NAMS 2002 Workshop - ICOM 2008

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Nanostructured Membranes II – 2 Tuesday July 15, 9:30 AM-10:00 AM, Moloka’i Aligned Carbon Nanotube Membranes: Transport Enhancement and Gatekeeper Activity M. Majumder, Univ. of KY, Lexington KY, USA K. Kiess, Univ. of KY, Lexington KY, USA J. Wu, Univ. of KY, Lexington KY, USA B. Hinds (Speaker), Univ. of KY, Lexington KY, USA, bjhinds@engr.uky.edu Carbon nanotubes have three key attributes that make them of great interest for novel membrane applications 1) atomically flat graphite surface allows for ideal fluid slip boundary conditions 2) the cutting process to open CNTs inherently places functional chemistry at CNT core entrance and 3) CNT are electrically conductive allowing for electrochemical reactions and application of electric fields gradients at CNT tips. Towards this goal, a composite membrane structure containing vertically aligned carbon nanotubes passing across a polystyrene matrix film have been fabricated. Fabrication steps, material characterization and ionic diffusion transport properties are described. Plasma oxidation during the fabrication process introduces carboxylic acid groups on the CNT tips that are modified using carbodiimide mediated coupling between carboxylic acid on the CNTs and accessible amine groups of the functional molecule. To explore the hypothesis of “Gatekeeper” selectivity, the entrances to CNT’s cores were functionalized with aliphatic amines of different lengths, charged dye molecule and an aliphatic amine elongated by spacers containing poly-peptides. The simultaneous permeation of two differently sized but equally charged molecules (ruthenium bi-pyridine [Ru-(bipy)3 +2 ] and methyl viologen [MV +2 ]) was studied and relative selectivity of was seen to vary from 1.9 to 3.6 as a function of tipfunctionalization chemistry. Anionic charged functional groups are seen to sharply increase flux of cationic permeates. This effect is reduced at higher solution ionic strength consistent with shorter Debye screening length screening attractive charge at the CNT core entrance. Using a hindered diffusion to model observed selectivities was consistent only with a geometry of only CNT tip functionalization, not along the length of CNT core. Bio-chemical gating of CNTs is also seen by tethering desthiobiotin to CNT tips with the reversible binding to streptavidin. The complete ATP cycle (phosphylation/dephosphylation) can be performed on CNT tips with corresponding modulation of flux across CNT membrane. Strong electrostatic effects of binding protein are seen with enhanced cationic flux seen for the relativel open anioic protein binding at CNT tip entrance. The functional density of tethered charge molecules can be substantially increased by the use of electrochemical grafting of diazonium salts. Functionality can be forced to occur at the CNT tip entrances by fast fluid flow of an inert solvent through the core during electrochemical functionalization. The selectivity
etween Ru(bi-pyridine)3 2+ and methyl viologen 2+ flux is found to be as high as 23 with -130mV bias applied to the membrane with tethered anionic dye molecule. Changes in the flux and selectivity support a model where charged tethered molecules at the tips are drawn into the CNT core at positive bias hindering/gating flux across the membrane. Applications towards controlled transdermal drug delivery are discussed. In general, the transport mechanisms through CNT membrane are a) ionic diffusion is near bulk expectation with no enhancement from CNT b) gas flow is enhanced by ~1-2 order of magnitude due to specular reflection off of flat graphitic surface c) and pressure driven flux of a variety of solvents (H2O, hexane, decane ethanol, methanol) are 4-5 ORDERS OF MAGNITUDE FASTER than conventional Newtonian flow due to atomically flat graphite planes inducing nearly ideal slip conditions.
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ICOM 2008 Oral Presentation Proceed
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Professor Yoram Cohen Professor Joh
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ICOM 2008 Staff: The University of
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ICOM 2008 Workshop Schedule: Saturd
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Monday, July 14 - Afternoon Session
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Tuesday, July 15 - Afternoon Sessio
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8:15AM 8:35AM EMS Barrer Prize (Mau
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Friday, July 18 - Morning Sessions
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Oral Presentation Abstracts Morning
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Gas Separation I - 1 - Keynote Mond
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esulting permeability selectivity o
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chain packing. To ensure a well pha
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Gas Separation I - 5 Monday July 14
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satisfactory way the corresponding
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Drinking and Wastewater Application
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an adjusted water management in the
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prospect for new energy sources as
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oxygen removal to the desired pH. C
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(Cl - , SO4 2- , As(V)) and water t
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[1] R. Lima de Miranda, J. Kruse, K
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Polymeric Membranes I - 4 Monday Ju
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Polymeric Membranes I - 5 Monday Ju
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Biomedical and Biotechnology I - 1
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Acknowledgments The Authors acknowl
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isolation of CD34+ cells was achiev
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membranes were then challenged with
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in crossflow mode operation were in
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hydroxide. For Mg/Ca = 0, the fouli
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improvement of filterability also t
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scale where fouling rates are commo
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observed in two subsequence phenome
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Membrane Modeling I - Fundamental A
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Membrane Modeling I - Fundamental A
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of the impact of the operating para
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Oral Presentation Abstracts Afterno
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Hybrid and Novel Processes I - 2 Mo
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Arora, M.B., J.A. Hestekin, S.W. Sn
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Conclusions Reverse electrodialysis
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energy recovery. This is a remarkab
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eaction with mediator due to the co
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Nanofiltration and Reverse Osmosis
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4.3x10 -6 to 7.4x10 -6 cm 2 /s. Bas
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The development of these membranes
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permeability, defined as water perm
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supports including charged (PSF/SPE
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[4] L. M. Robeson, Journal of Membr
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y conventional polymers and provide
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[3] P.M. Budd, K.J. Msayib, C.E. Ta
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Nanostructured Membranes I - 5 Mond
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Fuel Cells I - 1 Monday July 14, 2:
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Page 115 and 116: investigated at first. As a result,
Page 117 and 118: Desalination I - 2 Monday July 14,
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Page 135 and 136: NAMS Alan S. Michaels Award - 1a Tu
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Page 139 and 140: opportunities for improving membran
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Page 147 and 148: Nanofiltration and Reverse Osmosis
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Page 151 and 152: [4] K. Vanherck et al. Accepted for
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Page 161 and 162: fouling. Information obtained from
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Page 173 and 174: than 10 nm. XRD data suggest that t
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Page 201 and 202: References [1] S. Benita, Microenca
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concentration. These results are co
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Gas Separation II - 5 Tuesday July
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will be shown that homogeneous film
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which can adsorb on the surface of
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were collected, the viable bacteria
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pressure, and permporosimetry with
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Inorganic Membranes I - 3 Tuesday J
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Membrane Fouling - UF & Water Treat
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Membrane Modeling II - Gas Separati
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[10] Wang BG, Lv HL, Yang JC. Chem
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Membrane and Surface Modification I
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Gas Separation III - 1 - Keynote We
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Gas Separation III - 2 Wednesday Ju
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separation was next blended with di
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Polymeric Membranes II - 1 - Keynot
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Polymeric Membranes II - 3 Wednesda
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5. Erdodi, G.; Kennedy, J. P.; Prog
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observed for different locations in
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Biomedical and Biotechnology II - 3
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applied in the first two fields wil
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distribution of SBMA units within t
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5500 ppm (15 mM) was lowered to 30
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increasing the effective size of th
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etween 0 and 1), the automatic feed
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Membrane Modeling III - Process Sim
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Membrane Modeling III - Process Sim
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models developed suggests that ther
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start level has a huge impact on th
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Ultra- and Microfiltration I - Tran
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all three binary protein UF systems
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Synthetic solutions of ±-lactalbum
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Gas Separation IV - 2 Thursday July
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6. T. C. Merkel, Z. He, I. Pinnau,
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EMS Barrer Prize - 1b Thursday July
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EMS Barrer Prize - 3 Thursday July
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EMS Barrer Prize - 4b Thursday July
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EMS Barrer Prize - 5 Thursday July
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therapy options have been modelled
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Ultra- and Microfiltration II - Pro
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in the vicinity of the rising bubbl
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of feed water ionic strength) on re
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technology that has gained growing
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Optimize polymeric membranes for sa
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Inorganic Membranes II - 2 Thursday
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confirms that the carbon dioxide pe
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permeability, stability issues comp
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Fuel Cells II - 2 Thursday July 17,
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5. Conclusion In this work, the evo
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Oral Presentation Abstracts Afterno
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an essentially pure H2 product is c
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In the presentation, we will presen
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was observed, indicative of the sim
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References Arora, M.B., J.A. Hestek
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performance of fibers is analyzed a
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Membrane Fouling III - RO & Biofoul
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Pervaporation and Vapor Permeation
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[4] H. Noureddini, Book of Abstract
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component (PX, OX) separation via p
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Generally these results were in goo
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introduction of methyl groups into
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separation quality (10 µS/cm) and
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Desalination II - 3 Thursday July 1
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drop are linearly related (although
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antiscalant oxidation has been limi
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oth 15±5 kDa, which suggests that
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Atomic Force Microscopy (AFM), and
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y single gas permeation experiments
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PDMS toplayers were only partially
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noting that cross-linking agents co
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such extended parameter space in th
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Hybrid Membranes - 6 Thursday July
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Plenary Lecture III Friday July 18.
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Gas Separation V - 1 - Keynote Frid
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References: [1] H. Lin, E. Van Wagn
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elative contributions of Fickian di
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Gas Separation V - 4 Friday July 18
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Gas Separation V - 6 Friday July 18
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Electron Microscopy (TEM) analyses
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- Hybrid RO train: A hybrid RO trai
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concentration as well as on the sod
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scaling deposits in the DCMD device
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Silica colloidal solution with diff
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Membrane Fouling IV - RO & Desalina
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Polyacrylonitrile (PAN) UF membrane
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the polymer dope was PEI (12 wt%),
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Inorganic Membranes III - 1 - Keyno
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Inorganic Membranes III - 2 Friday
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CO2/H2 selectivity at high temperat
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ammonia complexes in aqueous soluti
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possible to have a membrane capable
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fired boiler flue gas, SOx and merc
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EPR/Ago/p-benzoquinone composite sh
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elated to the presence of free elec
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surroundings. When the temperature
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that no absorbent was detected in t
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days of filtration from 120 to 7-10
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was performed to restore membrane f
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with the SRT of 65 days, no correla
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Results Critical flux measurements
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MLSS is not directly proportional t
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Fuel Cells III - 2 Friday July 18,
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Fuel Cells III - 4 Friday July 18,
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Ultra- and Microfiltration III - Me
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can be deduced from the imaginary p
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membranes. The analysis of the ligh
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Membrane Contactors - 2 Friday July
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absorption liquid in the pores of t
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Packaging and Barrier Materials - 1
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Historically, all the approaches de
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