Transport of Small Molecules in Polymers:

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Transport of Small Molecules in
Polymers Overview of Research Activities
Benny D. Freeman Department of Chemical
Engineering University of Texas at
Austin, Office CPE 3.404 and CEER 1.308B Tel.
[phone], e-mail freeman_at_che.utexas.edu ht
tp//www.che.utexas.edu/graduate_research/freeman.
htm http//membrane.ces.utexas.edu
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Freeman Research Group Focus
Develop fundamental structure/function rules to
guide the preparation of high performance
polymers or polymer-based materials for gas and
liquid separations as well as barrier packaging
applications.
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Freeman Research Group Profile

• 15 Ph.D. students
• Gas Separations Qiang Liu, Kevin Stevens, Grant
  Offord, Tom Murphy, Katrina Czenkusch, David
  Sanders, Zach Smith
• Liquid Separations Wei Xie, Dan Miller, Joe
  Cook, Geoff Geise, Michelle Oh, Albert Lee, Peach
  Kasemset
• Barrier Materials Kevin Tung
• 2 Postdocs Dr. Claudio Ribeiro, Dr. Chaoyi Ba
• Sponsors
• NSF - 5 projects
• DOE 2 projects
• Office of Naval Research - 1 project
• Industrial sponsors PSTC, Air Liquide, Kuraray,
  Kraton Polymers, ConocoPhillips, Statkraft, Dow
  Water Solutions

group members who have won major fellowships
to support their work from either the US govt.
(NSF, DOE) or their home govt.
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Recent Graduates (within last 18 months)
Student Employer Area (Ph.D./Work) Area (Ph.D./Work)
Dr. Alyson Sagle Air Products, St. Louis, MO Fouling-resistant membranes/Gas separation membranes Fouling-resistant membranes/Gas separation membranes
Dr. Yuan-Hsuan Wu Intel, Portland, OR Fouling-resistant membranes/Microelectronics Fouling-resistant membranes/Microelectronics
Dr. Victor Kusuma Los Alamos (postdoc) Gas separation membranes Gas separation membranes
Dr. Lauren Greenlee NIST (postdoc), Boulder, CO High recovery desalination membranes/Nanoparticles in water treatment High recovery desalination membranes/Nanoparticles in water treatment
Dr. Bryan McCloskey IBM (postdoc), San Jose, CA Fouling-resistant membranes/Batteries Fouling-resistant membranes/Batteries
Dr. Hao Ju Dow, Midland, MI Fouling-resistant membranes/Battery separators Fouling-resistant membranes/Battery separators

Dr. Brandon Rowe NIST (postdoc), Gaithersburg, MD NIST (postdoc), Gaithersburg, MD Physical aging in gas separation membranes/Polymer physics of membranes
Dr. Liz van Wagner GE Global Research, Niskayuna, NY GE Global Research, Niskayuna, NY Fouling-resistant membranes/Membranes
Dr. Richard Li Advanced Hydro, Inc. Advanced Hydro, Inc. Fouling-resistant membranes
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Current Projects - 1

• Gas Separations
• Thermally-Rearranged Polymers for Gas Separation
• CO2/CH4 Separation for Natural Gas Purification
• Physical Aging in Glassy Polymers
• Physical Aging in Microlayered Polymers
• CO2/O2 Separation for Food Packaging Applications
• Melt Processing Strategies to Prepare Thin
  Membranes for Gas Separations
• Bioethanol Purification (Ethanol/Water Separation)

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Current Projects - 2

• Liquid Separations
• Chlorine-Tolerant Desalination Membranes
• Desalination Membranes Based on Novel Block
  Copolymers
• Fundamental Studies of Ion and Water Transport in
  Polymers
• Melt Processing Strategies to Prepare
  Desalination Membranes
• Bio-inspired Surface Modification of Water
  Purification Membranes to Improve Fouling
  Resistance

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Current Projects - 3

• Others
• Fundamental Studies of Oxygen Scavenging Polymers
  for High Oxygen Barrier Packaging
• Hydrocarbon/Hydrocarbon Pervaporation for
  Refinery Separations

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Fouling A Major Limitation in Liquid Filtration
Membranes
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Mimicking Mussel Adhesion (Bio-Glue)
H. Lee, S.M. Dellatore, W.M. Miller, and P.B.
Messersmith., Mussel-Inspired Surface Chemistry
for Multifunctional Coatings. Science, 318,
426-430 (2007).
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Polydopamine Novel Fouling Resistant Membrane
Coating
Polydopamine
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Polydopamine as Surface Primer to Graft PEG to
Membrane Surfaces
Proposed Polydopamine Structure
PEG ad-layer
Michael Addition/ Schiff Base Reaction
Polydopamine
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Oily Water Filtration Using Pegylated
Polydopamine Treated Teflon Microfiltration
Membranes
Modification 60 min PDOPA deposition time
followed by 60 min 5KDa PEG-NH2 (1mg/mL, 60 C)
Conditions DP0.3 atm, crossflow120 L/h
(Re2500) 1500 ppm soybean oil/DC193-water
emulsion (non-ionic)
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Field Validation - Visual

• Two identical UF PAN membranes that are highly
  hydrophilic
• One coated and one non-coated, both processed
  high fouling water stream from a bio-reactor with
  a lot of sludge.
• 10 minute filtration followed by 1 min backwash
  cycle for 48 hours.
• Both membranes were taken out and flushed with a
  hose / water
• Modified membrane washes clean
• Non-modified retains sludge film
• Membrane housings (hydrophobic) also showed
  significantly better anti-stick, fouling
  resistant surface

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Field Validataion Ultrafiltration of Bioreactor
Effluent
Unmodified
Modified
2X More Water Processed Between Cleanings
40 Lower Energy

• Pressure increases during single
  filtration/back-flush cycle due to fouling
• Almost twice the volume of water could be
  processed for same end-point pressures
• Unmodified shows pressure increase at a rate of
  1.55 psi/hr vs. 1.1 psi/hr for modified membrane

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Natural Gas Processing

• 100 trillion scf of natural gas used worldwide
  per year
• All requires pretreatment
• Amine absorption is the leading technology
• Membranes have lt 5 market share

R.W. Baker, K. Lokhandwala, Natural gas
processing with membranes An overview,
Industrial Engineering Chemistry Research. 47
(2008) 2109-2121.
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Science, vol. 318, 12 October 2007, pp. 254-258.
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CO2/CH4 Separation Performance
1 PIOFG-1 2 TR-1-350 3 TR-1-400 4
TR-1-450 5-19 OTHER TR POLYMERS
H.B. Park, C.H. Jung, Y.M. Lee, A.J. Hill, S.J.
Pas, S.T. Mudie, E. van Wagner, B.D. Freeman,
D.J. Cookson, Polymers with Cavities Tuned for
Fast, Selective Transport of Small Molecules and
Ions, Science, 318, 254-258 (2007).
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Cavity Size Distribution from Positron
Annihilation Lifetime Spectroscopy
(a) PIOFG-1 (b) TR-1-350 (c) TR-1-400 (d) TR-1-450
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Beating the Permeability-Selectivity Tradeoff
for H2 Purification
Lin et al., Science, 311, pp. 639-642 (2006).
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Reduction to Practice
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CO2 Selective Materials
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Using Nanocomposites to Enhance Membrane
Separations
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Using Nanolayering to Enhance Gas Barrier
Properties