of reactive interface between immiscible 

polymers was investigated by ellipsometry, transmission electron microscopy (TEM), and 

atomic force microscopy (AFM). It was found by ellipsometric measurements that the interfacial 

reaction significantly increased the interfacial thickness, even reaching the size larger 

than the coil size of the copolymer formed at the interface. The interfacial structure and the 

properties were affected by the position and type of functional groups incorporated to the 

polymer, namely reaction groups and architecture of copolymer (graft or block). From AFM 

measurement of the surface remained after one polymer layer was dissolved out by selective 

solvent, an undulated interface was found. This is probably because in situ formed copolymers 

entropically destabilized the interface by adopting a tightly packed conformation at high 

copolymer concentrations, which resulted in an increase of the interfacial area. The interfacial 

thickness determined by ellipsometry seems to include the contribution of the amplitude of 

the undulation. 

The reactive interface resulting in the graft copolymers tended to be thicker than that forming 

the block copolymers. It may mean that the graft copolymer formation induces larger amplitude 

of undulation at the interfacial area in comparison with the block copolymer formation. 

However, the thinner interface by the block copolymer formation demonstrated a superior 

adhesion to the thicker interface by the graft copolymer formation. It is considered that the 

concentration of block copolymers formed by interfacial reaction at the interface becomes 

larger than one of graft copolymers easily, due to the architecture of copolymer. 

- 27 -


BLOCK COPOLYMERS AS TEMPLATES TO DEVELOP 

NANOSTRUCTURES IN THERMOSET MATRICES AND 

COMPOSITES 

A. Tercjak, C. J. Ocando, J. Gutierrez, E. Serrano, I. Mondragon 

Materials and Technologies Group, Dept. Chemical & Environmental Engineering, 

University of the Basque Country. Pza. Europa, 20018 Donostia-San Sebastián, Spain 

inaki.mondragon@ehu.es 

Amphiphilic block copolymers (BC) can be used as both nanostructuring agent for thermosetting 

(TS) matrices and as dispersing agent in polymer matrices for low-molecular-weight liquid 

crystals and nanoparticles. This work has two main aims: 1) development of nanostructured 

TS/BC mixtures also containing nanoparticles, and 2) confinement of high amounts of 

nanoparticles in microphase separated block copolymers. 

Thermosetting matrices can be nanostructured by addition of amphiphilic block copolymers 

consisting of TS-miscible and TS-immiscible blocks. To promote compatibilization of one of 

the blocks with the epoxy resin, BC can be chemically modified. The morphology development 

of two epoxy-based systems (EP) has been investigated. In the first system, the modification 

of an epoxy matrix with poly(styrene-b-butadiene) diblock copolymers epoxidized at 

several degrees is analyzed. Microstructures of the mixtures are developed either by an initial 

self-assembly - microphase separation of one block before curing - or by reaction-induced 

microphase separation, as depending on compatibilization degree. Fracture toughness seems 

to be closely related to the morphology but also to the extent of interactions between phases. 

In the second system, the variation of surface properties for the modification of an epoxy matrix 

with a BC containing fluoride groups in one of the blocks is shown. 

A strategy to develop thermally reversible light scattering TS matrix films by using liquid 

crystals (LC) through the confinement concept is also shown. The effect of addition of amphyphilic 

poly(styrene-b-ethylene oxide) (PSEO) block copolymer on the formation of 

meso/nanoordered epoxy matrix materials which retain the LC ability to switch from opaque 

to transparent state when subject to external stimuli is presented. 

With the second aim, the effect of using a block copolymer to obtain novel hybrid inorganic/organic 

materials on the basis of TiO2 nanoparticles is analyzed. The conductive and 

optical properties of TiO2 nanoparticles can produce large electro-optic effects on these novel 

hybrid inorganic/organic thermosetting materials. 

- 28 -


CONTROLLING THE MORPHOLOGY OF COCONTINUOUS 

POLYMER BLENDS VIA BLOCK COPOLYMERS 

Joel R. Bell, Kwanho Chang, Carlos R. López-Barrón, Christopher W. Macosko, 

David C. Morse 

Department of Chemical Engineering and Materials Science, University of Minnesota, 

Minneapolis, MN 55455, USA 

macosko@umn.edu 

Cocontinuous morphologies of polymer blends are thermodynamically unstable: they will 

coarsen when held above their glass or melting transition temperature. We have found that 

properly chosen diblock copolymers (bcp) can arrest coarsening during quiescent annealing. 

The effects of bcp on the cocontinuous morphologies of polystyrene (PS)/polyethylene (PE), 

PS/poly(methyl methacrylate) (PMMA) and PS/styrene-ran-acrylonitrile copolymer (SAN) 

blends were studied using scanning electron microscopy (SEM) and laser scanning confocal 

microscopy (LSCM) with image analysis. Bcp effectiveness was dependent on copolymer 

molecular weight, concentration, and asymmetry. Our interpretation emphasizes the role of 

bcp micelle creation and destruction as potential bottlenecks in the kinetics of interfacial adsorption 

of copolymer during mixing and of interfacial desorption during coarsening. In cases 

where adsorption and desorption appear to be facile, our results for the rate of coarsening are 

consistent with equilibrium predictions for the dependence of interfacial tension upon copolymer 

asymmetry. We show that the coarsening of cocontinuous blends can provide a 

method to quantify the reduction in interfacial tension due to block copolymer addition, which 

is difficult to measure by conventional methods. 

- 29 -


BLOCK-COPOLYMER DERIVED PHOTOVOLTAIC DEVICES 

U. Steiner 

Cavendish Laboratory, University of Cambridge 

u.steiner@phy.cam.ac.uk 

The device performance of organic or organic/inorganic hybrid photovoltaic materials depends 

sensitively on the morphology of the photoactive layer. The use of block-copolymer 

morphologies to generate co-continuous morphologies by self-assembly is conceptionally 

attractive because the intrinsic periodicity of coil-coil block-coplyers of ~10 nm matches the 

electronic requirements imposed by semiconducting organic materials. 

My talk wit introduce three different strategies in which block-copolymers are used as structural 

motives in photovoltaic devices: (1) as molecular scaffolds for metal-oxides in dyesensitised 

solar cells, (2) as structure-dirceting agents for sol gel-chemistires, and (3) in conjugated 

polymer-polymer heterojunction devices 

- 30 -


MORPHOLOGICAL MEASURES FOR COMPLEX POLYMER 

GEOMETRIES 

Klaus Mecke, Gerd Schröder-Turk 

Institut für Theoretische Physik, Universität Erlangen-Nürnberg, Staudtstrasse 7, 

91058 Erlangen, Germany 

klaus.mecke@physik.uni-erlangen.de 

Micro- and nanostructured polymeric systems are of increasing technological importance due 

to their shape-dependent material properties. Although the shape of disordered structures is a 

remarkably incoherent concept, the topology (connectivity) and geometry of spatial structures 

can be characterised by Minkowski functionals, which provide a possible link between shape 

and material properties. These measures are well known in image analysis and integral geometry, 

are numerically robust, and can be calculated effectively from voxelized data. For 

instance, the dynamics of block copolymer micro-domains can be described by morphological 

maps of local scalar measures which enable us to track the time evolution of the phases. Recently 

self-assembly of complex polymer phases that are not isotropic has attracted attention, 

e.g thin film polymer self-assembly in external fields or equilibrium bicontinuous network 

structures with non-cubic symmetry. For a morphological analysis of such non-isotropic processes, 

suitable morphometric measures are needed that are explicitly sensitive to orientation 

and anisotropy. We introduce the so-called Minkowski Tensor Valuations, generalisations of 

the scalar functionals, as a set of such morphological measures and demonstrate their usefulness 

by application to planar microscopy data of thin films in external fields and electrontomography 

data of a self-assembled non-cubic network phase in linear terblock copolymers. 

- 31 -


A NEW MODEL FOR THE EFFECT OF ELASTOMER 

PARTICLE SIZE ON NOTCHED IMPACT BEHAVIOR OF 

POLYMER BLENDS 

C. B. Bucknall (1), D. R. Paul (2) 

(1) Cranfield University, Bedford MK43 0AL, UK 

(2) The University of Texas at Austin, Department of Chemical Engineering, Austin, 

TX 78712, USA 

drp@che.utexas.edu 

A model is proposed to explain the observed relationships between particle size and fracture 

resistance in high-performance blends of semi-ductile polymers with elastomers, which typically 

reach maximum toughness at particle diameters of 0.2-0.4 μm. To date there has been no 

satisfactory explanation for the ductile-brittle (DB) transition at large particle sizes. The 

model is based on a recently-developed criterion for craze initiation, which treats large cavitated 

rubber particles as craze-initiating Griffith flaws. Using this criterion in conjunction with 

Westergaard’s equations, it is possible to map the spread from the notch tip of three deformation 

mechanisms: rubber particle cavitation, multiple crazing and shear yielding. Comparison 

of zone sizes leads to the conclusion that maximum toughness is achieved when the particles 

are large enough to cavitate a long way ahead of a notch or crack tip, but not so large that they 

initiate unstable crazes and thus reduce fracture resistance. 

Calculations for a specific 80/20 polyamide/rubber blend show that when the rubber particles 

(assumed monodisperse in size) have very small diameters (D < 0.03 μm) they are unable to 

cavitate because the critical stress for cavitation lies above the (constrained) shear yield stress 

of the blend, which is itself extremely high. Increasing D beyond 0.03 μm enables the particles 

to cavitate before the material yields, and consequently reduces the shear yield stress, 

which at this stage is a function of the volume fraction of cavitated particles. Over a size 

range from 0.03 μm to 0.08 μm, the shear yield stress is controlled by the cavitation stress, 

and increasing D continuously decreases the major principle stress at yield, σ1y, leading to a 

rapid increase in toughness. Eventually, the cavitation stress falls below the shear yield stress 

of the fully-cavitated blend, and toughness reaches a maximum. 

A less desirable result of increasing particle size is that it reduces the critical stress for craze 

initiation, because large cavitated particles act as very effective Griffith flaws. Formation and 

subsequent failure of crazes causes fracture of the yield zone before it has fully developed. If 

the particles are very large and σcraze


POLYMER INCOMPATIBILITY CAUSED BY DIFFERENT 

MOLECULAR ARCHITECTURES 

J. Eckelt (2), F. Samadi (1), F.-J. López-Villanueva (3), H. Frey (3), B. A. Wolf (1) 

(1) Institut für Physikalische Chemie der Johannes Gutenberg-Universität Mainz, 

Jakob Welder Weg 13, 55099 Mainz, Germany 

(2) WEE-Solve GmbH Auf der Burg 6, 55130 Mainz, Germany 

(3) Institut für Organische Chemie der Johannes Gutenberg-Universität Mainz, Germany 

Bernhard.Wolf@Uni-Mainz.de 

According to early reports from polyolefin industry, polymers synthesized from the same 

monomeric units but differing in their molecular architecture may not be completely miscible. 

Since then numerous experimental and theoretical studies have dealt with that phenomenon. 

The theoretical part of this contribution demonstrates that a thermodynamic approach [1] accounting 

for the two most obvious deficiencies of the Flory-Huggins theory (neglect of important 

consequences of chain connectivity and not considering the conformational variability of 

macromolecules) can model this type of polymer incompatibility with only one physically 

significant, system specific parameter. Experimental evidence that linear and branched polymers 

may in fact become incompatible is provided for polyisoprene [2]. 

The calculation of phase diagrams according to the present approach subdivides the mixing 

process into two steps: (i) contact formation between the different components, keeping their 

chain conformations and the volume of the system constant and (ii) relaxation of the macromolecules 

into their equilibrium state by molecular rearrangements. For the present modeling 

it is assumed that it is step (ii), which causes the shape induced polymer incompatibility and 

that the degree of branching can be quantified in terms of the volumes the isolated coil of the 

branched polymer occupies in relation to the volume the linear product with the same molecular 

weight requires. Under these premises it is possible to work out how the segregation of a 

second phase depends on the molar masses of the components and on the degree of branching 

of the non-linear polymer by means of one system specific parameter, measuring the effects 

of the conformational relaxation. 

[1] Wolf, B. A. "Polymer Incompatibility Caused by Different Molecular Architectures: Modeling via Chain 

Connectivity and Conformational Relaxation" Macromol. Theory Simul. 2009, in print 

[2] Samadi, F.; Eckelt, J.; Wolf, B. A.; López-Villanueva, F.-J.; Frey, H. "Branched versus linear poly-isoprene: 

Fractionation and phase behavior" Eur. Polym. J. 2007, 43, 4236–4243. 

- 33 -


SEPARATION OF MINOR MACROMOLECULAR CONSTI- 

TUENTS FROM MULTICOMPONENT POLYMER BLENDS BY 

NOVEL LIQUID CHROMATOGRAPHIC TECHNIQUES 

Dusan Berek 

Polymer Institute, Slovak Academy of Sciences 

Dusan.Berek@savba.sk 

Multicomponent polymer systems - such as blends or block copolymers that contain their parent 

homopolymers - are to be separated to assess molecular characteristics of their constituents. 

Liquid chromatography under limiting conditions of enthalpic interactions, LC LC 

represents an unconventional, novel, isocratic, fast, robust and feasible tool to accomplish 

such separations on analytical and preparative scale. LC LC combines exclusion and interaction 

retention mechanisms in a column filled with porous particles. The difference in the slow 

elution of small, pore permeating molecules of solvents and the fast transport of pore excluded 

macromolecules is utilized. Appropriately chosen small molecules introduced in front 

of polymer sample promote enthalpic interactions of macromolecules in the liquid chromatographic 

system and thus create a slowly progressing barrier, which selectively decelerates 

elution of certain kind(s) of polymer species, while the not retained constituent is fast eluted 

in the exclusion mode. In this way, constituents of complex polymer systems of different nature 

are efficiently separated irrespective of their molar mass. Of the approaches tested, the 

procedure with narrow zones of adsorption promoting solvents injected in from of sample 

solution proved most efficient. It is called liquid chromatography under limiting conditions of 

adsorption, LC LCD. LC LCD with bare silica gel column packings is very robust, insensitive 

toward rather large eluent composition changes, pore size and purity of column packing, flow 

rate and concentration of injected polymer, as well toward temperature variations. Appropriately 

advised LC LCD systems produce focused peaks and exhibit high to almost complete 

sample recovery. This is a difference with all so far known coupled methods of polymer liquid 

chromatography applied in separation of multicomponent polymer systems such as liquid 

chromatography under critical conditions of enthalpic interactions and eluent gradient liquid 

chromatography, which often cope with reduced or even substantially reduced sample recovery. 

The retentive properties of barriers mostly depend on their composition, which can be 

easily adjusted. It was revealed that appropritely chosen barrier is able to quantitatively decelerate 

very small amout (


MODELING MECHANICAL BEHAVIOR OF ELASTOMERIC 

NANOCOMPOSITES BASED ON STYRENE BUTADIENE 

RUBBER 

A. L. Svistkov (1, 2), A. G. Pelevin (1, 2), B. Lauke (1), K.W. Stöckelhuber (1), 

G. Heinrich (1), A. A. Adamov (2) 

(1) Leibniz-Institut für Polymerforschung Dresden e.V., 01069 Dresden, Germany 

(2) Institute of Continuous Media Mechanics UB RAS, 614013 Perm, Russia 

pelevin@icmm.ru 

The work presents an analysis of rubber compounds by comparing the parameters of a phenomenological 

mechanical model of rubber for fourteen types of nanocomposites. Constitutive 

equations are constructed using a scheme that is illustrating the mechanical behavior of 

rubber compounds. The new model represents the superpostion of elastic, viscous, plastic and 

transmission elements. To describe the properties of each element, the known equations of the 

nonlinear theory for elasticity, the theory of nonlinear viscous fluids and the theory of plastic 

flow under finite deformations are used. The scheme shows how the tensorial nonlinear equations 

are combined into the system of equations proposed in [1]. A step by step algorithm is 

proposed to derive the constants of the model. It is shown that the constants of constitutive 

equations found at earlier steps remain unchanged at subsequent steps [2]. Experiments like 

cyclic loading tests including relaxation and creep provide useful information concerning the 

viscoelastic properties and the softening behavior of the rubber compounds. 

The model is used for simulating the mechanical behavior of different samples of rubber 

compounds. In all cases the rubber matrix consists of solution - styrene butadiene copolymers, 

filled with 20 or 40 phr with pyrogenic and precipitated silicas with different surface modifications 

by different silanes and one carbon black sample as reference.. 

The theoretical results describe accurately the mechanical behavior of rubbers for all samples 

considered in this work. 

The work was supported by integration project of fundamental research, performed jointly by 

scientists UB RAS, SB RAS and FEB RAS, Grant RFBR 09-08-00530-а, DFG-FOR 597 and 

DFG-Priority Program 1369 "Polymer-Solid Contacts: Interphases and Interfaces" 

[1] Svistkov A. L., Lauke B., Heinrich G.: Modeling of viscoelastic properties and softening of rubber materials//Proceedings 

of 5th European conference “Constitutive models for rubbers”, Paris, 2007, pp. 113-118. 

[2] Pelevin A. G., Lauke B., Heinrich G., Svistkov A. L., Adamov A. A.: Algorithm of constant definition for a 

visco-elastic rubber model based on cyclic experiments, stress relaxation and creep data//Proceedings of the 

sixth European conference on Constitutive models for rubber, Dresden, 2009, pp. 79–84, 113–120. 

- 35 -


EFFECT OF PRESSURE ON THE DYNAMIC HETERO- 

GENEITY IN MISCIBLE BLENDS 

G. Floudas 

(1) University of Ioannina, Department of Physics, P.O. Box 1186, 451 10 Ioannina, Greece 

(2) Foundation for Research and Technology-Hellas (FORTH), Biomedical Research 

Institute (BRI), Greece 

gfloudas@cc.uoi.gr 

Miscible polymer blends despite being thermodynamically mixed, can exhibit distinct dynamic 

behavior, known as dynamic heterogeneity [1]. Different models have been proposed 

to account for the distinct component dynamics that emphasize either intermolecular concentration 

effects through the concentration fluctuation approach, or intramolecular effects 

through the chain connectivity or various combinations of both. Herein we review recent 

work on the effects of pressure on the dynamic heterogeneity on two miscible polymer blends 

with large dynamic asymmetry. The first system is the poly(methyl methacrylate) 

(PMMA)/poly(ethylene oxide) (PEO) blend [2]. The system facilitates a test of the predictions 

of the self-concentration model proposed by Lodge and McLeish [1], at elevated pressures. 

We find that pressure increases the glass temperature and slows-down the segmental dynamics 

but does not affect the length-scale or the self-concentration associated with the dynamic 

glass transition. The second system is the polystyrene (PS)/poly(methyl phenyl siloxane) 

(PMPS) blend [3]. In these blends there is interplay between spinodal decomposition and 

glass transition resulting in the enrichment of the high Tg component by the more mobile 

component. Model calculations using a lattice-based equation of state lead to prediction of the 

phase diagram, as well as the effect of pressure on the critical temperature. The weak pressure 

sensitivity of the critical temperature (dTc/dP), compared to the two segmental relaxations, 

suggests that a transition to a thermodynamically miscible but dynamically heterogeneous 

state takes place for pressures above 300 MPa. 

[1] Zetsche, A., Fischer, E. W.: Acta Polymer, 1994, pp. 45, 168; Lodge, T. P., McLeish T. C. B.: Macromolecules 

2000, pp. 33, 5278; Chung G.-C., Kornfield, J. A., Smith, S. D.: Macromolecules 1994, pp. 27, 964 

[2] Mpoukouvalas, K., Floudas, G.: Macromolecules 2008, pp. 41, 1552 

[3] Gitsas, A., Floudas, G., White, R. P., Lipson, JEG Macromolecules 2009, pp. 42, 5709 

- 36 -


STRUCTURE-PROPERTIES OF A HIGH-PERFORMANCE 

PLA ALLOY: TOUGHENING BY THE EVOLUTION OF 

NEGATIVE PRESSURE 

Kazuhiro Hashima, Takashi Inoue 

Yamagata University, Japan 

tinoue@yz.yamagata-u.ac.jp 

Poly(lactic acid)(PLA) is a thermoplastic aliphatic polyester derived from renewable resources. 

Much attention is paid for the green polymer; however, it has many drawbacks: poor 

mechanical properties (Izod impact strength =3kJ/m2, elongation at break=3 %), low heat 

resistance (HDT≈60 o C), and poor processability (high temperature mold is required to result 

in a long cycle time for injection molding). 

By reactive blending of PLA with poly(ethylene-co-glycidyl methacrylate) together with hydrogenated 

styrene-butadiene-styrene block copolymer (SEBS) and polycarbonate, we successfully 

developed a super-tough alloy: high Izod impact strength (=63kJ/m2) and elongation 

at break (=91%). The alloy was not suffered from high temperature annealing (e.g., at 80 o C 

for 48 h); i. e., no serious deterioration of the mechanical properties. 

DMA analysis showed that the dynamic loss (tan δ) peak for Tg of EB (ethylene-co-butylene 

block of SEBS) at around -40 o C shifts to lower temperature (-50 o C) in the alloy. The Tg depression 

suggests the negative pressure imposed on the dispersed rubber (SEBS) phase, resulting 

from differential contraction due to the thermal shrinkage mismatch upon cooling from 

liquid state. The β-relaxation temperature (Tβ), at which local segmental motions start up, was 

observed at around -80 o C for neat PLA. The Tβ shifted to lower temperature (around - 

120 o C) in the alloy. The Tβ depression corresponds to a higher chain mobility of PLA matrix 

that should lead to the higher toughness and ductility. It may result from a dilational effect for 

the matrix ligament between the particles: caused by the negative pressure in the dispersed 

rubber particles. 

DSC analysis showed that the heat of fusion increased from 9 to 33 J/g by the high temperature 

annealing. It may suggest that the dilational effect works well even after the significant 

crystallization in PLA matrix. 

- 37 -


RELATIONSHIPS BETWEEN PROCESSING, PHASE 

DISPERSION AND MECHANICAL PERFORMANCE IN 

POLYPROPYLENE FILLED COMPOUNDS 

Pablo I. Aguayo 

Polyolefine GmbH, St.-Peter-Strasse 25, 4021 Linz, Austria 

pablo.aguayo@borealisgroup.com 

The importance of distributive and dispersive mixing for the high performance of filled polyolefin 

compounds has widely been investigated and documented in the literature. However 

quantitative methods to evaluate the quality of dispersion are still rare and complicated. Frequently 

a comparative study of micrographs is used to evaluate phase mixing and dispersion 

in solid specimens. Phase dispersion in compounds determines its mechanical properties and 

therefore it is very important to understand the link between processing and phase morphology. 

In the present investigation the link between processing conditions and mechanical properties 

has been systematically studied. Controlled extruder configuration, i.e. temperature zones and 

screw configuration, as well as process parameters have been selected to produce a model 

impact-PP/talc compound. The distribution and dispersion of the different phases has been 

studied in injection moulded specimens by microscopy methods. A quantitative analysis of 

the micrographs has been made by using computational methods. Mechanical performance of 

the material has been illustrated in form of impact/stiffness balance which is widely used in 

comparative studies of compounds. 

The major effect of screw and process configuration can be observed on the scattering of mechanical 

properties. On the one hand, slower screw speed combined with a short dispersing 

mixing section in the extruder screw, induces to large property scattering, also frequently accompanied 

with poor mechanical performance. On the other hand, at higher screw speeds and 

setting longer dispersing mixing sections, a significant increase of the average mechanical 

property as well as a reduced scattering of the values has been observed. In this work some 

indications about screw design and how to set process parameters (e.g. torque load, screw 

speed and throughput) to achieve specific mechanical performance are discussed. 

- 38 -


DYNAMIC VULCANIZATION OF PP/EPDM THERMO- 

PLASTIC ELASTOMERS CONTAINING PP OF VARIOUS 

MOLECULAR WEIGHT 

Eduard V. Prut, Tat'yana I. Medintseva 

Semenov Insitute of Chemical Physicas of Russian Academy of Sciences, Moscow, Russia 

evprut@center.chph.ras.ru 

Blends of PP with elastomers are widely used as high-impact materials when the elastomer 

content is low or as thermoplastic elastomers (TPE) when the elastomer content is high. Thus, 

owing to the unique combination of mechanical and rheological behaviors of the components 

in a final product, thermoplastic elastomers (TPE), based on PP and various elastomers, are 

among the most widely used industrial materials. TPE combines the advantageous mechanical 

properties of conventional rubbers with an easy processability inherently belonging to linear 

thermoplastic polymers above their melting temperatures. The properties of TPEs can be substantially 

improved using the method of dynamic vulcanization. Dynamic vulcanization is the 

process of vulcanizing an elastomer during its melt-mixing with a molten thermoplastic resin, 

wherein the vulcanized elastomers are present as finely dispersed particles in thermoplastic 

matrix. TPEs prepared by dynamic vulcanization are identified as thermoplastic vulcanizates 

(TPVs). TPVs based on PP and ethylene-propylene-diene rubber (EPDM) are the most important 

materials from the commercial and scientific points of view. 

In this work, the mechanical and rheological behavior of unvulcanized and dynamically vulcanized 

PP/EPDM blends (TPEs and TPVs) was investigated. The polymers used in this study 

were PP of various molecular weight, EPDM Dutral TER 4044 and oil-extended EPDM 

Dutral TER 4535 (content of paraffinic oil 50 wt %). Vulcanization was performed with sulfur 

curing system. 

The blends were prepared in a Brabender plasticorder mixer at 1900C. 

It was shown that the Young’s modulus and tensile strength of TPEs and TPVs decreased as 

the elastomer content grew. 

The Young’s modulus of unvulcanized and dynamically vulcanized PP/EPDM blends decreased 

with increasing molecular weight of PP when EPDM content was less than 

50 wt %. The Young’s modulus of unvulcanized and dynamically vulcanized PP/EPDM 

blends was independent of molecular weight of PP with EPDM content higher than 50 wt %. 

The Young’s modulus of TPEs samples was higher than the corresponding values for TPVs. 

The tensile strength of TPEs and TPVs increased with molecular weight of PP. The tensile 

strength of TPEs samples was higher than that of TPVs. 

The elongation at break of TPEs and TPVs presented a complicated function of the elastomer 

content. The elongation at break of PP/EPDM blends decreased as molecular weight of PP 

decreased. 

The amount and the type of EPDM had a strong effect on the rheological properties of TPEs 

and TPVs. It was shown that the dynamic vulcanization results in a significant increase of 

melt viscosity of PP/EPDM blends. It was found that the rheological properties of TPVs are 

higher than those of TPEs. The melt viscosity of PP/EPDM blends increased with molecular 

weight of PP. 

The rheological behavior of PP/EPDM based on oil-extended EPDM was improved while the 

Young’s modulus and the tensile strength were deteriorated. 

- 39 -


THERMOSTABLE POROUS POLYSTYRENE/POLY- 

CYANURATE IPNS VIA POLYMERIZATION OF HIGH 

INTERNAL PHASE EMULSIONS 

A. Fainleib (1), O. Grigoryeva (1), L. Bardash (1), A. Menner (2), A. Bismarck (2) 

(1) Institute of Macromolecular Chemistry of the National Academy of Sciences of Ukraine, 

Kyiv, Ukraine 

(2) Chemical Engineering, Polymer & Composite Engineering Group, Imperial College 

London, UK 

fainleib@i.kiev.ua 

In recent years high internal phase emulsions (HIPEs) with a continuous organic phase consisting 

of monomers, crosslinker and an emulsifier gained increasing interest. HIPEs are 

commonly defined as emulsions in which the dispersed phase occupied more than 74 % of the 

emulsion volume, i.e. more than the maximum packing fraction for identical spheres. The 

polymerisation of the monomer phase of the emulsion, which can be oil or aqueous phase, 

leads to the formation of highly porous (up to 95 %) low density polymer foams, so called 

polyHIPEs. Three kinds of polystyrene (PS)/polycyanurate (PCN) foams with the structure of 

IPNs, sequential and in situ sequential have been synthesized using HIPE approach. In a first 

method polystyrene/tri(oxyethylene)-a,w-dimethacrylate foam formed at 75 o C during 24 h 

was swelled by dicyanate ester of bisphenol E (DCBE) and then the latter was cured step by 

step at 150-250 o C during 15 h. In a second method all the components were mixed together 

and polystyrene network was obtained first and then the polycyanurate network was synthesized 

inside the polystyrene foam using the same temperature/time schedule. Third method 

was a combination of two previous ones: the in situ sequential PS/PCN IPNs were synthesized 

first, and then the product was swelled with DCBE additionally followed by thermal 

curing of the latter. The PS/PCN IPNs polyHIPEs with different component ratio were synthesized 

and characterized. It has been established that the final polyHIPEs from polystyrene/polycyanurate 

IPNs are characterized by higher thermal stability and higher glass transition 

temperature compared to the pure polystyrene foam. Depending on method of synthesis 

and composition the obtained polyHIPEs show varying in wide interval density values and 

porosity volume. 

- 40 -


RECENT STATE OF THE ART IN REAL TIME MORPHOLOGY 

ANALYSIS OF FLOWING POLYMER BLENDS AND 

NANOCOMPOSITES DURING EXTRUSION PROCESSING 

BY MEANS OF OPTICAL PARTICLE SENSING 

Stephan Grosse (1), Andreas Rudolph (1), Michael Stintz (2) 

(1) Topas GmbH Dresden 

(2) Technische Universität Dresden 

sgrosse@topas-gmbh.de 

To achieve tailor made product properties it is a common technique to mix various standard 

polymers within a twin screw extruder. Incompatibility of the involved polymers results in a 

multiphase system with disperse droplets of the minor polymer component distributed in a 

matrix of the major polymer component. Blend morphology is strongly depending on extruder 

configuration and processing parameters during extrusion. In general high shear forces during 

extrusion will result in a fine blend morphology which gives best final product properties. By 

applying a real time characterization of polymer blend morphologies at changed extrusion 

processing conditions a much more effective optimization of final product properties can be 

realized compared to standard offline morphology analysis. There are the same interrelations 

for the degree of dispersion and exfoliation of nanocomposite materials which will also be 

part of this contribution. 

In terms of a real time process analytical technology (PAT) an optical particle sensor based on 

a light extinction measurement has been designed, optimized and tested for several years. For 

extruder access of the sensor technique a standard ½”20UNF thread is used. Sensitivity, reliability 

and robustness of the sensor at typical extrusion processing conditions have been 

proven during long-term operation at industrial production environments. 

A versatile number of applications in polymer processing can be covered because different 

modes of signal evaluation are combined with different optical sensor configurations. From an 

integral signal analysis mean particle sizes at a known concentration of flowing polymer 

blends can be determined in real time. This quantitative calculation following Lambert-Beer’s 

law is possible because polymer blend particles usually show a spherical shape and narrow 

size distributions. The most critical limitation of this optical method is related to moderate 

blend concentrations in order to avoid multiple scattering effects. Refractive indices required 

as an input parameter for these calculations have been measured at processing temperature for 

the used polymers by a special inline refractometer. For investigation blends have been made 

from polystyrene, polypropylene, polyamide and polymethylmetacrylate. Blend morphology 

results of the inline sensor have been compared with the traditional offline analysis using 

SEM and image analysis. A good correlation has been observed between the two methods. 

At the moment research is focussed on real time evaluation of nanofiller dispersion during 

extrusion processing. As nanocomposites do not show spherical particles with a narrow size 

distribution a calculation of mean particle dimensions from light extinction measurements is 

not reasonable. Nevertheless changes of the nanofiller dispersion at changed extrusion processing 

conditions can be monitored in real time which makes this method a useful tool for a 

very effective product optimization. 

- 41 -


TOWARDS SUBMICRON THERMOPLASTIC VULCANI- 

ZATES: SYNTHESIS, MORPHOLOGY AND PROPERTIES 

Roy l'Abee, Han Goossens, Martin van Duin 

Eindhoven University of Technology, Department of Chemical Engineering and Chemistry, 

Laboratory of Polymer Technology 

j.g.p.goossens@tue.nl 

Thermoplastic vulcanizates (TPVs) are blends consisting of a large amount of cross-linked 

rubber particles dispersed in a thermoplastic matrix, which leads to a unique combination of 

elastic properties and melt (re)processability. Commercial TPVs are typically based on isotactic 

poly(propylene) (iPP) and ethylene-propylene-diene (EPDM) rubber and are prepared by 

dynamic vulcanization, where the rubber is selectively cross-linked during melt mixing with 

the thermoplastic. 

It has previously been shown that a decrease in the rubber particle size of TPVs leads to an 

improvement of the elongation at break and the tensile strength. In this talk, the influence of 

the rubber particle size on the tensile properties, the elastic recovery and the melt processability 

of TPVs is discussed. Since the rubber particle size of traditional iPP/EPDM-based TPVs 

prepared via dynamic vulcanization is limited to 1-3 µm, alternative approaches for the preparation 

of sub- µm TPVs were investigated. These approaches are based on an increased compatibility 

between the thermoplastic and the rubber phases. First, the dynamic vulcanization of 

highly compatible, yet immiscible blends of copolymers of atactic polypropylene (aPP) and 5ethylidene-2-norbornene 

(ENB) (aPP-co-ENB rubber) in combination with iPP is discussed. 

TPVs with refined morphologies and improved tensile properties were obtained, although the 

relatively high glass transition temperature of the aPP-co-ENB rubber retards the elastic recovery. 

Secondly, TPVs were prepared via reaction-induced phase separation (RIPS) of initially 

miscible blends of semi-crystalline thermoplastics and low-molar-mass rubber precursors. 

TPVs with small rubber particles (70-500 nm) were obtained over a very broad composition 

range; up to 80-90 wt% of cross-linked rubber could be dispersed in the thermoplastic 

matrix. This versatile approach leads to sub- µm TPVs with an interesting combination of 

mechanical and rheological properties. 

- 42 -


EFFECT OF STYRENE AND VINYL CONTENT OF STYRENE 

BUTADIENE RUBBER ON DISPERSION AND DISTRIBUTION 

OF CARBON BLACK IN SBR/NR BLENDS 

Sybill Ilisch (1), Hai Hong Le (1), Evemarie Hamann (2), Hans-Joachim Radusch (1) 

(1) Martin Luther University Halle-Wittenberg, Germany 

(2) Dow Olefinverbund GmbH, Germany 

sybill.ilisch@iw.uni-halle.de 

The majority of technical rubber materials used are composites on the basis of rubber blends. 

The properties of such composites depend to a large extend on the morphology and localization 

of the filler in the blend phases. For a carbon black filled natural rubber/solution styrene 

butadiene rubber (NR/SSBR (50/50)) blend system, the styrene and vinyl content of the SSBR 

was changed systematically. 

The morphology development during the mixing process was investigated by the online 

measured electrical conductance (OMEC) in a special prepared laboratory kneader. The filler 

macro dispersion was estimated by means of optical microscopy of samples taken out of the 

mixing process at different mixing times. From these images the dispersion index as measure 

for the carbon black macro dispersion was calculated. The phase specific carbon black localization 

in the NR and SBR phase was analyzed by thermo-gravimetric measurements on the 

rubber-filler gel. For the vulcanized samples, dynamic mechanical measurements were performed 

in dependence of the temperature. 

It was expected, that a higher styrene content in SBR causes a higher affinity to the carbon 

black surface, because of the increased polarity. For single mixtures this was shown: the infiltration 

time shifts to lower values with increasing styrene content in the SBR. 

For the blends, the behaviour in the mixing process and the resulting phase specific carbon 

black distribution is much more complicated. With increasing styrene content of the SBR, the 

difference of the solubility parameter of the rubbers increases and the viscosity relationship 

changes. Obviously, the morphology development during the mixing process of the rubber 

blends is influenced firstly by the wetting behaviour of the rubber chains to the carbon black 

surface, but also by the viscosity and compatibility of the rubbers and their affinity to the 

filler. 

The styrene content of the SSBR has a stronger influence on the phase specific localization of 

the carbon black in the binary blends than the vinyl content. 

- 43 -


PROCESSABILITY AND MORPHOLOGICAL ANALYSIS OF 

THERMOPLASTIC POLYURETHANE-CARBON NANOTUBE 

COMPOUNDS 

Domenico Acierno, Pietro Russo, Paola Spena 

Department of Materials and Production Engineering, University of Naples Federico II 

pietro.russo@unina.it 

ThermoPlastic Elastomers (TPE) combine toughness and processing advantages of thermoplastics 

with the elasticity of elastomers without the addition of any vulcanizing agent. 

Among these materials, polyurethanes (PU) are one of the most versatile materials because 

their properties can be widely modified by selecting appropriate monomeric materials, catalysts 

and auxiliary compounds and nowadays a wide range of these resins, developed to meet 

specific process requirements and, therefore, application requirements, is already commercially 

available. 

In details, polyurethane chains consist of two chemically distinct structural units, i.e. hard and 

soft segments with glass transition temperatures above and below the room temperature, respectively. 

In general, soft segments are constituted by aliphatic polyethers or polyesters having 

a low molecular weight (1000-3000) while hard segments are based on aromatic diisocyanates 

chain extended with small size diols or diamines. The thermodynamic incompatibility 

between these two segments, usually results in a phase-separated heterogeneous structure of 

hard and soft domains and interphases between them. Upon the microphase separation hard 

phases tend to aggregate by mutual hydrogen bondings increasing mechanical and thermal 

stability whereas the soft segments form random-coil conformations to impart elastic properties. 

Despite the above mentioned advantages, these materials show also some weaknesses such as 

low thermal and dimensional stability at elevated temperature; drawbacks that inevitably restrict 

their applications. 

For this reason, already in the early 90s, the incorporation of short fibers with high thermal 

resistance and high strength (Kevlar) stimulated a great interest. Similarly, recent attention 

has been devoted to polyurethanes filled with carbon nanotubes (CNTs) owing to their unique 

multifunctional properties. 

In this paper, we report the results of our study on processability and morphological aspects of 

a film grade TPU elastomer reinforced with multiwalled carbon nanotubes (MWNTs). In particular, 

TPU/MWNT nanocomposite were prepared by melt blending and the effect of the 

external diameter of nanotube samples having the same average length on the shear flow of 

composite melts as well as on their elongational parameters has been analyzed. Moreover, 

with the aim to optimize processing conditions and to obtain an opportune level of filler dispersion, 

rheological and viscoelastic parameters have been considered in correlation with 

morphological observations. 

- 44 -


CREEP ELONGATIONAL EXPERIMENTS – NEW TOOL FOR 

INVESTIGATIONS OF MORPHOLOGY DEVELOPMENT IN 


Zdeněk Starý, Florian Machui, Helmut Münstedt 

Institute of Polymer Materials, Friedrich-Alexander University Erlangen-Nürnberg, 

Martensstraße 7, 910 58 Erlangen, Germany 

zdenek.stary@ww.uni-erlangen.de 

Elongation is the dominant flow in many polymer processing technologies such as blow 

molding, fiber spinning, biaxial stretching and thermoforming. Elongational flow is also involved 

in extrusion when material enters and exits the die. However, there are not many literature 

data concerning elongational flow in polymeric systems and only few papers are focused 

on polymer blends under extensional deformation. The properties of immiscible polymer 

blend are distinctively influenced not only by the properties of blends components but 

also by its phase structure. Therefore, the understanding of the morphology development under 

elongation is of great interest from fundamental and application points of view. 

In this work the features of the elongational experiments at constant stress and their benefits 

regarding the morphology development are discussed. Contrary to the usually performed experiments 

at constant strain rate, the capillary number determining the deformation of the dispersed 

droplets is kept constant during whole experiment in creep setup. Therefore, the creep 

experiments are proper tool which can help to understand the fundamental problems of phase 

structure development under elongation. 

Blends of polystyrene and polyethylene (5, 10, 15 wt.%) as a typical example of immiscible 

system were studied. The morphology development during uniaxial elongation at constant 

stress was investigated using electron microscopy and consequent image analysis. The results 

obtained were compared with the predictions of capillary number model. A good agreement 

was found for the blend with 5 wt.% of PE whereas in the case of blends with higher amount 

of dispersed phase the preferential formation of long stable fibrils instead of droplet breakup 

at moderate values of capillary number was observed. 

In the last part of the contribution the influence of the presence of the compatibilizer at the 

interface on rheological properties and the morphology development is presented. It was 

found that addition of efficient compatibilizer changes substantially the deformation behavior 

of the dispersed droplets and markedly increases the elongational viscosity of the blend. 

- 45 -


ELECTRON INDUCED REACTIVE PROCESSING OF PP- 

EPDM THERMOPLASTIC VULCANIZATES 

Varun Thakur, Uwe Gohs, Udo Wagenknecht, Gert Heinrich 

Department of Polymer Processing, Leibniz Institute of Polymer Research Dresden e.V., 

Hohe Strasse 6, Dresden 01069, Germany 

gohs@ipfdd.de 

Thermoplastic vulcanizates (TPVs) exhibit a unique hybrid behavior of thermoplastic and a 

crosslinked rubber, which can flow under shear at elevated temperatures, yet behave as an 

elastomer at ambient temperature. TPVs based on Polypropylene (PP) and Ethylene Propylene 

Diene Monomer (EPDM) represents one of the commercially established TPVs with numerous 

applications. The rubber phase is generally crosslinked with phenolic resin or peroxides 

but despite of their advantages, both resin and peroxide crosslinked systems have their 

own limitations, e.g. moisture absorption, discoloration, foul smell etc. The present work 

deals with electron induced reactive processing of PP-EPDM TPVs, where the EPDM phase 

is crosslinked with high-energy electrons during the melt mixing with PP. The influence of 

various parameters like absorbed dose, electron treatment time, and electron energy on selected 

chemical, mechanical, and thermal properties as well as on morphology of the resulting 

TPVs has been discussed. 

- 46 -


IN-LINE MONITORING OF BLEND MORPHOLOGY BY 

SMALL ANGLE LIGHT SCATTERING DURING EXTRUSION: 

INFLUENCE OF PROCESSING CONDITIONS 

Bernd Steinhoff, Hans Kothe, Felix Simon, Ingo Alig 

Deutsches Kunststoff-Institut, Schloßgartenstraße 6, 64289 Darmstadt, Germany 

ialig@dki.tu-darmstadt.de 

Typical domain sizes of the two phase morphology in immiscible polymer blends to exhibit 

optimum mechanical performance (e.g. high impact strength) are between 100 nm and 1 micron. 

This length scale can be probed by small angle light scattering, and thus the method is 

well suited for in-line control of blend processing. 

First on-line light scattering experiments during extrusion were performed at about ten years 

ago at NIST (National Institute of Standards and Technology, USA) [1-3]. Analogue work 

can be found in [4-6]. 

The objective of this study was to understand the relationship between blend morphology (e.g. 

mean domain size and aspect ratio), processing conditions (e.g. shear rate) and material related 

parameters (e.g. melt viscosity). The advantage of in-line measurements for this purpose 

is that changes in morphology due to changes in the extrusion conditions can be detected instantaneously 

in the scattering pattern. 

For our experiments a slit die with sapphire windows and an optical detection system was 

developed [7] and attached to the outlet of a pilot plant twin screw extruder. A bypass was 

installed between the die and extruder to allow for a constant shear rate, while the total 

throughput of the extruder was varied. The angular range for detection of scattered light was 

1° to 30°. The extrusion experiments were performed on model blends of SAN/PMMA and 

PS/PC, and on technically relevant polypropylene/polyolefine (PP/POE) elastomers. For each 

set of processing conditions morphology parameters (e.g. diameter of droplets and strings, 

length of strings) were extracted from the scattering patterns using home made software. For 

comparison, samples from the extruded melt strands (quenched) were taken to analyze the 

morphology by scanning electron microscopy. From these results universal relationships between 

morphology parameters (e.g. numerical ratio of droplets and strings vs. capillary number) 

had been established. Furthermore, by using in-line light scattering in a pilot plant environment, 

it was demonstrated that the method is suited for industrial process control. 

[1] Li S., Migler K. B., Hobbie E. K, Kramer H., Han C. C., Amis E. J.: J. Polym. Sci. Part B. Polymer Physics 

35, 1997, p. 2935 

[2] Migler K. B., Hobbie E. K., Qiao F.: Polym. Eng. Sci 39, 1999, p. 2282 

[3] Qiao F., Migler K. B., Han C. C.: SPE ANTEC Conference Proceedings, 1999, p. 3911 

[4] Schlatter G., Serra C., Bouquey M., Muller R., Terrisse J.: Polym. Eng. Sci 42, 2002, p. 1965 

[5] Alig I.: Jahresbericht des DKI 2001 (ISBN 1618-0062), pp. 40-45 

[6] Lellinger D., Steinhoff B., Alig I.: PPS-21 Conference Proceedings (ISBN 3-86010-784-4) P13.5, 2005, 

pp. 19-23 

[7] Alig I.: Jahresbericht des DKI 2008 (ISSN 1618-0062), pp. 59-63. 

- 47 -


RELAXATION OF DROPLETS AND FIBRILS IN BLENDS 

WITH ONE VISCOELASTIC COMPONENT: BULK AND 

CONFINED CONDITIONS 

Ruth Cardinaels, Paula Moldenaers 

Department of Chemical Engineering, Katholieke Universiteit Leuven, 

Willem de Croylaan 46, 3001 Leuven (Heverlee), Belgium 

paula.moldenaers@cit.kuleuven.be 

Since the pioneering work of Taylor [1] droplet dynamics in blends and emulsions has been 

studied extensively [2-7]. In single droplet studies the focus is often on droplet deformation 

and breakup. However, for blends of molten polymers, the final morphology after processing 

will also depend on the details and kinetics of the shape relaxation. Several parameters such 

as cooling speed, fluid rheology and interactions with other droplets or the walls of the processing 

equipment can influence this relaxation process and consequently the droplet shape and 

size in the blend. The thus obtained blend morphology determines to a great extent the mechanical, 

barrier and other end-use properties of the final product. Therefore, a thorough understanding 

of the shape relaxation process of deformed droplets is crucial. In this work, the 

shape relaxation of deformed droplets in a quiescent matrix is studied microscopically. Both 

the effects of geometrical confinement and component viscoelasticity are systematically explored 

at viscosity ratios above and below [1]. The initial droplet deformation is varied by 

applying flow conditions that range from sub- to super-critical. Under all conditions, viscoelasticity 

of the droplet phase has no influence on the shape relaxation, whereas matrix viscoelasticity 

and geometrical confinement result in a slower droplet retraction. Up to high confinement 

ratios, the relaxation curves for ellipsoidal droplets can be superposed onto a master 

curve, even when matrix viscoelasticity causes a non-exponential relaxation. Droplets with a 

non-ellipsoidal shape, obtained by either introducing a high degree of confinement or applying 

a super-critical shear flow, relax in two stages; the first one consists of a shape change to 

an ellipsoid without significant retraction, the second one is the relaxation of this ellipsoid. 

The latter part of the relaxation process can be described by means of one single relaxation 

time that corresponds to the relaxation time of initially ellipsoidal droplets. The experimental 

results are compared to the predictions of a recently published phenomenological model for 

droplet dynamics in confined systems with viscoelastic components [8]. 

[1] Taylor G. I.: Proc. Royal Soc. London 146:501-523 (1934) 

[2] Rallison J. M.: Annu. Rev. Fluid Mech. 16:45-66 (1984) 

[3] Stone H. A.: Annu. Rev. Fluid Mech. 26:65-102 (1994) 

[4] Guido S., Greco F.: Rheology Reviews 2004:99-142 (2004) 

[5] Van Puyvelde P., Moldenaers, P.: Rheology Reviews 2005:101-145 (2005) 

[6] Tucker III C. L., Moldenaers P.: Annu. Rev. Fluid Mech. 34:177-210 (2002) 

[7] Van Puyvelde P., Vananroye A., Cardinaels R., Moldenaers P.: Polymer 51:5363-5372 (2008) 

[8] Minale, M., Caserta, S., Guido, S.: Langmuir, published online 

- 48 -


POLYMER BLENDS ON THE BASIS OF POLYPROPYLENE 

FOR LASER SINTER TECHNOLOGY 

Hans-Joachim Radusch (1), Lothar Fiedler (1), Andreas Hähndel (1) and Jörg Gerken (2) 

(1) Martin Luther University Halle-Wittenberg, Center of Engineering Sciences, 06099 Halle 

(Saale), Germany 

(2) Rapid Product Manufacturing GmbH, 38350 Helmstedt, Germany 

hans-joachim.radusch@iw.uni-halle.de 

Commonly polyamide (PA) is mainly used as the polymer basis for the production of technical 

parts in laser sinter technology belonging to the most important rapid prototyping technologies. 

For laser sintering of polymer materials the polymer should be characterized by specific 

general properties induced by the processing method. Hence, a free flowing polymer 

powder as the initial material state must be available, a high energy absorption and quick transition 

in the melt state is necessary, and the coalescence of the molten droplets in a rather 

short time has to run effectively. Furthermore, the physical and mechanical properties should 

allow a wide application range of the laser sinter products. In comparison to PA the application 

of polypropylene (PP) for laser sintering does not lead to satisfying results until now. 

Therefore, the goal of actual research is the development of PP based materials, which can 

fulfil the requirements for laser sinter materials concerning both processing behaviour and 

application properties. Because propylene homo-polymers cannot fulfil the high demands 

made on laser sinter polymers, and propylene copolymers are also not easily to adapt to the 

laser sinter technology, specific PP based blends were developed and tested, suitable for laser 

sintering. At first, identifying and evaluation of the properties of PP being essential for the 

laser sintering processability were necessary. For this purpose thermal and rheological analysis, 

FTIR spectroscopy, and granulometric experiments were performed. Strong differences in 

the materials behaviour influencing the laser sinter processability have been found concerning 

the degree of crystallinity, the capability to absorb the laser energy, and in the particle size 

distribution. In the result of the investigation strategies for materials modification of PP 

grades for adapting to laser sintering were proposed. For the generation of applicable PP 

based laser sinter material PP based blends were produced by means of melt mixing technology. 

Thereby, PP copolymer was used as basis component, and different copolymers, e.g., 

ethylene-α-olefin copolymers, propylene-ethylene copolymer, and maleic anhydride functionalized 

PP as compatibilizer were applied. For the development of innovative PP based laser 

sinter materials it is essential to provide the most important mechanical properties like impact 

and tensile strength as well as stiffness without any loss or detraction of the sinterability of the 

polymer material. Therefore not only the recipe but also the technological design of the blend 

mixing process is of great importance. In this connection the influence of variation of the 

technological parameters of the compounding process was investigated on the physical and 

mechanical properties of the PP sinter material. Experimental results generated in lab-scale 

were compared and verified with practice-relevant tests performed with an industrial laser 

sinter station. 

- 49 -


HALOGEN-FREE FLAME RETARDED BISPHENOL A POLY- 

CARBONATE BLENDS 

B. Schartel, E. Wawrzyn, K. H. Richter, B. Perret, H. Seefeldt 

Federal Institute for Materials Research and Testing, BAM, Unter den Eichen 87, 

12205 Berlin, Germany 

bernhard.schartel@bam.de 

For applications in electronical engineering, construction and transportation, the fire behaviour 

of bisphenol A polycarbonate (PC) blends is a key property and hence the flame retarding 

of PC blends is a key challenge. The search of halogen-free flame retardants has led to the 

development of alternatives, among which arylphosphates play the most important role. 

The fire behaviour and the pyrolysis of PC-blends containing arylphosphates as halogen free 

flame retardants were investigated. Main interest was focused on the flame retardant effect 

and mechanisms. Also the combination with different adjuvants, such as different metal borates, 

talc, boehmite, layered silicate, metal oxides and hydroxides was examined as well as 

the use of different impact modifiers such as acrylonitrile-butadiene-styrene (ABS) and silicone 

containing rubbers. 

The pyrolysis was characterised by the means of thermogravimetry (TG), TG coupled with 

evolved gas analysis (TG-FTIR) and kinetic analysis. The chemical compositions of the residues 

were analysed with solid state NMR and FTIR-ATR. Using different methods enable us 

to study the pyrolysis mechanisms and interactions in the combined system. The fire behaviour 

was investigated by cone calorimeter. The flammability (reaction to small flame) was 

determined by the LOI (limiting oxygen index) and UL 94 tests. The fire retardancy mechanisms, 

synergisms and antagonisms are discussed with respect to the different fire properties. 

The authors acknowledge the support received from the Bayer MaterialScience AG, and thank 

in particular V. Taschner, T. Eckel and D. Wittmann. 

[1] K. H. Pawlowski, B. Schartel. In: Recent Advances in Flame Retardancy of Polymeric Materials, Vol. 17, 

M. Lewin (Ed.), BCC, Norwalk, 2006, pp. 132-142 

[2] K.H. Pawlowski, B. Schartel. Polym. Int., 56, 1404-1414, 2007. 

[3] B. Schartel, K.H. Pawlowski, R.E. Lyon. Thermochim. Act., 462, 1-14, 2007. 

[4] K.H. Pawlowski, B. Schartel. Polym. Degrad. Stab., 93, I657-667, 2008. 

[5] B. Perret, K.H. Pawlowski, B. Schartel. J. Therm. Anal. Calorim., 97, 949-958, 2009. 

[6] E. Pikacz, H. Seefeldt, B. Schartel, U. Braun, A. Karrasch, C. Jäger. In: Recent Advances in Flame Retardancy 

of Polymeric Materials, Vol. 20, M. Lewin (Ed.), BCC, Norwalk, 2009, in press 

[7] K. H. Pawlowski, B. Schartel, M.A. Fichera, C. Jäger. Thermochim. Act., 

[8] in press, doi:10.1016/j.tca.2009.10.007, 2009 

[9] B. Perret, B. Schartel. Polym. Degrad. Stab., 94, 2194-2203, 2009 

[10] B. Perret, B. Schartel. Polym. Degrad. Stab., 94, 2204-2212, 2009 

[11] B. Schartel, K. H. Pawlowski, M. Böhning. submitted 2009 

[12] E. Wawrzyn, et al. several papers in preparation 

- 50 -


ELASTIC PROPERTIES OF POLYPROPYLENE/ETHYLENE- 

OCTENE COPOLYMER BLENDS 

Petr Svoboda (1), Rajesh Theravalappil (1), Keisuke Mori (2), Toshiaki Ougizawa (2) 

(1) Faculty of Technology, Tomas Bata University in Zlin, nam. TGM 275, 762 72 Zlin, 

Czech Republic 

(2) Department of Organic and Polymeric Materials, Tokyo Institute of Technology, 

2-12-1-S8-33, Ookayama, Meguro-ku, Tokyo 152-8552, Japan 

svoboda@ft.utb.cz 

Blends of polypropylene (PP) and ethylene-octene copolymer (EOC) were investigated with 

focus on mechanical properties. Charge was varied across the whole composition (10, 20, … , 

80, 90 wt.%). In the tensile testing machine, the samples (0-50 % of PP) were stretched to 

given elongation (100, 200 and 300 %) and then the crosshead returned to the initial position. 

The residual strain value was obtained from the hysteresis curve. These residual strain values 

were plotted as a function of applied strain and PP content. Stress at given elongation (M100, 

M200 and M300) was also plotted as a function of PP content. At low PP content (0-20 %), 

residual strain and stress at given elongation are close to that of pure EOC. A steeper increase 

in these values was observed for concentrations 20-50 % of PP. Other set of experiments involved 

tensile testing till break (full range of concentrations). From these experiments, tensile 

modulus, stress at break and yield stress were evaluated and plotted as a function of PP content. 

Modulus values are close that of pure EOC in the range of 0-25 % of PP. Then, the values 

start increase almost linearly with increasing PP content. A moderate increase in stress at 

break was observed for 0-70 % of PP and then a steep increase was observed with increasing 

PP content (70-100 % of PP). The mechanical properties of the blends were correlated with 

the structure observed by transmission electron microscopy (TEM). 

- 51 -


PHASE TRANSITIONS OF SEMIFLUORINATED SIDE-CHAIN 

POLYESTERS: SUBNANOMETER FREE VOLUMES FROM 

POSITRON LIFETIME IN COMPARISON WITH PRESSURE- 

VOLUME-TEMPERATURE EXPERIMENTS 

Yang Yu (1), G. Dlubek (2), D. Pospiech (3), D. Jehnichen (3), L. Häußler (3), J. Pionteck (3), 

R. Krause-Rehberg (1) 

(1) Institut für Physik, Martin-Luther-Universität Halle-Wittenberg, D-06099 Halle/S. 

(2) ITA Institut für Innovative Technologien, Köthen/Halle, Wiesenring 4, D-06120 Lieskau 

(3) Leibniz-Institut für Polymerforschung Dresden e.V., Hohe Strasse 6, D-01069 Dresden 

yang.yu@student.uni-halle.de 

This work deals with the use of positron annihilation lifetime spectroscopy (PALS) for the 

study of the temperature dependence of the size distribution of sub-nanometer-size local free 

volumes (holes) in semifluorinated side-chain polyesters. PALS involves the measurement of 

the lifetimes of positrons injected into a sample, extracting the mean lifetimes of those positrons 

forming ortho-positronium (o-Ps), and relating this, via a semi-empirical model, to the 

dimension of free volume holes [1,2]. The samples investigated were aromatic and aromaticaliphatic 

polyesters in which the side chain has an -oxydecylperfluorodecyl structure –O- 

(CH2)10-(CF2)9-CF3. These materials, which were studied recently by a combination of 

methods, namely by differential scanning calorimetry (DSC), pressure-volume-temperature 

(PVT) measurements, rheology, and temperature-resolved simultaneous small and wide-angle 

X-ray scattering (SAXS/WAXS) [3-5], show self-assembly of side chains, a strong microphase 

separation of alkyl- and perfluoroalkyl chains which leads to a very low surface free 

energy. We observed an extremely strong increase in the local free volume from 0.1 – 0.2 

nm3 to 0.5 nm3 at 330 – 350 K which correlates with changes the macroscopic volume. The 

transition was attributed to the melting of semifluorinated side chains. The changes of the 

microstructure of samples during this transition are discussed in detail. 

[1] G. Dlubek, Positron Annihilation Spectroscopy, in: Encyclopedia of Polymer Science and Technology, ed. 

by. A.Seidel, John Wiley&Sons, Hoboken, 2008 

[2] G. Dlubek, J. Pionteck, D. Kilburn, Macromol. Chem. Phys. 205, 500 and 512 (2004) 

[3] D. Pospiech, D. Jehnichen, A. Gottwald, L. Häussler, U. Scheler, P. Friedel, W. Kollig, C. K. Ober, X. Li, 

A. Hexemer, E. J. Kramer, D. A. Fischer, Polymeric Materials: Science & Engineering 84, 314 (2001) 

[4] D. Jehnichen D. Pospiech, L. Häußler, P. Friedel, S. S. Funari, J. Tsuwi, F. Kremer, Z. Kristallogr. 

Suppl. 26, 605-610 (2007) 

[5] A. Gottwald, D. Pospiech, D. Jehnichen, L. Häußler, P. Friedel, J. Pionteck, M. Stamm, F. Floudas: Macromol. 

Chem. Phys. 203, 854-861 (2002) 

See also: http://positron.physik.uni-halle.de 

- 52 -


EXFOLIATION-ABILITY AND PROCESSABILITY OF NANO- 

CLAY IN EPOXY/GLASS FIBER HYBRID COMPOSITES AND 

POLYAMIDE/POLYPROPYLENE BLENDS 

W. S. Chow, L. N. Chang, Z. A. Mohd Ishak 

School of Materials and Mineral Resources Engineering, Engineering Campus, 

Universiti Sains Malaysia, Nibong Tebal 14300, Penang, Malaysia 

chowwenshyang@yahoo.com 

Polymer-clay nanocomposites can exhibit excellent properties if the exfoliation-ability, dispersibility, 

compatibility and processing-ability of the materials can be achieved. For this 

presentation, the effects of nanoclay in both thermoset and thermoplastic systems will be 

highlighted. The epoxy/glass fiber/nanoclay composites were prepared using hand-lay up 

technique. The polyamide/polypropylene/nanoclay composites were prepared using twinscrew 

extrusion followed by injection molding. The exfoliation of the nanoclay was determined 

and confirmed by using X-ray diffraction (XRD), transmission electron microscopy 

(TEM) and atomic force microscopy (AFM). The mechanical (e.g. tensile, flexural, fracture 

toughness) and thermal properties of the epoxy/glass fiber composites and polyamide/polypropylene 

blends were improved significantly by the addition of nanoclay. The enhancement 

of the properties is attributed to the exfoliation of nanoclay. In addition, the nanoclay 

could act as interfacial agent and nucleating agent for epoxy/glass fiber composites and 

polyamide/polypropylene blends, respectively. The processability of the epoxy/glass fiber/clay 

composites is dependent on the viscosity, stirring speed, curing temperature and curing 

time. For the PA6/PP/clay, the processability is controlled by the extrusion speed, melting 

temperature profile, and injection molding parameter. 

- 53 -


CHARACTERIZATION OF THE ELASTOMERIC BEHAVIOUR 

OF BLOCK-DOUBLE GRAFT COPOLYMERS WITH AN 

ENERGY BASED SOFTENING MODEL 

Ralf Schlegel (1), R. Weidisch (1), N. Hadjichristidis (2), J. W. Mays (3), M. Klüppel (4), 

G. Heinrich (5) 

(1) Institute of Materials Science and Technology (IMT), Friedrich-Schiller-University Jena, 

Löbdergraben 32, D-07743 Jena, Germany 

(2) Department of Chemistry, University of Athens, Athens, 157 71 Greece 

(3) Department of Chemistry, University of Tennessee, Knoxville, USA 

(4) German Institute of Rubber Technology (DIK), Eupener Str. 33, D-30519 Hannover 

(5) Leibniz Institute of Polymer Research Dresden, Hohe Straße 6, 01069 Dresden, Germany 

roland.weidisch@uni-jena.de 

Thermoplastic elastomers based on styrene and isoprene are frequently used to study fundamental 

aspects regarding the influence of molecular architecture on mechanical behaviour. 

However, the impact of morphology is an additional factor, which has to be considered. 

TPE’s are used for compounding with other polymers to achieve the particular requirements 

for each end-use. In the present investigation we are discussing the softening behaviour of 

block-double graft copolymers with about 27-33 vol. % PS. The materials were characterized 

by tensile, hysteresis and multihysteresis tests. A softening model was applied to characterize 

the hysteresis behaviour. It was observed that improved elastomeric properties not necessarily 

require low PS contents. Despite a higher PS content a pronounced low softening characteristic 

was observed for a block-double graft copolymers with PI-PS arms grafted to the PI middle 

block and PS outer blocks. It was further found that the chemical cross link modulus is 

increasing with the overall length of PS arms. Similar, the softening parameter was observed 

to decrease in the same direction. The applied model offers a reliable way for the characterization 

of elastomers. 

- 54 -


PHYSICAL AGEING OF POLYETHYLENE OXIDE (PEO)/- 

POLYVINYL PHENOL (PVPH) BLENDS 

Abdelsallam Youssef, Valeria Arrighi 

Department of Chemistry, School of Engineering and Physical Sciences, 

Heriot-Watt University, Edinburgh, EH14 4AS, UK 

aey5@hw.ac.uk 

The phenomenon of physical ageing in glassy systems, including polymers, has been extensively 

studied but limited work has been carried out on blends. The aim of work described 

here is to investigate systems where a large Tg difference exists between the individual components, 

and are strongly interacting. 

As also observed by others [1,2], a strong hydrogen bonding interaction exists between the 

hydroxyl group of poly(vinyl phenol) (PVPh) and the ether oxygen of poly(ethylene oxide) 

(PEO) which can be followed by FTIR spectroscopy. Attempts are made to quantify this interaction 

and investigate the temperature dependence. 

Enthalpic ageing studies were carried out on a series of amorphous PEO/PVPh blends of different 

compositions. Values of the enthalpy relaxation (∆H(Ta, ta)) were determined from 

heat capacity experimental data, plotted against log10(ta) and then modelled by the 

Cowie/Ferguson (CF) model [3,4]. Although the blends appear to relax more quickly than 

pure PVPh, a comparison with other systems investigated [5,6] shows that PVPh/PEO blends 

relax more slowly than both PVME/PS and PVME/PVPh blends as result of the present of 

strong hydrogen bonding that is reported to hinder relaxation. Values of activation energy 

were also determined from the CF parameters and these are used to compare the ageing behaviour 

of our PEO/PVPh blends with that of other blend systems, with and without strong 

intermolecular interactions. 

[1] Moskala E. J., Varnell D. F. Coleman M. M.: Polymer, 1985, pp. 26, 228 

[2] Qin C., Pires A. T. N., Belfiore L. A.: Polym. Commun., 1990, pp. 31, 177 

[3] Cowie J. M. G., Ferguson R.: Macromolecules, 1989, pp. 22, 2307 

[4] Cowie J. M. G., Ferguson R.: Polymer 1993, pp. 34, 2135. 

[5] Cowie J. M. G., Ferguson R.: Macromolecules 1989, pp. 22, 2312 

[6] Arrighi V., Cowie J. M. G., Ferguson R., McEwen, I. J., McGonigle E.-A., Pethrick R. A., Princi E.: 

Polym. Int. 2005, pp. 55, 749 

- 55 -


TUNING THE LOCALIZATION OF FUNCTIONALIZED MWNT 

IN REACTIVE PC/SAN BLENDS 

Marén Gültner, Andreas Göldel, Petra Pötschke 

Leibniz Institute of Polymer Research Dresden, Hohe Str. 6, 01069 Dresden, Germany 

poe@ipfdd.de 

The incorporation of multiwalled carbon nanotubes (MWNT) in insulating polymer blends 

improves their electrical conductivity. When using co-continuous blends lower filler contents 

are required for electrical percolation compared to composites with one-phase-structures if the 

carbon nanotubes localize in one of the phases (double percolation). 

In this contribution, the influence of a reactive component (RC, N-phenylmaleimid styrene 

maleic anhydride) on the blend morphology, the localization of functionalized MWNT, and 

the electrical resistivity of the MWNT filled blend systems of polycarbonate (PC) and 

poly(styrene-co-acrylonitrile) (SAN) was investigated. The systems of PC, SAN, aminofunctionalized 

MWNT (Nanocyl ® 3152), and the RC were melt mixed in a DSM Xplore microcompounder. 

The RC containing maleic anhydride groups was found to be miscible with 

the SAN and is assumed to enhance its polarity and surface tension. On the other hand it has 

the potential to form chemical bonds towards the functionalized MWNT. 

By analyzing the blend systems with and without the RC co-continuous structures as well as 

the localization of the MWNT in one of the blend phases could be achieved. The influence of 

the reactive component on the morphology of the blend systems was studied at different ratios 

of PC and SAN, whereas for all blends with 40 wt% SAN and 60 wt% PC co-continuous 

morphologies were found. In non-modified PC/SAN blends the MWNT are localized in the 

PC phase independently from the mixing procedure used, even if the nanotubes were first 

mixed into SAN and then blended with PC. This behaviour can be e explained by interfacial 

tension effects. However, the modification of SAN using RC can change its properties in such 

a way, that the MWNT localize in the SAN-RC phase. This was found as well for mixing 

CNT first in SAN-RC, in PC, or adding all components together as well as adding RC to the 

ready PC/SAN/MWNT blend. 

The localization of the MWNT after addition of the RC depends on the concentration of the 

MWNT and the RC. By adapting that ratio and the mixing strategy, the localization of the 

nanotubes can be tuned. The investigations have shown that for 0.5 wt% CNT a high (50 %) 

or middle (5 %) content of RC in SAN leads to localization within the SAN phase, whereas 

using a low amount of RC (0.5 %) the MWNT localize in the PC phase. Using 5 wt% CNT an 

amount of 5 wt% RC in SAN is not enough to localize the MWNT in SAN and CNT localize 

in both phases, whereas 50 % is sufficient. 

Interestingly, when diluting a blend of PC/SAN-RC/MWNT= 60/38-2/5 wt% with PC and 

SAN to a blend of 60/39.8-0.2/0.5 wt% the nanotubes stay in the SAN-RC phase, whereas 

when preparing that blend composition directly, localization in PC was found. This indicates, 

that the mixing prehistory plays a big role on the localization. The MWNT once coupled with 

the RC remain in the SAN-RC Phase. Thus, the chemical reaction seems to be the driving 

force for localization of the MWNT in SAN-RC. 

- 56 -


FROM BLENDS TO BLOCK COPOLYMERS – DO COUPLING 

REACTIONS IN MELT RESULT IN DEFINED POLYMER 

STRUCTURES? 

Frank Böhme, Lothar Jakisch 

Leibniz-Institut für Polymerforschung Dresden e.V., Hohe Str. 6, 01069 Dresden, Germany 

boehme@ipfdd.de 

Reactive compatibilization is a frequently used principle in polymer blending. Reactions between 

the blend components result in the formation of block or graft copolymers during processing 

which stabilize blend structures and improve mechanical performance. Usually, such 

reactions occur mainly in the interface and comprise only a small part of the whole mixture 

whereas most of the polymer chains remain unreacted. Because of these incomplete conversions, 

it is difficult to obtain pure block or graft copolymers with defined structures by reactive 

blending. 

To overcome this problem, we developed new coupling agents containing at least two different 

reactive groups such as oxazoline, oxazinone and/or lactamate groups [1-3]. It could be 

shown that these groups react under certain conditions very selectively in high yields with 

carboxylic, amino and hydroxy groups, respectively. The reactivity of these groups is high 

enough so that the conversions could be performed under the conditions of reactive extrusion. 

Provided stoichiometry of the reacting groups is warranted, mixing of two polymers containing 

different reactive terminal groups with respective bifunctional or trifunctional coupling 

agents allows obtaining block and graft copolymers with defined block lengths. The application 

of two types of coupling agents will be introduced. 

The first type possesses one oxazoline group that reacts preferably with carboxylic groups and 

one oxazinone group that reacts with amino or hydroxy groups. The reactions are highly selective 

and were utilized in chain extension of AB polyamides and in synthesis of polyetherpolyamide 

block copolymers. 

The second type with one oxazinone group and one lactamate group can be used for mixtures 

containing amino and hydroxy groups. The selectivity is not so pronounced as in the upper 

example. However, stepwise addition of the reacting species and temperature control allows 

converting the lactamate group first with the hydroxy group and than the oxazinone group 

with the amino group. This reaction was used for the synthesis of polyester-polyamide block 

copolymers. Properties of the block copolymers will be discussed. 

[1] L. Jakisch, H. Komber, F. Böhme: J. Polym. Sci., Polym. Chem. 2003, 41, 655 

[2] L. Jakisch, H. Komber, R. Wursche, F. Böhme: J. Appl. Polym. Sci., 2004, 94, 217 

[3] L. Jakisch, H. Komber, F. Böhme: Macromol. Mater. Eng., 2007, 292, 557 

- 57 -


REACTION INDUCED MISCIBILITY AND PHASE BEHA- 

VIOUR OF POLY (TRIMETHYLENE TEREPHTHALATE)/- 

POLYCARBONATE BLENDS 

Indose Aravind (1), Klaus-Jochen Eichhorn (2), Manfred Stamm (2), Sabu Thomas (1) 

(1) Mahatma Gandhi University, Priyadarshini Hills P.O., Kottayam, Kerala, 

686 560 India 

(2) Leibniz Institute of Polymer Research Dresden, Hohe Str. 6, 01069 Dresden, Germany 

indosearavind@gmail.com 

The effect of annealing on the miscibility and phase behavior of poly (trimethylene terephthalate) 

and bisphenol-A polycarbonate (PC) blends was analyzed. These blends exhibited heterogeneous 

phase-separated morphology and a two well-spaced glass transition temperatures 

indicating immiscibility. The PTT/PC blends were thermally annealed at 260 °C for different 

times to induce various extents of transreactions between the two polymers. After annealing at 

high temperature the original two Tgs of blends were found to merge into one single Tg, exhibiting 

a homogeneous morphology. It is interesting to note that upon extended annealing the 

original semicrystalline morphology transformed into an amorphous nature. This is attributed 

to chemical transreactions between the PTT and PC chain segments as evidenced with FTIR, 

DSC, DMA, 1 H NMR and WAXS measurements. The sequence structures of the produced 

copolyesters were determined by a NMR triad analysis, which showed that the randomness 

increased with time of heating. WAXS analysis confirmed that the PTT/PC blends completely 

lost their crystallinity when annealed at 260 °C for a period of 120 min or longer, indicating 

the formation of fully random copolyesters. A random copolymer formed as a result of the 

transreactions between PTT and PC, serves as a compatibiliser at the beginning, and upon 

extended annealing this became the main species of the system which is finally transformed to 

a homogeneous and amorphous phase. 

- 58 -


CO-CONTINUOUS NANOSTRUCTURED BLENDS BY 

REACTIVE BLENDING: SYNTHESIS, MORPHOLOGIES, 

STRUCTURES AND PROPERTIES 

Sylvie Tencé-Girault (1), Léa Gani (1), Stéphane Bizet (2), Ludwik Leibler (1) 

(1) Matière Molle et Chimie (ESPCI-CNRS, UMR 7167), ESPCI, 10 rue Vauquelin, 

75231 Paris Cedex 05, France 

(2) ARKEMA, CERDATO, 27470 Serquigny, France 

sylvie.girault@espci.fr 

Co-continuous thermodynamically stable nanostructured blends of functionalized polyolefin 

and polyamide-6 have been designed and synthesised by reactive blending in our laboratory 

[1]. The grafting reaction occurs between the amino end-group of polyamide-6 and the maleic 

anhydride units randomly distributed along the backbone of polyethylene. Very fine morphologies 

were obtained after blending, depending on the molecular structure of the polyethylene 

and of the polyamide-6. These blends exhibit outstanding mechanical properties both at 

low and high temperatures and solvent resistance. Remarkably, even though neither the polyolefin 

nor the polyamide are transparent, the blends are transparent. We investigate and discuss 

here how these attractive properties are related to structure on nano and micro-scales and 

the very particular crystallization of the blends. 

Thanks to the high reactivity of the maleic anhydride (MAH) / amino (NH2) couple, a large 

amount of graft copolymers is created in-situ during the reactive extrusion. As the two components 

of this copolymer are incompatible, a nano-structure is formed. Indeed, the polydispersity 

of the backbone and of the grafts helps to stabilize disordered and co-continuous structure 

and facilitates the incorporation of the un-reacted homopolymers in the blend. While 

keeping the polyamide-6 as minority phase, the nanostructure obtained is co-continuous in a 

wide composition range. Both components crystallize and the blend does not flow until the 

melting point of the polyamide-6. 

The transparency properties are mainly related the nano-structure formation and absence of 

spherulites. Also the thermo-mechanical and solvent resistance properties are linked to the 

confined crystallization in this nano-structure. To understand and optimize further these outstanding 

properties, we have studied in more detail the crystallization of the polyethylene and 

of the polyamide in this confined structure after various moulding processes and thermal 

treatments. With transmission electron microscopy and a specific staining of the blends, we 

have been able to observe the nano-structures and unveil the crystalline lamellae of polyamide. 

Using non-isotherm crystallization experiments, a shift of the crystallization temperature 

of the polyamide-6 has been observed and an interesting correlation with the morphology 

could be pointed out. X-rays diffusion and diffraction experiments performed after various 

moulding processes have revealed the existence of crystalline lamellae of polyethylene and 

polyamide. Thanks to these investigations we are in position to propose a model for the organisation 

of graft copolymer and homopolymer chains in the co-continuous structures. All 

these structural characterizations shed a new light and help to understand better the thermomechanical 

properties of our blends for small and large deformations. 

[1] H. Pernot, M. Baumert, F. Court, L. Leibler: Nature Materials, 2002, 1, 54-58 

- 59 -


ESTABLISHMENT OF TTT DIAGRAMS FOR THE REIN- 

FORCED BLENDS BASED ON PP/PP-G-MAH/SGFR PA 66: 

EFFECT OF COMPATIBILIZER 

Z. Safidine (1), A. Belhadj (1), S. Fellahi (1), H.-J. Radusch (2), D. Benachour (3) 

(1) Macromolecular Chemistry Laboratory, EMP, BP 17 Bordj El Bahri 16111 Algiers, 

Algeria 

(2) Martin Luther University Halle-Wittenberg, Centre of Engineering Sciences, 06099 Halle, 

Germany 

(3) Polymer Engineering Department, Process Engineering, Ferhat Abbas University, 

19000, Setif, Algeria 

safi192003@yahoo.fr 

New materials based on unreinforced and reinforced blends based on polypropylene (PP) as a 

dispersion in the short and treated glass fibber reinforced polyamide 66 (SGFR PA 66) were 

prepared by the use of Twin Screw Extruder (TSE) within appropriate operating conditions, 

which leads to the homogenate blends. After each formulation, the morphological behaviour 

was checked to be sure as regards the mixing process. During this study of the global crystallisation 

of these blends according to the amount of compatibilizer, new approaches emanating 

from the modern metallurgy were introduced. In fact, the Temperature, Time, Transformation 

of relative (absolute) crystallinity, i. e. TTT diagrams were plotted under isothermal conditions 

and using DSC as an appropriate method for the given study. From the results, it is 

found that these diagrams are a useful tool to reveal the action of the compatibilizer on the 

crystallisation behaviour of the blend components. The minor phase was highly affected by 

the presence of PP-g-MAH. Furthermore, the major part still no affected or at least its aptitude 

for the crystallisation was slightly restricted due to formation of copolymer at the interface 

even the higher content of a compatibilizer. An optimal amount of PP-g-MAH was found 

equal to 2.5 wt % from which the all properties levels off. 

- 60 -


NANOPARTICLES AS INTERFACE-MODIFIERS IN 

IMMISCIBLE POLYMER BLENDS: EFFECT OF PARTICLE 

CONCENTRATION, SIZE AND SHAPE ON COALESCENCE 

AND BREAK-UP 

S. Vandebril, J. Vermant, P. Moldenaers 

Department of Chemical Engineering, K. U. Leuven, Belgium 


Polymer blending is an efficient way to generate interesting materials due to the synergy of 

their properties. These properties are closely related to the blend microstructure. To stabilize 

the morphology of polymer blends, block co-polymers can be added which should be located 

at the interface, their role being similar to that of surfactants used for the stabilization of water/oil 

emulsions. An alternative for surfactants in emulsion stabilization consists in adding 

colloidal particles, resulting in Pickering emulsions. In this work a similar route is followed 

for polymer blends: nanoparticles are incorporated in a blend at the polymer-polymer interface 

and the aim of this study is to investigate their effect on the morphological processes 

during blending, i.e. coalescence and break-up. Polydimethylsiloxane (PDMS) and polyisobutylene 

(PIB) are chosen as model blend components, with a 70/30 volume ratio, resulting in a 

droplet-matrix morphology. Silica nanoparticles of different size and shape (anisotropy) with 

a silanized surface are used as compatibilizers. Their specific location at the interface is confirmed 

by Cryo-SEM images. Rheological measurements are used to show that the particles 

slow down coalescence, in particular when PDMS is the matrix phase. Moreover, break-up of 

the dispersed phase is suppressed, resulting in a fixation of the blend microstructure. For 

small particles both coalescence and break-up can be controlled in a positive way by increasing 

the particle concentration and anisotropy. On the other hand, large particles have a negative 

effect. Interfacial rheological properties seem to be a significant factor to explain the observations. 

- 61 -


MORPHOLOGY AND PROPERTIES OF POLYPROPYLENE/- 

LOW DENSITY POLYETHYLENE BLENDS COMPATIBILIZED 

BY ETHYLENE-PROPYLENE-DIENE TERPOLYMER 

Nina Vranjes (1), Vesna Rek (1), Miroslav Slouf (2), Zelimir Jelcic (3) 

(1) Faculty of Chemical Engineering and Technology, Marulicev trg 19, 10 000 Zagreb, 

Croatia 

(2) Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, 

Heyrovsky sq. 2, 162 06 Prague 6, Czech Republic 

(3) PLIVA- Research and Development Ltd., Pharmaceutical Technology, Prilaz baruna 

Filipovica 29, 10 000 Zagreb, Croatia 

nvranjes@fkit.hr 

Processing and compatibilization effects on the phase morphology and thermal properties of 

polypropylene (PP) and low density polyethylene (LDPE) blends were investigated. Ethylenepropylene–diene 

terpolymer (EPDM) was used as compatibilizer. The influence of blends 

composition and EPDM content on the rheological behavior of the blends in the melt during 

processing, morphological structure and thermal behavior were studied. Processing characteristics 

were followed by torque (TQ) and melt pressure in twin screw extruder, while the thermal 

behavior of extruded and molded samples was measured with differential scanning calorimetry 

(DSC). Morphological structure were investigated by scanning electron microscopy 

(SEM) and scanning transmission electron microscopy (STEM) and compared with processing 

properties and thermal behavior. The addition of PP into LDPE increased torque values of 

the blends. The torque values of PP/LDPE blends were between the TQ values of the pure 

homopolymers. With EPDM addition the values of TQ and back pressure are lower in comparison 

with noncompatibilized blends, what indicated better processibility. The degree of 

crystallinity (χc) of PP phase was decreased and χc of LDPE phase was increased with higher 

LDPE content in PP/LDPE blends with and without EPDM. The higher content of EPDM 

decreased χc of PP phase in comparison with χc of PP phase in PP/LDPE blends without 

EPDM and in PP/LDPE blends with lower EPDM content. The higher influence of EPDM 

was obtained on the χc of PP phase then on χc of LDPE phase in all investigated blends. SEM 

and STEM micrographs of EPDM compatibilized PP/LDPE blends with compositions 80/20 

and 20/80 showed particulate morphology, whereas in the blends with compositions 60/40 

and 40/60 the morphology was co-continuous. The EPDM compatibilizer was localized 

mostly on the interface in all cases. The increase in compatibilizer concentration from 5 pph 

to 7 pph did not have an important impact on the phase morphology. 

- 62 -


TOUGHENING OF UNSATURADED POLYESTER RESINS 

WITH SOLVENT TREATED SCRAP TIRE RUBBER 

POWDERS 

Paulo J. R. O. Nóvoa (1), António J. M. Ferreira (2), António Torres Marques (2) 

(1) Composite Materials and Structures Research Unit, Institute of Mechanical Engineering 

and Industrial Management (INEGI), FEUP Campus, Rua Dr. Roberto Frias 400, 

4200-465 Porto – Portugal 

(2) Department of Mechanical Engineering, Faculty of Engineering, University of Porto, Rua 

Dr. Roberto Frias s/n, 4200-465 Porto – Portugal 

prnovoa@inegi.up.pt 

Fibre reinforced thermoset resins find extensive use in the fibre composites industry, where 

epoxy, vinylester and unsaturated polyester resins constitute the bulk of matrix materials. Despite 

increasing awareness towards favoring the use of thermoplastics due to ease of recycling, 

the argument is far more effective among unreinforced plastics applications. When 

composite materials are concerned, a high yield and cost effective phase separation, required 

for a closed-loop recycling process, is highly challenging regardless of the nature of the matrix 

material. Furthermore, continuous reprocessing of thermoplastics inevitably leads to material 

degradation due to both thermal and mechanical ageing. High performance thermoset 

polymers are also usually less expensive then engineering thermoplastics, and general purpose 

thermoset polymers exhibit better mechanical and thermal performance then low cost thermoplastics, 

such as polyolefins. 

In particular, unsaturated polyester resins exhibit reasonable properties at a very low cost, but 

like most thermosets has low toughness when compared to thermoplastics in general. The 

strategies that have been used for improving the toughness of thermoset resins include resin 

modification with reactive or non-reactive liquid rubbers or the introduction of a solid, well 

dispersed, immiscible soft phase. The modifier yields a rubbery domain in the brittle thermoset 

matrix and it is important to achieve a significant enhancement of fracture toughness at 

low modifier contents, to minimize deterioration of critical mechanical properties of the original 

resin – e. g., stiffness, strength and heat distortion temperature. This requires an effective 

mixing of phases, and therefore it is paramount to have a good compatibility between resin 

and modifier. 

Scrap tires constitute a significant waste problem but are a low-cost source for rubber. Some 

ways to help solve their disposal include use of tire rubber in civil engineering applications 

and the production of adsorbent materials. Their use as toughening additive for epoxy resins 

has also been reported. 

Our research focuses on using rubber powder obtained from scrap tires as a toughening additive 

for thermoset resins based on unsaturated polyester/styrene. The compatibility of the liquid 

resin with the rubber powder is investigated by optical microscopy for different mixing 

times, temperatures and rubber content. The use of solvents that swell the rubber material and 

may enhance compatibility is also considered. Dynamic mechanical spectroscopy is also used 

to assess mixing between phases. The effectiveness of the toughening strategy is evaluated 

studying the cured modified resin compositions for tensile and flexural mechanical properties, 

heat distortion temperature, and fracture toughness by single-edge notch bending, Charpy 

impact resistance and damage tolerance to repeated impacts. Changes in fracture mechanisms 

are determined by microscopy of fracture surfaces. 

- 63 -


INTERFACE ENGINEERING OF CARBON FIBRE REIN- 

FORCED POLY(VINYLIDENE FLUORIDE) 

Kingsley K. C. Ho, Siti Ros Shamsuddin, Alexander Bismarck 

Department of Chemical Engineering, Polymer and Composite Engineering (PaCE) Group, 

Imperial College London, London SW7 2AZ, UK 

a.bismarck@imperial.ac.uk 

The quality of interfacial interaction in composite materials is dictated by the surface chemistry 

of the carbon fibres and the composition of the matrix. The development of high performance 

fibre reinforced fluoropolymers that can deliver exceptional mechanical and chemical 

performance require careful interfacial engineering and manufacturing. Poly(vinylidene fluoride) 

(PVDF) is extensively used in the high-purity semiconductor market, as a binder for 

high-quality metal finishes for building components and in lithium ion batteries, solid and 

lined pipes, valves, and microporous and ultrafiltration membranes. In general, fluoropolymers 

exhibit excellent toughness and corrosion resistance to severe environmental stresses. 

Because of this, they offer great potential as a matrix for fibre-reinforced composites for applications 

in harsh environments, such as those encountered in the oil and gas and chemical 

industries. Nevertheless, due to the low surface free energy of fluoropolymers, it is difficult to 

bond to, and adhesion to reinforcing carbon fibres is poor. In this study, we investigated the 

influence of a reactive compatibilising agent for PVDF as a means to improve adhesion to 

atmospheric plasma fluorinated (APF) carbon fibres. The composition of PVDF was modified 

by the addition of maleic anhydride grafted PVDF. The engineered interface between APF 

carbon fibres and modified PVDF was studied by means of direct wetting measurements and 

single fibre pull-out tests to determine the apparent interfacial shear strength (IFSS), as measure 

of practical adhesion. 

- 64 -


PROTON CONDUCTING POLYMER ELECTROLYTES 

BASED ON 1-VINYL-1,2,4-TRIAZOLE AND VINYL- 

PHOSPHONIC ACID 

Sevim Ünügür Çelik (1), Ayşe Aslan (1), Ayhan Bozkurt (1), Ümit Akbey (1), Robert Graf (2), 

Hans W. Spiess (2) 

(1) Fatih University, Department of Chemistry, 34500 Büyükçekmece-İstanbul, Turkey 

(2) Max-Planck-Institut for Polymer Research, Ackermannweg 10, 55128 Mainz, Germany 

bozkurt@fatih.edu.tr 

The development of anhydrous proton conducting membrane is important for the operation of 

polymer electrolyte membrane fuel cell (PEMFC) at intermediate temperature (100–200 o C). 

The development of anhydrous neutral or basic proton conducting materials has progressed 

with particular interest in heterocyclic compounds. Recent attempts included hybrid electrolytes 

prepared by incorporation of imidazole or benzimidazole in acidic polymer matrices. 

Polymer electrolyte membranes consisting of an acidic polymer host and azole allowed for 

long range proton transport via structural diffusion. In the present work, two systems having 

triazole and acidic units were prepared and their proton conductivity properties were compared. 

In the first one poly(VPA-co-VTri) copolymer electrolytes were synthesized by by 

free-radical copolymerization of vinylphosphonic acid (VPA) and 1-vinyl-1,2,4-triazole 

(VTri). In the second one composite polyelectrolytes were produced by complexation of 

PVPA with PVTri at various concentrations to get PVTri-P(VPA)x where x designates the 

molar ratio of the polymer repeating units and varied from 0.25 to 4.The samples were characterized 

with GPC, elemental analysis, NMR and FTIR. The presence of triazole units in the 

samples suppresses the formation of phosphonic acid anhydrides up to 150 o C, as verified by 

both 31 P NMR and TGA. The DSC and SEM results demonstrated the homogeneity of the 

materials. The observation of defined glass transition temperatures indicated that the ionic 

interactions do not prevent segmental relaxations of the polymer chains. Proton conductivity, 

activation energy and water/methanol uptake of these membranes 

were also measured. In the absence of humidity, the copolymer electrolyte, poly(VPA-co- 

VTri), S2 (with 33 % triazole content) showed proton conductivity of 10 -3 S/cm at 120 o C, 

which is far higher than in imidazole based copolymers. PVTriP(VPA)2 showed a proton conductivity 

of 2.5×10 −5 Scm −1 at 180 o C in the anhydrous state. After humidification 

(RH = 50 %), PVTri-P(VPA)4 and PVTri-P(VPA)2 showed respective proton conductivities of 

0.008 and 0.022 S cm −1 at 100 o C, where the conductivity of the latter is close to Nafion 117 

at the same humidity level. 

- 65 -


POLYMER NANOBLENDS 

K. Jurczuk, E. Piorkowska, A. Galeski 

Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, 

Sienkiewicza 112, 94123 Lodz, Poland 

andgal@cbmm.lodz.pl 

An ongoing challenge in material science is to design novel polymeric materials with improved 

properties. This is often achieved by blending with other polymers or by adding filler 

materials. Fillers with at least one dimension in the nanometer range have proven to be of 

most interest for their dramatic influence on the final properties of the composite material. 

A promising new system of polypropylene (PP) and polytetrafluoroethylene (PTFE) nanofibres 

was sought. High viscosity PP and PTFE were the raw materials for preparing the nanoblends. 

Cryo-fracture surfaces of PP/PTFE nanoblends were examined by SEM to study the 

structure and PTFE dispersion. 

PTFE was in the form of nanofibers having the thickness above 30 nm homogeneously dispersed 

in PP matrix. The SEM images of cryo-fractured nanoblends reveal a plenitude of tens 

of micrometer long nanofibers. 

The tensile properties and Izod impact strength of injection molded specimens of PP/PTFE 

nanoblends were determined. The tensile mechanical properties of the nanoblends are improved 

over plain PP, however, Izod impact strength is significanlty increased. 

Melt elongation tests were performed using ARES rheometer with EVF attachment. The experiments 

revealed that melt strength of PP/PTFE nanoblends is more than six times higher 

than that of plain PP. 

Similar results were obtained when PP matrix was replaced with polystyrene or low-density 

polyethylene. The melt strength of these nanoblends was three times higher than that for neat 

polymers. 

- 66 -


IN-SITU SYNTHESIS OF POLYESTER NANOCOMPOSITES 

WITH INORGANIC NANOOBJECTS AND THEIR USE TO 

TAILOR PROPERTIES OF POLYMER BLENDS 

Doris Pospiech (1), Andreas Korwitz (1), Dieter Jehnichen (1), Liane Häußler (1), Bernd 

Kretzschmar (1), Petra Pötschke (1), Beate Krause (1), Maria auf der Landwehr (1), Polycarpos 

Pissis (2), Emmanuel Logakis (2), Andreas Wurm (3), Christoph Schick (3) 

(1) Leibniz-Institut für Polymerforschung Dresden e.V., Hohe Str. 6, D-01069 Dresden 

(2) National Technical University of Athens, Department of Physics, Zografu Campus, 

15780 Athens, Greece 

(3) University of Rostock, Polymer Physics, Universitätsplatz 1, 18051 Rostock, Germany 

pospiech@ipfdd.de 

Polymeric nanocomposites containing inorganic materials with dimension around and below 

100 nm very often suffer from imperfect distribution of the nanoobjects within the polymer 

matrix. However, a good distribution is one of the basic requirements to exploit the high potential 

of nanocomposites. Thus, distribution of the nanomaterials in monomers and their subsequent 

polymerization has been proposed and applied [1] to improve this situation, working 

well for polymerizable monomers. Polyester synthesis which is usually carried out as melt 

polycondensation represents another situation and has started rather late to be applied for 

preparation of in situ nanocomposites, see e. g., [2, 3]. 

Here, we will discuss the results of in situ synthesis of nanocomposites of different polyesters 

in presence of several types of nanomaterials, in particular, natural layered silicates like 

Montmorillonite and Halloysite, multiwalled Carbon nanotubes. The project aimed at preparation 

of nanocomposites with proper distribution of the nanoobjects at high loading for use as 

masterbatchs in polymer and polymer blend nanocomposites. The synthesis results depended 

strongly on the amount of nanomaterial used, on the chemical modification applied on the 

inorganic, as well as on the type of polyester (PET, PBT, phosphorus-containing polyesters 

and copolyesters). 

Particularly interesting were PET-MWCNT nanocomposites. In situ synthesis yielded materials 

with extremely low percolation thresholds pc (shown by both dielectric spectroscopy as 

well as volume resistivity) in the range of 0.05 wt% MWCNT (compared to pc of 0.15 wt% 

obtained with the same nanotubes in melt compounds, while the value of compounds prepared 

using the in situ synthesized batches were in between). 

Phosphorus-containing polyester nanocomposites were also used as additives in polymers and 

polymer blends to enhance the flame retardancy of these materials. The properties of the starting 

in situ materials already showed promising parameters. 

[1] M. Kato, A. Usuki “Polymer-Clay Nanocomposites”, in “Polymer-Clay Nanocomposites”, T.G. Pinnavaia, 

G.W. Beall, Eds., Wiley Series in Polym. Sci., John Wiley & Sons (2000), pp. 97-109. 

[2] D. Pospiech, A. Korwitz, D. Voigt, D. Jehnichen, J. Müller, A. Janke, T. Hoffmann, B. Kretzschmar, High 

Perf. Polym. 19 (2007), 565-580. 

[3] G. Broza, M. Kwiatkowska, Z. Roslaniec, K. Schulte, Polymer 46 (2005), 5860-5867. 

- 67 -


THE EFFECT OF SILICA NANOPARTICLES ON THE PHASE 

BEHAVIOR OF POLYMER BLENDS STUDIED VIA A HIGH- 

THROUGHPUT EXPERIMENTATION APPROACH 

Weizhen Li, Han Goossens 

Eindhoven University of Technology, Department of Chemical Engineering and Chemistry, 

Laboratory of Polymer Technology, the Netherlands 

j.g.p.goossens@tue.nl 

The phase behavior of blends of two polymers, i. e. poly(methyl methacrylate) (PMMA)/ 

poly(styrene-co-acrylonitrile) (SAN), was studied via a high-throughput experimentation 

(HTE) approach, which combines a composition and a temperature gradient. The evolution of 

the morphology was studied by optical microscopy and AFM. The effect of silica nanoparticles 

was studied for both systems and it was shown that the nanoparticles have a large effect 

on the morphology development due to their preferential segregation to the PMMA phase, as 

a result of the existence of hydroxyl groups on the surface of silica. Due to the preferential 

segregation, a slow-down effect of silica nanoparticles on the phase separation has been observed 

in PMMA/SAN due to the local increase of the viscosity and a concomitant reduction 

of the mobility of the PMMA-rich phase. 

- 68 -


NANO-STRUCTURED COMPOSITES – THE POTENTIAL OF 

SPHERICAL NANO-SILICA 

Regina Jeziórska 

Industrial Chemistry Research Institute 

regina.jeziorska@ichp.pl 

Nano-structured composites have received considerable attention in the past few years. The 

potential of this new class of materials is great, even small amounts (≤ 6 wt%) of nano-silica 

particles can increase tensile strength and stiffness as well as flexural strength and modulus, 

and in same cases also improve impact strength as compared to neat polymers. Simultaneously, 

physical properties of polymer matrices like heat and chemical resistance, barrier properties 

and flame resistance can be enhanced. In this paper, the effects of spherical nano-silica 

content and size as well as compatibilizer concentration on the phase behavior and microstructure 

of nano-structured composites were studied. Unmodified and modified silica with 

different sizes were taken into account and melt mixed with polymers using a co-rotating twin 

screw extruder (D=25 mm, L/D=33). It was revealed that content and size of silica as well as 

compatibilizer concentration affected the agglomeration degree of the nano-particles. Moreover, 

a strong impact of silica functionality on the properties of polymer composites was observed. 

From SEM it was found that agglomerations of silica particles within the polymer 

matrix increased with increasing silica contents whilst they decreased when modified silica 

and/or compatibilizer were used. It was observed that mechanical properties are mainly affected 

by the silica nano-particles as well as by the compatibilizer content. Higher concentrations 

of compatibilizer resulted in a further enhancement of mechanical properties due to silica 

agglomerate reduction. This finding was verified from SEM micrographs. Evidently the 

functional groups on silica surface react with functional groups of polymer and/or compatibilizer 

and lead to a finer dispersion of individual silica nano-particles in the polymer matrix. 

The enhanced adhesion at the interface of the two materials, as a result of the mentioned reaction, 

has been studied and proved by several equations. Storage modulus values of prepared 

nano-structured composites measured by DMTA were sensitive to the microstructure of the 

composites. Higher silica contents and bigger silica size resulted in higher storage modulus 

and lower flammability, evidence revealing that the material became stiffer. By adding the 

compatibilizer further increases of storage modulus were observed due to the finer dispersion 

of the filler in the matrix and increased interfacial adhesion. Both permitted a much more efficient 

transfer of stress from the polymer matrix to the silica nano-particles. Moreover, the 

presence of silica also affected the crystalline and thermal behavior of the polymers, due to 

the fact that glass transition temperature and crystallization temperature of the composites 

increased significantly. Furthermore, in comparison with the corresponding neat polymers 

increased thermal stability, better flame resistance, improved chemical resistance and significantly 

lower water absorption were observed. 

- 69 -


USING HDPE/PA6 BLEND AS A MATRIX FOR POLYMER/- 

LAYERED SILICATE NANOCOMPOSITES: MORPHOLOGY 

CONTROL AND MECHANICAL PROPERTIES 

I. Ghamarian (1), N. Yousefi (1), R. Bagheri (1), S. Zokaei (2) 

(1) Polymeric Materials Research Group, Department of Materials Science and Engineering, 

Sharif University of Technology, P.O. Box 11155-6499, Tehran, Iran 

(2) Parsa Polymer Sharif Co., Golestaneh St., Azadi ave, Tehran, Iran 

narimun@gmail.com 

HDPE is a commodity thermoplastic with applications ranging from pipes and fittings to hip 

joints. However, this polymer cannot be used in many engineering structures because of comparably 

low elastic modulus and yield strength. Although the modulus can be increased by 

incorporating a considerable amount of rigid microfillers such as calcium carbonate or talc, 

the yield and impact strength of the resulting composite is usually deteriorated to a large extent. 

Polymer nanocomposites have gained a lot of interest during the recent years. Among them, 

polymer/layered silicate nanocomposites have been at the center of attention because of the 

superior mechanical, barrier and thermal properties they can bring about by use of a relatively 

small amount of nanocaly. In these nanocomposite, a fully exfoliated structure where the clay 

platelets are completely dispersed in the polymer matrix, guarantee the maximum enhancement 

of properties. 

One major problem with non-polar matrices such as HDPE is the inability of the polymer in 

fully exfoliating the clay platelets, i. e. the clay remains untouched or at last there might be a 

degree of intercalation among the clay galleries. Contrastingly, polar matrices, such PA6 can 

readily exfoliate a properly modified clay and constitute a fully exfoliated nanocomposite. 

In order to combine the versatility of HDPE and polarity of PA6, blends of HDPE/PA6 can be 

used as a potential matrix for polymer/clay nanocomposites. Through this, a nanocomposite 

can be achieved that enjoys both the low price, ease of processing and versatility of HDPE 

and an exfoliated nanostructure that provides a balance of desirable mechanical properties. 

In this study, the morphology and mechanical properties of HDPE/PA6/nanocaly has been 

studied. Efforts have been made to control the nanostructure by means of altering the sequence 

of compounding of the polymer/clay in nanocomposite processing. The morphology 

has been studied by electron microscopy and XRD techniques. The mechanical properties 

have been studied by tensile and impact tests. To better understand the interaction of HDPE, 

PA6 and nanoclay, the crystallization of nanocomposites has been studied with DSC. 

Experimental studies show that the sequence of compounding of HDPE/PA6/nanoclay, i.e. 

one stage mixing of the constituents versus precompounding nanoclay and one polymer at one 

stage and further compounding the resulting composite with the second polymer, plays an 

important role in the morphology and the mechanical properties of the nanocomposite. Finally, 

using a polymer blend as a matrix for a layered silicate nanocomposite has been an effective 

tool for covering the weaknesses of HDPE and attaining a simultaneous increase in the 

elastic modulus and yield strength with incorporation of a small amount of nanoclay. 

- 70 -


POLYMER NANOCOMPOSITES CONTAINING FULLEROID 

NANOFILLERS 

V. V. Zuev 

Institute of Macromolecular Compounds of the Russian Academy of Sciences, 

Bolshoi pr., 31, 190004 Sankt Petersburg, Russian Federation 

zuev@hq.macro.ru 

Polymer nanocomposites have attracted enormous interest from the materials community because 

they theoretically promise substantial improvement of mechanical properties at very 

low filler loadings. Because of their excellent physical properties, nanosize in diameter, low 

density fullerene C60 has been considered as ideal reinforcing fillers in polymer nanocomposites 

with multifunctions. In this communication, we describe our investigation of PA-6, PA- 

12 and epoxy resins nanocomposites with fullerene C60 and their precursor in industry: mixture 

of fullerene C60/C70 (70/30) and fullerene soot with fullerenes contains 8-12 %. 

Fullerene soot is ultra dispersed carbon forming at voltaic arc of graphite in inert gas atmosphere 

at fullerene production with particles diameter 0.5-2.0 µm. The challenges for developing 

high-performance fullerene C60/ polymer nanocomposites are (i) homogeneous dispersion 

or solution of fullerene C60 in the polymer matrix and (ii) strong interfacial interactions so as 

to effect efficient load transfer from the polymer matrix to the fullerene C60. The nanocomposites 

were prepared or by simple melt-compounding (for PA-6 and PA-12) or by in situ 

polymerization in the presence of fullerene C60 (for epoxy resins, PA-6 and PA-12). The 

amount of fullerene C60 was varied of 0.001-0.1wt %. Many of the macroscopic properties of 

nanocomposites crucially depend on their morphology. Electron microscopic imaging was 

used for elucidating nanoscale morphologies. As we show in all cases the fullerene C60 is 

well dispersed or soluble in polymer matrix used and did not forms large-scale aggregates 

independently from the method of nanocomposite formation. This provides a good load transfer 

between the matrix and filler and leads to substantial improvement of mechanical properties 

at very low fullerene C60 loadings. Mechanical tests show that, compared with neat PA-6, 

PA-12, and epoxy resins, the tensile modulus, tensile strength, and the hardness of the composite 

are improved by about 40-50%. The more enhanced tensile mechanical properties were 

found for polymer nanocomposites enforced by fullerene C60/C70 mixture. Overall, the addition 

of fullerene fillers to the PA matrix had a more profound effect than loading such fillers 

as carbon black, graphite, and fullerene soot. This is attributed to the better dispersion and 

changes in morphology which is caused by the presence of fullerene C60. It was found that 

the fullerenes and fulleroid materials are more efficient in the reinforcement of soft polymers 

(PA-12) compared to hard polymers (epoxy resins).The improvement in thermal stability of 

nanocomposites under study was also observed. Detailed studies on the effect of addition of 

fullerene C60 on crystalline structure (morphology) and mechanical (such as fracture and 

strengthening mechanisms), thermal and electrical properties of nanocomposites are discussed. 

- 71 -


PHASE SEPARATION INDUCED SELECTIVE LOCALI- 

ZATION OF MULTIWALL CARBON NANOTUBES IN LCST- 

TYPE BLENDS: EFFECT ON PHASE SEPARATION 

KINETICS, VISCOELASTIC BEHAVIOR AND ELECTRICAL 

CONDUCTIVITY 

Suryasarathi Bose, Jan Vermant, Paula Moldenaers 

Department of Chemical Engineering and Leuven Materials Research Center, Katholieke 

Universiteit Leuven, Willem de Croylaan 46, B-3001, Leuven, Belgium. 


Thermally induced phase separation in poly[(α-methyl styrene)-co-acrylonitrile]/poly(methyl 

methacrylate) (PαMSAN/PMMA) blends is a well-known phenomenon [1]. In this work the 

phase separation was monitored in presence of amine functionalized (MWNT-NH2) and 

polyethylene surface modified multiwall carbon nanotubes (MWNT-PE) by melt-rheology, 

conductivity spectroscopy and microscopic techniques. The time evolution of dynamic 

modulii was investigated to correlate the viscoelastic response of the blends with the resulting 

morphology. It was observed that the phase separation kinetics and the linear viscoelastic behavior 

of the blends were strongly influenced by the presence of MWNTs. Electron microscopy 

revealed that the phase separation resulted in a heterogeneous distribution of MWNTs in 

the blends, driven by thermodynamic forces, which further led to an increase in their local 

concentration in a specific phase, potentially resulting in effective percolation. This heterogeneous 

distribution of the MWNTs manifested itself in a dramatic transition from an insulating 

one-phasic material at room temperature to highly conducting materials in the melt as a result 

of phase separation. Furthermore, the role of the MWNT-NH2 in stabilizing the PMMA droplets 

against flow induced coalescence in 85/15 PαMSAN/PMMA blends was also established. 

It was observed that at a typical loading of only 1.25 wt% MWNT-NH2 coalescence was 

completely suppressed on a practical time scale [2]. 

[1] Laun, H. M. Pure and App. Chem. 1998, 70, 1547. 

[2] Bose, S.; Özdilek, C.; Leys, J.; Seo, J. W.; Wübbenhorst, M.; Vermant, J.; Moldenaers, P. ACS Appl. Mater. 

Interfaces. 2009 (submitted). 

- 72 -


SPONTANEOUS EMISSION OF ORGANOPHILIC CDSE 

NANOPARTICLES DISPERSED IN SEGMENTED 

POLY(CARBONATE URETHANE) COPOLYMER FIBERS BY 

ELECTROSPINNING 

Mustafa M. Demir, Caner Ünlü, Serdar Özçelik 

İzmir Institute of Technology Department of Chemistry, Urla 35430, Turkey 

mdemir@iyte.edu.tr 

Copolymers have been recognized as one of the frequently used building blocks in formation 

of nanostructured materials that exhibit periodicity both in structure and composition. These 

materials have found application in various fields such as optoelectronics, photonics, and optical 

data storage [1]. The association of functional inorganics with self-assembled copolymers 

offers substantial opportunities for novel nanoscale electronic and optoelectronic devices. 

In this work, mesoscale diameter composite fibers based on segmented poly(carbonate 

urethane) copolymers and TOPO-coated CdSe nanoparticles have been produced by electrospinning 

process. This process has proven to be an efficient method for fabrication of micron 

to nanoscale diameter polymeric fibers out of polymer solutions/melts [2]. The nature of the 

process is depends on generation of continuous charged jet ejected from a polymer solution 

droplet to a grounded conductive sheet. Electrostatic potential enforces copolymer phases into 

lamella morphology along the fiber axis in a high degree of order. Due to elongational flow 

and high stretching during electrospinning, the domains as well as guest CdSe nanoparticles 

are oriented along the fiber axis that leads to a hierarchical self-assembly structure. Multiple 

sharp peaks were observed in the visible photoluminescence spectra of the composite fibers 

which may presumably be due to Fabry-Pérot cavity interference [3]. 

[1] Paquet, C.; Kumacheva, E. Materials Today 2008, 11, 48. 

[2] Greiner, A.; Wendorff, J. H. Angewandte Chemie-International Edition 2007, 46, 5670. 

[3] Demir, M. M.; Soyal D.; Ünlü C.; Kuş M.; Özçelik S. J. Phys. Chem. C 2009, 113, 11273. 

- 73 -


INFLUENCE OF THE HYDROGEN BONDING ON THE 

MECHANICAL PERFORMANCE OF SEGMENTED BLOCK 

COPOLYURETHANE ELASTOMERS 

Cristina Prisacariu, Elena Scortanu 

Institute of Macromolecular Chemistry “Petru Poni”, Iasi, Aleea Grigore Ghica Voda, 

Nr. 41 A, 700487, Romania 

crispris@icmpp.ro 

The mechanical properties of polyurethane elastomers (PUs) are mainly determined by their 

microphase morphologies. The effect of hydrogen bonding is frequently used to explain various 

anomalies or improved properties. In the present work this problem was addressed by 

studying a series of PUs with analogous structures but achieved with and/or without hydrogen 

bonding. The effect of hydrogen bonding on the PUs mechanical behaviour was undertaken. 

The following preparation procedures were adopted to obtain deuterated materials: (a) the 

substitution of hydrogen bonding with deuterium of heavy water, in the case of thin, up to 

0.02 mm thin PUs films; (b) the deuteration by synthesis on employing deuterated chain extenders 

(CE) and macrodiols (MD). The hydrogen substitution with inert (-CH3) groups was 

carried out using the following synthesis routes: (a) chemical modification of usual PUs by 

substitution after synthesis, using lithium hydride and methyl chloride; (b) using dichlorophormiates 

based on poly(ethylene adipate) (PEA) and diethylene glycol (DEG) reacted with 

–NN’- dimethyl diaminodiphenyl methane. For thicker PU sheets, the deuteration by synthesis 

was approached by using deuterated diol chain extenders. For PUs derived from deuterated 

CE, it obtained better elastomeric mechanical properties. When proceeding to the hydrogen 

substitution with inert (-CH3) groups, the polymer inelasticity increased, which resulted in a 

dramatic increase of the residual elongation and a pronounced tendency of polymer plasticization. 

For the series of deuterated materials with deuterated CE, the hysteresis energy dissipation 

(E * 1H) [1] and Mullins Factor (M) were determined by subjecting the materials to 

load/unload cycles. Results were related to microstructural changes, on the basis of evidence 

from x-ray scattering (WAXS and SAXS). A quantitative correlation was found between the 

magnitude of the Mullins effect and the fractional energy dissipation by hysteresis (E * 1H) under 

cyclic straining, giving a common relation that was approached by all the materials studied. 

It revealed a remarkable correlation between these two parameters. For the range of materials 

studied (both hydrogenated and deuterated PUs), all materials achieved with polyesteric 

MD lied on the straight line shown, which was M = E * 1H. The results of this study showed 

that this relation is independent of PUs composition (hydrogenated or deuterated materials) 

and that the Mullins effect is clearly linked to the mechanism of hysteresis, The deuterated 

polymers derived from polyetheric MD showed SAXS peak areas much higher than the others, 

indicating a higher degree of phase separation. The Mullins effect is linked to the mechanism 

of hysteresis, but is accentuated by a high degree of phase separation. 

[1] Prisacariu C., Olley R. H., Caraculacu A., Bassett D. C., Martin C.: Polymer 2003, 44: 5407 

- 74 -


MORPHOLOGY AND PHYSICAL PROPERTIES OF POLY 

(BUTYLENE TEREPHTHALATE)/POLYLACTIDE REACTIVE 


Piotr Franciszczak, Zbigniew Rosłaniec 

West Pomeranian University of Technology, Institute of Materials Science and Engeenering, 

Szczecin, Poland 

piotr.franciszczak@zut.edu.pl 

Poly(butylene terephthalate) (PBT) is a commercial polyester which attracts increasing interest 

due to its good processability and properties. PBT is rather rigid because of its high crystallinity. 

Therefore in the recent studies attempts were made to improve its impact strength by 

modification with such aliphatic polymers as: polycaprolactone (PCL) and polypivalolactone 

(PVL). In this work PBT was modified with another aliphatic polymer - polylactide (PLA). 

The modification was performed by the means of reactions in a vacuum mixer between 

diester of terephthalic acid and 1,4-butanediol and PLA monomers. The main objective of this 

approach was to obtain two-phase microstructure providing better elastic properties. Reactive 

polymer blends with different PBT/PLA weight ratios were prepared and their morphology 

and physical properties were evaluated using differential scanning calorimetry (DSC), dynamic 

mechanical thermal analysis (DMTA), scanning electron microscopy (SEM) and nuclear 

magnetic resonance spectroscopy (NMR). Furthermore the possibility of producing 

these blends by reactive extrusion with addition of chain extender was confirmed using a 

twin-screw extruder. 

- 75 -


BIODEGRADABLE POLY(3-HYDROXYBUTYRATE)/- 

POLY(BUTYLENE SUCCINATE) (PHB/PBS) BLENDS: 

EFFECT OF PBS ON CRYSTALLIZATION BEHAVIOR AND 

THERMAL STABILITY OF PHB 

P. Ma, D. G. Hristova-Bogaerds, P. J. Lemstra 

Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, 

The Netherlands 

d.g.bogaerds-hristova@tue.nl 

Biodegradable materials have received considerable attention during the past two decades 

because of their use in applications areas like packaging, personal care products, and medical 

applications. 

Poly (3-hydroxybutyrate) (PHB) is biodegradable and also bio-based polymer which is produced 

by a bacteria. However, its wide use is still limited due to several drawbacks of this 

material like brittleness, thermal degradation and low crystallization rate. The brittleness of 

PHB is ascribed to its thermal degradation, cracks of large PHB spherulites and progressive 

crystallization during storage. 

PHB is produced by a fermentation process directly in the bacteria and therefore it is extremely 

pure material. This makes his crystallization very slow caused only by eventual homogeneous 

nucleation. The target of this work is to improve the crystallization rate of PHB 

via melt blending with another biodegradable polymer Poly(butylenes succinate) PBS. PBS is 

a flexible biodegradable polymer with the potential to be also bio-based (currently many attempts 

are focused on producing it from renewable resources). 

Biodegradable PHB/PBS blends were prepared by melt blending. Isothermal crystallization 

of PHB (at temperatures where only PHB can crystallize (well above the melting point of 

PBS) and non-isothermal crystallization behavior of the blends were studied by DSC, DMTA, 

OM and SEM. All results indicated that the crystallization rate of PHB was dramatically increased 

after incorporation of PBS, especially at 50 wt% PBS loading. For this blend it was 

found that the morphology is co-continuous in contrast to the discreet phase-matrix morphology 

observed for the rest of the blends. An increase of the crystallization temperature of PHB 

(during cooling process) by more than 30 o C was observed, accompanied by an increased 

level of crystallinity. At the same time PBS was also influenced by the presence of PHB. This 

influence was, however, not very noticeable and expressed mostly by the decrease of PBS 

crystallinity in its blends with PHB. 

The enhanced crystallization of PHB was explained by the effect of heterogeneous nucleation 

of PBS on PHB and by additional self-enhanced type nucleation of PHB, namely nucleation 

proceeded gradually using already crystallized PHB domains as nucleation sites for the rest of 

the not crystallized yet PHB. 

Sequential DSC heating scan results indicated that PBS enhanced also the thermal stability of 

PHB. 

- 76 -


COMPATIBILIZATION OF BINARY AND TERNARY BLENDS 

OF BIODEGRADABLE PLASTICS 

Ivan Chodák (1), Pavol Alexy (2), Zuzana Nógellová (1), Tomáš Mlynský (2), 

Roelof van der Meer (3), Dietrich Scherzer (4) 

(1) Polymer Institute of the Slovak Academy of Sciences, 842 36 Bratislava. Slovakia 

(2) Faculty of Chemical and Food Technologies, Slovak Technical University, Bratislava, 

Slovakia 

(3) BASF Nederland B.V., Performance Chemicals, 8466SN Nijehaske, the Netherlands 

(4) BASF SE, 67056 Ludwigshafen, Germany 

upolchiv@savba.sk 

Biodegradable plastics (BDPs) are important materials prospective for many interesting applications. 

However, in many cases the applications are limites by limited versatility of properties 

so that it is diffcult to tailor the materials for a specific purpose. For many important 

BDPs such as polyhydroxyalkanoates or polylactic acid the main concern consists in an unacceptable 

brittleness of the polymers. Besides preparation of copolymers, e. g. polyhydroxybutyrate-co-valerate, 

mixing with other, more ductile BDPs is a suitable way, however, high 

compatibility is a must in that case what is not always a case. In this contribution the effect of 

compatibilization of BDPs blends on mechanical properties is investigated. 

Three main plastics have been selected, namely polyhydroxybutyrate (PHB), polylactic (PLA) 

acid and biodegradable copolyester PBAT (BASF production). Various combinations of the 

three were investigated in detail, taking always two main components as a basic polymeric 

substrate. The suitable plasticizer was added as the third component, helping to broaden the 

versatility range of properties. In all cases appropriate compatibilizers have been tested. 

In all cases compatibilization resulted in a dramatic changes of mechanical properties, leading 

to certain decrease of Young’s modulus and in some cases also of tensile stregth while resulting 

in a significant increase in elongation at break and toughness. Although in all cases then 

general tendency was the same, as metioned above, the values of mechanical parameters varied 

significantly regarding the selection of the blend components (PLA/PBAT, PHB/PBAT, 

PLA/PHB), content of plasticizer, or the mode of compatibilization. Besides peroxide initiated 

crosslinking which was investigated in the past for various systems, chemically reactive 

epoxy additives proved to be very effective for certain pairs of BDPs, however, various different 

types, even similar regarding the chemical composition, were found to differ very much 

considering the compatibilization efficiency. The materials based on various combinations of 

BDPs could be applied either as hard construction plastics, or ductile plastic materials for extrusion 

od injection moulding, or films suitable for biodegradable packagings prepared by 

film blowing. The changes in mechanical properties were interpreted in detail using data from 

electron microscopy, DMTA, DSC and rheological measurements. 

- 77 -


ABS/PA-ALLOYS – INFLUENCE OF THE COMPOUNDING 

PROCEDURE ON THE MATERIALS PERFORMANCE 

M. Weber, B. Staal, W. Heckmann, M. Abdul Manan, A. Knieper 

BASF SE Polymer Research, 67056 Ludwigshafen, Germany 

martin.weber@basf.com 

Polymer alloys based on ABS (Acrylonitrile-Butadiene-Styrene) and Polyamide 6 offer an 

excellent combination of toughness, stiffness, chemical resistance and processing behavior. 

Therefore such compounds are widely used in automotive and other engineering applications 

[1-2]. Although these materials are on the market since more than 20 years, still a lot of work 

in this area is going on in academic and industrial labs [3-6]. The compatibility between the 

two immiscible components SAN and PA 6 is usually achieved by SAN-g-PA 6 copolymers, 

which are formed during the melt mixing step by the reaction of Styrene-Acrylonitrile-Maleic 

Anhydride Terpolymers (SANMA) and the PA 6. Hence, the concentration of SAN-g-PA 6 

formed during the melt mixing is generally not known [7]. 

In order to improve the performance of commercial formulations, the influence of different 

compounding sequences was studied in detail. Several feeding protocols of the main components 

are technically feasible: 

- pre-compounding of PA 6 and SANMA 

- feeding of components at different sections of the extruder. 

Especially the pre-compounding of the PA 6 and SANMA turned out to be an interesting 

method to improve the mechanical performance of commercial ABS/PA 6 formulations. The 

observed changes in properties will be discussed in relation to the morphologies of the different 

samples and the chemical properties of the compounds, e.g. the molecular weight of the 

PA-fractions. 

[1] L. Dunning, Kunststoffe 1996, 86, 98. 

[2] M. Weber, Macromol. Symp. 2002, 182, 189. 

[3] S. H. Jafari; P.Pötschke; M. Stephan; H. Warth; H. Alberts, Polymer 2002, 43, 6985. 

[4] E. M. Araujo; E. Hage Jr.; A. J. Carvalho, J. Appl. Polym. Sci. 2003, 87, 842. 

[5] S. L. Sun; Z. Y. Tan; X. F. Xu; C. Zhou; Y. H. Ao; H. X. Zhang, J. Polym. Sci, Part B: Polym. Phys. 2005, 

43, 2170. 

[6] J. H. Park, Y.-C. Yu, EP 1 276 814, 10.04.2001. 

[7] R. E. Lavengood, A. F. Harris, A. R. Padwa, EP 202 214, 09.05.1986. 

- 78 -


TRANSFER MECHANISMS AND LOCALIZATION OF 

CONDUCTIVE NANOFILLERS IN DIFFERENT POLAR 

BLEND PHASES DURING MELT MIXING PROCESSES 

Andreas Göldel, Gaurav Kasaliwal, Petra Pötschke 

Leibniz Institute of Polymer Research Dresden, Germany, Hohe Str. 6, 01069 Dresden, 

Germany 

poe@ipfdd.de 

The combination of blend systems with conductive nanoscaled fillers by melt mixing processes 

offers compared to single-polymer-composites much higher potential for the development 

of conductive composites with significantly lower filler concentrations. This can be 

achieved either by the selective localization of fillers at the interface or in one of the phases of 

an immiscible blend, that ideally has a co-continuous blend morphology. The adjustment of 

such blend structures in combination with the localization of conductive high aspect ratio fillers 

directly at the blend interface is one of the few remaining concepts that promise a break 

through on the market of conductive thermoplastic polymers. Aiming at tailoring new blend 

nanocomposite systems, a comprehensive understanding of the mechanisms responsible for 

the localization of conductive fillers like carbon nanotubes (CNT) or carbon black (CB) is 

required. 

In the recent past, new results revealed that CNTs can be very quickly transferred from one 

blend phase to the other during melt mixing, thus resulting in morphological structures where 

the CNTs can be explicitly located even in the previously unfilled blend phase whereas the 

initial CNT-carrier polymer is completely free of nanotubes after the mixing process [1]. A 

main difference to carbon black, that although can be transferred from one phase to the other, 

is the explicit selectivity of tube localization in the final blend morphology. This difference 

was attributed to the higher aspect ratio of carbon nanotubes as compared to that of spherical 

carbon black, which is assumed to greatly increase speed and efficiency of the transfer 

mechanism. The question about the origin of the driving force that transfers the nanofiller 

from one particular blend phase into the other is commonly discussed based on the wetting 

coefficient that represents a mathematical description of the system’s tendency to minimize its 

interfacial energy. Unfortunately, for nanoparticles, the application of this well established 

concept significantly suffers from the enormous insecurities that are connected to the difficulties 

in correctly measuring their surface properties and/or interfacial tensions towards polymers. 

The present study tries to access the interfacial interactions by analyzing the localization of 

MWNTs in different dual phase polymer blend systems made of polar polymers. The blends 

were produced using 5 min of melt mixing in a small-scale co-rotating microcompounder. 

MWNT-polymer interactions are discussed by means of nanotube localization, nanotube aspect 

ratio, wetting coefficients and characteristic features like the molecular architecture of 

the blend partners. 

[1] A. Göldel, G. Kasaliwal, P. Pötschke, Selective Localization and Migration of Multiwalled Carbon Nanotubes 

in Blends of Polycarbonate and Poly(styrene-acrylonitrile) Macromolecular Rapid Communications 

30(2009) 6, 423-429 

- 79 -

ABSTRACTS 

OF 

POSTERS


MODELING OF BRANCHING AND GELATION IN LIVING 

COPOLYMERIZATION OF MONOMER AND DIVINYL CROSS- 

LINKER ATRP PROCESS - STUDY IN FRAME OF DYNAMIC 

LATTICE LIQUID MODEL (DLL) 

Piotr Polanowski (1), Krzysztof Matyjaszewski (2) 

(1) Department of Molecular Physics, Technical University of Lodz, 90-924 Lodz, Poland 

(2) Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, 

Pennsylvania 15213 

ppolanow@p.lodz.pl 

Using the dynamic lattice liquid model we have studied the structural properties of randomly 

cross-linked polymer melts obtained by atom transfer radical polymerization processes 

(ATRP). It was found, that this simple model allows to predict gel point in several different 

ATRP experiments with good agreement with experimental data and it is also able to predict 

the effect of solvent dilution on the gel points. Molecular weights, polydispersities and the 

distribution of primary linear chains amongst the branched copolymer molecules can be modeled 

as a function of conversion. We also have shown source of discrepancy between results 

obtained by DLL method and the mean-field theory 

- 83 -


FOAMING BEHAVIOR OF POLYSTYRENE CONTAINING 

DISSOLVED CO2 DURING DEPRESSURISATION 

Salah Al-Enezi, Meshal Al-Samhan 

Kuwait Institute for Scientific Research 

senezi@prsc.kisr.kw 

This paper examines the effects derived from the ability of high pressure carbon dioxide to 

foam polystyrene. This has potential applications in the shape foaming of polymers at lower 

temperatures, dye impregnation and the foaming of polystyrene. This study was conducted in 

foaming behaviour of polystyrene containing dissolved CO2 during depressurisation. The 

polymer foaming was investigated using cylindrical high pressure view cell with 2 optical 

widows. This study differs from previous published work in that conditions were chosen to be 

near the glass transition temperature (Tg) of the polymer. Foaming was not observed when the 

polymer was initially at conditions below Tg, but was observed above the Tg. The radius of 

bubbles was measured with time and the results compared against models for bubble growth. 

Best fits were obtained with a viscous-diffusion model. 

- 84 -


MONTE CARLO SIMULATION OF MACROMOLECULAR 

REACTIONS IN HETEROGENEOUS POLYMER BLENDS 

Daria V. Guseva (1), Alexander V. Chertovich (2), Yaroslav V. Kudryavtsev (3), 

Arkadiy D. Litmanovich (4) 

(1) Physics Department, Moscow State University, Leninskie Gory, Moscow 119991, Russia 


(3) Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 

Leninsky pr. 29, Moscow 119991, Russia 

(4) Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 

Leninsky pr. 29, Moscow 119991, Russia 

guseva@polly.phys.msu.ru 

Simulations provide a powerful tool for visualizing the processes that take place at the interphase 

boundaries of molten polymers. In this work, an off-lattice Monte Carlo simulation of 

the reaction and interdiffusion in an initially bilayer A/B polymer blend is carried out using 

the coarse-grained bead-spring model with Morse potentials. Two types of macromolecular 

reactions are studied: (i) an interchain exchange via end-group mechanism and (ii) a polymeranalogous 

autocatalytic unit transformation A→B (B-units cause the reaction). 

(i) The evolution of the local molecular mass and block length distributions in close vicinity 

to a phase boundary is studied for an initially incompatible system. It is found that at the early 

stage the reaction takes place within a narrow interfacial layer until rather short copolymer 

AB blocks are formed, which then penetrate the bulk phases. In the simulation box of a finite 

size, a stationary state is finally formed, in which short homopolymers and copolymer blocks 

are distributed uniformly over the system whereas long blocks are located in the corresponding 

phases. At higher temperatures, this state is more homogeneous while the time of its establishment 

depends mainly on the interchange reaction rate. Chain length effects are investigated. 

(ii) The evolution of the number density of A-units and units initially belonging to polymer A 

chains is studied. Irrespectively of the compatibility of a starting homopolymer system, all 

reactive A-units gradually undergo transformation. Local average characteristics of the composition 

distribution of reacting chains and length distribution of A and B blocks are calculated. 

It is demonstrated that these distributions are much broader than those for a Bernoullian 

copolymer of the corresponding mean composition. Such effect is due to the diffusive intermixing 

of reacting chains as predicted earlier for the theoretical model that describes largescale 

interdiffusion in reacting polymer blends. 

This work was supported by the Russian Foundation for Basic Research (project no. 07-03- 

00988) 

- 85 -


EVIDENCE OF MICROPHASE SEPARATION IN RANDOM 

COPOLYMER MELTS BY DISSIPATIVE PARTICLE 

DYNAMICS SIMULATION 

Alexei A. Gavrilov (1), Pavel G. Khalatu (2), Yaroslav V. Kudryavtsev (3), 

Alexander V. Chertovich (1) 


(2) Nesmeyanov Institute of Organo-Element Compounds, Russian Academy of Sciences, 

Vavilova str. 28, Moscow 119991, Russia 

(3) Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Leninsky pr. 

29, Moscow 119991, Russia 

gavrilov@polly.phys.msu.ru 

The phase behavior of random copolymer melts is a yet unresolved fundamental problem attracting 

stable attention. Experimental considerations are not easy due to the high viscosity of 

polymer melts and hence extremely long times for establishing the thermodynamic equilibrium 

under quenching conditions. Known theoretical approaches work well for copolymers 

with long blocks but rapidly lose their applicability with increasing the degree of blockiness 

as the conformation of a block consisting of a few monomer units strongly depends on its 

length. Another complication is caused by the polydispersity in the molecular mass and block 

length distributions. In this situation, macromolecular simulation techniques, which gained a 

lot from the considerable increase in computing capacities during the last years, can be used 

to answer many old questions at an absolutely new level. 

The majority of theoretical works predicts that a copolymer with the completely random distribution 

of units cannot undergo phase transition from a homogeneous to microphase separated 

state. In this work, we report on the possibility of such transition for systems incompatible 

on a monomer unit level and describe the characteristics of the well-defined final structure. 

To this end, we use the dissipative particle dynamics (DPD) method and massive parallel 

simulations to model the melt of an AB multiblock copolymer of equimolar composition, the 

Flory molecular mass distribution and Bernoullian block length distribution. The mean chain 

length is fixed to 32 units, whereas the mean block length is varied (2, 4, or 8 units). The results 

are compared with those for the monodisperse chains and regular blocks of the corresponding 

length. 

For all systems, we detect a phase transition order-disorder, which results in the formation of 

lamellar structure with a period depending on the strength of unit-unit interactions (effective 

temperature) and increasing with the degree of polydispersity. The results of this study can 

stimulate experimental research focused on creating polymer nanocomposites from random 

copolymers. 

This work was supported by the RFBR (09-03-12263-OFI-M) Russian Federal Agency for 

Education (P334). 

- 86 -


THE MICROPHASE SEPARATION IN MELTS OF DIBLOCK- 

COPOLYMER INCLUDING LINEAR AND AMPHIPHILIC 

BLOCKS (MATHEMATICAL MODELLING) 

A. A. Glagoleva (1), V. V. Vasilevskaya (2), A. R. Khokhlov (1, 2) 

(1) Moscow State University, Physics Department, Chair of Polymer and Crystal Physics 

(2) Institute of Organoelement Compounds, Russian Academy of Science 

starostina@polly.phys.msu.ru 

The microphase separation in melts of (A-graft-Bm)xAy diblock copolymer is studied by 

means of computer simulations (DPD and Monte Carlo). 

It is shown that similarly to the case of AxBy diblock copolymer the type of microstructure 

arising upon the microphase separation depends on the ratio x/y of lengths of linear and amphiphilic 

blocks, but in opposite to AxBy diblock copolymer the diagram of state is non 

symmetrical with respect to the relative content of A and B component. 

Computer modeling shows that in case of relatively short amphiphilic A-graft-Bm block (x/y 

>1), the bicontinuous 

structures with hyroid-like ordering are formed. It was found that these bicontinuous 

structures are stable both under weak and strong incompatibility between A and B groups. 

Thus, to create materials with stable bicontinuous microstructures, it would be efficiently to 

use macromolecules with amphiphilic block. 

- 87 -


MODELING OF THE PHASE SEPARATION BEHAVIOR OF 

BLENDS CONTAINING DI- AND TRIBLOCK CO-POLYMERS 

Peter Friedel, Saija Ptacek, Doris Pospiech, Dieter Jehnichen 

Leibniz Institute of Polymer Research Dresden 

friedel@ipfdd.de 

Pure and blended triblock co-polymers open new opportunities for nanoscaled morphologies. 

The calculation of the order-disorder-transition (ODT) of these systems was performed first 

by application of the random phase approximation on a three-component polymer system in 

the group of Hashimoto about 20 years ago [1]. The scattering behavior near the ODT of 

triblock copolymers was discovered by the group of Bates [2], but a full view of a spinodal 

phase diagram is still lacking because of the large number of triblock architectures and interaction 

parameters. Here, the method of Hashimoto was applied for presenting the scattering 

and spinodal behavior of blends containing three components including triblock copolymers 

in a general form. Possible extensions of this method to express other block architectures, the 

introduction of semi-flexibility, and poly-dispersity [3] including the calculation of the corresponding 

morphologies will be discussed briefly. 

[1] Y. Ijichi, T. Hashimoto. “RPA calculations for scattering functions from three component polymer systems 

in the disordered state”. Polymer Communications, 29 (1988), 135-138 

[2] E.W. Cochran, D.C. Morse, F.S. Bates. “Design of ABC Triblock Copolymers near the ODT with the Random 

Phase Approximation”. Macromolecules, 36 (2003), 782-792 

[3] A. John, P. Friedel, D.Pospiech, D. Jehnichen, C. Kunert. “Modeling of the phase separation behavior of 

semiflexible and polydispers diblock copolymers”. Macromol. Theory Simul. 13 (2004),702-710 

- 88 -


SCALE-UP OF AN IN-LINE PROCESS MONITORING 

SYSTEM TO AN INDUSTRIAL EXTRUDER FOR THE 

PRODUCTION OF NANOCOMPOSITES 

Dieter Fischer (1), Jan Müller (1), Sven Kummer (1), Enrico Masarati (2) 

(1) Leibniz-Institut für Polymerforschung e. V., Dresden, Germany 

(2) LyondellBasell, Ferrara, Italy 

fisch@ipfdd.de 

Introduction 

Extrusion is one of the most applied technologies for polymer processing in the molten state. 

We use extrusion to create multifunctional nanostructured materials. In the industrial processing 

is a need to control amount, dispersion and particle size of the nanofillers in the polymer 

matrix during melt processing and to control the influence of the processing conditions on the 

nanocomposite formation. For an adequate real time characterization it is necessary to make 

measurements in the extruder. Spectroscopic and Ultrasonic methods are outstanding methods 

for in-line monitoring. We illustrate the opportunities of in-line near infrared (NIR) and Ultrasonic 

measurements. The novelty of this paper is the real time investigation at an industrial 

extruder (scale up) for the processing of PP nanocomposites. 

Experimental 

We used a Maris TM45 extruder located at LyondellBasell, Ferrara with a special designed 

measuring adapter as bypass at the die. The Ultrasonic and NIR sensors are built in ½ " industry 

standard. The polymer used was PP modified with maleic anhydride (MA) and as nanofillers 

different modified layered silicates (MMT). 

For the correlation of the in-line data with the desired properties we used concentration, 

TEM/SEM, impact strength (Charpy unnotched on injection moulded samples) and rheology 

(shear thinning exponent). Different extrusion processing conditions (T, output, screw speed) 

are chosen in order to find the best exfoliation state and to study the influence of the morphology 

on the final macroscopic properties. Chemometric analyses were performed to correlate 

concentrations, particle size, mechanical properties and shear thinning coefficients of the different 

nanocomposites with the in-line measured data. 

Results 

We could show that we are able to monitor the process fluctuations (screw speed, temperature, 

dosing, flow rate) and to detect dosing problems by raw signals and by chemometric 

evaluation. By using both monitoring methods it is possible to control the constant feeding of 

the nanofiller during industrial nanocomposite processing in real-time. 

One important aim of our investigations was the prediction of the shear thinning exponent to 

determine the degree of exfoliation as an indicator for the dispersion of the nanofiller. We 

could determine the degree of exfoliation for PP/PP-g-MA/MMT at different process conditions 

(screw speed, temperature) and for different MMT’s. One further important aim was to 

determine the mechanical properties of nanocomposites on-line by using multivariate data 

analysis. Aim was the prediction of the impact strength as an example for the determination of 

mechanical properties. The impact strength of these different nanocomposites could be predicted. 

Furthermoe we were fable to predict particles size and agglomerates of all different 

nanocomposites. 

- 89 -


REAL TIME INVESTIGATION OF THE NANOSTRUCTURING 

PROCESS OF PP NANOCOMPOSITES IN THE MELT 

ALONG THE EXTRUDER WITH NIR AND ULTRASONIC 

SPECTROSCOPY 

Dieter Fischer, Sven Kummer, Jan Müller 

Leibniz-Institut für Polymerforschung e. V., Dresden, Germany 

fisch@ipfdd.de 

Introduction 

Extrusion is one of the most applied technologies for polymer processing in the molten state. 

We use extrusion to create polymer nanocomposites. There is a lack of information about the 

nanostructuring during extrusion in the extruder and the influence of the processing conditions 

on the nanocomposite formation. Off-line analytics can not give the exact condition of 

the material during the extrusion process. For the determination of the nanostructuring it is 

necessary to make measurements along the extruder. Spectroscopic and Ultrasonic methods 

are the methods of choice therefore. We illustrate the opportunities of in-line near infrared 

(NIR) and Ultrasonic measurements. The novelty of this paper is the real time investigation of 

the nanostructuration process along the extruder at different measurement points for the processing 

of PP nanocomposites by different processing conditions. 

Experimental 

We used a Micro-Leistritz extruder with special designed measuring bypass adapters as side 

adapters along the extruder and as an end adapter at the die. The Ultrasonic and NIR sensors 

are built in ½ " industry standard and all measurements were made in transmission mode. The 

polymer used was PP modified with maleic anhydride (MA) and as nanofillers different modified 

layered silicates (MMT). 

Different extrusion processing conditions (T, output, screw speed) are chosen in order to find 

the best dispersion and exfoliation state. We used the raw signals of both in-line methods to 

show the different dispersion states of the different nanocomposites and to show the influence 

of the processing conditions on the nanostructuration process. 

Results 

For the determination of the degree of intercalation and exfoliation and also agglomeration we 

investigated 3 different MMT’s with different degrees of intercalation/exfoliation in PPm (inorganic 

content: 5 %). The results for NIR and Ultrasonic data show that we can determine 

different degrees of exfoliation in-line in real-time in the melt along the extruder. So we are 

able to describe the nanostructuring process. We could find an improvement of the exfoliation 

state towards the die. 

Additionally, we investigated the different PPm/MMT at different screw speeds to study the 

influence of changes in process conditions on the formation of the nanostructure. We could 

determine different exfoliation states caused by different processing conditions.These results 

clearly show that we have a better exfoliation with higher screw speeds, caused by higher 

shear forces. That means, screw speed induces particles size changes which are visible in the 

NIR and Ultrasonic spectra. The combination of these both independent methods increased 

the reliability of the in-line measurement. It is possible to optimise the extrusion process 

through this monitoring of the nanostructuration process. 

- 90 -


PREPARATION AND SENSING PROPERTIES OF NOVEL 

POLYURETHANE-CARBON NANOTUBE COMPOSITE 

FIBERS 

Qingqing Fan, Zongyi Qin, Long Chen, Jinghua Gong, Yue Tang, Meifang Zhu 

State Key Lab for Modification of Chemical Fibers & Polymer Materials, College of Material 

Science and Engineering, Donghua University, 2999 Ren-min Road, Shanghai, 201620, 

China 

phqin@dhu.edu.cn, zhumf@dhu.edu.cn 

Fiber-based sensitive materials have potential applications in smart textile for gesture monitoring, 

posture recognition and so on. The essential qualities for sensing fibers include high 

conductivity, excellent elasticity and resilience, resistance to rubbing and flexibility. Incorporating 

the electric property of carbon nanotubes (CNTs) into high elastic polyurethane fibers 

may have potential to produce flexible sensing fibers. However, the conductivities of 

CNT/PU composite fibers prepared by blending CNTs with PU or by in situ polymerization 

of PU on the surface of CNTs are extremely low, and the elasticity of original PU fibers decreased 

obviously. 

Herein, a facile and mass-producible process has been utilized to fabricate conductive and 

elastic PU-CNT fibers by inserting CNTs on surface layers of the swelling PU fibers. The 

high conductivity (σ~100 Ω•cm-1) of resulting composite fibers is attributed to the enrichment 

of CNTs on surface layers. And the original excellent elasticity of PU matrix still remains 

because the slight disturbance to the structure of PU fibers is induced by the induction 

of CNTs onto fiber surfaces. The resulting PU-CNT fibers were rinsed in distilled water under 

ultrasound irradiation, and even rubbed in a standard method, which demonstrated their excellent 

stability of conductive property. Moreover, it is difficult to peel off the CNT networks 

from the composite fibers due to the strong interaction between CNTs and PU matrix. 

The deformation induced rearrangement of CNT networks along with the elongation of matrix 

induces significant increase in the resistance of resulting PU-CNT composite fibers. Reversible 

resistance response is observed due to the arrangement and restoration of CNT networks 

along with matrix under cyclic loading. These composite fibers with sensing property have 

potential applications in fabricating real-time physiological information monitoring system. 

- 91 -


MORPHOLOGY AND RHEOLOGICAL PROPERTY OF 

PLA/PCL BLEND COMPATIBILIZED BY ELECTRON BEAM 

IRRADIATION IN THE PRESENCE OF FUNCTIONAL 

MONOMER 

Boo Young Shin, Bong Shik Kim 

School of Display and Chemical Engineering, Yeungnam University 

byshin@ynu.ac.kr 

Poly(lactic acid)(PLA) is an important biobased and biodegradable polymer that is now finding 

commercial use in single-use disposable items and medical applications. The need for 

biobased and biodegradable polymers in the context of designing materials for the environment 

opens up new markets and opportunities for PLA-based polymers. However, one of the 

limitations of PLA for various commercials is its brittleness. To overcome this disadvantage, 

polycaprolactone (PCL) was blended with PLA [1]. However, it was known that PLA/PCL 

blend was incompatible. Thus, compatibilization studies on the PLA/PCL blend have been 

carried out these days by using compatibilizer such as PLA-g-PCL [2], reactive extrusion with 

reactive processing agent,5 and radiation method [3, 4]. 

The aim of this study was to increase compatibility of immiscible PLA/PCL blend by using 

electron beam irradiation in the presence of glycidyl methacrylate (GMA). The blends of 

PLA/PCL containing GMA were irradiated at doses of 10, 50 and 100 kGy and then the irradiated 

samples were characterized by observing morphology and rheological properties. 

Blends irradiated with 50 and 100 kGy presented greatly improved interfacial adhesion between 

two phases in the morphology (Figure 1). PLA/PCL(9/1) blend irradiated at dose of 

100 kGy in the presence of 3phr GMA showed drastically improved complex viscosity and 

storage modulus properties. The compatibilizer such as PLA-g-PCL was formed by a grafting 

reaction between the two phases when it was irradiated in the presence of GMA. The morphology 

and rheology studies concluded that the compatibility of immiscible PLA/PCL can 

be improved by electron beam irradiation in the presence of GMA. 

[1] Wu, D.; Zhang, Y.; Zhang, M.; Zhou, W. Europ. Polym. J. 2008, 44, 2171. 

[2] Aslan, S.; Calandrelli, L.; Laurirenzo, P.; Malinconico, M.; Migliaresi, C. J. Mater. Sci: mater Med. 2000, 

35, 1615. 

[3] Wang, L.; Ma, W.; Gross, R. A.; McCarthy, S. P. Polym. Deg. Stab. 1998, 59, 161. 

[4] Zhu, G.; Xu, S.; Wang, J. Zhang, L. Rad. Phys. Chem., 2006, 75, 443. 

- 92 -


PROPER USE OF RICE STRAW IN PREPARING OF 

RUBBER COMPOSITES WITH INDUSTRIAL APPLICATIONS 

Galal A. M. Nawwar 

Green Chemistry Department National Research Center, Dokki, Cairo, Egypt 

g.nawwar@link.net 

Open burning of rice straw cause a big environmental problem in Egypt. Attempt to utilized it 

probably as a source of paper pulp has been retarded by it is reach in silica black liquor. Recently 

we reported an Egyptian patent [1] on rice straw pulping and we succeeded to obtain 

good yield of pulp contain almost the straws silica and have (strength properties at 45SR) as 

breaking length 5550, burst factor 43and tear factor 59. 

The corresponding lignin was characterized by FTIR, HNMR and UV and the result found 

were comparable with the expected lignin characteristics. Lignin could be blended without 

modification with synthetic rubber and the proper ratio of it was found to be 20 prh using a 

plasticizer prepared from PET recycling. The obtained composites exemplified by (NBR 

blend) showed curing time ~12m instead of 14.5m when using DOP as plasticizer, also it’s 

mechanical properties after thermal oxidative aging were enhanced to be 7.1 instead of 

5.22MPa with DOP and 1.95MPa in plasticizer absence. 

Adhesive utilizing the obtained lignin instead of the expensive resorcinol could be prepared 

and used as a binder in blending of the obtained unbleached pulp and EPDM rubber. The vulcanizate 

with 50 % pulp gives tensile strength 7.8 MPa and compression strength 670N/cm 2 , 

it’s thermo oxidative aging study showing retained value 98.5% while that without lignin 

showed 96 % which illustrated that lignin worked not only as a reinforcing agent but also as 

an antioxidant [2]. The Ligno-rubber composites under investigation could be used in the 

manufacturing of rubber board for either sound or thermal insulator, also as motor mounts, 

gaskets and roof lining. Thus, utilizing of rice straw in rubber composites could be an economic 

and eco-friendly alternate to burning of rice straw. 

[1] Simple pulping method for rice straw utilizing solar energy, Galal A.M.Nawwar, Egyptian patent 

No.2008030422. 

[2] B. Kosikova, A. Gegorova, A. Osvald, J. Krajcovicova, J.of Appl.. Poly.Sc, 2006, 99, 553. 

- 93 -


ELECTRICALLY STIMULATABLE SHAPE-MEMORY 

MATERIALS BASED ON CARBON BLACK FILLED 

ETHYLENE-OCTENE COPOLYMER (EOC) AND THEIR 

BLENDS 

Hai Hong Le, Sybill Ilisch, Hans-Joachim Radusch 

Center of Engineering SciencesMartin Luther University Halle-Wittenberg, 

06099 Halle/Saale, Germany 

hai.le.hong@iw.uni-halle.de 

Electrically stimulatable shape-memory composites based on CB filled ethylene-octene copolymer 

(EOC) and its blends with ethylene-propylene rubber (EPDM) were prepared. In 

such compounds the stiffness and the level of the electrical resistivity are the two main factors 

determining the shape memory (SM) behavior of the material. During the preparation process 

including compounding and cross-linking in a hydraulic press the value of the resistivity 

changed significantly, which influences the SM behavior strongly. In order to control the 

preparation process the electrical resistivity of the composites along the whole manufacturing 

process was measured. It has been found that the resistivity of the composites depends 

strongly on the development of blend morphology, CB dispersion and phase specific distribution 

of the filler in the blends during compounding. Furthermore, resistance increases strongly 

during the cross-linking process due to the de-agglomeration of CB aggregates. After completion 

of cross-linking CB aggregates re-agglomerate causing a decay of resistance. Morphological 

investigation by means of atomic force microscopy (AFM) and different characterization 

techniques support the discussion of background of resistance development. The electrically 

stimulated SM behavior of the composites with different composite structure induced by 

different blend compositions and different preparation conditions was characterized and discussed. 

- 94 -


MELT SURFACE TENSION OF MISCIBLE BLENDS OF 

POLY(ETHYLENE OXIDE) AND POLY(METHYL ACRYLATE) 

D. Pfefferkorn, S. Sonntag, S. Kyeremateng, Z. Funke, H. W. Kammer, J. Kressler 

Department of Chemistry, Martin Luther University Halle-Wittenberg, 

06099 Halle (Saale), Germany 

joerg.kressler@chemie.uni-halle.de 

An important thermodynamic quantity of polymeric systems is their surface tension since it 

rules wetting, adsorption and adhesion processes. Thus, surface tension may have a strong 

influence on industrial surface processes such as coating and film formation. Consequently, 

surface tensions of polymers have been reported for numerous homopolymers and copolymers 

[1]. Some reports deal with surface tension of polymer melts as a function of copolymer composition, 

e.g. for ethylene-vinyl alcohol copolymers or for olefin copolymers [2]. However, 

reports on surface tension of polymer blends measured over the whole composition range are 

rare. A prominent system where the composition-dependence has been studied extensively is 

the miscible blend system of polystyrene and poly(vinyl methyl ether) [3]. 

In miscible and also in immiscible blends it can be assumed that the component with the 

lower surface energy tends to enrich at the surface [4]. Hence, the surface tension varies nonlinearly 

with the blend composition and shows usually negative deviations from additivity. As 

a consequence, the surface composition differs from the bulk composition. 

In the present work, the surface tension of melt-miscible blends of poly(ethylene oxide) (PEO, 

Mn = 5000 g/mol) and poly(methyl acrylate) (PMA, Mn = 5400 g/mol) is measured as a function 

of composition using the sessile drop technique. Measurements are carried out in the 

temperature range from 60 to 160 o C. The surface tension at 120 o C varies non-linearly with 

PMA content as expected and, surprisingly, displays a minimum at 25 wt% PEO, i.e. the 

value of this particular blend is smaller compared to that of neat PMA (low surface energy 

component). This is a very unusual behaviour. As far as the authors are aware this has not 

been observed in binary polymer blends. Nevertheless, extreme values of surface tension as a 

function of composition in mixtures of low-molecular weight liquids have been reported 

[5-8]. The results on PEO/PMA blends are presented and discussed in thermodynamic terms. 

[1] S. Wu, Polymer Interface and Adhesion. Marcel Dekker: New York, 1982 

[2] Z. Funke, Y. Hotani, T. Ougizawa, J. Kressler, H.W. Kammer, Europ. Polym. J. 2007, 43, 2371; T.J. Menke, 

Z. Funke, R.D. Maier, J. Kressler, Macromolecules 2000, 33, 6120 

[3] Q.S. Bhatia, D.H. Pan, J.T. Koberstein, Macromolecules 1988, 21, 2166; H.W. Kammer, Polym Networks 

Blends 1994, 4, 145 

[4] Z. Funke, C. Schwinger, R. Adhikari, J. Kressler, Macromol. Mater. Eng. 2001, 286, 744; M.A. Sawpan, Z. 

Funke, M. Weber, H.W. Kammer, J. Kressler, Macromol. Chem. Phys. 2009, 210, 60 

[5] A. I. Gaman, I. Napari, P.M. Winkler, H. Vehkamäki, P.E. Wagner, R. Strey, Y. Viisanen, M. Kulmala, J. 

Chem. Phys. 2005, 123, 244502 

[6] J. Deng, Y. Yang, Y. He, G. Ouyang, Z. Huang, J. Chem. Eng. Data 2006, 51, 1464 

[7] S. Karlsson, S. Backlund, R. Friman, Colloid Polym. Sci. 2000, 278, 8 

[8] Á. Piñeiro, P. Brocos, R. Bravo, A. Amigo, Fluid Phase Equilibria 2001, 182, 337 

- 95 -


THE TEMPERATURE DEPENDENCE OF THE SUBNANO- 

METRE FREE VOLUMES IN SEMICRYSTALLINE POLY- 

ETHYLENE AND POLYTETRAFLUOROETHYLENE: 

A POSITRON LIFETIME AND PRESSURE-VOLUME- 

TEMPERATURE STUDY 

Yang Yu (1), G. Dlubek (2), J. Pionteck (3), R. Krause-Rehberg (1) 

(1) Institut für Physik, Martin-Luther-Universität Halle-Wittenberg, D-06099 Halle/Saale 

(2) ITA Institut für Innovative Technologien, Köthen/Halle, Wiesenring 4, D-06120 Lieskau 

(3) Leibniz-Institut für Polymerforschung Dresden e.V., Hohe Strasse 6, D-01069 Dresden 

yang.yu@student.uni-halle.de 

The structure of the free volume and its temperature dependence in polyethylene (PE) and 

poly(tetrafluoroethylene) (PTFE) was studied by positron annihilation lifetime spectroscopy 

[1] (PALS, T = -173 ~ 250 o C, P = 10-5 Pa) and pressure-volume-temperature (PVT) experiments 

(T = 27 ~ 380 o C, P = 0.1 – 200 MPa). The crystallinity of the samples (Xc = 30 – 

80 %) was considered as parameter which effects the microstructure. This work continues our 

former studies on PE [2,3] and PTFE [4] and includes also TFE copolymers with perfluoro(propyl 

vinyl ether) (PPVE 4 wt.-%) denoted as PFA and hexafluoropropylene (HFP, 8 

mol-%) denoted as FEP. From the analysis of PALS data the mean volume, , and the 

width, σh, of the local free volume size distribution (holes of subnanometre size) were obtained. 

A comparison of with the macroscopic volume delivered the hole density Nh'. 

The volume parameters show that the rigid amorphous fraction (RAF) has a distinctly smaller 

specific free and total volume than the mobile amorphous fraction (MAF). During cooling the 

contraction of the RAF slows down and finally, below room temperature, the RAF possesses 

a larger free volume than the MAF shows. Obviously, the restriction of the segmental mobility 

in the RAF by the crystals limits at high temperatures the free volume expansion and at 

low temperatures dense packing of the polymer chains. 

[1] G. Dlubek, Positron Annihilation Spectroscopy, in: Encyclopedia of Polymer Science and Technology, ed. 

by. A.Seidel, John Wiley&Sons; Hoboken, 2008. 

[2] D. Kilburn, D. Bamford, T. Lüpke, G. Dlubek, T. J. Menke, M. A. Alam, Polymer 43, 6973 (2002). 

[3] G. Dlubek, D. Bamford, A. Rodriguez-Gonzalez, S. Bornemann, J. Stejny, B. Schade, M. A. Alam, M. Arnold, 

J. Polym. Sci.: Part B: Polym. Phys. 40, 434 (2002). 

[4] G. Dlubek, A. Sen Gupta, J. Pionteck, R. Häßler, R. Krause-Rehberg, H. Kaspar, K. H. Lochhaas, Polymer 

46, 6075, 2005. 

See also: http://positron.physik.uni-halle.de 

- 96 -


PHASE SEPARATION BEHAVIOR IN A RUBBER-MODIFIED 

EPOXY SYSTEM 

Raju Thomas (1), Jürgen Pionteck (2), Sabu Thomas (3) 

(1) Department of Chemistry, Mar Thoma College, Tiruvalla-689 103, Kerala, India 

(2) Leibniz-Institute of Polymer Research, Dresden, Germany 

(3) School of Chemical Sciences, Mahatma Gandhi University, Priyadarshini Hills P.O., Kottayam, 

Kerala, 686 560, India 

rajuthomastvla@rediffmail.com 

The phase separation behavior and the resultant phase morphology development of blends of 

anhydride cured diglycidyl ether of bisphenol-A based epoxy resin with carboxyl-terminated 

copolymer of butadiene and acrylonitrile were investigated by means of small angle laser light 

scattering, optical microscopy, scanning electron microscopy, and P-V-T measurements. The 

components are initially partially miscible, become homogeneous on heating, but phase separate 

at some point on high temperature curing. Dynamic as well as isothermal curing studies 

were conducted. The blends in the range of 5 to 25 phr elastomer content were analyzed and 

changes in the cloud point temperature and phase separation behavior with increase in concentration 

of elastomer content were noted. DSC studies also confirmed this delay in modified 

blends. All blend systems underwent demixing phenomenon via spinodal decomposition during 

isothermal curing due to the dynamic asymmetry in systems and shifted finally to a bimodal 

phase separated state. A secondary phase separation was also noted. 

P-V-T analysis on modified blends helped to follow the cure reaction by monitoring the cure 

induced changes in the specific volume. 

- 97 -


INCORPORATION OF HIGH MOLECULAR WEIGHT 

POLYMERS IN CO-CONTINUOUS NANOSTRUCTURED 

BLENDS BY REACTIVE BLENDING 

Léa Gani (1), Sylvie Tencé-Girault (1), Michèle Milléquant (1), Stéphane Bizet (2), 

Ludwik Leibler (1) 

(1) Matière Molle et Chimie ESPCI-CNRS, UMR 7167 , ESPCI 10 rue Vauquelin, 

75231 Paris Cedex 05, France 

(2) ARKEMA, CERDATO, 27470 Serquigny, France 

lea.gani@espci.fr 

Our group has demonstrated recently that by a rational choice of molecular parameters, thermodynamically 

stable nanostructured co-continuous blends can be synthesized by reactive 

blending of functional polyolefins and polyamides [1]. The design relies on the rational use of 

randomness of distribution of reactive groups along polyolefin backbone and polydispersity of 

chains. The reaction has to be fast and efficient to produce in situ during blending a large 

amount of graft copolymers. This implied using low mass polyamides. Remarkably then cocontinuous 

structures are formed in a large composition range and both polyolefin and polyamide 

crystallise imparting the blends unique and rather outstanding thermo-mechanical and 

solvent resistance properties. Such blends are now commercial products. One of the most 

challenging issues remaining in the design and the synthesis of even better nanostructured 

blends is incorporating long crystallizable chains while preserving the co-continuity of the 

phases and preventing macroscopic phase separation. Indeed, long chains should entangle and 

play the role of tie chains between crystallites and improve, for example, mechanical properties 

at high temperature and resistance to oils. 

Here, we demonstrate that by reactive blending of functionalized polyethylene bearing randomly 

maleic anhydride and a bimodal mixture of short and long polyamides (PA), such cocontinuous 

structures can be also synthesized. The short chains react more readily to form 

graft copolymers that facilitate both grafting of long chains and formation of nanostructures. 

A two steps selective extraction is performed to separate the three phases of our blends (ungrafted 

polyethylene, ungrafted polyamides and graft copolymers) and to characterize them 

(Gel permeation chromatography, Transmission Electron Microscopy). Microscopic observations 

of blends and graft copolymers reveal that the substitution of a low amount of the short 

PA chains by the long ones can affect and modify the interface curvature of the copolymer 

and then the morphology of the blends. We focus on the influence of different mixing strategies 

on the nature and the composition of the graft copolymer. We discuss how the feeding 

mode of the raw materials in the micro-compounder can be decisive for the grafting of both 

PA on the same polyethylene backbone, or for the grafting of two different kinds of copolymer 

chains, ones with only short PA grafts and the others with only long PA grafts. The grafting 

of long PA chains is promoted by a premixing of long and short PA chains and subsequent 

blending with the functionalized polyethylene. This mixing strategy yields grafted copolymers 

containing both short and long PA grafts. 

After annealing, beyond the melting PA temperature, the structure evolves into nanostructured 

and cellular morphologies, where the minor PA phase forms the walls of the cells. 

[1] Pernot, H; Baumert, M; Court, F; Leibler, L. 2002. NATURE MATERIALS 1 (1):54-58 

- 98 -


BORON NITRIDE FILLED SEBS/EVA BLENDS: 

PROCESSING AND PROPERTIES 

Sebnem Kemaloglu, Gamze Karsli, A. Aytac, Guralp Ozkoc 

Kocaeli University, Department of Chemical Engineering 

guralp.ozkoc@kocaeli.edu.tr 

The aim of this study is to investigate the effect of hexagonal boron nitride (BN) particle 

shape/size and loading level on the thermal, mechanical, electrical properties and morphology 

of styrene-ethylene-butylene-styrene terpolymer (SEBS)/poly(ethylene-co-vinyl acetate) 

(EVA) blends to be used as thermal interface materials (TIM). It is observed from the scanning 

electron microscopy (SEM) of BN powders that each type has a characteristic particle 

size distribution and particle shape. SEM analysis conducted on matrices (i. e. SEBS/EVA 

blends) does not indicate any sign of interfacial delamination or phase separation between 

components. Moreover, viscometric studies prove the presence of a the compatibility between 

blend components. The surface energy measurements and subsequent wettability coefficient 

calculations point out that the dispersion of BN in SEBS is thermodynamically more favorable 

than that of BN in EVA. In other words, SEBS tends to encapsulate BN particles in comparison 

to EVA. Thermal conductivity of composites increases with increasing filler loading 

level regardless of filler size and shape. It is found that the composites with smaller BN particles 

(i.e. high aspect ratio and plate-like particles) shows higher thermal conductivity than that 

of the composites with larger particles at the same filler content. The tensile strength of the 

composites reduces with the incorporation of BN regardless of BN content and matrix composition. 

The increasing content of BN in the matrix gradually improves the moduli of the composites. 

The hardness of composites enhances with BN loading level and SEBS/EVA ratio 

regardless of filler type. The increasing amount of EVA in the composites results in a decrease 

in dielectric constant of neat matrices and composites. 

- 99 -


THE EFFECTS OF CARBON BLACK CONTENT AND 

STRUCTURE ON THE PERFORMANCE OF THE NATURAL 

RUBBER VULCANIZATES 

Hamidreza Esfahany, Payam Zahedi 

Polytechnic of Tehran-Iran 

Hamidrezaisfahany@yahoo.com 

In this work, three types of furnace CB (HAF), N-330, N-339 and N-375 were used in NR 

(SMR 20) compound samples. In order to investigate the effects of CB content and structure 

on the mechanical properties of these samples, Mooney viscosity, elastic modulus; resilience, 

abrasion and hardness variations were determined. The results show that the reasons for the 

mechanical properties improvements of these samples are an increase the bound rubber and 

occlusion of rubber as a result of strong interactions between the rubber chains and CB. NR 

compound with N-330 CB was taken as a reference sample. It was found that samples containing 

N-375 CB because of its structure compared with samples N-330 and N-339 CB have 

stronger interaction with NR chains. The reasons for filler network formation can be due to 

the formation of aggregates as a result of stronger structures or higher chemical factors on the 

surface of N-375 CB. As a result, an increase of iodine number due to surface absorption and 

surface activity of CB is observed. 

- 100 -


PERMEABILITY CHARACTERIZATION OF HDPE/PA-6/EVOH 

BOTTLES: THE EFFECTS OF ORDER OF MIXING AND 

DISPERSE PHASE CONTENT 

M. R. Saeb (1), M. Farahani (1), A. Kiani (1), S. Sarami (2), H. Garmabi (3) 

(1) Islamic Azad University of Mahshahr, Khoozestan, Iran 

(2) Islamic Azad University, North Tehran Branch, Tehran, Iran 

(3) Amirkabir University of Technology, Tehran, Iran 

mrsaeb2008@gmail.com, garmabi@aut.ac.ir 

Multi-component plastic containers with enhanced barrier properties are very interesting due 

to their selectivity against different solvents. The final products consist of a high content of 

disperse phase(s) as the barrier component of the container. Recently, besides the progress in 

multilayer technology, few studies [1-3] have been focused on enhancing the barrier properties 

through morphological manipulation of blend structure and developing laminar morphology. 

According to these studies [2-3], EVOH and PA-6 as minor phases in the matrix phase of 

HDPE would improve the barrier properties of blow-molded containers. However, they have 

just considered the effects of material type and content of disperse phases on the permeability 

of such containers, and probing the influence of processing parameters such as order of mixing 

has not been examined. The order of mixing of the constituents of a multiphase blend 

would highly affect the interfacial adhesion between the phases; however, this variable has 

been somehow disregarded in the field of laminar morphology development. 

In this study, we assessed the effect of order of mixing on permeability characteristics of 

HDPE/PA-6/EVOH blow-molded bottles in which HDPE-g-MAH was used as a coupling 

agent to improve the interfacial bonding between the ternary blend components. In this regard, 

three procedures of mixing, namely M1, M2 and M3, were exploited. In M1 procedure, 

all the components were dry blended and fed into the blow-molding machine, while in M2, 

minor phases of PA-6 and EVOH were first melt blended with the coupling agent and then 

added to HDPE continuous phase in blow molding process, and in M3, first HDPE and 

HDPE-g-MAH were melt blended and added to other ingredients. Moreover, the total content 

of minor phases of PA-6 and EVOH (50/50 % w/w) were altered in the range of 10-20 phr 

based on 100 weight part of HDPE. The permeability of gasoline through the blow-molded 

bottles at 50 °C was measured once a day, then, the normalized weight of each bottle could be 

calculated as the ratio of the measured value to the initial weight of filled bottle from which 

we could evaluate the effects of order of mixing and the content of disperse phases on the 

permeability of the blow molded bottles against gasoline. The results exhibited that the disperse 

phase content had minor effects; however, the order of mixing had a significant influence 

and the least gasoline permeability was achieved in the case of M1 procedure in which a 

laminar morphology was successfully developed. Scanning electron micrographs of fracture 

surfaces, also, confirmed the development of laminar structure in containers produced by M1 

procedure. 

[1] Lee SU, Kim SC, Polym. Eng. Sci., 463,37, 1997 

[2] Yeh J-T, Huang S-S, Yao W-H, Macromol. Mater. Eng., 532,287, 2002 

[3] Yeh J-T, Huang S-S, Yao W-H, Wang I-J, Chen C-C, J. Appl. Polym. Sci., 2528,92, 2004 

- 101 -


TEMPERATURE DEPENDENCY OF PERMEABILITY IN 

HDPE AND HDPE/PA-6/EVOH BLOW MOLDED BOTTLES 

AGAINST GASOLINE 

A. Kiani (1), M. R. Saeb (1), M. Farahani (1), H. Garmabi (2) 

(1) Islamic Azad University of Mahshahr, Khoozestan, Iran 

(2) Amirkabir University of Technology, Tehran, Iran 

mrsaeb2008@gmail.com, garmabi@aut.ac.ir 

It is clearly understood that the hydrocarbon liquids can easily permeate through HDPE containers. 

Among these, gasoline is distinguished due to its utilization as fuel in industrial and 

automotive applications. The permeation resistance of HDPE against gasoline is expected to 

be low; therefore, the need for barrier components and accordingly a multi-component structure 

in gasoline storage containers is of crucial importance. Yeh and his coworkers [1-3] have 

been convincingly focusing on this fascinating area during the last decade. They made use of 

EVOH and PA-6, as the disperse phase, to improve the permeability resistance of HDPE 

blow-molded bottles against gasoline and could enhance their barrier properties by several 

times. Despite these conspicuous achievements, they did not notice the role of processing parameters, 

such as temperature profile along the barrel, on the morphology and permeability of 

containers. Subramanian [4, 5] found that the platelets of PA-6 disperse phase would be 

shaped at an optimum temperature profile along the barrel in blow molding process. Moreover, 

the temperature at which these containers are functioning would undoubtedly influence 

their permeability resistance against gasoline. 

Regarding the critical significance of temperature, both during the processing stage and the 

service life of the containers, in this study, we aimed to explore the effects of temperature 

profile along the barrel as well as the temperature at which the permeability tests were run on 

bottles. To do so, two temperature profiles along the barrel and die exit (TL as 200-220-225- 

230 ºC and TH as 220-240-245-250 ºC) were adopted in blow molding of HDPE/PA-6/EVOH 

ternary blend containing a small amount of HDPE-g-MAH as compatibilizer. The results exhibited 

that the permeability rates of the bottles were thoroughly dependent on the processing 

temperature profile and the lower permeability would be obtained with those bottles processed 

at TL; inasmuch as the more developed laminar morphology of disperse phases formed 

in the matrix of HDPE. The formation of such morphology was also approved by scanning 

electron micrographs taken from fracture surfaces of the bottles. Furthermore, three temperatures 

of 40, 50, and 60 ºC were selected for the measurements of permeability in HDPE bottles. 

It was observed that the permeation rate at 50 ºC was 1.85 times of its value at 40 ºC and 

it was increased 1.75 times by raising the temperature from 50 ºC to 60 ºC. 

[1] Yeh J-T, Huang S-S, Yao W-H, Macromol. Mater. Eng., 532, 287, 2002 

[2] Yeh J-T, Huang S-S, Yao W-H, Wang I-J, Chen C-C, J. Appl. Polym. Sci., 2528, 92, 2004 

[3] Yeh J-T, Huang S-S, Chen H-Y, J. Appl. Polym. Sci., 1333, 97, 2005 

[4] Subramanian PM, Polym. Eng. Sci., 483, 25, 1985 

[5] Subramanian PM, Polym. Eng. Sci., 663, 27, 1987 

- 102 -


ELECTRICALLY CONDUCTING BLEND BASED ON EPOXY 

RESIN WITH POLYANILINE/POLY (BUTYL ACRYLATE- 

VINYL ACETATE) COMPOSITE 

Abdolreza Mirmohseni, Fahimeh Farshi Azhar 

Polymer Research Technology Laboratory, Department of Applied Chemistry, 

Faculty of Chemistry, University of Tabriz, Tabriz, Iran 

mirmohseni@tabrizu.ac.ir, fahimeh.farshi@gmail.com 

Electrically conducting epoxy blends are promising materials for various applications such as 

electromagnetic shielding, antistatic and anticorrosive coatings. These materials were designed 

by combining epoxy resin and a conducting polymer. Among conducting polymers, 

polyaniline (PANI) is one of the most promising candidates for industrial applications due to 

its straightforward polymerization, good environmental stability, and relatively high conductivity 

properties. But it is not readily processable. So the preparation of PANI/poly (butyl 

acrylate-vinyl acetate) (BuA-VAc) composite with more processability followed by blending 

with epoxy is a novel method for developing conducting blends. 

The preparation of PANI/poly (BuA-VAc) composite was carried out through the chemical 

polymerization of aniline in an emulsion containing (BuA-VAc) copolymer. The modified 

epoxy matrix with improved mechanical properties was prepared by employing some modifiers. 

The induction of electrical properties to epoxy was done by blending modified epoxy matrix 

with PANI/poly (BuA-VAc) composite. 

The optimum contents of modifiers in epoxy matrix were determined by evaluation of mechanical 

properties. The electrical conductivity of PANI/poly (BuA-VAc) composite was 

measured by four-point probe method and a conductivity of 0.9 Scm-1 obtained. By incorporation 

of conducting composite into epoxy matrix, the electrical conductivity of the blends 

increased from the value of 10-11 Scm-1 (corresponds to the neat epoxy matrix) to 2.04×10-6 

Scm-1 for 15 phr of PANI/poly (BuA-VAc) composite that reaches to electrical conductivity 

in the antistatic rang. The percolation threshold with electrical conductivity of 1.86×10-6 

Scm-1 occurs at about 12.5 wt% PANI-poly (BuA-VAc) composite. 

- 103 -


RADIATION CURING OF SILICONE BLENDS 

A. Fainleib (1), V. Sakhno (2), D. Kolesnik (3) 


Kyiv, Ukraine 

(2) Institute of Nuclear Research of the National Academy of Sciences of Ukraine, 

Kyiv, Ukraine 

(3) State Scientific-Technological Center for Inspection of Quality and 

Certification of Road Production 

fainleib@i.kiev.ua 

Radiation curing of silicone monomers and oligomers is a very specific area of research. 

There are no many publications in this field. The blends of different silicone monomers and 

oligomers are not very well studied. The purpose of the current work was to investigate the 

curing processes occurred in the blends, consisting of silicones, which are able to polymerize 

by different mechanisms, using electron beam of high energy (50 Mrad). Different blends of 

vinylheptamethylcyclotetrasiloxane, octamethylcyclotetrasiloxane, polymethylsiloxanes (oligomers 

PMS-20 and PMS-100) and curing agents (diallyldimethylsilane, tetraallylsilane, divinyltetraallyldisiloxane) 

with varying compositions were prepared and characterized. Viscosities 

and surface energies (limiting wetting angle) of the liquid silicone compositions were 

measured. Radiation curing process of the silicone compositions under the influence of different 

dozes (25-300 KGy) of electron beam irradiation was monitored using FTIP spectroscopy. 

From the FTIR spectra of the cured silicone polymer blends it was established that vinylheptamethylcyclotetrasiloxane 

is undergone to radical polymerization through vinyl functional 

group, but there are no any evidences of cycle-opening polymerization. Polycondensation 

processes via reaction between hydroxyl groups have been fixed in the blends containing polymethylsiloxanes. 

It was established that the higher the radiation doze absorbed by the composition, 

the higher conversion of reacting roups. All the initialy soluble in organic solvents 

liquid silicone blends lost their solubility after irradiation by electron beam and transformed to 

the rubber-like or solid materials, even at low absorbed doze (25 KGy). The crosslink degree 

of the irradiated polymer blends have been determined using sol-gel analysis with Soxhlet 

technique. 

- 104 -


COMPATIBILIZATION OF PP/TPU BLENDS WITH 

DIFFERENT FILLERS 

Emi Govorčin Bajsić, Vesna Rek, Ivana Pleić, Mirela Leskovac 

Faculty of Chemical Engineering and Technology, University of Zagreb, Marulićev trg 19, 

10000 Zagreb, Croatia 

egovor@fkit.hr 

In this work, the compatibilising effect of talc, clay and nanosilica on the termal and mechanical 

properties of thermoplastic polyurethane (TPU) and polypropylene (PP) was investigated. 

Pure TPU, PP, TPU/PP blends and filled TPU/PP blends (TPU/PP/F) were prepared via a 

melt blending in a twin-screw extruder (Rondol, 21 mm LAB TWIN) and then injectionmolded 

into speciments with an injection-molding mashine (Rondol, High Force 5). Properties 

of the blends were investigated using different scanning calorimetry (DSC), dynamic mechanical 

analysis (DMA) and tensile testing. DSC and DMA analysis showed that the glass 

transition temperature (Tg) of TPU/PP and TPU/PP/F blends change and to be affected 

mainly by the type of filler and content of TPU and PP components. The shift of Tg gave the 

evidence that the TPU and PP were miscible to some extent. DSC results indicated that talc 

acted as effective nucleating agent and incresing the degree of crystallinity of TPU/PP blends. 

The addition of nanosilica in TPU decreased the Tg in TPU as effect of interactions between 

the ester carbonyl groups in the TPU and silanol groups on the silica surface which formed 

the degree of phase separation between the hard (isocyanate + chain extender) and soft 

(polyol) segments in the TPU. The effects of fillers on mechanical properties of TPU/PP 

blends were investigated. It was shown that in the presence of all used fillers in the blends the 

tensile strength increases. 

- 105 -


BLENDS OF PARTLY AROMATIC POLYAMIDES WITH 

HYPERBRANCHED AROMATIC POLYMERS (POLYESTERS 

AND POLYETHERAMIDES) - MISCIBILITY AND 

PROPERTIES 

Klaus Jähnichen (1), Brigitte Voit (1), Zhirong Fan (2), Phillippe Desbois (3) 

(1) Leibniz-Institut für Polymerforschung Dresden e.V, Hohe Straße 6, 01069 Dresden 

(2) DWI an der RWTH Aachen e.V., Pauwelsstraße 8, 52056 Aachen, Germany 

(3) Global Polymer Research Performance Polymers, BASF SE, GKT/C-B001, 67056 

Ludwigshafen, Germany 

jaehni@ipfdd.de 

Hyperbranched (hb) polymers have continuously drawn much attention both from industry 

and academia. They are known to have several interesting properties derived from their three 

dimensional structure and large number of functional groups[1]. These properties contribute 

to make them be considered as suitable blend components or melt modifiers. The large number 

of functional groups in hb polymers provides big chances for possible interactions with 

functionalities of the matrix material and are excepted to result in novel materials with amazing 

properties by blending. Actually, a couple of hb polymers have already been used as blend 

components or additives following different purposes[2]. 

Two hb aromatic polyesters with phenolic end groups (AB2 and A2B3 approach[3]) and high 

glass transition temperatures (Tg) as well as a hb polyetheramide (from an AB2 monomer[2d]) 

were synthesized and used for blend formation with partly aromatic polyamide. 

Miscible blends were be formed by compounding the hb AB2 polyester and the AB2 polyetheramide 

with polyamide. The aromatic polyester based on 3,5 dihydroxybenzoic acid and 

the polyetheramide were the most effective modifiers with respect to the increase of Tg, reduction 

of the complex melt viscosity. Most probably, in both cases reactive blends were 

formed. The addition of hb polyetheramide resulted in blends with enhanced Tg and improved 

processability keeping the mechanical properties of the matrix material nearly constant. 

Acknowledgement: The authors acknowledge BASF SE for the financial support. The authors 

are very grateful to H. Komber (NMR), A. Lederer and P. Treppe (SEC), L. Häussler and K. 

Arnhold (DSC), R. Vogel (melt rheology) for the analytical measurements and their helpful 

discussions. 

[1] J. M. J. Frechet, C. J. Hawker, Synthesis and Properties of Dendrimers and Hyperbranched Polymers, in: 

Comprehensive Polymer Science, 2nd Suppl. Vol., S. Aggarwal, S. Russo, Eds., Elsevier Science Ltd., Oxford 

1996, chapter 3, p. 71ff 

[2] a) D. J. Massa et al. Macromolecules 1995, 28, 3214; b) D. Schmaljohann et al Macromolecules 1999, 32, 

6333; c) T. J. Mulkern et al. Polymer 2000, 41, 3193; d) T. Huber et al. Macromol. Mater. Eng. 2000, 

280/281, 33; e) O. Monticelli et al. Macromol. Mater. Eng. 2003, 288, 318-325; f) O. Monticelli, S. et al. 

Polymer 2005, 46, 3597; f) Z. Fan et al. J. Polym. Sci. Part A, Polym. Chem. 2009, 47, 3558 

[3] a) Reisch, A. et al. Macromolecules 2007, 40, 6846; b) Z. Fan et al., Polymer, 2009, 50, 3431 

- 106 -


INFLUENCE OF CHEMICAL CROSSLINKING ON GLASS 

TRANSITION TEMPERATURE, CRYSTALLIZATION AND 

MELTING BEHAVIOR OF PE/EVA BLENDS 

H. A. Khonakdar, A. Haghighi-Asl 

Islamic Azad University, Omidiyeh Branch, P.O. Box 164, Omidiyeh, Iran 

halikh@yahoo.com 

Uncrosslinked and chemically crosslinked binary blends of low- and high-density polyethylene 

(PE), with ethylene vinyl acetate copolymer (EVA), were prepared by a melt-mixing 

process using different amounts of tert-butyl cumyl peroxide (BCUP) as a crosslinking agent. 

The results showed that the crosslinking process led to a decrease in glass transition temperature 

(Tg) of LDPE and HDPE. The similar behavior was observed in their blends with EVA 

too. It is suggested that the confined crystallization process, due to restriction imposed on the 

chain folding by the chemical crosslinks, increases net free volume in the amorphous phase 

and hence reduces Tg. The Tg depression intensifies with increasing crosslink density, 

whereas the degree of crystallinity and consequently the density of the system decreases with 

an increase in the peroxide content. The uncrosslinked blends revealed two distinct unchanged 

melting peaks corresponding to the individual components of the blends, but with a reduced 

overall degree of crystallinity. The crosslinking further reduced crystallinity, but enhanced 

compatibility between EVA and polyethylene, with LDPE being more compatible than 

HDPE. Blended with 20 wt % EVA, the EVA melting peak was almost disappeared after the 

addition of BCUP, and only the corresponding PE melting point was observed at a lowered 

temperature. But blended with 40 % EVA, two peaks still existed with a slight shift toward 

lower temperatures. 

- 107 -


COATING OF SURFACES BY POLYELECTROLYTE AND 

SURFACTANT MIXTURES 

Saule Aidarova (1), Altynai Sharipova (1), Miras Issakhov (1), Kuanishbek Mussabekov (1), 

Victoria Dutschk (2) 

(1) "Excellence PolyTech" International Postgraduate Institute of Kazakh National Technical 

University named after K .I. Satpayev, Almaty, Kazakhstan 

(2) Leibniz-Institut für Polymerforschung Dresden e. V., Dresden, Germany 

(3) Max-Plank-Institut, Golm, Germany 

zvezda.s.a@gmail.com 

Corrosion is actual problem and there are many papers directed to corrosion protection and 

ways to decide this problem. Films formed by polymers and surfactants can be useful for the 

corrosion protection because they can hydrophobize solid surfaces. 

That is why it was interesting to study how spontaneous adsorption happens on the solid surface 

and how polymers and surfactants effect to the adsorption layer formation. By adding 

surfactants properties of polymers are changed. Interfacial tension of polymers, surfactants 

and their mixtures at water/oil interface were studied and it was interesting to see if the adsorption 

nature remains on the solid surface or not. 

Wetting angles of polymer, surfactants and their mixtures on the different solid surfaces 

which have different charges and roughness were studied by Drop Shape Analysis system 

DSA-10 (Kruss, Germany) and microscope Nanofocus Usurf explorer. As polyelectrolyte 

polyallylamine hydrochloride, as surfactants sodium dodecylsulfate and sodium hexadecylsulfate 

were used. Al, Al-Mg, stainless steel, glass and wafer were used as solid surfaces. 

It was shown that polymers and surfactants mixtures at certain concentrations increase wetting 

contact angle and it is about 90 o C while surfactants increase wettability of surfaces. Nature 

of solid surfaces also influences to the adsorption and wettability of the surfaces. Depending 

on the surface charge the adsorption of polymers and surfactant mixtures is changed. 

- 108 -


STUDIES ON TRANSREACTION KINETICS IN PET/PEN 

BLENDS USING RHEOLOGICAL MEASUREMENTS 

H. A. Khonakdar (1), M. A. Zolali (1), M. B. Teimouri (1), S. H. Jafari (2), 

U. Wagenknecht (3), B. Kretzschmar (3) 

(1) Iran Polymer and Petrochemical Institute, P.O. Box 14965/115, Tehran, Iran 

(2) School of Chemical Engineering, College of Engineering, University of Tehran, Iran 

(3) Leibniz Institute of Polymer Research Dresden, 01069, Dresden, Germany 

h.khonakdar@ippi.ac.ir 

Blends of Poly (ethylene terephthalate) (PET) and poly (ethylene naphthalene 2,6dicarboxylate) 

(PEN) were prepared in a twin-screw extruder. This resulted in transesterification 

reactions and formation of copolymer structures with various average sequence block 

lengths (LnPET, LnPEN) and degree of randomness (RD). Samples were investigated by differential 

scanning calorimetry (DSC) and proton nuclear magnetic resonance (1H NMR) 

measurements to evaluate the extent of transesterification reaction, LnPET, LnPEN and RD. 

The PET/PEN blend systems consist of a microseparated phase of PEN droplets in a matrix of 

PET. It was seen that with an increase in time and temperature of mixing copolymer content 

(TEN %) and RD increased, whereas the (LnPET), (LnPEN) values were decreased. The 

transreaction kinetic in PET/PEN system was studied by a rheological method. For this purpose 

the extent of transreaction monitored during rheological measurements was quantified by 

1HNMR technique. The results showed that the reaction between PET and PEN can be classified 

as a pseudo-second-order reaction. 

- 109 -


DETERMINATION OF SURFACE ANISOTROPY AND 

VISCOELASTIC RESPONSE OF COCONTINUOUS BLENDS 

Carlos R. Lopez-Barron, Christopher W. Macosko 

Department of Chemical Engineering and Materials Science, University of Minnesota 

macosko@umn.edu 

One of the challenges in the study of cocontinuous blends is to relate their rheological response 

with their morphology. Doi and Ohta [J. Chem. Phys. 95, 1242 (1991)] proposed a 

semiphenomenological model that relates the rheology of 50/50 mixtures of two immiscible 

Newtonian liquids of equal viscosity with the morphology (i.e. size and anisotropy). Although 

this model was developed for cocontinuous blends, it has been tested almost exclusively in 

systems with droplet-matrix morphologies. To our knowledge, Vinkier and Laun [J. Rheol. 

45, 1373 (2001)] published the only comparison of experimental data of cocontinuous blends 

with predictions from Doi-Otha’s theory. 

We propose a simplification of Doi-Ohta’s model for the case of oscillatory flow under small 

amplitudes (SAOS). This simplification is based on the experimental evidence that the degree 

of anisotropy generated during small amplitude oscillations is negligible. The simplification 

gives a linear relation between the characteristic size and time and an asymptotic decrease of 

the elastic modulus with a limit at long times given as G’ ~ t -1 . 

Cocontinuous blends made of fluorescently labeled polystyrene and styrene-ran-acrylonitrile 

copolymer were imaged with laser scanning confocal microscopy. 3D images of the blend 

microstructure were obtained from the reconstruction of confocal images. Using differential 

geometry on the 3D images we measured the specific interfacial area and the normal vector 

field. The normal vector field was used to compute, for the first time, the anisotropy tensor of 

the cocontinuous interfaces. The anisotropy tensor is key in Doi-Ohta's model. Thus, we compared 

experimental data of the evolution of the morphology and rheology with the predictions 

of the Doi-Ohta's model simplification. Good agreement was obtained for blends with relatively 

low interfacial tension. 

- 110 -


MACRO POROSITY IN HYBRID ORGANIC-INORGANIC 

POLYMER SYSTEMS FILLED WITH INORGANIC 

PARTICLES 

Maksym Iurzhenko (1), Yevgen Mamunya (1), Gisele Boiteux (2), Eugene Lebedev (1) 

(1) Institute of Macromolecular Chemistry of NAS of Ukraine, Kharkivske shossee, 48, 

02160, Kyiv, Ukraine 

(2) Laboratoire des Matériaux Polymères et des Biomatériaux (LMPB) - UMR CNRS 5223 

"Ingénierie des Matériaux Polymères" Université Claude Bernard Lyon 1, Bâtiment 

ISTIL, 15 Boulevard A. Latarjet, 69622, Villeurbanne Cedex, France 

4ewip@ukr.net 

During the last years an intensive research of a new class of polymer materials - hybrid organic-inorganic 

polymer systems (OIS) has been begun. An interest is due to the OIS availability 

with a wide range of properties that enables to get materials with predetermined characteristics. 

For example, it can be materials with high ionic conductivity, synthesized by solgel 

method, and intended for use as solid electrolytes. Also it can be OIS with high chemical 

and radiation resistance and thermostability. Some organic-inorganic systems can have a wide 

range of electrical, dielectric and sorption properties, depending on their composition. 

Usual route of the preparation of hybrid organic-inorganic systems is sol-gel process, which is 

the most effective for the synthesis of tailored organic-inorganic systems. However this multistep 

process involves rather complicated reactions. Joint polycondensation is new original 

method of OIS synthesis, which is very attractive from a technological point of view. The 

main concept of this method is the polymerization of OIS in reactive mixture of the liquid 

organic and inorganic oligomers, which have the reactive groups. By changing of chemical 

composition of the organic and inorganic oligomers and their ratio the properties of final 

product, OIS, can be varied in wide range. 

Organic component of OIS consists of two isocyanate-containing products: 

-macrodiisocyanate (MDI) with Mw = 4500, which contains 3,6 % of free NCO-groups. MDI 

was synthesized on the base of 2,4-toluene diisocyanate and oligooxypropylene-glycol with 

Mw = 2100. 

-poly(isocyanate) (PIC) with a composition 50/50 of diphenylmethandiisocyanate 

(Mw=250)/iso-cyanate isomers and which contains 32 % of free NCO-groups. PIC of type D 

was used. 

Weight ratio MDI/PIC was varied in the range from 0/100 to 100/0. 

The ratio organic/inorganic components (MDI+PIC)/SS=70/30 for all cases. 

Inorganic component was sodium silicate (SS) existing in the form of oligomer in the water 

solution. 

Aerosil A175 and powdered glass (chemical composition SiO2 for both of them) were used as 

nano- and micro-dimensional inorganic fillers. 

The structure of filled OIS obtained was found in the form of membrane with regularly 

shaped interconnecting pores with 50-120 μm in diameter. The formation of such structure 

was due to the emission of carbon dioxide in the set of reactions, which run during OIS polymerization. 

The gassing was the most intensive nearby the surface of inorganic filler. 

Probably, it was due to chemical reactions between SiO2 and sodium silicate. In case of 

aerosil nano-dimensional bubbles were generated, while macro-dimensional bubbles formed 

interconnecting pores in OIS with powdered glass. 

- 111 -


INITIAL FORMATION PROCESS OF INTERFACE BETWEEN 

DISSIMILAR POLYMERS BY HIGH-SPEED ELLIPSOMETRY 

Yuki Mishima, Rikki Honma, Seisuke ATA, Toshiaki Ougizawa 

Department of Organic and Polymeric Materials, Tokyo Institute of Technology 

tougizawa@op.titech.ac.jp 

Recently, polymer blends have attracted increasing interest in improving properties of polymer 

materials for desired applications with minimum cost. However, most polymer pairs are 

immiscible and thus phase separation occurs. Mechanical properties of blend materials such 

as the adhesiveness or the toughness depend strongly on the structure of the interface between 

different polymers. Therefore, it is important to understand the behavior of the molecules in 

the vicinity of the interface and the formation process of the interfacial region to get desirable 

polymer materials. To measure the change of the interfacial thickness with time or temperature 

is an effective method to consider the behavior of the interfacial molecules. However, 

there is little known about the growing process of interfacial thickness, especially at the initial 

stage, due to the long measuring time of existing methods. In this study, an ellipsometer 

(Photonic Lattice, Inc) which has the photonic crystal arrays (PCA) inside the light detector to 

analyze the thickness and refractive index of polymer films instantly (~0.1s) was applied in 

order to chase the initial process of interfacial formation in detail. 

Polymers used in this investigation were poly(methyl methacrylate) and poly(styrene-coacrylonitrile). 

It is known that the miscibility in blends of these polymers can be controlled 

easily by the AN content in SAN [1]. The optically flat bi-layer films, the ellipsometry requires 

the samples to be, were laminated on Si wafer substrate by spin-coating. The changing 

process of the interfacial thickness between bi-layer films was measured on a hot stage. The 

measurement was performed during heating from ambient temperature to above the glass 

transition temperature (Tg) at different heating rates. 

In this measurement, we found that the initial diffusion of polymers at the interface showed 

peculiar behavior. During heating, the diffusion started below Tgs of bulk polymers and the 

diffusion rate was rapid, two or three digits larger than the value of normal mutual diffusion 

between miscible polymers [2]. After the thickness has reached about the coil size of one 

molecule, the growing rate of the interfacial region changed to be slower. These phenomena 

were observed correspondingly both in the miscible and the immiscible systems and not able 

to be explained by the reptation model. It is considered that the initial diffusion is exclusively 

induced with the polymer molecules in the vicinity of interface, which have higher mobility 

than bulk molecules due to the lower density of entanglements [3]. Therefore the rapid initial 

diffusion occurred only in the limited region from temperature below Tgs of bulk polymers. 

[1] M. Swiss, J. Kressler, H. W. Kammer, Polymer, 1987, 28, 957 

[2] S. Yukioka, K. Nagato, T. Inoue, Polymer, 1992, 33, 1171 

[3] T. Kajiyama, K. Tanaka, A. Takahara, Macromol. Symp., 2003, 192, 265 

- 112 -


EFFECT OF CONFINEMENT AND VISCOSITY RATIO ON 

DROPLET COALESCENCE IN SHEAR FLOW 

Ruth Cardinaels, Pieter De Bruyn, Dongju Chen, Paula Moldenaers 

Department of Chemical Engineering, Katholieke Universiteit Leuven, 

B-3001 Leuven (Heverlee), Belgium 

Paula.Moldenaers@cit.kuleuven.be 

The ability to create structures and patterns on micron and smaller length scales has led to the 

utilization of microfluidic devices in a variety of applications [1-4]. Multiphase flows provide 

several mechanisms for enhancing and extending the performance of single phase microfluidic 

systems [1, 5]. However, when transporting complex two-phasic fluids in microdevices, 

deviations from bulk behaviour can be expected if the dimensions of the channel become 

comparable to the size of the dispersed phase [1, 3 ,6]. In order to fully understand the underlying 

physics, morphology development in confined shear flow is often studied as a model 

type problem. For systems with Newtonian components, the effects of geometrical confinement 

on single droplet deformation and droplet breakup are well-known [6], whereas coalescence 

of confined droplets has only been studied for a limited range of parameter values [7]. 

However, in more concentrated systems, droplet collisions and coalescence frequently occur 

and should therefore be taken into account in models and theories on morphology development 

in confined geometries. In the present work, a counter rotating parallel plate shear flow 

cell is used to visualize two interacting droplets in shear flow. Droplet collisions are studied 

for a range of droplet sizes, both in bulk shear flow and for gap spacings that are comparable 

to the droplet size. For droplets with a diameter of about 20-30 % of the gap width, the critical 

Ca-number for coalescence increases with increasing values of the degree of confinement. In 

addition, coalescence in a confined geometry occurs at a lower orientation angle of the droplet 

pair as compared to droplet coalescence in bulk shear flow at the same Ca-number, even for 

ratios of droplet diameter to gap spacing below 0.2. This enhancement of coalescence due to 

wall effects is observed for systems with a ratio of droplet to matrix viscosity between 0.1 and 

2.5. In order to obtain a better understanding of the forces and fluid dynamics that govern this 

process, the droplet trajectories, the time-dependent orientation angles of the droplet doublets 

and the droplet deformation during the interaction process are systematically studied. 

[1] Shui, L., Eijkel, J.C.T., van den Berg, A., Adv. Colloid Int. Sci. 133:35-49 (2007) 

[2] Stone, H.A., Kim, S., AIChE J. 47:1250-1254 (2001) 

[3] Stone, H.A., Stroock, A.D. Ajdari, A., Annu. Rev.Fluid Mech. 36:381-411 (2004) 

[4] Squires, T.M., Quake, S.R., Rev. Modern Physics 77:977-1026 (2005) 

[5] Günther, A., Jensen, K.F., Lab Chip 6:1487-1503 (2006) 

[6] Van Puyvelde, P., Vananroye, A., Cardinaels, R., Moldenaers, P., Polymer 49: 5363-5372 (2008) 

[7] Chen, D., Cardinaels, R., Moldenaers, P., Langmuir, doi: 10.1021/la901807k (2009) 

- 113 -


PCL/PA12 GRAFT COPOLYMERS BY COUPLING 

REACTIONS IN MELT 

Lothar Jakisch, Andrea Gube, Frank Böhme 

Leibniz-Institut für Polymerforschung Dresden e.V., Hohe Str. 6, D-01069 Dresden, Germany 

jakisch@ipfdd.de 

Using a novel trifunctional coupling agent with two lactamate and one oxazinone group graft 

copolymers consisting of a polycaprolactone (PCL) main chain and polyamide 12 (PA12) side 

chains are synthesized under conditions of reactive extrusion. 

The preparation of the coupling agent based on aminoterephthalic acid, terephthalic acid 

monomethylesterchloride, and ε-caprolactam is described in detail. 

It is shown by means of model reactions that in the presence of aliphatic hydroxy compounds 

the reaction of the coupling agent is highly selective, similar to the behavior of a bifunctional 

coupling agent with one lactamate and one oxazinone group described in earlier works [1]. At 

180 – 210 °C, a conversion of the lactamate group of about 98 % is observed under elimination 

of ε-caprolactam. In a second reaction the oxazinone group is converted with an aliphatic 

amino compound. 

This high selectivity is utilized in the synthesis of PCL/PA12 graft copolymers with side 

chains of defined length and distance by sequential conversion of the coupling agent with 

PCL-diol oligomers and monoamino terminated PA12 oligomers. The first step comprises 

chain extension of PCL in the course of which oxazinone groups are introduced into the backbone 

in a regular sequence. The molecular weight can be controlled by an excess of the coupling 

agent which also prevents partial cross-linking caused by reactions of terminal hydroxy 

groups with oxazinone groups. 

The graft copolymers are phase separated on the nanometer-scale, as evidenced by AFM and 

represent thermoplastic elastomers with hard and soft domains. The mechanical properties are 

characterized by high elongations and impact strengths. DSC measurements show a higher 

crystallinity of the PA12 phase in comparison with analogous segmented multiblock copolymers 

[1]. Because of the good compatibility of PCL to numerous polymers, such graft copolymers 

could be of interest as compatibilizer in different blend systems. 

[1] L. Jakisch, H. Komber, F. Böhme: Macromol. Mater. Eng. 292 (2007), pp.557-570 

- 114 -


REACTIVE AND NON-REACTIVE POLYPYRROLES AS 

MODIFIER FOR ELECTRICAL CONDUCTIVE BLENDS AND 

COMPOSITES 

J. Pionteck (1), J. Hegewald (1), M. Omastová (2) 

(1) Leibniz Institute of Polymer Research Dresden, Hohe Str. 6, D-01069 Dresden, Germany 

(2) Polymer Institute, Slovak Academy of Sciences, Dúbravská cesta 9, 842 36 Bratislava, 

Slovakia 

pionteck@ipfdd.de 

Polypyrrole (PPy) has been used for a long time as conductivity modifier and antistat for a 

wide variety of plastics. In our early works we used PPy to improve the conductivity of thermoplastics 

by the in-situ synthesis of PPy in presence of dispersed thermoplastic particles. 

This method resulted in core-shell particles (CSP) which easily could be transformed by compression 

moulding (CM) into compact materials with high conductivity at low PPy loadings. 

However, the conductivity was sensitive to shear and melt mixing resulted in materials with 

good mechanical strength but poor electrical conductivity. 

To overcome this limitation nanocomposites of a new type have been prepared containing 

montmorillonite (MMT) in a polypropylene (PP) matrix and modified with different amounts 

of conducting PPy. When the chemical-oxidative polymerization of pyrrole is performed in 

dispersion of PP particles and exfoliated MMT, some PPy locates at the MMT surfaces which 

then tend agglomerate, and the other part is coating as well the MMT/PPy-agglomerates as the 

PPy powder particles. Compression moulding of these mixture results in a conductivity 1 order 

of magnitudes higher than the MMT-free system at 16.7 wt.-% PPy-conten. More importantly, 

the systems are more stable against shear and the percolation threshold concentration 

shifts to lower concentrations [1]. 

Furthermore, new types of PPy’s containing reactive sites have been prepared by copolymerization 

of pyrrole with pyrroles containing carboxyl-, oxazoline-, or oxazinone functionalities. 

The copolymers exhibit much lower conductivities than the non-substituted pyrrole 

homopolymers but under proper synthesis conditions conductivities as high as 0.03 S/cm can 

be reached [2]. The functionalities are stable during polymerization and can be used for further 

modifications. Our approach was to use bifunctional PPy with selective reactivities as 

compatibilizer in heterogeneous blends of reactive polymers. In this case the PPy should act 

as reactive compatibilizer providing simultaneously electrical conductivity to the blend, especially 

when it locates at the interface between the blend components of blends with cocontinuous 

morphologies [3]. The compatibilizing effect could be proven, while conductivity 

is reached only at higher concentrations due to the tendency of the PPy to agglomerate. 

[1] M. Omastova, M. Mravcakova, I. Chodak J. Pionteck, L. Häussler, Polym. Eng. Sci. 46 (2006) 8, 1069 

[2] J. Hegewald, L. Jakisch, J. Pionteck, Synthetic Metals, 159 (2009), 103 

[3] J. Hegewald, J. Pionteck, L. Jakisch, B. Voit, Polym. Prepr. 49 (2008), 326 

- 115 -


SYNTHESIS OF DEFINED PP-CO-(PS MACROMONOMERS) 

AND THEIR APPLICATION AS COMPATIBILIZER IN 


Ulrich Schulze (1), Tamás Fónagy (2), Jürgen Pionteck (1), Béla Iván (2) 

(1) Leibniz Institute of Polymer Research Dresden, Germany 

(2) Department of Polymer Chemistry and Material Science, Chemical Research Center, 

Hungarian Academy of Sciences, Pusztaszeri u. 59-67, Budapest, Hungary 

uschulze@ipfdd.de 

For compatibilization of immiscible polymer blends typically block or graft copolymers are 

used. While AB or ABA block copolymers are widely studied, the correlation between structural 

parameters of graft copolymers, such as the absolute and relative length of side chains 

and backbone, and their compatibilization efficiency is hardly investigated. Thus, for studying 

the relationship between the microstructure and the compatibilization efficiency new methods 

for preparation of well-defined graft copolymers with designed structural parameters, such as 

length and stereoregularity of side chains and backbone, side chain density and distribution, 

must be developed first. One possible way is the macromonomer method [1] which allows the 

precise regulation of length and size distribution of side chains. 

In a first series of poly(propene-g-styrene) (PP-g-PS) graft copolymers the influence of the 

PP-g-PS graft copolymer structure on the compatibilization efficiency for PP/PS blends was 

investigated [2, 3]. By adjusting the reaction conditions high control of the microstructure of 

the polymer backbone and the structure of the resulting graft copolymers can be achieved. 

The resulting graft copolymers were tested as blending agents for PP/PS blends. It was found 

that grafts with shorter polystyrene chains provide better blending efficiency. One limiting 

factor of the relatively small compatibilizing efficiency of PP-g-PS with long PS side chains 

seems to be the rather small PS content in these graft copolymers. 

In the second series the feed concentration of PS macromonomer (PS-M) was varied beside 

the variation of the molecular weight of the macromonomers. On this way graft copolymers 

with increased PS content could achieved. At low conversion the number of polystyrene side 

chains per 1000 propene units is proportional to the feed concentration of PS-M, while the 

length of polypropene backbone decreases with increasing feed concentration. The side chain 

length is predetermined by the Mn of PS macromonomer, but it also affects the side chain 

density and backbone length. At constant ratio of propene to PS-M the backbone length can 

be controlled by alteration of the polymerization temperature while the side chain density is 

almost uniform. The synthesized copolymers have the potential to become efficient compatibilizer 

in polyolefin blend materials. 

[1] K. Ito, Prog. Polym. Sci. 1998, 23, 581 

[2] U. Schulze, T. Fónagy, H. Komber, G. Pompe, J. Pionteck, B. Iván Macromolecules 2003, 36, 4719 

[3] T. Fónagy, U. Schulze, H. Komber, D. Voigt, J. Pionteck, B. Iván Macromolecules 2007 40, 1401 

- 116 -


JANUS PARTICLES IN PS/PMMA POLYMER BLENDS 

Thomas Ruhland (1), Andreas Walther (1, 2), A. H. E. Müller (1) 

(1) Macromolecular Chemistry II, University of Bayreuth, 95440 Bayreuth, Germany 

(2) Molecular Materials Group, Department of Applied Physics, Helsinki University of Technology, 

Finland 

thomas.ruhland@uni-bayreuth.de 

Polymer blends are one of the most dynamic sectors of polymer research. Due to the unique 

combination of amphiphilicity combined with the particle character, Janus particles are able to 

strongly adsorb and orient at interfaces. This renders them an interesting tool for the nanostructuring 

of blend interfaces. Therefore, Janus particle are a very versatile particle group 

for the engineering of polymer blend systems. 

Recently, we developed a new way of compatibilizing polymer blends and for controlling the 

location of the particles within the blend structure using spherical Janus micelles based on a 

polystyrene-block-polybutadiene-block-poly(methyl methacrylate) (SBM) block terpolymer 

[1]. The nanostructuration of these blends is much better than that of blends compatibilized 

with the corresponding linaer triblock terpolymers. Motivated by these results, we now apply 

Janus cylinders, having one PS and one PMMA hemicylinder, for the compatibilization of the 

model blend system PS/PMMA. Therefore we investigate PS/PMMA blends at different 

weight ratios and with various amounts of Janus cylinders. Janus cylinders also act as stabilizers 

at the interface of the PS/PMMA blends. The biphasic character of the Janus cylinders 

and the Pickering effect causes their strong adsorption at interfaces. 

[1] Walther, A.; Matussek, K.; Müller, A.H.E ACS Nano 2008, 2, 1167. 

- 117 -


ELABORATION AND CHARACTERIZATION OF BINARY 

NANOCOMPOSITES BASED ON POLY(n-BUTYL 

METHACRYLATE-CO-ACRYLIC ACID)/BENTONITE 

Hiba Chaouadi, Farid Metref, Said Djadoun 

Laboratoire des Matériaux Polymères, Faculté de chimie, Université Sciences et de la Technologie 

Houari Boumediene, BP 32 El-Alia Bab-Ezzouar, 16111 Dar-El-Beida Alger, Algérie 

fmetref@yahoo.fr 

Polymer-clay nanocomposites constitute a new class of materials in which the polymer matrix 

is reinforced by uniformly dispersed inorganic particles (usually 6 wt.% or less) having at 

least one dimension in the nanometer scale. Nanocomposites exhibit improved properties 

when compared to pure polymer or conventional composites, such as enhanced mechanical 

and thermal properties and improved chemical stability. In this communication, the synthesis 

of poly(butylmethacrylate-co-acrylic acid) (BMAA)/clay nanocomposites is described via two 

methods: 

1. The polymerization of pures poly(butylmethacrylate-co-acrylic acid) copolymers (BMAAx) 

(were x is the mole % in acrylic acid monomer) in the first step and the dispersing of the 

pure or modifieded Maghnia (Algeria) bentonite in the polymeric solution follow-up of an 

agitation in the second step. 

2. The in situ technique (polymerization after dispersing the pure or the fonctionalized clay in 

the monomers). 

Nanocomposites thus synthesized are characterized by X-ray diffraction XRD, differential 

scanning calorimetry DSC, thermogravimetric analysis TGA and Scanning electron microscopy 

SEM techniques. The obtained results by DRX and SEM techniques show that the prepared 

nanocomposites are intercaled or semi exfoliated. Finally, the TGA and DSC analysis 

indicated that the introduction of clay to the polymer network resulted in an increase in thermal 

stability. 

- 118 -


EFFECT OF CLAY ON THE MORPHOLOGY AND 

PROPERTIES OF HIGH DENSITY POLYETHYLENE/ 

POLYSTYRENE/CLAY NANOCOMPOSITES PREPARED BY 

MELT MIXING 

Assia Siham Hadj Hamou (1), Farida Yahiaoui (1), Abderahmane Habi (2), 

Said Djadoun (1) 

(1) Laboratoire des Matériaux Polymères, Faculté de Chimie, Université des Sciences et de 

la Technologie Houari Boumediene, BP 32, El Alia, Alger, Algérie 16111 

(2) Laboratoire de chimie organique industrielle, Faculté des sciences et sciences de 

l’ingénieur, Université Abderrahmane MIRA, 06000, Béjaïa, Algeria 

hadjhamouassia@yahoo.fr 

It is well known that polystyrene and polyethylene high density are immiscible. This communication 

concerns the elaboration and characterization of materials based on blends of these 

polymers and a very small amount of bentonite clay originated from Maghnia (Algeria), organically 

modified with hexadecyl ammonium chloride. 

Compounds containing 3 % by weight of organically modified Maghnia bentonite (OBT) 

were prepared by melt blending process using a Barbender Duisburg at 180 °C. 

The effect of incorporation of OBT on the composite structures and morphology of these materials 

were investigated by X-Ray diffraction (XRD), Scanning Electron Microscopy (SEM) 

and Differential Scanning Calorimetry (DSC). 

The results confirm that the incorporation of 3 % by weight of OBT into immiscible 

PS/PEHD mixtures increased the compatibility of these latter blends. 

A Thermogravimetric analysis (TGA) indicated that the addition of such a small amount of 

OBT improved the thermal stability of the elaborated ternary materials. 

- 119 -


A NOVEL COMPATIBILIZATION TECHNIQUE INVOLVING 

MULTIWALL CARBON NANOTUBES IN POLYAMIDE6/ 

ACRYLONITRILE BUTADIENE STYRENE BLENDS 

Bhagwan F. Jogi, Arup R. Bhattacharyya 

Department of Metallurgical Engineering & Materials Science, Indian Institute of Technology 

Bombay, Powai, Mumbai-400076, India 

arupranjan@iitb.ac.in 

Binary polymer blends are often characterized by their coarse and unstable phase morphology 

due to the high interfacial tension between the components. Classical compatibilization technique 

is found to be an excellent strategy to reduce the interfacial tension between the blend 

components, which manifests in the finer morphological observation of the dispersed phase. 

In this context, reactive compatibilizer has also been found very effective in order to reduce 

the coalescence process in the binary polymer blends, wherein the reactive compatibilizer is 

found to observe at the interface. Further, incorporation of fillers in binary immiscible polymer 

blends also stabilizes the phase morphology by increasing the melt-viscosity of the dispersed 

phase, in which fillers are predominantly restricted in the matrix phase. Considering 

these important issues in mind a novel strategy has been developed in melt-mixed 80/20 

(wt/wt) polyamide6/acrylontrile-butadiene-styrene (PA6/ABS) blends system to reduce the 

interfacial tension between the components. In this technique, styrene maleic anhydride 

(SMA) encapsulated multiwall carbon nanotubes (MWNT) are used as a compatibilizer. Morphological 

analysis reveals the finer morphology of 80/20 PA6/ABS blends in presence of 

SMA encalsulated MWNT, wherein MWNT are varied from 0.5-2.5 wt% as compared to the 

blends of either SMA or MWNT of similar composition. Morphological observation also reveals 

that MWNT are migrated from the interface to the PA6 matrix phase even if MWNT are 

intended to localize at the interface during melt-mixing. A detail morphological observation 

has been carried out with SMA of various amount of MA content in order to improve the polarity 

of SMA which may restrict the MWNT at the interface. Further, morphological analysis 

has also been carried out with octadecyl triphenyl phosphonium bromide (OTPB) modified 

MWNT encapsulated by SMA, which shows a better morphological refinement as compared 

to even SMA modified MWNT. The morphological observations are further substantiated by 

FTIR spectroscopy and DSC non-isothermal crystallization studies. Torque data during meltmixing 

has been utilized to understand the role of reactive compatibilization and MWNT to 

alter the melt-viscosity of the blends system. An attempt has been made to understand the 

morphological changes in PA6/ABS binary blends system in presence of SMA encapsulated 

MWNT through torque data during melt-mixing, FTIR spectroscopy and DSC studies. 

- 120 -


PHASE MORPHOLOGY DEVELOPMENT IN PA6/PP/ABS 

TERNARY POLYMER BLENDS: INFLUENCE OF 

COMPATIBILIZERS AND MULTIWALL CARBON 

NANOTUBES 

Biswajit Panda, Arup R. Bhattacharyya, Ajit R. Kulkarni 

Department of Metallurgical Engineering & Materials Science, Indian Institute of Technology 

Bombay, Powai, Mumbai-400076, India 

arupranjan@iitb.ac.in 

Morphological investigation of melt-mixed ternary polymer blends of polyamide6/polypropylene/acrylonitrile 

butadiene styrene (PA6/PP/ABS) was carried out in presence 

of a single (styrene maleic anhydride of 8 wt% MA, SMA8) or a dual compatibilizer (SMA8 

and polypropylene grafted maleic anhydride, PP-g-MA) in an intention to understand the influence 

of compatibilizer/s on morphology development. 80/10/10 (wt/wt/wt) PA6/PP/ABS 

blends exhibit a ‘core-shell’ type of morphology wherein PP forms the core and ABS is found 

to form the shell in the PA6 matrix. The ‘core-shell’ morphology of this composition is found 

to be unaltered in the presence of the compatibilizer/s, however, the respective phase size is 

found to reduce significantly. Further, another set of blends were prepared wherein multiwall 

carbon nanotubes (MWNT) were varied from 1-5 wt% in 80/10/10 PA6/PP/ABS ternary 

polymer blends. The morphological observations suggest a compatibilization action of 

MWNT in this blends system which manifests in lower dispersed phase size of ‘core-shell’ 

type. Along with morphological stabilization in presence of MWNT, an increased electrical 

conductivity is also observed in these blends with electrical percolation threshold of 3-4 wt% 

of MWNT. Dielectric relaxation spectroscopy reveals that relaxation peak corresponding to 

PA6 phase in 80/10/10 PA6/PP/ABS ternary blends is found to shift at higher temperature 

side at a fixed frequency in presence of either compatibilizer/s or MWNT. This result indicates 

that the mobility of the PA6 chain is getting restricted in presence of either compatibilizer 

or MWNT. Non-isothermal crystallization studies for these blends show that the fractionated 

crystallization associated with PA6 phase in 80/10/10 PA6/PP/ABS blends is found 

to be affected further due to the refined dispersed size of ‘core-shell’ type brought out by the 

presence of compatibilizers/MWNT. 

It is important to note that spreading coefficients between the polymer pairs are found to dictate 

the development of phase morphology in ternary polymer blends which manifests in either 

‘core-shell’ type or separately dispersed phase morphology. In view of this various experiments 

have been conducted for 80/10/10 type ternary blends of PA6, PP and ABS wherein 

PA6 major phase has been replaced by either PP or ABS in the respective blends. Morphological 

investigations reveal the formation of separately dispersed domains of PA6 and PP in 

the ABS matrix in 80/10/10 ABS/PP/PA6 ternary blends, while ‘core-shell’ type of morphology 

has been observed in 80/10/10 PP/PA6/ABS ternary blends in which PA6 forms the core 

and ABS is found to form the shell. Further, crystallization studies indicate once again the 

fractionated crystallization phenomenon of PA6 phase which is found to depress in presence 

of compatibilizer. An attempt has been made to understand the morphological development of 

PA6/PP/ABS ternary blends in presence of compatibilizer or MWNT. 

- 121 -


A NEW SINGLE-STEP SYNTHESIS METHOD FOR HYBRID 

POLYMER/INORGANIC NANOPARTILCE LATEXES 

A. S. Pakdel (1), H. Eslami (2), S. Pourmahdian (2) 

(1) Polymer Engineering Department, Amirkabir University of Technology, Tehran, Iran 

(2) Chemistry Department, Amirkabir University of Technology, Tehran, Iran 

amir.pakdel@aut.ac.ir; eslamih@aut.ac.ir 

Nano-composites have been increasingly studied because of their unique characteristics resulted 

from incorporating of nano-size building blocks (particles) in a continuous matrix. 

However, these particles induce some problems in manufacturing processes because of their 

high surface and inter-particle attraction energies. For example, mixing of inorganic nanoparticles 

with polymers in a high shear process shows excessive energy demand and persistent 

agglomeration of nano-particles. This agglomeration in turn causes mechanical problems like 

lower strength due to stress concentration in the agglomeration spots. Many processes have 

been envisaged to overcome the resulting problems, and emulsion polymerization that conventionally 

produces latexes in nanometer range has been utilized to synthesize hybrid nanostructures 

in the last decade. Thus, self-assembly of the inorganic nano-particles present in 

water on the nano-sized monomer droplets with simultaneous polymerization produces hybrid 

nano-structures with no agglomeration of inorganic nano-particles. The nano-particles used 

this way are usually referred to as "Pickering emulsifiers". In this study we report a generic 

single-step precipitation/polymerization process that can be used to prevent the agglomeration 

of inorganic nano-particles under controlled condition of system e.g. temperature and pH 

value. This process can reduce the time, energy and hence total cost of nano-particle dispersion. 

We studied the effect of different parameters on the resulting core-shell morphologies. 

In our work, methyl methacrylate was used as monomer, cetyltrimethylammonium borimde as 

modulator and silica as inorganic nano-particle. The resulting structures have potential use in 

various applications, like plastics, cosmetics, paints, and pharmaceuticals. 

- 122 -


PREPARATION OF VINYL ESTER/NANO ALUMINA NANO- 

COMPOSITES AND STUDY OF THEIR MECHANICAL, 

PHYSICAL AND THERMAL PROPERTIES 

M. Esfandeh, H. Rahimi, M. Oroujzadeh 

Iran Polymer and Petrochemical Institute 

m.esfandeh@ippi.ac.ir 

In this work nanocomposites based on vinylester/nano alumina (Bohemite) are prepared. The 

nano particles were dispersed via two different methods i. e. high shear mixer (homogenizer) 

and ultrasonic bath. EDAX technique was used to follow the extent of the dispersion. The 

effect of dispersion method on various properties of nanocomposites was investigated. A better 

mechanical properties (tensile, flexural,…) was achieved with ultrasonic dispersion. These 

were further improved when surface treated alumina nano particles were used. Thermo gravimetric 

analysis and burning tests were carried on the samples and an improved thermal and 

fire properties were obtained as compared with neat resin. Water absorption and hardness of 

the samples are also studied. 

- 123 -


NON-ISOTHERMAL CRYSTALLIZATION BEHAVIOR OF 

POLYPROPYLENE /POLY (TRIMETHYLENE 

TEREPHTHALATE) BLENDS IN PRESENCE OF NANOCLAY 

PARTICLES 

Ali Kalati Vahid (1), Seyed-Hassan Jafari (1), Hossein Ali Khonakdar (2), 

Rüdiger Häßler (3), Dieter Jehnichen (3) 

(1) School of Chemical Engineering, University of Tehran 

(2) Iran Polymer and Petrochemical Institute 

(3) Leibniz Institute of Polymer Research Dresden 

shjafari@ut.ac.ir 

In this work, firstly the crystallization behavior, non-isothermal crystallization kinetics, crystalline 

structures and the morphology of melt mixed polypropylene (PP)/poly(trimethylene 

terephthalate)(PTT) blends compatibilized by poly(ethylene–butylacrylate-glycidyl methacrylate) 

(Elvaloy PTW) were investigated by differential scanning calorimetry (DSC), wide angle 

X-ray scattering (WAXS) and transmission electron microscopy (TEM) techniques. Then the 

influence of addition of two kinds of organoclays (Cloisite 30B and 20A), two compatibilizers 

(PP-grafted maleic anhydride (PP-g-MAH) and Elvaloy PTW) on crystallization behavior of 

the blends was studied. The neat PP showed the highest degree of crystallinity among all the 

prepared blends and nanocomposites. PP component in all samples showed characteristics of 

α-phase crystalline structure and incorporation of nanoclays, compatibilizers and blending did 

not affect its crystalline structure. The introduction of clay caused an obstacle on the molecular 

chains movement and reduced their tendency to crystallize. Results showed that crystallization 

of PP/PTT/PP-g-MA is similar to PP/PTT blend and presence of PP-g-MA as compatibilizer 

had a negligible effect on crystallization of PP component. Elvaloy PTW was more 

effective than PP-g-MA in reducing crystallinity of PP component of the blend and nanocomposites. 

By increasing Elvaloy PTW content from 5 to 10 wt% the peaks related to clay at 

2θ=7.08° was disappeared and height of the peak at 2θ=3.42° became very low, indicating an 

exfoliated clay morphology confirmed by TEM investigation. 

- 124 -


INFLUENCE OF ENHANCED TRANSESTERIFICATION ON 

THERMAL DEGRADATION AND RHEOLOGICAL BEHAVIOR 

OF PHENOXY/PTT BLENDS IN PRESENCE OF NANOCLAY 

PARTICLES 

Javad Seyfi (1), Seyed-Hassan Jafari (1), Hossein Ali Khonakdar (2) 

(1) School of Chemical Engineering, University of Tehran, P.O. Box 11155-4563, Tehran, 

Iran 

(2) Iran Polymer and Petrochemical Institute, P.O. Box 14965/115, Tehran, Iran 

shjafari@ut.ac.ir 

Blends of phenoxy resin and poly(trimethylene terephthalate) (PTT) undergo transesterification 

reactions during melt mixing process. This study is concerned with transesterification of 

phenoxy/PTT blends in presence of nanoclay particles. 1HNMR analysis showed that the incorporation 

of nanoclay particles enhances the transesterification of phenoxy with PTT with 

the exception of adding 5 wt. % nanoclay for which the extent of transreactions was slightly 

lower than that of the pristine blend. Thermogravimetry analysis revealed that only addition 

of 1 wt. % nanoclay improves thermal stability of the pristine blend. Higher amounts of clay 

content induce an acceleration of the thermal degradation even higher than the rate of degradation 

of the pristine blend. This was attributed to the steric hindrance effect of silicate layers 

on the progress of transesterification reactions which causes a reduction in formation of 

crosslinked structures, and thermal stability of nanocomposites. In order to deeper elucidate 

the mechanism of degradation kinetic parameters were calculated using KAS isoconversion 

method. From rheological measurements, we observed an unexpected reduction of storage 

modulus (G’) values at low frequency region when 1 wt. % nanoclay added to the blend. It 

can be explained by the fact that the maximum extent of transreactions occurs in the nanocomposites 

containing 1 wt. % nanoclay which means that a high extent of entanglements is 

formed due to the formation of transesterification products such as PTT-grafted phenoxy 

chains. Introduction of higher amounts of nanoclay result in obvious pseudo-solid-like behaviors 

of nanocomposites melts. Percolation structure as well as large interfacial area between 

polymer chains and nanoclay are responsible for the rheological behavior. 

[1] M. Farmahini-Farahani et al. Investigation of exchange reactions and rheological response of reactive blends 

of poly(trimethylene terephthalate) and phenoxy resin. Polym. Int. 2008;57:612–617. 

[2] J. Kuljanin-Jakovljević et al. Thermal degradation kinetics of polystyrene/cadmium sulfide composites. 

Polymer Degradation and Stability 2009; 94(6):891-897. 

- 125 -


STUDY OF ELONGATIONAL FLOW ON MECHANICAL 

PROPERTIES AND OXYGEN PERMEABILITY OF 

LLDPE/LDPE/OMMT NANOCOMPOSITE BLOWN FILMS 

Hamidreza Esfahany, Hamid Garmabi 

Polytechnic of Tehran, Iran 

Hamidrezaisfahany@yahoo.com 

Polyethylene nanocomposite blown films containing organoclay were prepared by melt extrusion 

followed by film blowing. The effect of intensity of elongational flow in biaxial direction 

(draw down ratio(DDR) and blow up ratio(BUR)) on the mechanical properties, morphology 

and oxygen permeability of nanocomposite blown films were investigated. 

X-Ray diffractometry pattern and AFM pattern for the most impermeable sample shows that 

the morphology of nanocomposite film is a coexistence of intercalated tactoids and exfoliated 

layers which is confirmed by parallel plate rheometer. The results show that the oxygen permeability 

coefficient, mechanical properties in nanocomposite blown films with increasing 

intensity of elongational flow in machine direction exhibited a significant improved compared 

to the pristine LDPE/LLDPE blends of the same composition. It is believed that strong interfacial 

interactions between NanoClay/ PEMA and LLDPE/LDPE(40/60) blend and orientation 

of silicate layer in machine direction are responsible for the distinct improvement observed 

in all properties of the obtained nanocomposite blown films . 

- 126 -


SELECTIVE SEQUESTERING OF CNTS IN BLOCK 

COPOLYMERS 

Florian Wode (1), Martin Kirsten (1), Manfred Stamm (1), Apostolos Avgeropoulos (2), Nick 

Zafeiropoulos (2) 

(1) Leibniz-Institut für Polymerforschung Dresden e.V., Dept. Nanostructured Materials 

(2) Department of Materials Science & Engineering, University of Ioannina, Greece 

wode@ipfdd.de 

The ordered phase morphology of block copolymers (BCP) can be used for the alignment of 

nanofillers [1]. Because of their outstanding properties, carbon nanotubes (CNTs) form a 

promising class of fillers. Selective sequestering of the CNTs in one of the copolymer phases 

is a pathway to oriented nanocomposites. At the moment, this was mastered only in a few 

studies. Park et al. selectively located poly(styrene) (PS) grafted CNTs in the PS phase of a 

high molecular weight (570.000) poly(styrene-b-isoprene) matrix [2]. Peponi et al. used a 

dispersant for the selective sequestering of octadecylamine functionalized CNTs in the PS 

phase of a poly(styrene-b-isoprene-styrene) matrix [3]. Recently, Liu et al. succeeded in selectively 

locating PS functionalized CNTs in the PS phase of a poly(styrene-b-butadiene-bstyrene) 

BCP [4]. To our knowledge, our approach is the first applying mechanical shear 

force for the selective location of CNTs in a BCP phase. 

A poly(4-vinylpyridine-b-styrene) block copolymer (BCP) was sheared for 8 h in a plate-plate 

rheometer (gap 1 mm, diameter 8 mm). The neat BCP was compared to BCP filled with 1wt% 

of unfunctionalized CNTs and poly(2-vinylpyridine)-grafted CNTs respectively. The morphology 

after shear was analyzed by small angle x-ray scattering (SAXS) and transmission 

electron microscopy (TEM) in three directions (normal, tangential, radial). 

The CNTs cause a substantial increase in storage module G, loss module G’ and tan delta 

(G/G’), with the highest increase for the functionalized CNTs. The BCP morphology is lamellar 

in all cases. SAXS measurements and FFT of TEM micrographs revealed that the lamella 

were partly oriented. The CNTs, especially the functionalized ones, disturb the lamellar ordering 

process. Unfunctionalized CNTs show a slight preference of the P4VP domains over the 

PS domains, while the P2VP-functionalized CNTs selectively sequester in the P4VP domains. 

[1] M. R. Bockstaller; R. A. Mickiewicz; E. L. Thomas, Advanced Materials 2005, 17, (11), 1331-1349 

[2] I. Park; W. Lee; J. Kim, et al., Sensors and Actuators B: Chemical 2007, 126, (1), 301-305 

[3] L. Peponi; L. Valentini; L. Torre, et al., Carbon 2009, 47, (10), 2474-2480 

[4] Y.-T. Liu; Z.-L. Zhang; W. Zhao, et al., Carbon 2009, 47, (7), 1883-1885 

- 127 -


STRUCTURAL CHANGES IN THIN FILMS OF SUPRA 

MOLECULAR ASSEMBLIES BY BLENDING WITH 

HOMOPOLYMERS 

Marcus Böhme, Bhanu Nandan, Manfred Stamm 

Leibniz-Institut für Polymerforschung Dresden e.V., Dresden, Germany 

boehmem@ipfdd.de 

We investigated the impact of blending with corresponding homopolymers on the characteristics 

of a supramolecular assembly thin film consisting of Poly- (styrene-block-4vinylpyridine) 

and 2-(4’- hydroxybenzene)azobenzoic acid. Beside the expected changes in 

domain spacing, we observed changes both in morphology and orientation of the microphase 

separated structure. An upper limit for the homopolymer content depending on molecular 

weight and casting solvent was also found. 

- 128 -


HIGHLY ORDERED ARRAYS OF FE3O4 MAGNETIC 

NANOPARTICLES VIA BLOCK COPOLYMER SELF 

ASSEMBLY 

Andriy Horechyy (1), Nikolaos E. Zafeiropoulos (1, 2), Peter Formanek (1), Anton Kiriy (1), 

Manfred Stamm (1) 

(1) Leibniz-Institut für Polymerforschung Dresden e.V., Hohe Straße 6, 01069 Dresden, 

Germany 

(2) Department of Materials Science & Engineering, University of Ioannina, Greece 

horechyy@ipfdd.de 

Block copolymers (BCP) acting as a template for spatial arrangement with different types of 

nanoparticles (NP), such as metal, metal oxides, semiconductors, quantum dots, are an attractive 

system with potential application in high density data storage, optoelectronic materials, 

sensor devices. The self-assembling aspect of BCPs offers a simple and cost effective way to 

create periodic and well ordered structures in the nanometer scale, whilst the additional selective 

incorporation of specific NPs into one of the BCP phases leads to the formation of polymer 

matrix with discrete targeting properties. 

Different methods have been applied in order to achieve specific arrangement of NP inside of 

one of the BCP domains, e. g. “in situ” synthesis via complex decomposition, micellemediated 

NP synthesis and deposition, nanoparticles surface modification by specific ligands 

or by polymer brush approach. 

Nevertheless, it is still a tremendous challenge to generate well ordered nanostructured templates 

with precise and uniform nanoparticle distribution within one of the co-polymer blocks 

under reproducible conditions. In case of magnetic nanoparticles (MNPs) additional challenges 

arise from strong dipole-dipole interparticle interactions leading to their clustering and 

agglomeration and as results macrophase segregation. 

In the present study, we report a convenient route for preparation of nearly monodisperse 

Fe3O4 magnetic nanoparticles (d=6nm) with apparent affinity towards polyvinylpyridine 

(PVP). As-synthesized MNPs with no further need for any additional processing, e.g. surface 

treatments, ligand exchange steps, grafting of polymer brush and so on, could be selectively 

incorporated into PVP domains of a linear poly(styrene-b-vinylpyridine) block copolymer 

yielding excellent results. Such affinity is attributed to a presence of a loose stabilizing organic 

shell, providing them sufficient dispersability and stability in organic media but in the 

same time allowing that simultaneous coordination with PVP species could be realized. 

Different compositions of symmetric PS-b-P2VP (BCP1, Mn=100 000, 50 000-b-50000 

PDI=1.16) with MNP were prepared in organic solvents with a concentration of nanoparticles 

ranging between 0.1-10 % (w/w with respect to the polymer weight) and deposited onto Siwafers. 

After solvent vapour annealing well-ordered nanoparticles arrays are formed within 

the PVP domain of lamellae-structured BCP matrix. Alternatively, PS-b-P4VP (BCP2, 

Mn=76 000, 57 500-b-18 500, PDI=1.14) was used to prepare BCP2-MNP composites with a 

purpose to obtain cylindrically structured templates. The nanoparticles are oriented within 

P4VP cylinders (minor block). Perfect hexagonal order of phase-segregated BCP is achieved. 

- 129 -


COMPARISON OF NANO COMPOSITES BASED POLY- 

(ACRYLONITRILE-BUTADIENE-STYRENE) MODIFIED 

EPOXY RESIN AND TiO2 OR MWCNT 

P. Jyotishkumar (1), J. Pionteck (2), S. Thomas (1) 

(1) School of Chemical Sciences, Mahatma Gandhi, University, Priyadarshini Hills, Kottayam, 

Kerala 686560, India 

(2) Leibniz-Institut für Polymerforschung Dresden e.V., Hohe Str. 6, 01069 Dresden, Germany 


Poly(acrylonitrile-butadiene-styrene) (ABS) was used to modify diglycidyl ether of bisphenol-A 

(DGEBA) type epoxy resin cured with diamino diphenyl sulfone (DDS). The modified 

epoxy resin was used as matrix for making nano composites in order to get improved mechanical 

and thermal properties. Nano TiO2 (up to 10 phr) and MWCNT (up to 1 phr) were 

used as nanofiller. The cure kinetics, morphology and structure development, rheology, dynamic 

mechanical, tensile, flexural, impact, and thermal properties and the fracture toughness 

of the systems were analysed. 

The blends containing low amounts ABS exhibited considerable improvement in mechanical 

properties compared to the crosslinked epoxy network. Furthermore, the mechanical properties 

of CNT and TiO2 containing hybrid composites, especially the storage modulus and fracture 

toughness, are improved compared to filler-free epoxy blends. 

Scanning electron micrographs of the fractured surfaces of the blends and composites revealed 

the toughening effect of the ABS and of the nano-fillers. The morphology is dependent 

on the ABS and nanofiller content, and could be correlated to the composite properties. 

Thermogravimetric analysis revealed good thermal stability of both the blends and composites. 

- 130 -


MODIFICATION OF THE ELECTRICAL PROPERTIES OF 

POLYPROPYLENE BY MODIFIED EXPANDED GRAPHITES 

(EGS) 

J. Pionteck (1), M. Kaiser (1), F. Piana (1), P. Pötschke (1), I. Krupa (2), M. Omastová (2) 

(1) Leibniz-Institut für Polymerforschung Dresden e. V., Hohe Str. 6, 01069 Dresden, 

Germany 

(2) Polymer Institute, Slovak Academy of Sciences, Dúbravská cesta 9, 842 36 Bratislava, 

Slovakia 


For some applications it is necessary that polymers exhibit a certain degree of conductivity, 

which can be reached by mixing conventional isolating polymers with electrically conductive 

fillers. We analyzed the influence of different types of flaky EGs [1] and of virgin expanded 

EG on the conductivity of polypropylenes (PP). The composites were prepared by compounding 

of the EGs with two types of PP varying in viscosity using a DSM 5 mL Microextruder. 

Due to the high aspect ratio of the EGs, especially in their non-processed form, only a very 

low amount of EG should be necessary to form percolating EGs paths when mixing with 

thermoplastics, resulting in a conductive material. However, agglomeration and orientation 

often hinder the formation of percolation and in praxis much higher EG concentrations in the 

range of few percent are necessary for reaching conductivity [2, 3]. To overcome this limitation 

we varied the processing conditions and used EGs after modification with PPy to produce 

PP/EG-PPy ternary composites. Conductivities and morphologies of PP/EGs and PP/EGs-PPy 

composites were analysed and related to the material and processing parameters. 

It was shown by SEM and comparison of the conductivities of coated and non-coated graphites 

that the coating of the EGs with PPy is complete. All EGs exhibit rather good adhesion to 

PP, but still there is a tendency for agglomeration when melt mixing, which is reduced in 

coated particles. However, the PPy-coating is unstable during mixing and neither an increase 

in conductivity nor a reduction in percolation due to PPy-coating is observed. Surprisingly, 

the flaky EGs cause in comparison to the virgin expanded graphite higher conductivities of 

the composites. The composites prepared with the viscous PP exhibit in average higher conductivities 

than these with the low viscous matrix. Furthermore, the conductivities are 

strongly dependent on processing conditions. 

The authors appreciate the financial support by the DAAD within the program PPP Slovakia, 

D/07/01261. We are grateful to SGL Technologies GmbH for providing the graphites, to H. 

Kunath for his technical assistance, and to L. Häußler and K. Arnhold for TGA analysis. 

[1] Data sheet for ECOPHIT G, SGL-Carbon 

[2] W. Zheng, X. H. Lu, S. C. Wong, J. Appl. Polym. Sci. 91 (2004), 2781 

[3] M. Zhang, D.J. Li, D. F. Wu, C. H. Yan, P. Lu, G.M. Qiu, J. Appl. Polym. Sci. 108 (2008), 1482 

- 131 -


NANOCOMPOSITE BLENDS: MULTIWALLED CARBON 

NANOTUBE FILLED POLYCARBONATE MELT MIXED WITH 

MONTMORILLONITE FILLED POLYPROPYLENE 

Petra Pötschke (1), Bernd Kretzschmar (1), Liane Häussler (1), Mahmoud Abdel-Goad (2), 

Andreas Janke (1) 

(1) Leibniz-Institut für Polymerforschung Dresden e.V, Hohe Str. 6, 01069 Dresden, 

Germany 

(2) Petroleum and Chemical Eng. Dept, College of Engineering, Sultan Qaboos University, 

P.O.Box 33, Al Khod 123, Muscat, Sultanate of Oman 

poe@ipfdd.de 

Nanocomposite blends were prepared by melt mixing based on a conductive polycarbonate 

(PC) composite containing multiwalled carbon nanotubes and polypropylene (PP) containing 

nanoclay (montmorillonite). The PC composite with 2 wt% MWNT (PC-2NT) was prepared 

by diluting a PC masterbatch by melt extrusion [1]. The PP nanoclay composite with 3 wt% 

MMT (PP-3MMT) was produced by two step melt compounding. The blends were prepared 

in a small scale Daca Microcompounder over the whole composition range. 

The aim of blending the conductive PC composite with another material was to get a conductive 

material at lower amounts of MWNT than required for the pure PC component. Using the 

concept of double percolation, first introduced by Sumita et al. [2] for carbon black filled 

blend, conductive materials can be achieved already if the filled phase starts to form a continuous 

phase in a co-continuous structure. This can occur at much lower concentrations than 

needed for this phase to form the matrix of a matrix-particle structure. MMT filled PP was 

selected as blend component due to its good mechanical and barrier properties. It was of interest 

which kind of morphology will be formed if both components consist nanofiller and 

whether additional synergistic effects can be observed. In addition, we studied whether melt 

rheology is suitable to detect the range of co-continuity in this double percolated system. 

This blend system is immiscible and shows particle-matrix morphologies at low concentrations 

of both phases. Between 50 and 80 wt% of the filled PC phase a co-continuous composition 

range was observed as verified by selective extraction of PC and PP and morphological 

investigations [3]. 

Significantly increased conductivity values, i. e., in the range of 10-7 S/cm could be obtained 

in the composition range in which the filled PC forms a continuous phase, i. e. starting at 

50 wt% of the filled PC phase. Here, the absolute MWNT content is about 0.7 vol%. 

DSC investigations showed that Tg, melt enthalpy, and melting temperature of PP are slightly 

reduced comparing values of a 50/50 wt% blend with PP-3MMT. In addition, the nanofiller 

acts nucleating for PP as revealed from the crystallization runs. 

Moreover, melt rheology was found to be a suitable tool to detect the co-continuous composition 

range in these blends which exhibit double percolation. The effects of percolation structure 

of MWNT and exfoliation of MMT were observed in increasing the dynamic mechanical 

moduli and viscosity of the PC and PP nanocomposites as compared to the respective base 

polymer components. The co-continuous structure formation in the blends is clearly reflected 

in dynamic mechanical moduli and viscosity of the blends which are improved above the values 

of the parent components. 

[1] P. Pötschke, T. D. Fornes, D. R. Paul, Polymer 43 (2002) 11, 3247-3255 

[2] M. Sumita et al, Polym. Bulletin, 25, (1991) pp. 265 

[3] P. Pötschke, B. Kretzschmar, A. Janke, Comp. Sci. Techn. 67(2007)5, 855–860 

- 132 -


NANOSCALED MOLECULARLY IMPRINTED POLYMERS 

(MIPS) FOR SPECIFIC RECOGNITION OF AMINO ACIDS VIA 

INVERSE MINIEMULSION POLYMERISATION 

D. Wojciukiewicz (1), J. Riegler (1, 2), T. Hirth (1,2), G. Tovar (1, 2) 

(1) Institute for Interfacial Engineering, University of Stuttgart 

(2) Fraunhofer Institute for Interfacial Engineering and Biotechnology, Nobelstraße 12, 

70569 Stuttgart, Germany 

guenter.tovar@igb.fraunhofer.de 

Molecular Imprinting is a method which allows for the creation of specific recognition sites of 

a desired molecule (template) in synthetic polymers. A template, a functional monomer and a 

cross-linker self-assemble by weak interactions e. g. hydrogen bonds prior to the polymerisation. 

After the polymerisation the template is extracted from the polymer, leaving an imprint i. 

e. complementary recognition sites in the polymer network. Molecularly Imprinted Polymers 

(MIPs) often exhibit specifity and selectivity similar to natural antibodies but they have much 

higher physical and chemical stability than typical biological molecules [1]. For this reason, 

they can be used for applications where in addition to a high specifity a superior stability is 

required, for example purification processes or waste water treatment. 

Classically, MIPs are prepared by a bulk polymerisation followed by grounding to particles, 

which often exhibit an irregular shape and a high polydispersity. The inverse miniemulsion 

polymerisation allows for the preparation of spherical and nanoscaled MIPs with well-defined 

size and shape for specific recognition of water soluble molecules like amino acids and peptides 

[2]. The synthesis is carried out in two steps. First the formation of miniemulsion consisting 

of aqueous nanodroplets filled with the monomer, cross-linker and template molecule 

as the dispersed phase, and surfactant and initiator dissolved in an organic solvent as the continuous 

phase. The miniemulsion is formed via high shearing by ultrasonification. The second 

step is a photo initiated polymerisation where the MIPs in the size range of 50 nm to 300 nm 

are synthesised from these nanodroplets. 

One of the greatest challenges of preparing MIPs is the selection of suitable monomers. In the 

past, this selection was often based on the trial-and-error method. The fast progress in the development 

of computer science has made it possible to calculate the interactions between the 

monomer and the template molecule. The monomer with strong interactions to the template 

would be more suitable for successful preparation of MIPs than the monomer with weak interactions 

[3]. 

In this approach a computational prediction method based on semi-empirical quantum simulations 

was chosen to select most promising monomers for imprinting amino acids. The results 

of the calculations were experimentally validated using the inverse miniemulsion polymerisation. 

[1] Alexander, C., et al., J. Mol. Recognit., 2006. 19: p. 106-180 

[2] Gruber-Traub, C., et al., Polymer Preprints (American Chemical Society, Division of Polymer Chemistry), 

2006. 47: p. 901-902 

[3] Dineiro, Y., et al., Biosensors and Bioelectronics, 2006. 22: p. 364-371 

- 133 -


OPTIMIZATION OF ELECTRICAL AND MECHANICAL 

PROPERTIES OF A PC/ABS BLEND BY A HYBRID FILLER 

SYSTEM 

A. Kamper, S. Ilisch, H. H. Le, H.-J. Radusch 

Martin Luther University Halle-Wittenberg, Center of Engineering Sciences, 

Polymer Technology, Germany 

anja.kamper@iw.uni-halle.de 

Today, the specific requirements to polymeric components used in technical applications especially 

in communication technology are highly multifarious. Not only the mechanical properties 

should be improved, but also the electrical properties are very important to be optimized 

to obtain high performance components. Because of this complex situation blend technology 

is used, which gives the opportunity to combine the different properties of different materials. 

Furthermore, the use of fillers can be useful to further improve these properties. In case of a 

hybrid filler system the properties can synergistically add up to a higher grade. 

The dispersion and distribution of the fillers in the polymer matrix are highly important for 

the resulting properties. The knowledge of the filler dispersion and distribution during the 

mixing process gives the opportunity to estimate the optimal mixing parameters, for example 

the shortest possible mixing time. In this way it is possible to avoid thermal destruction of the 

matrix material and to obtain the optimal filler dispersion. The used method, called online 

measured electrical conductance (OMEC), was developed in previous works. 

The investigated blend system consists of a polycarbonate (PC) and an acrylonitrile butadiene 

styrene (ABS) phase in different blend ratios. The idea was to improve the electrical properties 

by giving carbon nanotubes (CNT) into the PC matrix. The mechanical properties should 

be influenced by adding carbon black (CB) into the ABS phase. Through variation of the filler 

content and the process parameters the morphology development of the blend system was 

investigated by different types of microscopy. We were able to control the morphology and 

therefore the properties, which were tested by tensile test and dynamic mechanical analysis 

(DMA). The electrical properties measured online were proved by comparison with the offline 

measured conductivity, where a correlation was found. 

- 134 -


NOVEL TITANIUM DIOXIDE/POLYSTYRENE NANO- 

COMPOSITES AS PRECURSOR FOR ADVANCED 

GRAPHITE ELECTRODE MATERIALS 

Jan U. Wieneke (1, 3), David Ruiz Abad (1, 3), Gerd Brosig (2,3), Hartmut Wiggers (2, 3) 

Christof Schulz (2, 3), Mathias Ulbricht (1, 3) 

(1) Lehrstuhl für Technische Chemie II, Universität Duisburg-Essen, 45141 Essen, Germany 

(2) Institut für Energie- und Umwelttechnik e.V. (IUTA), 47229 Duisburg, Germany 

(3) CeNIDE-Center for Nanointegration Duisburg-Essen, 47057 Duisburg, Germany 

jan.wieneke@uni-due.de 

Our approach towards a new kind of mixed matrix graphite electrode materials containing 

well-dispersed TiO2 nanoparticles is based on the preparation of homogeneous solid blends of 

the nanoparticles with precursor polymers for subsequent pyrolysis. Here, we will report 

about the preparation and characterization of the nanocomposite material. 

TiO2 nanoparticles with anatase crystal structure are prepared by gas phase synthesis via burning 

titanium tetra isopropoxide (TTIP) in a flame reactor. Depending on the reaction conditions, 

almost spherical nanoparticles with sizes between 5 and 20 nm are obtained. Prefunctionalizations 

to improve the compatibility of the inorganic nanoparticles with organic liquids 

are performed by silanization reactions from liquid or gas phase. The solid nanocomposites 

for electrode materials are created through dispersion of nanoparticles in a polystyrene (PS) 

matrix. Two different routes are explored: a) the dispersion of TiO2 in polystyrene/toluene 

solutions followed by solvent evaporation and/or precipitation, and b) the in situ polymerization 

of styrene containing dispersed TiO2 and a small fraction of divinylbenzene as a 

crosslinker. The dispersions are characterized by UV-Vis spectroscopy, dynamic light scattering, 

and rheology. The finally obtained solid nanocomposite is investigated by scanning and 

transmission electron microscopy, X ray diffraction, and porometry. 

The feasibility of mixed matrix graphite preparation via pyrolysis is also tested, and correlations 

are established between the structure and properties of the liquid dispersions, the solid 

nanocomposites, and the final mixed matrix materials. 

- 135 -


NATURAL RUBBER BLENDED WITH POLYSTYRENE 

NANOPARTICLES PREPARED BY DIFFERENTIAL 

MICROEMULSION POLYMERIZATION 

Saowaroj Chuayjuljit, Anyaporn Boonmahitthisud 

Department of Materials Science, Faculty of Science and National Center of Excellence for 

Petroleum, Petrochemicals and Advanced Materials, Chulalongkorn University 

schuayjuljit@yahoo.com 

This research aims to improve the application properties of rubber by blending natural rubber 

(NR) latex with nanolatex of polystyrene (PS). PS nanoparticle was synthesized by means of 

differential microemulsion polymerization of styrene monomer using sodium dodecyl sulfate 

(SDS) and azobisisobutyronitrile (AIBN) as a surfactant and an initiator, respectively. Solid 

content (% solid) of the particles in the nanolatex was measured by weighing method. Morphology 

of the obtained nanoparticles was explored using a transmission electron microscope 

(TEM). The NR latex was well mixed with the prepared PS nanolatex at the amount of 3, 5, 7 

and 9 phr (based on dry weight of NR and PS) using a mechanical stirrer at 150 rpm for 3 h at 

room temperature. The homogeneous mixtures were then cast into sheets on a glass mold, air 

dried for 1 day and then cured at 110 o C for 3 h. After curing, the blends were examined for 

their mechanical properties, dynamic mechanical properties and flammability. The incorporation 

of an appropriated amount of PS nanoparticles apparently improved the mechanical properties 

and flammability of NR. From dynamic mechanical analyzer, the partial semiinterpenetrating 

structure had been observed when the amount of the PS in NR was over 5 

phr. 

- 136 -


POLYMER BLENDS OF EVA/NANO-SIZED PS FILLED WITH 

NANOSILICA 

Saowaroj Chuayjuljit, Nutnicha Piyawong 

National Center of Excellence for Petroleum, Petrochemicals and Advanced Materials, Chulalongkorn 

University 

nutnicha.p@gmail.com 

Polymer blends based on ethylene vinyl acetate copolymer (EVA) and polystyrene (PS) 

nanoparticles filled with nanosilica have been prepared via a latex compounding process and 

characterized by several techniques. The nanolatex of PS was synthesized by differential microemulsion 

polymerization using sodium dodecyl sulfate and azobisisobutyronitrile as a surfactant 

and an initiator, respectively. Solid content, particle size and morphology of PS in the 

obtained nanolatex were determined by a weighing method, dynamic light scattering analyzer 

and transmission electron microscope, respectively. Blends of EVA and PS at EVA/PS dry 

weight ratios of 90/10, 80/20, 70/30 and 60/40 were mixed with nanosilica at the amount of 

0.5 wt% using a mechanical stirrer at 100 rpm for 2 h. The blended latices were cast into 

sheets on a glass mold, air dried for 1 day and then in an oven at 70 o C for 6 h. After that, the 

samples were examined for their tensile properties, dynamic mechanical properties and morphology 

using a universal testing machine, dynamic mechanical analyzer and scanning electron 

microscope, respectively. It is apparent that PS and silica nanoparticles provide a good 

reinforcing effect on the EVA. However, the incorporation of high PS content results in its 

aggregation and poor dispersion. 

- 137 -


MECHANICAL PROPERTIES AND MORPHOLOGY OF 

XSBR/NR BLENDS FILLED WITH PS NANOPARTICLES 

Saowaroj Chuayjuljit, Wasuthep Luecha 

National Center of Excellence for Petroleum, Petrochemicals and Advanced Materials, 

Chulalongkorn University 

wasumint@hotmail.com 

This research aims to investigate the mechanical properties and morphology of caboxylated 

styrene butadiene rubber (XSBR)/natural rubber (NR) blends filled with polystyrene (PS) 

nanoparticles. The specimens were prepared by latex compounding method. The rubber 

blends of XSBR and NR at XSBR/NR dry weight ratios of 70/30, 50/50 and 30/70 were 

mixed with 3 phr of PS nanoparticles prepared by differential microemulsion polymerization. 

The blended latices were cast into sheets on a glass mold, air dried and then cured in an oven 

at 80 o C for 3 h. After that, the specimens were examined for their tensile properties, tear 

strength and morphology. The results showed that the tensile strength, elongation at break and 

tear strength increased with increasing amount of NR in the rubber blends, but the Young’s 

modulus decreased. In addition, all these properties have been improved by adding the PS 

nanoparticles. Overall results showed that rubber blend of 30/70/3 XSBR/NR/PS gave the 

optimum mechanical properties. Moreover, the phase morphology of the blends could be understood 

from the scanning electron micrographs. 

- 138 -


PREPARATION AND CHARACTERIZATION OF EVA/PS 

NANOPARTICLES/MMT NANOCOMPOSITES 

Saowaroj Chuayjuljit, Chutima Worawas 

Department of Materials Science, Faculty of Science, National Center of Excellence for 

Petroleum, Petrochemicals and Advanced Materials, Chulalongkorn University, Bangkok, 

10330 Thailand 

c.worawas@gmail.com 

Nanocomposites of ethylene vinyl acetate copolymer (EVA)/polystyrene (PS) nanoparticles/montmorillonite 

(MMT) have been prepared by latex compounding. Nanolatex of PS 

were synthesized by differential microemulsion polymerization using sodium dodecyl sulfate 

and 2,2'-azobisisobutyronitrile as a surfactant and an initiator, respectively. Solid content of 

the prepared PS nanoparticles is about 22 %. Particle sizes of less than 50 nm have been 

achieved. Morphology of the obtained nanoparticles was investigated using a transmission 

electron microscope. Blends of EVA and PS at EVA/PS dry weight ratios of 90/10, 80/20 and 

70/30 were mixed with MMT at the amount of 1, 3 and 5 wt% using a high speed mixer at 

3000 rpm for 5 min. The latex mixtures were cast on a glass mold and then compressed into 

thin sheets. After that, the samples were examined for their structures, tensile properties, dynamic 

mechanical properties and morphology using an X-ray diffractometer, universal testing 

machine, dynamic mechanical analyzer and scanning electron microscope, respectively. The 

results showed that the tensile strength and Young’s modulus of the blends were enhanced 

with the addition of MMT at 3 and 5 wt%. In addition, the compatibility of EVA and PS has 

been improved by the incorporation of the MMT. 

- 139 -


SYNTHESIS AND CHARACTERIZATION OF MIXED PROTON 

AND ELECTRON CONDUCTING POLYMER 

NANOCOMPOSITES 

Vijaykumar Ijeri (1), Stefano Bianco (1), Mauro Tortello (2), Lucandrea Cappelletto (1), 

Elena Tresso (1), Paolo Spinelli (1) 

(1) Department of Materials Science and Chemical Engineering, Politecnico di Torino, 

C.so Duca degli Abruzzi 24, 10129 Torino, Italy 

(2) Department of Physics, Politecnico di Torino, C.so Duca degli Abruzzi 24, 10129 Torino, 

Italy 

vijaykumar.ijeri@polito.it 

Carbon nanotubes (CNTs) exhibit extraordinary mechanical, electronic and thermal properties, 

because of which they have been used in several applications like mechanical reinforcement 

of polymers, electrocatalysis, sensors, electronics, batteries, etc. Nafion is a sulfonated 

fluoropolymer that has become standard material in fuel cell applications for its excellent proton 

conducting property, and for its thermal and mechanical stability [1]. 

Recently, Nafion/CNTs composites with CNT amounts less than the percolation threshold 

have been used to increase the mechanical stability and decrease methanol permeation of 

nafion, with very little effect on proton conductivity [2]. Above the percolation threshold, 

such membranes show the potentialities to allow a separate proton/electron conduction paths 

within the membrane. This aspect opens new ways for applications in selective membranes 

for artificial innovative devices capable of using sunlight to produce hydrogen from water 

splitting [3]. 

In our work, Nafion/multi-walled CNTs nanocomposite films with varying amounts of filler 

were fabricated and their proton/electron transport behavior were characterized. Samples were 

prepared by recasting Nafion with CNTs and conditions were optimized to obtain free standing 

films of thickness in the range 15-25 μm. After ultrasonication we observed a uniform 

dispersion of the carbon fillers inside the matrix, with a good affinity between the two materials 

without the need of CNT surface functionalization. Membranes were characterized by 

Scanning Electron Microscopy, Electrochemical Impedance Spectroscopy and Electronic 

Conductivity tests at temperatures ranging from ambient to 100 o C. Under ambient conditions 

the electronic conductivity is of the order of 6 mS/cm for 5 % wt carbon nanotube filling. The 

experimental results will be presented; the effects of the CNTs content, of the humidity and 

temperature conditions will be discussed and interpreted in terms of simple models for electrons 

and protons conduction mechanisms within the membrane. 

[1] L. Carrette, K. A. Friedrich, U. Stimming, Fuel Cells, 1 (2001) 5-39 

[2] J. M. Thomassin, J. Kollar, G. Caldarella, A. Germain, R. Jerome, C. Detrembleur, J. Membrane Sci., 

303 (2007) 252–257 

[3] FP7-Energy, Collaborative project 227192-2 “Solhydromics” 

- 140 -


DSC AND WAXS STUDIES OF COLD CRYSTALLIZATION OF 

PLLANANOCOMPOSITES 

F. Ublekov , J. Baldrian , J. Kratochvil , E. Nedkov 

Institute of Polymers, Bulgarian Academy of Sciences 

ublekov.philip@gmail.com 

In order to study the effect of organophilic clay concentration on crystallization, poly (Llactide 

acid) (PLLA) (MMT) nanocomposites were prepared by mixing various amounts of 

commercial MMT and PLLA. Melt-blending at 190 o C in a brabender for 10 minutes was 

used. Crystallization of PLLAsamples was carried out in following way: after melt mixing at 

190 o C, the samples were rapidly cooled to room temperature at a rate of -20 o C min -1 . The 

effect of MMT content on melting and crystallization behavior of PLLAnanocomposites was 

investigated by DSC and wide–angle x-ray scattering analysis. The study was focused on the 

effect of filler concentration on the thermal and structure properties of non-isothermally crystallized 

nanocomposite PLLA. The results obtained showed that at filler loadings higher than 

5 wt.%, intercalation of the clay is observed. At lower clay concentrations exfoliation dominates. 

DSC and WAXS analysis data show that the crystallinity of PLLAcomposites increases 

remarkably at clay loadings higher than 5 wt.% . Thermal measurements reveale that in neat 

PLLA, PLLA 1wt.% MMT and PLLA 3 wt.% MMT nanocomposites, cold crystallization 

takes place. In nanocomposites with 5, 7 and 9 wt.% clay loading the heat of cold crystallization 

disappears. This phenomenon has to be attributed to hindered PLLA chains movement in 

the clay galleries. In nanocomposite samples containing 1 and 3 wt.% of clay, the reduced 

mobility of PLLA chains leads to decreased enthalpy of cold crystallization. On melting during 

the first run, PLLA chains are released from the organized composite structure and subsequently 

undergo melt and cold crystallization during cooling and reheating. PLLAnanocomposites 

crystallize non-isothermally in an orthorhombic crystal structure, which has to be assigned 

to the α form of PLLA. This significant alternation of the PLLA crystallization behavior 

is definitely due to the presence of Cloisite ® 30B organophilic clay in the system. 

- 141 -


NOVEL CNTS/POLYSTYRENE COMPOSITES BY USING IN 

SITU -POLYMERIZATION AND EXTRUSION 

Minna Annala, Jukka Seppälä 

Helsinki University of Technology, Polymer Technology, P.O.Box 6100, 02015 TKK, Finland 

minna.annala@tkk.fi 

The use of carbon nanotubes (CNTs) in polymer composites opens up new possibilities for 

innovations in advanced functional materials. The challenge in the use of CNTs in polymer 

composites is the production of well dispersed structures in nanoscale and the generation of 

good interfacial adhesion. Direct mixing in solution or melt blending is seldom efficient way 

to obtain a stabile nanoscale dispersion of CNTs. The shear forces in extruders are not high 

enough to break CNTs agglomerates into individual CNTs, which increases the percolation 

threshold and the mechanical properties are not improved significantly. 

Combining in situ -polymerization and extrusion is one solution to produce nanocomposites 

with good mechanical properties and conductivity. Using mild ultrasound treatment to form 

seed emulsion with CNTs and in situ -polymerization of styrene, stabile dispersion of CNTs 

in polystyrene has been obtained. TEM-images confirmed that melt-processing after drying 

the emulsions did not cause reagglomeration of CNTs. There are several advantages in using 

the in situ -polymerized masterbatch in extrusion. The molecular weight of the polymer, the 

surfactant, and the initiator can be tailored to introduce different properties into the masterbatch. 

These properties can be further transferred to the composite in extrusion. For example, 

mechanical properties of the final composite were enhanced in two ways: with good dispersion 

of CNTs and using very high molecular weight of the masterbatch. The morphology of 

the final composites can be modified by using traditional concepts of polymer blending in 

extrusion. 

- 142 -


PHASE BEHAVIOR OF BINARY BLENDS OF BLOCK 

COPOLYMERS WITH COMPLEMENTARILY ASYMMETRIC 

COMPOSITIONS 

Sang-Byung Park, Jeong-Kyu Lee, Jung-Guk Ha, Wang-Cheol Zin 

Pohang University of Science and Technology 

wczin@postech.ac.kr 

We investigated phase behavior of binary blends of block copolymers which have almost 

same molecular weight and complementary composition in respect to composition of blend 

and temperature. The binary blends are composed of two kinds of poly(styrene-b-butadiene) 

block copolymers. One of the block copolymer forms cylindrical microdomains of polybutadiene 

(PB) in polystyrene (PS) matrix and the other is in the disordered state in room temperature. 

Small angle X-ray scattering (SAXS) experiment is performed at various temperature 

during heating to obtain order-disorder transition temperature (TODT) and temperature dependency 

of domain spacing according to the composition. TODT increases as volume fraction 

of one component approaches to 0.5, each blend has larger domains spacing than those of 

neat block copolymers, which means that the mixtures have one microphase due to cosurfactant 

effect. We found that each blend shows different behavior of domain spacing with temperature 

and it is related to composition of disordered block copolymer. From the results, it is 

suggested that the disordered block copolymers leave partially from the interface with temperature 

increases and that the disordered block copolymer is a significant factor to anomalous 

behavior of domain spacing rather than molecular weight ratio. 

- 143 -


NANOCOMPOSITES OF CELLULOSE ACETATE, 

POLY(EPICHLOROHYDRIN) AND ORGANIC-CLAY: 

MORPHOLOGY AND THERMAL BEHAVIOR 

Juliana Aristéia de Lima, Maria Isabel Felisberti, Maria do Carmo Gonçalves 

Instituto de Química, Universidade Estadual de Campinas, PO Box: 6154, 13083-970, 

Campinas – SP, Brazil 

julima@iqm.unicamp.br 

Cellulosic plastics as cellulose acetate (CA), a thermoplastic produced by the esterification of 

cellulose materials such cotton, recycled paper, wood cellulose and sugarcane has already 

been used in several areas, such as filters, membranes, packing films, adhesives, coatings for 

paper and plastic products, electrical isolation and drug delivery systems [1-2]. CA can also 

be considered a good candidate for the preparation of biopolymer-clay nanocomposites owing 

to its potential biodegradability, excellent optical clarity and stiffness [3-5]. However, CA 

suffers from some disadvantages like poor dimensional stability, low softening temperature, 

fair mechanical properties and narrow processibility and thermal sensitivity. By suitable blend 

of CA with the polyepichlorohydrin (PEPi) elastomer some of these problems could be 

avoided. 

In this work, cellulose acetate/poly(epichlorohydrin)/organically modified montmorilloniteclay 

(CA/PEPi/OMMT) nanocomposites were prepared from melting state in a twin-screw 

extrusion and different plasticizers were tested, such as ethyl phthalate and triethyl citrate. 

The influence of plasticizer type on the nanocomposite structures, morphologies and thermal 

properties was investigated by X-ray diffraction (XRD), small angle X-ray scattering (SAXS), 

field emission scanning electron microscopy (FESEM), transmission electron microscope 

(TEM) and dynamical mechanical analysis (DMA). The polymer blend showed immiscibility 

in the range of composition studied. The results indicated a better intercalation of polymer 

chains in the clay gallery in the case of binary (CA/OMMAT) composites as compared with 

the composites prepared in the presence of PEPi elastomer. 

[1] Balser K, Eicher T, Wnadel M, Astheinmer HJ. In: Gerhartz W, Yamamoto YS, editors. Cellulose esters. 

Ulmann’s encyclopedia of industrial chemistry, vol. A5. VCH, 438–57, 1986 

[2] Edgar KJ, Buchanan CM, Debenham JS, Rundquist PA, Seiler BD, Shelton MC, Progress in Polymer Science. 

26, 1605–88, 2001 

[3] Wang XY, Du YM, Luo JW. Carbohydrate Polymer. 69, 41–9, 2007 

[4] Park HM, Mohanty AK, Drzal LT, Lee E, Mielewski DF, Misra M. Journal of Polymer Environment. 14, 

27–35, 2006 

[5] Kim J, Yun S. Macromolecules. 39, 4202–4206, 2006 

- 144 -


CHEMICAL REACTIONS AT CURING OF POLYCYANURATE 

ESTER RESIN/EPOXY FUNCTIONALIZED POLYHEDRAL 

OLIGOMERIC SILSESQUIOXANE BLENDS 

A. Fainleib (1), O. Starostenko (1), O. Grigoryeva (1), B. Youssef (2), J.- M. Saiter (2), 

D. Grande (3) 


Kharkivske shose, 48, 02160 Kyiv, Ukraine 

(2) L’ECAP-PBM-UMR6522, Université de Rouen Site du Madrillet, UFR Sciences, Avenue 

de l’Universite BP 12, 76801 Saint Etienne du Rouvray, France 

(3) Institut de Chimie et des Matériaux Paris-Est, UMR 7182 CNRS, Université Paris XII - 

Val-de-Marne, 2, rue Henri Dunant, 94320 Thiais, France 

fainleib@i.ua 

Polyhedral oligomeric silsesquioxanes (POSS) are interesting organosilicone compounds with 

the formula [RSiO1.5]n, that combine unique hybrid inorganic-organic chemical compositions 

with nanosized cage structures and offer a unique opportunity for preparing truly 

molecularly dispersed composites. POSS reagents can be incorporated into polymer chains to 

modify the local structure the local structure and chain mobility in polymeric materials and 

eventually enhance the mechanical, thermal, and other physical properties of conventional 

polymer systems. These enhancements have been shown to apply to a wide range of thermoplastics 

and just a few thermoset systems. Importantly, POSS molecule may contain a nonreactive 

organic substituent and one or more covalently bonded reactive functionalities suitable 

for grafting, polymerization, or blending with organic polymer. Furthermore, through the 

proper choice of polymerizable R groups, the organic component can be varied to control 

crosslink density about the cube, segment distances between the crosslinks, packing of individual 

cubes with respect to one another, and stability of the cube-organic bond. Cyanate ester 

resins have attracted much interest in recent years because of their excellent properties. Especially, 

cyanate/epoxy composites provide superior performance through the co-reaction between 

cyanate and epoxy groups of blend components, modify crosslink density of the network; 

as a result, fine properties of the final composite are reached. 

In this study, the chemistry and curing kinetics of the model polymer blends of dicyanate ester 

of bisphenol E (DCBE) and three different epoxy functionalized POSS such as PSS-Glycidyl- 

Heptacyclopentyl substituted (PSS-GH), tris[(epoxypropoxypropyl)dimethylsilyloxy]-POSS 

(TE-POSS) and PSS-Octa[(3-glycidyloxypropyl)dimethylsiloxy] substituted (PSS-OCTA) 

were studied. Polymer blends with a ratio of cyanate/epoxy functional groups 1/1 were prepared 

and heated at 150 o C. The kinetics of the blend curing process was monitored using 

FTIR spectroscopy technique. FTIR spectrometer a Bruker Tensor 27 DTGS was used to 

carry out the kinetic investigation. It was found that the polycyclotrimerization of the DCBE 

leading to the formation of a polycyanurate (PCN) network took place along with a coreaction 

between cyanate groups of DCBE and epoxy groups of POSS. Several sequential and 

parallel chemical reactions leading to formation of isocyanurate, oxazolidinone and oxazoline 

heterocycles have been fixed. Finally, after complete conversion of the cyanate groups the 

heterocyclic polymer network containing six- and five-membered cycles in the network junctions 

was synthesized. Some differences in the chemistry and kinetic peculiarities for the 

blends studied have been observed and analyzed. 

- 145 -


PREPARATION AND CHARACTERIZATION OF DENTAL 

NANOCOMPOSITE RESIN 

Baolei Zhu, Mo Zhu, Ling Qi, Qinghong Zhang, Bing Sun, Meifang Zhu 

State Key Lab for Modification of Chemical fibers and Polymer Materials, Donghua University, 

Shanghai, China 

zhumf@dhu.edu.cn 

Resin-based composites incorporating nanofillers are currently among the most popular dental 

restorative materials due to their good esthetic and mechanical properties, which can be used 

to the restoration of anterior lesions and the treatment of smaller and medium-sized defects in 

the posterior region. 

In the present contribution, Series of composite resins with 65 wt% and 50 wt% micro/nano 

filler content have been successfully fabricated by mainly using 2,2-Bis [4-(2-hydroxy-3methacryloyloxy 

propoxy) phenyl] propane (Bis-GMA) as organic matrix, Methacryloxypropyltrimethoxysilane(MPTMS) 

as coupling agent. The properties of the modified silica particles 

by MPTMS have been preliminary characterized by IR, GA, EM, Contact Angle(CA) 

and particle size Analysis. It has been shown that after modification process MPTMS is 

grafted onto the surface of SiO2 particle and the hydrophobic and dispersed properties of SiO2 

particle have been apparently improved by surface modification. The SiO2 particle modified 

by 15 wt% MPTMS has much more excellent performances compared with 5 wt %, 10 wt % 

and 20 wt % MPTMS. The mechanical properties, polymerization shrinkage and compatibility 

between inorganic filler and organic matrix of Poly (Bis-GMA)/Nano-SiO2 composite resins 

have also been evaluated by Vicker’s Microhardness, Flexural Strength, Density Method 

and SEM. It was found that cohesive force between SiO2 and matrix has been enhanced, and 

the polishability and mechanical properties of composites increase as particles size decreases. 

Further studies are focused on their application in dental restoration. 

- 146 -


NOVEL POLYURETHANE BLENDS DERIVED FROM 

POLYETHERIC MACRODIOLS 


Institute of Macromolecular Chemistry “Petru Poni”, Iasi, Aleea Grigore Ghica Voda, 

Nr. 41 A, 700487, Romania 


Two systems of polyurethane elastomers (PU) based on 2,2’-diphenyl methane diisociyanate 

(MDI) and on 4,4’- dibenzyl diisocyanate (DBDI) [1] structures were synthesized. The polyetheric 

macrodiol polytetrahydrofurane (PTHF) was used. When employing MDI, irrespective 

of the approached synthesis route it obtained homogeneous soluble polymers inseparable in 

fractions, by selective dissolution in DMF. The sequence of ordering on the macromolecular 

chain differed from a PU synthesis route to another. DBDI displayed approximately the same 

reactivity as MDI against n-butanol. When employing the ‘one shot’ technique either in solution 

or in melt and using a diisocyanate of variable geometry it obtained PU composites made 

up by two copolymers with a different composition, separable by selective dissolution in dimethylformamide 

(DMF). In opposition, in the case when under the same conditions there 

were used model isocyanates of rigid structure as MDI, it obtained homogeneous soluble 

polymers inseparable in fractions. When DMF was replaced by 1-Methyl-2-pyrrolidinone 

(NMP) the situation changed to the normal behaviour similar to the MDI based PU reaction. 

In this case the interaction between solvent-oligomer was higher than the interaction between 

polymer-oligomer, and it obtained only a single type of soluble copolymer. As a result of the 

polyaddition of the DBDI based PU by the ‘one shot‘ synthesis route in melt, it obtained 

opaque solid elastomer blends which contained 2 copolymers simultaneously, one of which 

was soluble in DMF (87 %), the other was insoluble in DMF (12 %). On approaching the ‘one 

shot’ synthesis in solution it obtained a suspension containing simultaneously 2 copolymers 

one of which was soluble in DMF (72.5 %), the other was insoluble in DMF (27.5 %). When 

replacing DMF by NMP, it obtained a homogeneous viscous solution which contains 1 single 

copolymer. With regard to the heterogeneous synthesis with DMF, it should be mentioned 

that the NMR analysis has revealed that in comparison to the soluble polymer, the insoluble 

polymer has a high content of hard segments. Unexpectedly, the molecular weights of these 

polymers, expressed by the inherent viscosity in solution of NMP, are very closed to each 

other. 

[1] Prisacariu C.; Buckley C.P.; Caraculacu A, PU Deutsche Magazin, (2006), 4, 253- 258. 

- 147 -


STRESS RELAXATION AND RESIDUAL STRAIN OF POLY- 

URETHANE ELASTOMERS AND FILMS BASED ON 

DIBENZYL MONOMERS 


Institute of Macromolecular Chemistry “Petru Poni”, 

Iasi, Aleea Grigore Ghica Voda, Nr. 41 A, 700487, Romania 


A series of polyurethane (PUs) materials including elastomers, and films based on dibenzyl 

monomers have been achieved. These monomers belong to a large category of diaromatic 

compounds with a variable geometry which induces significant effects in the macromolecular 

chains, especially those in connection to the rearranging capacity of the molecular fragments 

and thus to a pronounced increase in the degree of crystallinity. The introduction of these 

structures on the main backbone of a PU long chain molecule compels the chains to adopt a 

special conformation in which the two phenyl rings are separated by an ethylenic bridge giving 

rise to a biaromatic system which is able to display rotational isomerism. In the solid state, 

in the absence of substituents, the two aromatic rings of dibenzyl are situated in parallel 

planes. The angle between the plane and the –CH2-CH2- linkage is 70.5 0 [1]. A series of intermediates 

with two identical functional groups situated in different rings were synthesized: 

2,2’-, 2,4’- and 4,4’- dibenzyldiisocyanate (DBDI) [1]. They were compared to similar materials 

based on the rigid model diisocyanate diphenilmethane (MDI). An investigation was 

made of the effects of varying hard and soft segment chemistry, crosslinking and preparation 

procedures, on the mechanical response of melt-cast PUs. The soft segment macrodiol was 

polytetrahydrofuran (PTHF), poly(buthylene adipate) (PBA), or poly(ethylene adipate) (PEA) 

of molar mass 2000±50. The chain extenders were ethylene glycol (EG), 1,4-butanediol (BG) 

or diethylene glycol (DEG). The role of the hard segment structure was also investigated. In 

particular, three hard segments were compared, based on the diisocyanates: 4,4'-methylene 

bis(phenyl isocyanate) (MDI), 1,5-toluilene diisocyanate (TDI) and DBDI. Rotation around 

the central –CH2-CH2- bridge in DBDI allows alignment of aromatic rings and hence crystallization 

within the hard phase, which is not available with MDI and other rigid conventional 

isocyanates in melt-cast polyurethanes. The degree of phase segregation and degree of crystallinity 

of the hard segment was varied systematically by changing the choice of hard segment 

and chain extender, and by the use of annealing treatments.. Stress relaxation in interrupted 

tests was found to increase with the hard segment crystallinity, reflecting the higher flow 

stress of the reinforcing hard domains. The presence of DBDI hard segments instead of MDI 

led systematically to increases in the residual strain under cyclic loading, and stress relaxation. 

The observed effects of varying hard segment could all be explained by the hard domains 

having a higher flow stress in the presence of DBDI relative to MDI, associated with 

increased hydrogen bonding in DBDI-based polymers, which is enhanced by hard segment 

crystallinity. 

[1] Prisacariu C, Olley RH, Caraculacu A, Bassett DC and Martin C. Polymer 2003; 44: 5407. 

- 148 -


SYNTHESIS AND CHARACTERIZATION OF SEGMENTED 

POLYURETHANE ELASTOMERS WITH AN ENHANCED 

SEQUENTIAL ORDERING OF THE HARD SEGMENTS 


Institute of Macromolecular Chemistry Petru Poni,Aleea Grigore Ghica Vodă Nr. 41 A, 

700487, Iasi, Romania 


A series of polyurethane (PU) elastomers was achieved based on the chain extenders (CE) 

diethylene glycol (DEG) and ethylene glycol (EG), and macrodiols poly(ethylene adipate 

(PEA), polyterathydrofuran (PTHF) and poly(tetramethylene adipate) (PBA). The hard segments 

were based on the following isocyanates (I): the dibenzylic monomer 4,4’-dibenzyl 

diisocyanate (DBDI) [1] or the model 4,4’-diphenyl methane diisocyanate (MDI). Different 

synthesis routes were approached. When the reaction rate of the soft (S) and hard (H) segments 

inclusion on the increasing macromolecular chain was equal, it obtained a statistical 

sequential distribution of the H and S segments. When the H and S reaction rates were unequal 

there appeared initially accumulations on the increasing chain of the sequences characteristic 

to the quickest process, followed by consequently bonding of the sequences which 

formed with a slower rate. To assess the effect of hard and soft segment order on the PUs 

stress-strain behaviour, three types of polymers were achieved: (a) materials with a complete 

uncontrolled H and S segment ordering obtained by the one-step one shot preparation technique; 

(b) similar PUs but with an usual quasi ordered structure of the H and S segments, obtained 

via the prepolymer polyaddition procedure; (c) materials with an enhanced sequential 

ordering of the type -S-HH-S-HH-S-HH- made up by a special inverse step by step synthesis 

which started with the construction of a hard ordered reactive intermediate of the type OCN- 

HH-NCO (or I-CE-I-CE-I) structure and only then reacted with the macrodiol. The structural 

changes and variation of the stress-strain data were followed. A high sequential ordering of 

the hard and soft domains determined a higher tendency of phase separation and crystallization 

and a moderate decrease in the PU elastomeric character. Changing the preparation technique 

from a PU sheet as casted from synthesis to a film obtained by evaporation, resulted in 

an improvement of the mechanical properties, especially in the case of the materials derived 

from DBDI and EG, with a significant crystallinity, In the case of the polymer of the type (c) 

with an induced structural sequential ordering, the energy recovered on load/unload cycles to 

a 300 % level of stretching was always higher with MDI than with DBDI due to the flow 

stress of the hard phase relative to the stress required to deform the elastic soft phase which 

was higher with DBDI than with MDI, irrespective of the adopted chain extender (DEG or 

EG). In all of the cases, the SAXS peak areas of all the materials based on the polyetheric 

macrodiol PTHF were much higher than the those of the materials derived from the polyesteric 

macrodiols PEA PBA, indicating a higher degree of phase separation. 

[1] Prisacariu C, Olley R.H., Caraculacu A., Bassett D.C. and Martin C., -Polymer 44, 5407- 5421, 2003. 

- 149 -


TENSILE MODULUS AND HYSTERESIS BEHAVIOUR OF 

SEGMENTED POLYESTERIC COPOLYURETHANES BASED 

ON SINGLE OR MIXTURES OF ISOCYANATES 


The Romanian Academy’s Institute of Macromolecular Chemistry Petru Poni, Iasi, Romania 


A study was made of how aspects of the mechanical responses of block copolyurethane elastomers 

(PUs) vary with composition. PUs hard segment, soft segment and chain extender 

were varied systematically. Hard segments were chosen to be generated from 4,4’-methylene 

bis(phenyl isocyanate) (MDI), or from 4,4’-dibenzyl diisocyanate (DBDI) [1], or from mixtures 

of these diisocyanayes. A further series of mechanical tests was designed to compare 

inelasticity of the various polyurethane elastomers under cycling to fixed and/or increasing 

extension. The materials were cycled between an extension of 3, and zero load, for 3 cycles. 

Notable features were the pronounced hysteresis, unrecovered strain and Mullins effect, 

whereby re-loading follows a stress-strain path closer to the unloading path than the original 

loading path. The dominant result from these tests was the differences between polymers 

based on the two hard segments DBDI, MDI or mixtures of these. For all combinations of 

chain extender and macrodiol, residual strain and hysteresis energy dissipation were highest 

for hard segments of DBDI than of MDI. Some large variations were found in the responses 

to first loading to a given strain. Tensile modulus and work input increased significantly with 

degree of hard phase crystallinity, but were independent of degree of phase separation. First 

cycle hysteresis was found to increase with reduced phase separation and with replacement of 

MDI by DBDI. For second and subsequent load cycles, below the previous maximum strain, a 

remarkable degree of uniformity of response was observed, with all materials showing much 

lower relative hysteresis than on first loading, and thereby exhibiting the Mullins effect. A 

unique linear relation was obtained between second cycle hysteresis and second cycle work 

input, for all strain levels, and also for all materials which showed slightly lower second cycle 

hysteresis. 

[1] E. Scortanu, C. Prisacariu, A. Caraculacu, High Performance Polymers, 16, (1), (2004), 113-121 (2004). 

- 150 -


THE SELF-ASSEMBLY OF AMPHIPHILIC MACRO- 

MOLECULES 

Valentina Vasilevskaya 

Nasmeyanov Institute of Organoelement Compounds, Russian Academy of Science 

The self-assembly of macromolecules containing amphiphilic A, i. e. (H-graft-P), monomer 

units is studied by means of computer modeling. 

Amphiphility of each monomer unit favors structures with rather large surface allows monomer 

units arrange themselves at the surface so that the hydrophobic part are on the inside of 

the globule, and the hydrophilic part are exposed to the solvent. Such monomer unit structure 

is, in particular, responsible for the stage of pearl-necklace comprised by micellar structures 

appearing in the coil-globule transition of amphiphilic macromolecules. It was found that at 

compacted state the amphiphilic macromolecules can form cylindrical, tor, disk-, and collagen-like 

structures, as well as structures with elements of secondary structures. The globule 

shape of macromolecules consisting of amphiphilic units depends on the value of the interaction 

parameters, the macromolecular length, the stiffness of macromolecule and its composition. 

The self-assembly in concentrated solution of such macromolecules is considered as 

well. 

- 151 -


POLY(LACTIC ACID)/POLY(3-HYDROXYBUTYRATE-CO-3- 

HYDROXYVALERATE) BLENDS: TOUGHENING EFFECT OF 

PHBV 

P. Ma (1), D. G. Hristova-Bogaerds (1), P. J. Lemstra (1), Sh. Wang (2), Y. Zhang (2) 

(1) Faculty of Chemistry & Chemical Engineering, Technische Universiteit Eindhoven, Eindhoven, 

the Netherlands 

(2) Shanghai Jiao Tong University, Shanghai, 200240, China 

p.ma@tue.nl 

Fully biodegradable and bio-based polymer blends consisting of poly (lactic acid) (PLA) and 

poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) were prepared by melt blending in a 

Haake mixer. Phase morphology and mechanical properties of the blends were investigated. 

The two polymers were found immiscible in all their blends. The tensile strength and modulus 

of the blends containing 10-30 wt% PHBV decreased with 40-50 % in comparison to the values 

of these parameters for pure PLA. Interestingly, for those blends a dramatic increase of 

the elongation at break was observed - from 5 % for neat PLA to more than 220 % for 

PLA/PHBV=80/20 wt% blend. A change in the fracture behavior from brittle to ductile after 

incorporation of 10-20 wt% PHBV into the PLA matrix was observed and the measured impact 

strength for those blends showed values one order of magnitude higher than the values 

for neat PLA. The phase morphology of the blends was investigated and a mechanism for the 

toughening effect of PHBV on PLA is proposed. 

- 152 -


ETHYLENE VINYL ACETATE/CELLULOSE COMPOSITES: 

FUNCTIONAL MODIFICATION, MORPHOLOGY AND PHASE 

INTERACTIONS 

Md. Minhaz-Ul Haque (1), Vera Alvarez (2), Mariano Pracella (3) 

(1) Dept. of Chemical Engineering & Materials Science, University of Pisa, Pisa, Italy 

(2) Polymer Division, INTEMA-CONICET, University of Mar del Plata, Mar del Plata, 

Argentina 

(3) Institute of Composite and Biomedical Materials, IMCB-CNR, Pisa, Italy 

minhaz1978@yahoo.com 

Incorporation of cellulosic fibres into polymers matrices offers the possibility to design new 

composite materials with reduced environmental impact, due to the biodegradability, renewability 

and low cost of natural fillers. Indeed, good dispersion of fibres in the polymer matrix 

and good adhesion is an important prerequisite for obtaining good mechanical properties of 

the resulting composites. To increase the compatibility of the components, improving the interfacial 

adhesion and fibre dispersion within the polymer matrix, either surface modification 

of fibre and/or matrix are necessary [1-2]. 

The present communication is aimed at analysing the effect of compatibilization processes of 

ethylene vinyl acetate (EVA) composites with natural fibres, such as cellulose and hemp, on 

the morphological, thermal and mechanical properties. The composites were obtained by melt 

mixing EVA copolymers of different types with fibre contents in the range of 20-50 wt% using 

a Brabender internal mixer. Commercial samples of EVA (28 wt.% vinyl acetate), maleic 

anhydride grafted EVA (EVA-MA) and glycidyl methacrylate modified EVA (EVA-GMA) 

were used. The effect of polymer functionalization, fibre treatment and content, on the composite 

properties was then examined by SEM, FT-IR, NMR, DMTA, DSC, TGA and tensile 

mechanical tests. 

FT-IR spectroscopy demonstrated the occurrence of chemical interactions between the functional 

groups (MA, GMA) of EVA and the hydroxyl groups of cellulose. Accordingly, SEM 

microscopy pointed out a strong interfacial adhesion in both EVA-MA/Cell and EVA- 

GMA/Cell composites, as compared to EVA/Cell composites. DSC data indicated that the 

crystallization temperature of the polymer matrix increases in the presence of cellulose fibres, 

supporting a nucleating effect of cellulose on the growth of polymer crystals from the melt. 

Glass transition behaviour and filler effectiveness (FE) were analysed by DMTA [3]. Cellulose 

was found to be more effective filler for EVA-GMA (FE= 0.02) compared to EVA-MA 

(FE= 0.22). Tg of EVA and EVA-GMA was changed by the incorporation of cellulose fibre 

markedly. Tensile tests pointed out a consistent increase of elastic modulus (> 700 %) with 

the filler content for all examined systems. Samples containing GMA grafted copolymers displayed 

larger changes of tensile strength and failure strength. Finally, significant changes of 

tensile parameters were also observed for composites of EVA-MA with esterified hemp fibres, 

supporting the occurrence of enhanced fibre-matrix interactions in the presence of anhydride 

groups on EVA copolymers. 

[1] Pracella M., Chionna D., Anguillesi I., Kulinski Z., Piorkowska E, Composite Sci. Technol., 2006, 66, 

2218-2230 

[2] Pracella M., Guerra G D., M. Minhaz-Ul Haque, Barbani N., Piorkowska E., Proc. Int. Conf. on Science & 

Technology of Composite Materials, San Sebastian (E), 2009, 643-646 

[3] Pathan L A, Oommn Z, Thomas S. Composites Sci. Technol. 2003, 63, 283-293 

- 153 -


INVESTIGATION OF PHYSICOCHEMICAL PROPERTIES 

AND MICRO-STRUCTURE OF CITRIC ACID/GLYCEROL 

BLENDED CORN STARCH 

Ebru Uslu (1), Sevilay Atmaca (1), Sebnem Kemaloglu (1), Semin Ozge Ozkoc (2), 

Guralp Ozkoc (1) 

(1) Department of Chemical Engineering, Kocaeli University, 41380, Kocaeli-Turkey 

(2) The Scientific and Technological Research Council of Turkey, MRC, 41470, Kocaeli, 

Turkey 


The aim of this study is to investigate the properties of corn starch blended with glycerol and 

citric acid (CA) in order to prepare plasticized thermoplastic starch. In the context of this 

study, vertical force (an indication of polymer melt viscosity), water solubility index (WSI), 

glass transition temperature, and micro-structure of co-plasticized starch samples were examined 

as a function of different citric acid contents and different screw speeds. Additionally, 

FTIR and X-ray spectra of the samples were also obtained in order to understand the changes 

in chemical structure. Vertical force results demonstrated that citric acid addition resulted in 

decrease in vertical force indicating a decrease in melt viscosity, meaning that citric acid is a 

good plasticizer for glycerol/starch system. As citric acid content increased, solubility of 

starch, accordingly WSI values increased, glass transition temperature of the samples decreased. 

According to DSC analysis, it was seen that as screw speed increased, glass transition 

temperature of samples, at any CA content, decreased. X-ray patterns of samples including 

glycerol and citric acid, at varying concentrations were obviously different than native starch. 

It was proven by FTIR spectroscopy that CA can form stronger hydrogen bonds with starch 

rather than glycerol. Screw speed was not found to be significantly effective on crystal structure 

of samples. It can be seen from SEM pictures that as CA introduced to the matrix, number 

of residual granular structures decreased. Moreover, it was observed that residual starch 

granules were smaller and far away from each other in samples including CA. 

- 154 -


PREPARATION AND CHARACTERIZATION OF POLYMER 

ELECTROLYTE MEMBRANES BASED ON POLY(1-VINYL- 

1,2,4 TRIAZOLE) AND POLY(STYRENE SULFONIC ACID) 

Ayşe Aslan (1), Sevim Ünügür Çelik (1), Ünal Şen (2), Ayhan Bozkurt (1) 

(1) Fatih University, Department of Chemistry, 34500, Büyükcekmece, Istanbul, Turkey 

(2) Gebze Institute of Technology, Materials Science and Engineering, 41400, Gebze, 

Kocaeli, Turkey 

bozkurt@fatih.edu.tr 

During the last decade, research trend has been focused on the development of anhydrous or 

low humidity polymer electrolytes to maintain adequate proton conductivity at higher temperatures. 

New class of polymer electrolyte membranes (PEM) was produced by the combination 

of Poly(1-vinyl-1,2,4 triazole) (PVTri) and Poly(styrene sulfonic acid) (PSSA) at several 

stoichiometric ratios with respect to molar ratio of polymer repeating units. PVTri was synthesized 

by free radical polymerization of the monomer, 1-Vinyl-1,2,4-triazole and PSSA was 

produced from polystyrene by direct sulfonation. The proton exchange reaction which resulted 

in complexation between polymers was illustrated by FT-IR spectroscopy. Thermogravimetric 

analysis (TGA) showed that the membranes are thermally stable up to approximately 

300 o C. The existence of glass transition temperatures of the polymer electrolytes were shown 

by differential scanning calorimetry (DSC). The surface morphology of the membranes was 

illustrated by scanning electron microscopy (SEM) and also the results demonstrated the homogeneity 

of the materials. The electrochemical stability of the materials was studied by cyclic 

votammetry (CV). Proton conductivities of the anhydrous samples were measured using 

impedance spectroscopy. Under anhydrous state, maximum proton conductivity of 

PVTriP(SSA)4 and PVTriP(SSA)2 membranes was measured as 0.015 S/cm at 150 o C and 

0.033 S/cm at 120 o C, respectively. 

- 155 -


THE NON-ISOTHERMAL CRYSTALLIZATION KINETICS OF 

UNPLASTICIZED AND PLASTICIZED POLY(LACTIC ACID)/ 

ORGANOCLAY NANOCOMPOSITE FILMS 

Serap Gumus, Guralp Ozkoc, Ayse Aytac 

Kocaeli University, Department of Chemical Engineering, Umuttepe Campus, 41380, 

Izmit-Kocaeli, Turkey 


The aim of this study is to examine the non-isothermal crystallization kinetics of plasticized 

PLA nanocomposite films. Melt intercalation technique was used to prepare nanocomposites. 

The plasticizer was poly(ethylene glycol) at a content of 20 %. Differential scanning calorimetry 

(DSC) method was used to investigate the non-isothermal crystallization behavior of 

samples. Different kinetic models such as Avrami, Ozawa, combined Ozawa and Avrami 

models were utilized. It was seen that plasticization of PLA accelerated the crystallization due 

to enhanced chain mobility, whereas clay addition decreases the crystallization rate at any 

cooling rates. Furthermore, the Avrami plots showed that the primary crystallization of the 

samples could be “two-dimensional crystal growth” with thermal nucleation. The nucleation 

activity of the organoclays is determined using a simple method suggested by Dobreva and 

Gutzow. It was concluded that clay acted as a nucleation agent. 

- 156 -


LIQUID SENSING PROPERTIES OF MELT-PROCESSED 

POLYPROPYLENE AND POLY(ε-CAPROLACTONE) 

BLENDS WITH CARBON NANOTUBES 

Petra Pötschke (1), Kazufumi Kobashi (1,3), Tobias Villmow (1), Timo Andres (1), 

José António Covas (2), Maria Conceição Paiva (2) 

(1) Department of Polymer Reactions and Blends, Leibniz Institute of Polymer Research 

Dresden, Hohe Str. 6, 01069 Dresden, Germany 

(2) Institute for Polymers and Composites, Department of Polymer Engineering, University of 

Minho, 4800-058 Guimarães, Portugal 

(3) National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Japan 

poe@ipfdd.de 

The liquid sensing properties of polymer blends based on poly(ε-caprolactone) 

(PCL)/polypropylene (PP) blends filled with multi-walled carbon nanotubes (MWNT) were 

investigated in terms of electrical property changes. The sensing experiments included compression-moulded 

disks and melt-drawn filaments. The composites resistance evolution during 

immersion in n-hexane, ethanol, methanol, water, toluene, chloroform, and tetrahydrofuran 

and subsequent drying in air was recorded. 

Co-continuous blends with double percolated networks were prepared by melt mixing of electrically 

conductive PCL/3.0 wt% MWNT composite with neat PP. The percolation threshold 

for PCL/MWNT was determined at 0.5 wt%. The PCL/PP/3.0 wt% MWNT composites presented 

a co-continuous structure over a broad range of blend compositions, whereas the nanotubes 

were localized in the PCL phase. The electrical percolation threshold of these blends 

was found at an overall nanotube concentration of 1.05 wt% for a PCL/PP composition of 

35/65. 

In order to compare the sensing properties of the blends with conductive PCL/CNT composites, 

these single-phase composites containing 0.5 to 3 wt% MWNT were tested regarding 

their relative resistance changes during immersion in various solvents. Composites with lower 

MWNT content and thus less dense nanotube network presented larger resistance changes. 

This effect was further enhanced for immersion of composites in good solvents. 

PP and PCL were tested separately regarding their solvent sorption behaviour towards ethanol 

and n-hexane. Both showed a low mass uptake of n-hexane over time, whereas the ethanol 

sorption was large for PCL and almost absent for PP. The 50/50 blend composites with 3 wt% 

MWNT presented greater resistance changes for n-hexane, showing larger sensing ability for 

this solvent compared to PCL composites. The opposite response was observed for immersion 

in ethanol. This behaviour may be interpreted as follows: since both polymer phases adsorb nhexane, 

the nanotube rich phase (PCL) will be spatially more constrained during immersion in 

n-hexane as compared to ethanol, resulting in a faster disconnection of the nanotube network. 

The sensing ability of compression-moulded disks and extruded filaments of PCL/PP/3.0 wt% 

MWNT was compared. Samples with similar area-to-volume ratio were tested in poor and 

good solvents, showing good sensing ability. However, compression-moulded disks presented 

larger relative resistance changes for all tested solvents. This behaviour might be due to differences 

in the co-continuous blend morphology developed in the samples prepared by these 

two different sample shaping techniques. 

We gratefully acknowledge the financial support from INTELTEX (Intelligent multi-reactive 

textiles integrating nano-filler based CPC-fibres), a European Integrated Project supported by 

the Sixth Framework Programme for Research and Technological Development of the European 

Commission (NMP2-CT-2006-026626). 

- 157 -


EVALUATION OF PVA/GUAR GUM BASED POLYMER 

BLEND FILMS 

A. P. Gupta, Gopal Arora 

Delhi Technological University (formerly Delhi College of Engineering), Bawanna Road, 

Delhi 110042, India 

argopaldce2k7@rediffmail.com 

Guar gum is dispersible in cold or hot water to produce a colloidal dispersion of exceptionally 

high viscosity these properties make guar gum a highly valued gum in the food textile, cosmetics, 

pharmaceuticals, drilling and oil recovery industry, Guar gum is a natural polysaccharide 

which is capable of forming film by using the solution casting techniques. A series of 

blend films made of polyvinyl alcohol-Guar gum (PVA-GG) and polyvinylalcoholhydroxypropyl 

Guar gum (PVA-HGG), is to be prepared by solution casting. The aim of this 

project was to study the varying concentration of citric acid and glycerol on the solution blend 

of (PVA-GG) and (PVA-HPG) and was dried at room temperature. The miscibility and other 

properties were studied by Fourier Transform Infrared Spectroscopy FTIR, Wide Angle X-ray 

Diffraction, Thermal Stability and the Glass Transition temperature were studied by Thermogravimetric 

(TG) and Differential Scanning Calorimetry (DSC).Guar gum is known to give 

brittle films with extremely poor flexibility, films based on Guar gum and it’s derivative are 

important because of their therapeutic value on tropical drug Delivery system. The nontoxic 

properties of citric acid will benefit the incorporation of citric acid in PVA-GG and PVA- 

HPG films would have potential application in biomedical fields. 

- 158 -


FUNCTIONAL PROTEIN-POLYMER BLENDS ON THE BASIS 

OF POLYACRYLAMIDE GEL AND GUMIC ACIDS FOR 

SORPTION IMMOBILIZATION OF ENZYMES 

Gulnara A. Bektenova 

A. B. Bekturov Institute of Chemical Science, 050010, Almaty, Sh. Walikhanov Str. 106, 

Republic of Kazakhstan 

gbektenova@rambler.ru 

Investigation of possibility of use new polymer materials for sorption immobilization or bioseparation 

of proteins and enzymes is one of the main goals of polymer chemistry and applied 

enzymology. In this aspect functionalization or modification of synthetic and natural polymers 

to give them the new useful properties plays a big role. 

Sorption properties of gumic acids (GA), obtained from dark-brown coals, are generally wellknown. 

They are caused by presence of functional groups such as carboxylic, phenolic, quinoid 

and also paramagnetic centers in a structure. Owing to complex forming abilities, ion 

exchange properties and high enough sorption capacity, GA can be attributed to perspective 

natural sorbents. However use of GA as independent sorbents is districted by their insufficient 

technological properties that connected with their solubility. In this connection we used gumic 

acids as modifying agents to improve their exploitational and technological characteristics as 

well as for functionalization of polyacrylamide (PAAm) gel to increase its sorption capacity. 

Several species of hydrogels with different content of GA, included in composition of PAAm 

during polymerization, have been obtained. Some their properties and sorption interaction 

with proteins on the example of enzyme catalase were investigated. Obtained results permit to 

recommend this polymeric ion exchange swelling materials as effective adsorbents for sorption 

purification and bioseparation of proteins as well as carriers for sorption immobilization 

of enzymes. 

Immobilized preparations of catalase have been obtained and some their properties as well as 

biocatalytic activity in different conditions have been investigated. It was shown that additional 

functionalization of PAAm gel with gumic acids is followed both by increasing of enzyme 

sorption and its stability at storage. 

- 159 -

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Kerstin Wustrack 

Ulrike Schulze 

Julia Dorok 

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