Universal testing machine Zwick/Roell Z005, 5kN cell ... - irasm.ro

Horia Hulubei National
Institute of Physics and
Nuclear Engineering
ARCON - PN2/92083/2008
Disinfestation by ionizing radiation: A chance for
future of archives
Physical, chemical and
microbiological tests for
irradiation of paper
Ioan Valentin Moise 1 , Marian Virgolici 1 , Mihaela Manea 1 , Mihalis Cutrubinis 1 ,
Daniel Negut 1 , Rodica Maria Georgescu 1 , Mioara Alexandru 1 , Laura Trandafir 1 ,
Florina Lucica Zorila 1 , Mihai Constantin 1 , Ioana Stancurescu, 1, 5 Catalina Mihaela
Talasman 2 , Maria Haiducu 3 , Elena Ilie 4
1 IFIN-HH – “Horia Hulubei” National Institute for Physics an Nuclear Engineering
2 CEPROHART SA – Pulp and Paper Research Institute
3 – “Alexandru Darabonţ” National Institute for Work Safety
4 – Braila Museum
5 – University of Bucharest, Physical Chemistry Department

Mechanical properties vs. TGA/DSC
� Materials:
• Xerox Business, 80g/m 2 , 0.1mm;
• Ceprohart, 80g/m 2 , , 0.1mm;
• Whatman (nr. 42, ICHR)
• Hardwood and softwood pulp (chemically bleached)
May 2011- IAEA TC
RER/8/015
• Watermark paper Letea SA (1996)
• Coated paper SC GHIMBAV SA (1996)
• Neutral sized copy paper Austria (2006)
• Pronosport paper 70 g/m2 (1996)
• 1A type paper 60 g/m2 (1996)
- Book printed in 1923 in France (private collection)
- Official Journal of RSR (newspaper) – 1968 (IFIN-HH archive)
- Book printed in 1894 (Perspessicius Collection – Braila Musem)
RTC on Demonstration of Techniques
for Cultural Heritage Protection 2

Mechanical properties vs. TGA/DSC
May 2011- IAEA TC
RER/8/015
� Methods:
IFIN-HH: <strong>Universal</strong> <strong>testing</strong> <strong>machine</strong>
<strong>Zwick</strong>/<strong>Roell</strong> <strong>Z005</strong>, <strong>5kN</strong> <strong>cell</strong>; <strong>testing</strong> speed: 10
mm/min
TENSILE TEST: Samples according to ISO 3167 type 1A and
ISO 37 type 1; TEAR TEST: Samples according to ISO 8067;
PUNCTURE: ISO 3036:1975Conditioning: 24 hours at 23°C
and 50% rH;
CEPROHART SA: <strong>Universal</strong> <strong>testing</strong> <strong>machine</strong>
INSTRON 4411, 5 kN force <strong>cell</strong>, test speed:
20 mm/min
– accredited pulp and paper <strong>testing</strong> laboratory (ISO 536,
ISO 534, ISO 1924/2, EN 21974, ISO 2471, STAS 4748, ISO
2470, ISO 5627, ISO 2758, EN 20535, ISO 5626 )
Netzsch STA 409
PC Luxx
Simultaneous
Thermal Analyzer -
TG/DSC-S sample
carrier, inert (nitrogen,
40-80 ml/min) and
oxidative (sintetic air,
40 ml/min) dynamic
atmosphere at
2,5,10,20 K/min.
RTC on Demonstration of Techniques
for Cultural Heritage Protection 3

Thermo-Gravimetric Analysis Differential Scaning Calorimetry
TG /%
90
80
WHATMAN
[1.6] DSC-S-10K-N2-WHATMAN-W0-100717.dsv
TG
70
BORSR-1968
[3.6] DSC-S-10K-N2-BORSR-68-P0-100710.dsv
TG
60
50
40
30
20
10
CALENDAR [4.6] DSC-S-10K-N2-CALENDAR-CP0-100726.dsv
1894
TG
150
DTG /(%/min)
200 250 300 350
Temperature /°C
400 450 500 550
0
-5
-10
-15
-20
150 200 250 300 350
Temperature /°C
400 450 500 550
May 2011- IAEA TC
RER/8/015
WHATMAN
[1.6] DSC-S-10K-N2-WHATMAN-W0-100717.dsv
DTG
BORSR-1968
[3.6] DSC-S-10K-N2-BORSR-68-P0-100710.dsv
DTG
CALENDAR [4.6] DSC-S-10K-N2-CALENDAR-CP0-100726.dsv
1894
DTG
DSC /(mW/mg)
1.0
0.5
0.0
-0.5
-1.0
↑ exo
WHATMAN
[1.6] DSC-S-10K-N2-WHATMAN-W0-100717.dsv
DSC
BORSR-1968
[3.6] DSC-S-10K-N2-BORSR-68-P0-100710.dsv
DSC
CALENDAR [4.6] DSC-S-10K-N2-CALENDAR-CP0-100726.dsv
1894
DSC
150 200 250 300 350 400 450 500 550
Temperature /°C
STA = Simultanous
Thermal Analysis
RTC on Demonstration of Techniques
for Cultural Heritage Protection 4

NETZSCH Peak Separation Project: TG CEPROHART
dMass/dt/(%/min)
0
-2
-4
-6
-8
-10
DTG /(%/min)
0
-5
-10
-15
-20
-25
0 kGy
100 200 300 400 500
Temperature/°C
May 2011- IAEA TC
RER/8/015
[4.6] HARTIE_WHATMANN42-0kGy-TG-DSC-S-10K-N2-3-scan 50-600C-090804.dsv
DTG
[5.6] HARTIE_WHATMANN42-5kGy-TG-DSC-S-10K-N2-1-scan 50-600C-090714.dsv
DTG
[6.6] HARTIE_WHATMANN42-10kGy-TG-DSC-S-10K-N2-1-scan 50-600C-090714.dsv
DTG
[7.6] HARTIE_WHATMANN42-25kGy-TG-DSC-S-10K-N2-1-scan 50-600C-090715.dsv
DTG
[8.6] HARTIE_WHATMANN42-50kGy-TG-DSC-S-10K-N2-1-scan 50-600C-090731.dsv
DTG
[9.6] HARTIE_WHATMANN42-100kGy-TG-DSC-S-10K-N2-1-scan 50-600C-090801.dsv
DTG
150 200 250 300 350 400
Temperature /°C
NETZSCH Peak Separation Project: TG CEPROHART
dMass/dt/(%/min)
0
-2
-4
-6
-8
-10
100 kGy
100 200 300 400 500
Temperature/°C
RTC on Demonstration of Techniques
for Cultural Heritage Protection 5

100
80
60
40
20
0
50
40
30
20
10
Mechanical properties vs. TGA/DSC
0
F break, MD / N
0 50 100 150 200
Dose / kGy
F break, CD / N
0 50 100 150 200
Dose / kGy
May 2011- IAEA TC
RER/8/015
50
45
40
35
30
25
20
DSC Area / J/g
0 50 100 150 200
Dose / kGy
Rank Xerox
RTC on Demonstration of Techniques
for Cultural Heritage Protection 6

100
50
40
30
20
10
80
60
40
20
0
Mechanical properties vs. TGA/DSC
0
Fbreak, MD / N
May 2011- IAEA TC
RER/8/015
y = -0.2005x + 83.974
R 2 = 0.9954
0 25 50 75 100 125 150 175 200
Dose / kGy
Fbreak, CD / N
y = -0.0285x + 27.117
R 2 = 0.9875
0 25 50 75 100 125 150 175 200
Dose / kGy
DSC Area, J/g
50
45
40
35
30
25
20
y = -0.0282x + 42
R 2 = 0.9413
0 25 50 75 100 125 150 175 200
Dose / kGy
Rank Xerox
RTC on Demonstration of Techniques
for Cultural Heritage Protection 7

100
40
30
20
10
80
60
40
20
0
Mechanical properties vs. TGA/DSC
0
Fbreak, MD / N
May 2011- IAEA TC
RER/8/015
y = -0.8144x + 88.062
R 2 = 0.9653
0 3 6 9 12 15 18 21 24
Fbreak, CD / N
Dose / kGy
y = -0.1876x + 25.683
R 2 = 0.6254
0 3 6 9 12 15 18 21 24
Dose / kGy
50
45
40
35
30
DSC Area, J/g
y = -0.1429x + 45.125
R 2 = 0.8308
0 3 6 9 12 15 18 21 24
Rank Xerox
Dose / kGy
RTC on Demonstration of Techniques
for Cultural Heritage Protection 8

Mechanical properties vs. TGA/DSC
Lbreak, MD / m
8000
7000
6000
5000
4000
0 3 6 9 12 15
DSC Peak -1 / 100/K
0.17
0.165
0.16
May 2011- IAEA TC
RER/8/015
Dose / kGy
0.155
0 3 6 9 12 15
Dose / kGy
Lbreak, MD/ m
Rank Xerox Whatman
4000
3500
3000
2500
2000
0.157
0.156
0.155
0.154
0 3 6 9 12 15
Dose / kGy
DSC Peak -1 / 1/°C
0.153
0 3 6 9 12 15
Dose / kGy
(Adamo, 2001: no significant changes below 5 kGy)
RTC on Demonstration of Techniques
for Cultural Heritage Protection 9

Mechanical properties - Summary
May 2011- IAEA TC
RER/8/015
Property
Paper
~ % change*
Fbreak & Lbreak ,
MD/CD
Copier paper
Whatman paper
- 10%/ -15%
+5% / +10%
Folding Rank XEROX Copier paper - 40% / -15%
endurance, CEPROHART Copier paper -20%
MD/CD Whatman
-6%
Rank XEROX Copier paper -10%
Tearing resistance CEPROHART Copier paper -20%
Whatman
-6%
Rank XEROX Copier paper
-5%
Burst strength CEPROHART Copier paper
-3%
Whatman
-5%
Puncture
resistance
Rank XEROX Copier paper
CEPROHART Copier paper
Whatman
-5%
-3%
-10%
Cobb60 size test
Hartie copiator XEROX
Hartie Whatman - ICHR
+ 15% / +5%
-7%
* Change from nonirradiated for irradiation in the range of 6-13kGy
RTC on Demonstration of Techniques
for Cultural Heritage Protection 10

Folding / No
60
50
40
30
20
10
0
Bending / No
Folding endurance
XEROX copier paper
0 5 10 15
Dose / kGy
70
60
50
40
30
20
10
0
May 2011- IAEA TC
RER/8/015
MD CD
Folding / No
25
20
15
10
5
0
Whatman paper
MD CD
0 5 10 15
Dose / kGy
XEROX copier paper
BORSR'68
RTC on Demonstration of Techniques
for Cultural Heritage Protection 11
Folding / No
6
5
4
3
2
1
0
MD CD
0 5 10 15
Dose / kGy
0 20 40 60 80 100 120 140 160 180 200
Dose / kGy
MD CD

Colour
Instrument: Miniscan XE Plus, Hunter Lab.
Geometry: diffuse / 8° (sphere);
specular component included
View diameter: 4 mm
Illuminant / standard observer: D 65 / 10°
May 2011- IAEA TC
RER/8/015
RTC on Demonstration of Techniques
for Cultural Heritage Protection 12

L* [CIELAB units]
98
96
94
92
90
88
86
84
0 20 40 60 80 100
May 2011- IAEA TC
RER/8/015
Dose [kGy]
copier paper (l.q.)
copier paper (l.q.), aged
copier paper (h.q.)
Whatman paper
b* [CELAB units]
a* [CIELAB units]
10
5
0
-5
-10
2
1
0
0 20 40 60 80 100
Dose [kGy]
0 20 40 60 80 100
Dose [kGy]
RTC on Demonstration of Techniques
for Cultural Heritage Protection 13

457-nm Brightness
110
100
90
80
70
60
50
0 20 40 60 80 100
•No significant changes of lightness, L*, except for aged low quality copier paper
•Red/green value, a*, decreases (less red) with absorbed dose for low and high quality copier paper
•All the samples are less blue / more yellow after irradiation (b* value increases with absorbed dose)
•Total colour difference induced by ageing is higher than that induced by irradiation at 100 kGy
•Both 457-nm Brightness and WI E313 indexes decreased with the absorbed dose; aged samples
show the most important reduction in indexes values
May 2011- IAEA TC
RER/8/015
Dose [kGy]
WI E313
140
120
100
80
60
40
20
0
0 20 40 60 80 100
Dose [kGy]
RTC on Demonstration of Techniques
for Cultural Heritage Protection 14

Trapped free radicals
Instrument: X band ESR
spectrometer Magnettech
MiniScope MS 200
Measurement settings: B0
field 3350 Gauss, Sweep 200
Gauss, Modulation 5 Gauss,
MW attenuation 21 Db
Reference: EN 1787 /
Foodstuffs – Detection of
irradiated food containing
<strong>cell</strong>ulose by ESR
spectroscopy
May 2011- IAEA TC
RER/8/015
Intensity (a.u.)
140000
120000
100000
80000
60000
40000
20000
Paper Whatman42 5 kGy
after irradiation 3 days 1 w eek 2 w eeks 3 w eeks 4 w eeks
0
329 330 331 332 333 334 335 336 337 338 339
Magnetic field (mT)
RTC on Demonstration of Techniques
for Cultural Heritage Protection 15

Intensity (a.u.)
4000
3500
3000
2500
2000
1500
1000
500
Trapped free radicals
0
May 2011- IAEA TC
RER/8/015
Intensities after irradiation
Leafy Resinous Printing paper Cotton w ool Whatman 42
0 25 50 75 100
Dose (kGy)
Intensity
4000
3500
3000
2500
2000
1500
1000
500
0
Paper Whatman 42
5 kGy 10 kGy 25 kGy 50 kGy 100 kGy
0 5 10 15 20 25 30
Measurement after irradiation (days)
RTC on Demonstration of Techniques
for Cultural Heritage Protection 16

Trapped free radicals
May 2011- IAEA TC
RER/8/015
10000
9000
8000
7000
6000
5000
4000
3000
2000
1000
Lbreak,MD m
0
0 5 10 15 20 25
Rank Xerox
4 months after
irradiation
1 month after
irradiation
RTC on Demonstration of Techniques
for Cultural Heritage Protection 17

Dose rate effects
May 2011- IAEA TC
RER/8/015
70
60
50
40
30
20
10
0
Bending / No
0 3 6 9 12 15
Dose / kGy
Rank Xerox
4 months after
irradiation, 21 kGy/h
1 month after
irradiation, 6 kGy/h
1 month after
irradiation, 0.5kGy/h
RTC on Demonstration of Techniques
for Cultural Heritage Protection 18

FT-IR and FT-Raman
FT-IR spectrometer Vertex 70 class, Bruker
Optics:
-Raman module (RAM II) and probe
(RAMPROBE)
- Probe for non-contact and non-destructive
FT-IR
May 2011- IAEA TC
RER/8/015
RTC on Demonstration of Techniques
for Cultural Heritage Protection 19

FT-IR and FT-Raman
1000 3000 5000 7000
Transmittance [%]
3500
3357.43
3357.09
E:\Acer\doctorat\sem I 2010\date marian\FTIR-Raman BORSR attachments_2010_09_25\VALI-spectroscopie-20100924\VALI-spectroscopie-201009 12/06/2009
E:\Acer\doctorat\sem I 2010\date marian\FTIR-Raman BORSR attachments_2010_09_25\VALI-spectroscopie-20100924\VALI-spectroscopie-201009 12/06/2009
May 2011- IAEA TC
RER/8/015
3000
2919.30
2904.09
2500
2000
Wavenumber cm-1
Hardwood and softwood pulp
Page 1/1
1639.15
1500
1432.95
1430.92
1058.96
1058.49
1000
875.67
613.72
613.51
500
CF :
1372–1375 cm-1 (C-H)
2900 cm-1 (C-H stretch)
HB :
1429 cm-1 (CH 2 scissoring)
898 cm-1 (H bonded)
RTC on Demonstration of Techniques
for Cultural Heritage Protection 20

FT-IR and FT-Raman
1000 3000 5000 7000
Transmittance [%]
3500
3357.43
3357.09
E:\Acer\doctorat\sem I 2010\date marian\FTIR-Raman BORSR attachments_2010_09_25\VALI-spectroscopie-20100924\VALI-spectroscopie-201009 12/06/2009
E:\Acer\doctorat\sem I 2010\date marian\FTIR-Raman BORSR attachments_2010_09_25\VALI-spectroscopie-20100924\VALI-spectroscopie-201009 12/06/2009
May 2011- IAEA TC
RER/8/015
3000
2919.30
2904.09
2500
2000
Wavenumber cm-1
Hardwood and softwood pulp
Page 1/1
1639.15
1500
1432.95
1430.92
1058.96
1058.49
1000
875.67
613.72
613.51
500
CF :
1372–1375 cm-1 (C-H)
2900 cm-1 (C-H stretch)
HB :
1429 cm-1 (CH 2 scissoring)
898 cm-1 (H bonded)
RTC on Demonstration of Techniques
for Cultural Heritage Protection 21

FT-IR and FT-Raman
FT-IR spectra for pyrolised (600°C) paper
May 2011- IAEA TC
RER/8/015
CaCO 3 : 1445,51 cm-1,
874,33 cm-1 and 712,82
cm -1
CaSO 4 : 1100-1020 cm -1
H 2 O (adsorbed): 3446-
3467cm-1
RTC on Demonstration of Techniques
for Cultural Heritage Protection 22

FT-IR and FT-Raman
May 2011- IAEA TC
RER/8/015
RTC on Demonstration of Techniques
for Cultural Heritage Protection 23

FT-IR FT-Raman
0 2 4 6 8 10 12
Absorbance Units
3500
G:\Acer\arcon\derulare\Etapa 3\ARCON ETAPA III SPECTROSCOPIE 20101024\CARTE VECHE ir\ORIGEN1512 PAG3 P1 1000scans 0 OR19/10/2010
G:\Acer\arcon\derulare\Etapa 3\ARCON ETAPA III SPECTROSCOPIE 20101024\CARTE VECHE ir\ORIGEN1512 PAG3 P3 1000scans 0 OR19/10/2010
G:\Acer\arcon\derulare\Etapa 3\ARCON ETAPA III SPECTROSCOPIE 20101024\CARTE VECHE ir\ORIGEN1512 PAG3 P4 1000scans 0 OR19/10/2010
G:\Acer\arcon\derulare\Etapa 3\ARCON ETAPA III SPECTROSCOPIE 20101024\CARTE VECHE ir\ORIGEN1512 PAGMIJL P1 1000scans 0 19/10/2010
G:\Acer\arcon\derulare\Etapa 3\ARCON ETAPA III SPECTROSCOPIE 20101024\CARTE VECHE ir\ORIGEN1512 PAGMIJL P3 1000scans 0 19/10/2010
G:\Acer\arcon\derulare\Etapa 3\ARCON ETAPA III SPECTROSCOPIE 20101024\CARTE VECHE ir\ORIGEN1512 PAGMIJL P4 1000scans 0 19/10/2010
G:\Acer\arcon\derulare\Etapa 3\ARCON ETAPA III SPECTROSCOPIE 20101024\CARTE VECHE ir\ORIGEN PAG3 P1 1000scans-10kGy 0 23/11/2010
G:\Acer\arcon\derulare\Etapa 3\ARCON ETAPA III SPECTROSCOPIE 20101024\CARTE VECHE ir\ORIGEN PAG3 P3 1000scans-10kGy 0 23/11/2010
G:\Acer\arcon\derulare\Etapa 3\ARCON ETAPA III SPECTROSCOPIE 20101024\CARTE VECHE ir\ORIGEN PAG3 P4 1000scans-10kGy 0 23/11/2010
G:\Acer\arcon\derulare\Etapa 3\ARCON ETAPA III SPECTROSCOPIE 20101024\CARTE VECHE ir\ORIGEN PAGmijloc P1 1000scans-10kGy 0 23/11/2010
G:\Acer\arcon\derulare\Etapa 3\ARCON ETAPA III SPECTROSCOPIE 20101024\CARTE VECHE ir\ORIGEN PAGmijloc P2 1000scans-10kGy 0 23/11/2010
Page 1/1
May 2011- IAEA TC
RER/8/015
3000
2500
2000
Wavenumber cm-1
1500
1000
2 4 6 8 10 12
Raman Intensity
ORIGENES ADAMATI VOL I (XVI century)
3500
3000
2500
2000
1500
Wavenumber cm-1
G:\Acer\arcon\derulare\Etapa
G:\Acer\arcon\derulare\Etapa
3\ARCON
3\ARCON
ETAPA
ETAPA
III
III
SPECTROSCOPIE
SPECTROSCOPIE
20101024\CARTE
20101024\CARTE
VECHE
VECHE
raman\ORIGEN1512
raman\ORIGEN1512
HARTIE
HARTIE
PAG3
PAG3
P1-500SCAN
G:\Acer\arcon\derulare\Etapa 3\ARCON ETAPA III SPECTROSCOPIE 20101024\CARTE VECHE raman\ORIGEN1512 HARTIE PAG3
P3-500SCAN
21/11/2010
G:\Acer\arcon\derulare\Etapa 3\ARCON ETAPA III SPECTROSCOPIE 20101024\CARTE VECHE raman\ORIGEN1512 HARTIE PAGMIJL
P4-500SCAN
21/11/2010
G:\Acer\arcon\derulare\Etapa 3\ARCON ETAPA III SPECTROSCOPIE 20101024\CARTE VECHE raman\ORIGEN1512 HARTIE PAGMIJL
P1-500S
21/11/2010
G:\Acer\arcon\derulare\Etapa 3\ARCON ETAPA III SPECTROSCOPIE 20101024\CARTE VECHE raman\ORIGEN1512 HARTIE PAGMIJL
P3-500S
21/11/2010
G:\Acer\arcon\derulare\Etapa 3\ARCON ETAPA III SPECTROSCOPIE 20101024\CARTE VECHE raman\ORIGEN1512 PAG3 P1-500SCANS
P3-500S
21/11/2010
G:\Acer\arcon\derulare\Etapa 3\ARCON ETAPA III SPECTROSCOPIE 20101024\CARTE VECHE raman\ORIGEN1512 PAG3 P3-500SCANS
500m
21/11/2010
G:\Acer\arcon\derulare\Etapa 3\ARCON ETAPA III SPECTROSCOPIE 20101024\CARTE VECHE raman\ORIGEN1512 PAG3 P4-500SCANS
500m
24/11/2010
G:\Acer\arcon\derulare\Etapa 3\ARCON ETAPA III SPECTROSCOPIE 20101024\CARTE VECHE raman\ORIGEN1512 PAGMIJL P1-500SCANS
500m
24/11/2010
G:\Acer\arcon\derulare\Etapa 3\ARCON ETAPA III SPECTROSCOPIE 20101024\CARTE VECHE raman\ORIGEN1512 PAGMIJL P3-500SCANS
50
24/11/2010
G:\Acer\arcon\derulare\Etapa 3\ARCON ETAPA III SPECTROSCOPIE 20101024\CARTE VECHE raman\ORIGEN1512 PAGMIJL P4-500SCANS
50
24/11/2010
50
24/11/2010
24/11/2010
Page 1/1
PAGE X P1
irradiated/nonirradiated
PAGE X P2
irradiated/nonirradiated
PAGE X P3
irradiated/nonirradiated
PAGE XX P1
RTC on Demonstration of Techniques
for Cultural Heritage Protection 24
1000
500

FT-IR
0 1 2 3 4 5
Absorbance Units
May 2011- IAEA TC
RER/8/015
3500
3000
2500
2000
Wavenumber cm-1
1500
CEPROHART copy paper
0 kGy
100 kGy
RTC on Demonstration of Techniques
for Cultural Heritage Protection 25

0 2 4 6 8 10 12 14 16
Absorbance Units
FT-IR
3500
G:\Acer\arcon\derulare\Etapa
G:\Acer\arcon\derulare\Etapa
3\ARCON
3\ARCON
ETAPA
ETAPA
III
III
SPECTROSCOPIE
SPECTROSCOPIE
20101024\CARTE
20101024\CARTE
VECHE
VECHE
ir\ORIGEN1512
ir\ORIGEN1512
PIELE
PIELE
CF1
CF1
1000scans-2
1000scans-10kGy
0
G:\Acer\arcon\derulare\Etapa 3\ARCON ETAPA III SPECTROSCOPIE 20101024\CARTE VECHE ir\ORIGEN1512 PIELE CF1 1000scans 0
0
18/10/2010
G:\Acer\arcon\derulare\Etapa 3\ARCON ETAPA III SPECTROSCOPIE 20101024\CARTE VECHE ir\ORIGEN1512 PIELE CF2 1000scans-2 0
O
23/11/2010
18/10/2010
G:\Acer\arcon\derulare\Etapa
G:\Acer\arcon\derulare\Etapa
3\ARCON
3\ARCON
ETAPA
ETAPA
III
III
SPECTROSCOPIE
SPECTROSCOPIE
20101024\CARTE
20101024\CARTE
VECHE
VECHE
ir\ORIGEN1512
ir\ORIGEN1512
PIELE
PIELE
CF2
CF3
1000scans-10kGy
1000scans-2 0
0
18/10/2010
23/11/2010
G:\Acer\arcon\derulare\Etapa
G:\Acer\arcon\derulare\Etapa
3\ARCON
3\ARCON
ETAPA
ETAPA
III
III
SPECTROSCOPIE
SPECTROSCOPIE
20101024\CARTE
20101024\CARTE
VECHE
VECHE
ir\ORIGEN1512
ir\ORIGEN1512
PIELE
PIELE
CF3
CS1
1000scans-10kGy
1000scans-2 0
0
18/10/2010
23/11/2010
G:\Acer\arcon\derulare\Etapa
G:\Acer\arcon\derulare\Etapa
3\ARCON
3\ARCON
ETAPA
ETAPA
III
III
SPECTROSCOPIE
SPECTROSCOPIE
20101024\CARTE
20101024\CARTE
VECHE
VECHE
ir\ORIGEN1512
ir\ORIGEN1512
PIELE
PIELE
CS1
CS2
1000scans-10kGy
1000scans-2 0
0
18/10/2010
23/11/2010
G:\Acer\arcon\derulare\Etapa
G:\Acer\arcon\derulare\Etapa
3\ARCON
3\ARCON
ETAPA
ETAPA
III
III
SPECTROSCOPIE
SPECTROSCOPIE
20101024\CARTE
20101024\CARTE
VECHE
VECHE
ir\ORIGEN1512
ir\ORIGEN1512
PIELE
PIELE
CS2
CS3
1000scans-10kGy
1000scans-2 0
0
18/10/2010
23/11/2010
G:\Acer\arcon\derulare\Etapa 3\ARCON ETAPA III SPECTROSCOPIE 20101024\CARTE VECHE ir\ORIGEN1512 PIELE CS3 1000scans-10kGy 0
18/10/2010
23/11/2010
Page 1/1
ORIGENES ADAMATI VOL I (XVI century) – leather cover
May 2011- IAEA TC
RER/8/015
3000
2500
2000
Wavenumber cm-1
1500
1000
RTC on Demonstration of Techniques
for Cultural Heritage Protection 26

TD-GC-MS & Py-GC-MS
DTU „UNITY” (Markes) → GC 6890N (Agilent) → 5975 inert MSD (Agilent)
May 2011- IAEA TC
RER/8/015
RTC on Demonstration of Techniques
for Cultural Heritage Protection 27

1
4, 5, 6
7
2
3
9, 10, 11
8
TD-GC-MS
13, 14, 15, 16, 17
24, 25
23
27, 29
18
19, 20
21
26
28 30
32, 33
31
35,36
34
37, 38
1.00 1.20 1.40 1.60 1.80 2.00 2.20 2.40 2.60 2.80 3.00 3.20 3.40 3.60 3.80
Retention time (min)
May 2011- IAEA TC
RER/8/015
39 40
41
42
A - Volatile Radiolysis Products qualitative identification
TIC: High quality copier paper irradiated at 100kGy in PET canisters filled with air [1]
45, 46
43, 44 48
50
51, 52
53 55, 56, 57
49 54
60
58
59
6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00 14.00 15.00 16.00 17.00
GC/MS chromatogram, dynamic headspace - thermal desorption of air samples from irradiated canisters
(A). Identification made by means of calibration standards and retention index calibration combined with
mass spectra matching in NIST 2005 GC/MS library
1: Carbon dioxide; 2: Water; 3: Propane; 4: Methyl Alcohol; 5: *Acetaldehyde; 6: Butane; 7: *Methyl formate; 8:
Ethanol; 9: Acetone; 10: *Furan; 11: Pentane; 12: *Formic acid; 13: *Formic acid, ethyl ester; 14: Ethyl ether;
15: *2-Propanol, 2-methyl-; 16: *Acetic acid, methyl ester; 17: Methylene Chloride; 18: *1-Propanol; 19:
*Silanol, trimethyl-; 20: *Methacrolein; 21: *Formic acid, 1-methylethyl ester; 22: *2,3-Butanedione; 23:
*Butanal; 24: Hexane; 25: *2-Butanone; 26: *Furan, 2-methyl-; 27: Acetic acid; 28: Ethyl Acetate; 29: *Formic
acid, propyl ester; 30: *Furan, tetrahydro-; 31: *2-Butenal; 32: Benzene; 33: *1-Butanol; 34: *Disiloxane,
hexamethyl-; 35: *2-Pentanone; 36: *1-Heptene; 37: *Pentanal; 38: Heptane; 39: *Silane, trimethylpropoxy-; 40:
*Formic acid, butyl ester; 41: *3-Pentanone, 2-methyl-; 42: Toluene; 43: *Cyclopentanone; 44: *1-Octene; 45:
Octane; 46: *Hexanal; 47: *Silane, butoxytrimethyl-; 48: *Furfural; 49: Xylene; 50: *Trisiloxane, octamethyl-; 51:
Nonane; 52: *Silane, trimethyl(pentyloxy)-; 53: *Heptanal; 54: *Benzaldehyde; 55: Benzene, 1,3,5-trimethyl-;
56: *1-Decene; 57: *2-Octanone; 58: Decane; 59: *Octanal; 60: *Cyclotetrasiloxane, octamethyl-; 61: *D-
Limonene; 62: *2-Octenal, (E)-; 63: *1-Undecene; 64: Undecane; 65: *Nonanal; 66: *unassigned Cyclohexanol
derivative; 67: *1-Dodecene; 68: Dodecane; 69: *Decanal; 70: Tridecane; 71: *Undecanal; 72: *1-
Tetradecene; 73: Tetradecane; 74: *Dibutyl phthalate;
RTC on Demonstration of Techniques
for Cultural Heritage Protection 28
62
63
64
65
66
68
67
69
70
71
73
72
→ Degradation
markers

TD-GC-MS
The VCs concentration increases with the radiation absorbed dose in a nonlinear
manner. A part of the VCs formed after irradiation can be further found
also after accelerated ageing tests, which may propose them as <strong>cell</strong>ulose
structure degradation markers. In this case their absorbed dose concentration
dependence follows almost a linear trend. Although the concentration level of
the monitored VCs ranges up to some hundreds of ppm at higher doses
than 50 kGy, at usual doses used for archives conservation the order
concentration level ranges up to tens of ppm and further quantitative
measurements can be made to prove safe levels of possible toxic VCs. There
is known that large quantities of irradiated paper have a certain smell. VOC
analysis at the doses on interest for the irradiation treatment of paper
documents may not supply reliable results (there are close to the limit of
detection) but the studies at higher doses will eliminate one of the fears about
the toxicity of the treatment. The following studies will focus on ageing tests on
irradiated paper to make further correlations between ageing markers
concentration and the end of life criteria established by color and mechanical
tests.
May 2011- IAEA TC
RER/8/015
RTC on Demonstration of Techniques
for Cultural Heritage Protection 29

Py-GC-MS
Abundance
x 10 6
3,4
3,0
2,6
2,2
1,8
1,4
1,0
0,6
0
May 2011- IAEA TC
RER/8/015
TIC:\data.ms
0,00
5,00 10,00 15,0
0
20,00 25,00 30,0 35,00 40,00 45,00 50,00 55,0060,00
Time
0
(min)
Whatman
RTC on Demonstration of Techniques
for Cultural Heritage Protection 30

Py-GC-MS
T r (min)
1,28
1,68
1,80
1,89
2,23
2,68
5,80
6,68
6,93
8,57
8,78
9,30
9,84
10,49
12,93
14,41
14,75
15,81
15,86
16,91
19,24
20,20
42,40
43,18
May 2011- IAEA TC
RER/8/015
Formaldehidă
Hidroxi-acetaldehidă
2-metil-furan
Acid acetic
2,5-dimetil-furan
Furfural
2-Furanmetanol
2-propil-furan
1-(2-furanil)-etanonă
2(5H)-Furanonă
1,2-Ciclopentandionă
3-metil-2,5-furandionă
5-metil-2-furancarboxaldehidă
3-metil-1,2-ciclopentandionă
Esterul metilic al acidului 3furancarboxilic
Esterul metilic al acidului 3furancarboxilic
Levoglucosenonă
Maltol
Target
1-hidroxi-2-propanonă
2,3-dihidro-3,5-dihidroxi-6-metil-4H-Piran-
4-onă
1,4:3,6-Dianhidro-à-d-glucopiranoză
5-(hidroximetil)-2-furancarboxaldehidă
1,6-Anhidro-á-D-glucopiranoză
(levoglucosan)
1,6-Anhidro-à-d-galactofuranoză
Conc. (%)
1
6
1
1
1
0
6
0
1
0
1
1
0
1
1
0
2
13
0
2
6
2
6
Whatman
3
→ Degradation markers
RTC on Demonstration of Techniques
for Cultural Heritage Protection 31

Microbiological tests
May 2011- IAEA TC
RER/8/015
RTC on Demonstration of Techniques
for Cultural Heritage Protection 32

Radiation resistance
May 2011- IAEA TC
RER/8/015
RTC on Demonstration of Techniques
for Cultural Heritage Protection 33

Bioburden
Book 1992
Paper
Journal 1968
File cover 1977
Notebook 1981
Form 1983 (1)
Form 1983 (1)
Newsletter 1983
Book 1894 (MzBr)
Book 1952 (INCDPM)
May 2011- IAEA TC
RER/8/015
CFU/g
25
45
235
115
20
60
140
5
650
CFU/A4
94.5
170.1
2961
579.6
100.8
302.4
705.6
31.5
4095
CFU/50xA4
4725
8505
148050
28980
5040
15120
35280
1575
CFU/cm2
(surface
swab test)
0.04
0.04
0.14
0.04
0.12
0.04
0.06
0.04
CFU/A4
(surface
swab test)
25.2
25.2
88.2
25.2
75.6
25.2
37.8
25.2
RTC on Demonstration of Techniques
for Cultural Heritage Protection 34

Validation techniques
(work in progres)
Medical devices sterilization (ISO 11137):
Method 1:
• Average bioburden (3x10 items)
• SAL 10 -2 verification dose (from table) → irradiation of 100 samples
• Number of positives from 100 sterility tests (according to standard) →
Sterilization dose (from table) ≡ SAL 10 -6
Method 2:
• Incremental dose irradiation +sterility test (3x9x20 items)
• Number of positives (according to standard) → SAL 10-2 verification dose
→ irradiation of 100 samples
• Number of positives from 100 sterility tests (according to standard) →
Sterilization dose ≡ SAL 10-6
Method 2:
• Average bioburden (3x10 items) < 1000
• SAL 10-1 verification dose (from table) → irradiation of 10 samples
Number of positives from 10 sterility tests (according to standard) →
25 kGy ≡ SAL 10-6
May 2011- IAEA TC
RER/8/015
RTC on Demonstration of Techniques
for Cultural Heritage Protection 35

Thank you for your attention!
May 2011- IAEA TC
RER/8/015
RTC on Demonstration of Techniques
for Cultural Heritage Protection 36