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28th
Annual International Symposium on Polymer
Analysis and Characterization
Book of Abstracts
June 7-10, 2015
Houston, Texas
Since 1988
International Symposium on
Polymer Analysis and Characterization
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TABLE OF CONTENTS
Welcome to ISPAC 2015 -------------------------------------- 6
What is ISPAC? -------------------------------------- 7
Governing Board -------------------------------------- 8
ISPAC 2015 Committee -------------------------------------- 9
Previous ISPAC Conferences -------------------------------------- 10
Conference Agenda -------------------------------------- 11
Invited Speaker’s Abstracts -------------------------------------- 20
Contributed Talk Abstracts -------------------------------------- 37
Poster Abstracts ------------------------------------- 73
List of Participants ------------------------------------- 101
Area Maps ------------------------------------- 111
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WELCOME TO ISPAC 2015
Dear ISPAC Participants:
Welcome to the 28th
annual ISPAC Conference. This conference is unique in that it brings
together experts in polymer characterization with experts in polymer materials science in an
attempt to advance the participant’s understanding of polymer characterization. This year, as is
the case for every ISPAC conference, the focus areas were chosen based on the venue. The
Houston area is known for having two of the largest polyolefins companies in the world along
with a large medical center. These lead the organizing committee to choose polyolefins and
biopolymers as the first two sessions of the conference. The last three sessions covering
microscopy, spectroscopy and scattering were selected because they have historically been topics
that ISPAC has covered.
We are very fortunate this year to have very strong support from the polymer industry and
instrument vendors. This strong financial support allows the conference to do a few additional
things to hopefully make the conference environment more conducive to networking and
learning. First, we were able to have two separate short courses. This hopefully made the
conference more attractive to people wanting to expand their knowledge into other fields. In
addition, it brought in more world class experts to participate in the conference. Next, the
additional funding allows the conference to offer all meals on site at no extra charge. This
hopefully will increase everyone’s opportunity to network and expand their knowledge. Finally,
the strong vendor participation complements everyone’s conference experience by bringing in
some of the world’s best polymer characterization vendors and their experts.
On behalf of this year’s ISPAC Organizing Committee I want to encourage everyone to take full
advantage of all this year’s conference has to offer. I hope you enjoy your stay at Hotel ZaZa
and the Houston area and that you leave the conference with a better knowledge of polymer
characterization. Please don’t hesitate to contact any of us should you have any questions or
concerns.
Regards;
ISPAC 2015 Planning Committee
Willem deGroot, The Dow Chemical Company - ISPAC 2015 Conference Chair
Jimmy Mays, University of Tennessee
Pat Brant, ExxonMobil
Rafael Verduzco, Rice University
H.N. Cheng, USDA Southern Regional Research Center
Debbie Mercer, The Dow Chemical Company
Chanda Klinker, The Dow Chemical Company
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What is ISPAC?
ISPAC stands for International Symposium on Polymer Analysis and
Characterization. It is a non-profit scientific organization formed to provide an
international forum for the presentation of recent advances in the field of polymer
analysis and characterization methodologies. This unique Symposium brings
together analytical chemists and polymers scientists involved in the analysis and
characterization of polymeric materials. Meetings are held annually, rotating to
venues in the USA, Europe and Asia.
ISPAC sessions comprise a two and a half day program with invited lectures,
submitted lectures, poster sessions, discussions and information exchange on
polymer analysis and characterization approaches, techniques and applications.
Invited talks include state-of-the art developments. Each session features lectures
and a 30 to 45 minute open discussion period. The participants typically come
from academic, industrial, and government settings and work with different aspects
of polymer analysis and characterization approaches, techniques and applications.
The conferences aim is to promote networking with one another, exchanging
information and tips about different techniques, and learning about the latest
developments.
Lecturers are urged to include introductory material in their presentation to bring
participants "up to speed", and are allotted the time to accomplish this. The
discussion periods allow for extended interaction among the lecturers and the
conference participants.
If your work involves any aspect of polymer characterization, physical testing,
materials analysis, or polymers in general, please consider attending this
conference. You are welcome to submit a contributed oral paper or a poster.
Full papers of invited talks and poster presentations are published in the
International Journal of Polymer Analysis and Characterization, an ISPAC
affiliated journal published by Taylor & Francis. Instructions for authors will be
available at the conference.
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ISPAC Governing Board
W. F. Reed, Tulane University, USA; [email protected], ISPAC GB Chair for the Americas,
ISPAC-2013 Chair
G. J. Vancso, University of Twente, The Netherlands; [email protected], ISPAC GB Chair for Europe and Asia, ISPAC-2012 Chair
Oscar Chiantore, University of Torino, Italy; [email protected]
Taihyun Chang, Pohang University of Science and Technology, Republic of Korea;
H.N. Cheng, USDA Southern Regional Research Center, USA; [email protected]
Patricia M. Cotts, Dupont, USA, [email protected]
A.Willem deGroot, Dow Chemical Co., USA; [email protected], ISPAC-2015 Chair
Nikos Hadjichristidis, KAUST, King Abdullah University of Science and Technology, Saudi
Arabia; [email protected]
Josef Janca, Institute of Scientific Instruments, Academy of Sciences of the Czech Republic,
Brno, Czech Republic; [email protected]
Jimmy W. Mays, University of Tennessee, USA, [email protected]
Harald Pasch, University of Stellenbosch, South Africa; [email protected]
Marguerite Rinaudo, CERMAV-CNRS, France; [email protected], ISPAC-2014 Chair
Emeritus Members of the Governing Board
H.G. Barth, DuPont Co., USA, ISPAC Founding Chair Emeritus
G.C. Berry, Carnegie Mellon University, USA; [email protected], ISPAC GB Honorary Chair Emeritus
S.T. Balke, University of Toronto, Canada
J.V. Dawkins, Loughborough University, UK
P. Kratochvil, Institute of Macromolecular Chemistry, Czech Republic
S. Mori, Mie University, Japan
P. Munk, University of Texas at Austin, USA
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ISPAC 2015 Organizing Committee
Willem deGroot (ISPAC 2015 Chair) - The Dow Chemical
Company, [email protected], @awillem0
Patrick Brant – ExxonMobil Chemical, [email protected]
H.N. Cheng - USDA Southern Regional Research
Center, [email protected], @hncheng
J. W. Mays, University of Tennessee, [email protected]
Rafael Verduzco, Rice
University, [email protected], http://polymers.rice.edu, @RafRice
Chanda Klinker, The Dow Chemical
Company, [email protected], @chandaklinker
Debbie Mercer, The Dow Chemical Company, [email protected]
Acknowledgements
This year’s ISPAC Conference Organizing Committee would like to thank the Rice University
Department of Chemical and Biomolecular Engineering for administrative and technical support. We
would like to extend a special thanks to Ania Howard for her time and efforts managing the audio video
needs of the conference. Finally, the committee would like to thank Brian Habersberger for his help in
designing all of the graphics/artwork for the conference. This includes the design of the coffee mugs, the
cover of the agenda booklet, as well as, the design of several of the posters.
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PREVIOUS ISPAC CONFERENCES
Toronto, Canada
1988
Austin, TX, USA
1989
Brno, Czechoslovakia
1990
Baltimore, MD, USA
1991
Inuyama, Japan 1992
Crete, Greece
1993
Les Diablerets, Switzerland
1994
Sanibel Island, FL, USA
1995
Oxford, UK
1996
Toronto, Canada
1997
Santa Margherita,
Italy 1998
La Rochelle, France 1999
Pittsburgh, PA, USA
2000
Nagoya, Japan 2001
Univ. Twente The
Netherlands 2002
Baltimore, MD, USA
2003
Heidelberg, Germany
2004
Sheffield, UK
2005
Oak Ridge, TN, USA
2006
Crete, Greece
2007
Wilmington, DE, USA
2008
Zlin, Czech Republic
2009
Pohang, Rep. of Korea
2010
Torino, Italy 2011
Kerkrade, The
Netherlands 2012
New Orleans, USA 2013
Les Diablerets, Switzerland
2014
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Agenda
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Sunday, June 7, 2015
ISPAC Short Course: Polymer Analysis and Characterization
7:45 AM BREAKFAST – Phantom Ballroom B & C 8:00 AM REGISTRATION, ALL DAY – Phantom Pre-Function Lounge
SESSION 1 HEMINGWAY ROOM
SESSION 2 DÉJÀ VU ROOM
8:30 AM Basics of Gel Permeation Chromatography, Including
Multi-Detectors -Dr. John McConville
Introduction to Polymer Electron Microscopy -Professor Matthew Libera
10:00AM Break – Phantom Pre-Function Room Break – Phantom Pre-Function Room 10:15 AM Mass Spectrometry Methods for the Characterization of
Synthetic Polymers and Materials -Professor Chrys Wesdemiotis
Travels in Reciprocal Space: A Tutorial on Images, Microstructures, Scattering and Fourier Transforms - Dr. Jeff Butler
11:45 AM LUNCH – Fountain Room LUNCH – Fountain Room 12:45 AM Advanced Liquid Chromatography, including 2D-LC and
Hyphenated Methods (LC-NMR, LC-FTIR, LC-MS) –Professor Harald Pasch
Small Angle Neutron Scattering: A Tool to Explore Structure in Complex Fluids and Polymers under Manufacturing-Related Conditions -Dr. Ronald Jones
2:15 PM Break – Phantom Pre-Function Room Break – Phantom Pre-Function Room 2:30PM Characterization and Applications of Some Biopolymers:
from Sol to Gel States -Professor Marguerite Rinaudo
Watching the Molecules: a Tutorial on Light Scattering and Dielectric Spectroscopy - Professor Alexei Sokolov
4:00 PM Break – Phantom Pre-Function Room Break – Phantom Pre-Function Room 4:15 PM Introduction to Scattering-Based Polymer
Characterization Methods - Professor Paul S. Russo
Scanning Probe Microscopy for Discrimination and Quantitative Differentiation of Polymer Materials Dr. Dalia Yablon
5:00 PM Registration- Phantom Pre-Function Lounge 6:00 PM Welcome Reception – Fountain/Ultimate Ransom Room
Heavy hors d’ouevres and open bar
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Monday, June 8, 2015 – PHANTOM BALLROOM
Morning Session Theme: Characterization of Polyolefins 7:00 AM REGISTRATION, ALL DAY – Phantom Pre-Function Lounge 7:00 AM BREAKFAST – Phantom Ballroom B & C 8:00 AM ISPAC Chair Opening Remarks – Phantom Ballroom B & C
-Willem deGroot & Wayne Reed Invited Lectures:
Phantom Ballroom B & C Characterization of Polyolefins – Moderator: Jimmy Mays
8:15 AM L1 - Contributions of Polyolefin Characterization Techniques to Polymer Catalysis Development and Reaction
Engineering The Dow Chemical Invited Lecture: Joao Soares, University of Alberta
8:45 AM L2 - Characterization of Complex Polyolefins by Cross-Fractionation Techniques
- Benjamin Monrabal, Polymer Char Spain 9:15 AM L3 - Flow-induced Crystallization and Nucleation in Isotactic Polypropylenes
-Scott Milner, Penn State University 9:45 AM DISCUSSION 10:15 AM REFRESHMENT PAUSE – Phantom Ballroom A
Contributed Lectures`:
Phantom Ballroom B - Characterization of Polyolefins – Moderator: Harald Pasch
Phantom Ballroom C Characterization of Biopolymers – Moderator: Petra Mischnick
10:45 AM O1 - Size Exclusion Chromatography of Polyoxymethylene
and its Polyolefin Blends- Possibilities and Limitations -Gadgoli Umesh,SABIC
O5 - Conversion and Characterization of Agri-based Materials -H.N. Cheng, USDA
11:05 AM O2 - Spectroscopic Characterization of Plasma
Nitrogenation of Polymer Surfaces at Atmospheric Pressure -Zohreh Khosravi, Technische Universitat Braunschweig
O6 - DNA-Chitosan Electrostatic Complex Formation: Stoichiometry and Conformation -Marguerite Rinaudo, CERMAV-CNRS
11:25 AM O3 - Dissolution and Scattering Behavior of Polyethylenes
in Dilute solutions and Relations between Molecular parameters -Jacques Tacx, Sabic
O7 - New Approaches in Analysis of Drug Delivery Formulations: Measuring Domain Sizes in Multi-Component Celluloses Using NMR -Staffan Schantz, AstraZeneca R&D
11:45 AM O4 - Multidimensional High Temperature Liquid
Chromatography - Robert Brüll, Fraunhofer Institute
O8 - Preparation and Characterization of Microporous Hydrogels of Cellulose Ether Cross-Linked with di- or poly Functional Glycidyl Ether Made for the Delivery of Bioactive Substances - Olayide Samuel Lawal, Olabisi Onabanjo University
12:05 PM - LUNCH – Phantom Ballroom B & C - VENDOR TALKS – Fountain Room Poster Setup in “Room with a View” 11
th Floor
12:20 PM Vendor Talk 1
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Cont’d - Monday, June 8, 2015 – PHANTOM BALLROOM
12:40 PM Vendor Talk 2
1:00 PM Cont’d Lunch in Phantom Ballroom B & C; Poster Setup in “Room with a View” 11th Floor
Vendor Talk 3 – Fountain Room
Invited Lectures: Phantom Ballroom B & C
Characterization of Biopolymers – Moderator: H.N. Cheng 1:35 PM L4 - A New Frontier in Proteomics: Identifying Proteoforms and Elucidating Proteoform Families from
Measurements of Intact Mass and Lysine Count -Lloyd Smith, Wisconsin
2:05 PM L5 - Self-assembly and Responsiveness of Polypeptide-based Star and Triblock Copolymers: Design, Characterization and Function -Dan Savin, University of Florida
2:35 PM L6 - Analysis of the Substituent Distribution in Cellulose Ethers -Petra Mischnick, TU Braunschweig
3:05 PM DISCUSSION 4:30 PM REFRESHMENT PAUSE – Phantom Ballroom A 4:40 PM Vendor Talk 4 – Fountain Room 5:00 PM Vendor Talk 5 – Fountain Room Contributed Lectures`: Phantom Ballroom B Characterization of
Polyolefins – Moderator: Benjamin Monrabal Phantom Ballroom C Characterization of Biopolymers – Moderator: Marguerite Rinaudo
5:30 PM O9 - The Recent Advances and Challenges in Polyolefin
Comonomer Distribution Analysis -Rongjuan Cong, Dow Chemical
O12 - Study of Complex Coacervation of Gelatin A and Pectin for Microencapsulation of Theophylline -Nirmala Devi, Gauhati University
5:50 PM O10 - New NMR Techniques Developed Recently for
Studying Polyolefin Microstructures -Zhe Zhou, Dow Chemical
O13 - Thermoplastic Elastomer as Toughening Agent for Polylactic Acid (PLA): Effect of Blending Ratio on Morphology and Performance -Vidhya Nagarajan, University of Guelph
6:10 PM O11 - Characterization of Polypropylene in
Dibutoxymethane by High Temperature Gel Permeation Chromatography with Triple Detection -Steve O'Donohue, Agilent Technologies
O14 - New Insights on Cellulosic Ether Hydrogels -Bob Sammler, Dow Chemical
6:30 PM Poster Exhibits in Room with a View 11th Floor
Heavy hors d`ouevres and Open Bar
15
Tuesday, June 9, 2015 – PHANTOM BALLROOM 7:00 AM REGISTRATION, ALL DAY – Phantom Pre-Function Lounge 7:00 AM BREAKFAST – Phantom Ballroom B & C Invited Lectures:
Phantom Ballroom B & C Characterization of Polymers Using Scattering Techniques – Moderator: Moderator: Rafael Verduzco
8:00 AM L7 - Probing Semi-crystalline and Amorphous Structure in Polymer Systems using Neutron Scattering, Neutron
Imaging, and Neutron Spectroscopy -Chevron Phillips Invited Lecture: Ron Jones, NIST
8:30 AM L8 - In situ Thin Film Processing Characterization Using X-rays
-Alexander Hexemer, Lawrence Berkeley National Laboratory 9:00 AM L9 - Characterizing Block Copolymer Thin Films with Grazing-Incidence Small Angle X-ray Scattering
-Gila Stein, University of Houston 9:30 AM DISCUSSION 10:00 AM REFRESHMENT PAUSE – Phantom Ballroom A Contributed Lectures:
Phantom Ballroom B Characterization of Polymers Using Scattering Techniques – Moderator: Ron Jones
Phantom Ballroom C General Polymer Characterization – Moderator: Oscar Chiantore
10:30 AM O15 - In Situ SANS Studies of Semi-Crystalline Polymers
Under Tensile Deformation -Jamie Stull, Los Alamos National Laboratory
O19 - Full Molecular Characterization of Complex Polymers: Mission Impossible? - Harald Pasch University of Stellenbosch
10:50 AM O16 - Quantifying Tie-Chain Content in Semicrystalline
Polyolefins with Vapor-Flow Small-Angle Neutron Scattering - Amanda McDermott, NIST
O20 - Monitoring the Onset and Evolution of Polymer Stimuli Responsive Behavior During Synthesis -Wayne Reed, Tulane University
11:10 AM O17 - Heterogeneous Deuterium Distribution in
Commercial Polyolefins: Measurement and SANS Model -Brian Habersberger, Dow Chemical Company
O21 - Synthesis and Characterization of Neem (Azadirachta Indica A.Zuss.) Seed Oil-based Alkyd Resin Nirmala Devi, Gauhati University -
11:40 AM O18 - Hydrophobically Modified Ethylene Oxide Urethane
(HEUR) Based Coatings: Mesoscale Structure Under Shear and Viscosity -Tirtha Chatterjee, Dow Chemical
O22 - Characterization of a New High Temperature Thermoplastic Elastomer Synthesized by Living Anionic Polymerization in Hydrocarbon Solvent at Room Temperature -Weiyu Wang, University of Tennessee
12:00 PM Phantom Ballroom B & C
- LUNCH Fountain Room -LUNCH & VENDOR TALKS
12:15 PM Vendor Talk 6 12:35 PM Vendor Talk 7
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Cont’d -Tuesday, June 9, 2015
Invited Lectures: Phantom Ballroom B & C - Characterization of Polymers using Spectroscopy and Microscopy –
Moderator: Julius Vancso
1:15 PM L10 - Understanding the Inner Morphology of Polymeric Nanoparticles: Expect the Unexpected
-Roberto Simonutti, University of Milan Bicocca 1:45 PM L11 - Nanoscale Molecular Imaging in Polymer Systems
-Greg Meyers, The Dow Chemical Company
2:15 PM L12 - FT-IR Imaging Advances in Polymer Characterization
-Rigoberto Advincula, Case Western Reserve University
2:45 PM L13 - An Interfacial Layer – The Key to Properties of
Polymer Nanocomposites -Alexei Sokolov, University of Tennessee
3:15 PM DISCUSSION 4:00 PM REFRESHMENT PAUSE – Phantom Ballroom A 4:10 PM Vendor Talk 8 – Fountain Room 4:30 PM Vendor Talk 9 – Fountain Room Contributed Lectures: Phantom Ballroom B
Characterization of Polymers Using Spectroscopy and Microscopy – Moderator: Greg Meyers
Phantom Ballroom C General Polymer Characterization Session II – Moderator: Wayne Reed
5:00 PM O23 - Characterization of a Polyethylene – Polyamide
Multilayer Film Using Nanoscale Infrared Spectroscopy and Imaging -Curtis Marcott, Anasys Instruments, Inc.
O26 - Field-Flow Fractionation: Solving the Challenges where Size Exclusion Chromatography meets its Limitations and Now Complementing Size Exclusion in Applications that Were not Expected -Trevor Havard, Postnova Analytics
5:20 PM O24 - Solid-State NMR in Industrial Polymer Research
-Victor Litvinov, DSM Resolve O27 - Unique Three-Phase Self-Assembly and Order-Disorder Transition of Poly(cyclohexadiene)-Based Copolymers - Konstantinos Misichronis, University of Tennessee
5:40 PM O25 - Conformational, Crystallinity and Orientation
Changes in Poly (Trimethylene Terephthalate) (PTT) During Crystallization Studied by FTIR Spectroscopy -Nadarajah Vasanthan, Long Island University
O28 - Use of ACOMP to Monitor Residual Monomer Concentration and Polymer Intrinsic Viscosity Throughout Industrial Scale Polymerization Reactions -Michael F. Drenski, Advanced Polymer Monitoring Technologies, Inc.
7:00 PM CONFERENCE BANQUET – ROOM WITH A VIEW 11TH FLOOR
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Wednesday, June 10, 2015 – PHANTOM BALLROOM
7:00 AM REGISTRATION, ALL DAY – Phantom Pre-Function Lounge 7:00 AM BREAKFAST – Phantom Ballroom B & C Invited Lectures: Phantom Ballroom B & C Polymer Surface and Interface Characterization – Pat Brant 8:00 AM L14 - Block Copolymer Bottlebrushes: New Routes to Ever
Smaller Microdomain Sizes -ExxonMobil Invited Lecture: Mahesh Mahanthappa, University of Wisconsin
8:30 AM L15 - Microstructured Polymers
-Ned Thomas, Rice University
9:00 AM L16 - Manipulating Polymers with Light Activated
Interfacial Chemistries -Chris Ellison, University of Texas
9:30 AM DISCUSSION 10:00 AM REFRESHMENT PAUSE – Phantom Ballroom A Contributed Lectures`: Phantom Ballroom B
Mixed Topics – Moderator: Rafael Verduzco
Phantom Ballroom C Mixed Topics – Moderator: Gila Stein
10:30 AM O29 - High temperature AFM Imaging and
Nanoindentation During the β→α Transformation of Isotactic poly(Propylene) - Davide Tranchida Borealis
O32 - Characterization of Polyelectrolyte Multilayers by Temperature-Controlled Quartz Crystal Microbalance with Dissipation -Jodie Lutkenhaus, Texas A&M University
10:50 AM O30 - Design of Interpenetrating Networks for the
Formation of Tough Epoxy Resins -Megan Robertson, University of Houston
O33 - EIS in Characterization of Polymer based Hydrogel Support for Biomimetic Membrane Applications -Agnieszka Mech-Dorosz, Technical University of Denmark
11:10 AM O31 - Sample Preparation in Polymer Mass Spectrometry
-Clemens Schwarzinger, Johannes Kepler University Linz O34 - Strain-Induced Phenomena in Multi-Phase Polymers -Victor Litvinov, DSM Resolve
11:45 PM Phantom Ballroom B & C
-LUNCH
20
Invited Lecture Abstracts
L1
21
Contributions of polyolefin characterization techniques to polymer catalysis
development and reaction engineering
João B. P. Soares
Department of Chemical and Materials Engineering, University of Alberta
Edmonton, AB, Canada
Abstract
Polyolefins are made with comonomers that contain only carbon and hydrogen atoms. Despite of
their apparent simplicity, polyolefins find applications ranging from domestic appliances,
automotive and aeronautical parts, and biomedical devices, among others. The key to their
versatility lies in the variety of ways that their simple monomers can be combined to form
different polymer microstructures.
The many existing polyolefin characterization techniques reflect the importance polymer
microstructure has on polyolefin applications. Polyolefins are routinely analyzed not only with
general techniques such as NMR, FTIR, DSC, and G PC, but also by other methods that were
specifically developed to investigate their microstructures, such as TREF, CRYSTAF, CEF,
TREF-SEC, and more recently HT-TGIC. These microstructural analyses help understand how
polyolefin microstructure affects their mechanical, rheological and thermal properties. Equally
importantly, they also allowed many developments in polyolefin catalysis and polymer reaction
engineering.
This talk will review how advances in polyolefin characterization techniques were paralleled by
advances in olefin polymerization catalysis and polyolefin reaction engineering.
L2
22
Characterization of complex Polyolefins by Cross-Fractionation techniques
B. Monrabal
Polymer Char, Spain [email protected]
The introduction of single-site catalysts and multiple reactor/zone production technologies in the
polyolefins industry has allowed the design of new resins with improved performance for
specific applications.
Given the microstructure complexity of these resins (in terms of size, comonomer content,
tacticity and their overall interdependence), the characterization of these polymers is, very often,
a challenging task that requires multiple separation methods [1].
A good understanding of the existing separation processes is essential, especially in the relatively
new adsorption and crystallization based techniques, where mixed and equivocal separation
mechanisms may take place when dealing with polypropylene-polyethylene copolymers [2].
The use of combined separation process (Cross-Fractionation) like TREF and TGIC
(composition) followed by SEC/GPC (molar mass) provides an improved understanding of the
polymer microstructure which can be further extended to an additional dimension by the use of
infrared detection to measure the number of branches in the chain [3].
References
[1] - B. Monrabal in Polyolefins : 50 years after Ziegler and Natta I., W. Kaminsky Ed.,
Advances in Polymer Science 257, Springer-Verlag 2013.
[2] - B.Monrabal and L. Romero, Macromolecular Chemistry and Physics, 215, 1818-1828,
2014.
[3] - B. Monrabal in “Characterization of complex Ethylene-Propylene copolymers. A journey
inside the analytical techniques” presented at ICPC 2014, Valencia.
L3
23
Flow-induced crystallization and nucleation in isotactic polypropylenes
Scott Milner
Joyce Chair and Professor of Chemical Engineering
Flow-induced crystallization (FIC) occurs when a brief interval of strong flow precedes a
temperature quench; many more nuclei form, resulting in a much more fine-grained solid
morphology and better material properties. Common industrial polymer processing (injection
molding) depends on FIC, which has been the subject of many experimental studies, most
commonly on isotactic polypropylene (iPP). The prevailing hypothesis is that FIC results from
flow aligning chains in the melt, increasing the melt free energy with respect to the crystal, hence
acting like undercooling. Here, I combine new experimental results for FIC and homogeneous
nucleation with new theoretical estimates for critical nuclei, to assess the prevailing
hypothesis. Current best information supports the view that chain stretching (not just alignment)
is necessary and sufficient to explain the observed increase in nucleation rate. Post-shear optical
and atomic force microscopy suggests a change in crystallization mechanism above a threshold
value of applied work. Important puzzles remain: 1) shear applied at temperatures well above
the equilibrium melting temperature Tm=187C is effective for FIC; 2) a sheared sample may be
held for hours above Tm, and still crystallize faster when quenched; 3) a sheared sample,
remelted, crystallizes at a higher temperature (130C vs. 115C) than an unsheared sample, a
phenomenon that anneals away only very slowly.
L4
24
A New Frontier in Proteomics: Identifying Proteoforms and Elucidating
Proteoform Families from Measurements of Intact Mass and Lysine Count
Lloyd M. Smith*, Michael R. Shortreed, Mark Scalf, Rachel A. Knoener, Anthony
J. Cesnik, and Brian L. Frey
Department of Chemistry and Genome Center of Wisconsin
University of Wisconsin- Madison
Madison, WI 53706
The dominant paradigm of modern proteomics today is the "bottom-up" strategy, in which a
mixture of proteins of interest is cleaved into peptides and analyzed by liquid
chromatography/mass spectrometry (LC-MS). While the bottom-up strategy is powerful and
widely practiced, the digestion of the proteins into peptides means that information as to the
protein context within which that peptide is found is lost. Proteins produced from the same gene
can vary substantially in their molecular structure: genetic variations, splice variants, RNA
editing, and post-translation modifications (PTMs), all give rise to different forms of the
proteins: these are referred to as "proteoforms". Knowledge of the proteoforms that are present
in a system under study is absolutely essential to understanding that system, as the different
proteoforms often have dramatically different functional behaviour, and regulation of their
production is a central aspect of pathway control.
We are developing a new strategy for proteoform analysis, in which the determination of just two
pieces of information for each proteoform, namely the accurate mass and the number of lysine
residues contained, suffices to identify it. The accurate mass is determined by standard LC-MS
analysis of the undigested protein mixture in an orbitrap mass spectrometer, and the lysine count
is determined using a recently developed isotopic tagging method. A key enabling concept is a
search strategy that reveals post-translationally modified protein variants. The strategy is
demonstrated by elucidating hundreds of proteoform families present in yeast cell lysate. This
simple and readily implemented new proteomic strategy provides an unprecedented view of the
proteoforms present in biological systems, and will thereby make possible critical new insights
into the functioning of biological systems and pathways.
L5
25
Self-assembly and Responsiveness of Polypeptide-based Star and Triblock
Copolymers: Design, Characterization and Function
Daniel A. Savin, Gregory D. Strange, Ian R. Smith and Craig D. Machado
Department of Chemistry, University of Florida, Gainesville, FL
USA. [email protected]
This study involves the bottom-up design and tunability of responsive, peptide-based block
copolymers. The self-assembly of amphiphilic block copolymers is dictated primarily by the
balance between the hydrophobic core volume and the hydrophilic corona. In these studies,
amphiphilic diblock, triblock and star copolymers containing poly(lysine) (PK) and
poly(glutamic acid) (PE) were synthesized and their solution properties studied using dynamic
light scattering, circular dichroism spectroscopy and transmission electron microscopy.[1] These
materials exhibit hydrodynamic size that is responsive to pH, due in part to the helix-coil
transition in the peptide chain, but also due to changes in curvature of the assembly at the
interface. This talk will present some recent studies in solution morphology transitions that
occur in these materials as a result of the helix-coil transition and associated charge-charge
interactions.[2,3] We exploit the responsiveness of these materials to encapsulate and release
therapeutics such as doxorubicin and demonstrate the potential to achieve triggered release as a
function of pH due to morphology transitions.
Figure 1: Morphology transitions in ABA triblock copolymers.[2]
References [1] J. Ray, A. Johnson, D. Savin. J. Polym. Sci., Part B: Polym. Phys. 2013. 51(7): p. 508–523.
[2] J. Ray, S. Naik, E. Hoff, A. Johnson, J. Ly, C. Easterling, D. Patton, D. Savin. Macromol
Rapid Commun. 2012. 33(9): p. 819–826.
[3] J. Ray, J. Ly, D. Savin. Polym. Chem. 2011, 2, 1536-1541.
L6
26
Analysis of the Substituent Distribution in Cellulose Ethers
P. Mischnick1, M. Bol
1, J. Cuers
1, K. Voiges
1, I. Unterieser
1, R. Adden
2, M.
Rinken3
1Technische Universität Braunschweig, Institute of Food Chemistry, Schleinitzstr.
20, D-38106 Braunschweig, Germany, 2 Dow Pharma and Food Solutions, August-
Wolff-Str. 13, 29699 Bomlitz, Germany, 3 Dow Deutschland Anlagengesellschaft
mbH, Werk Stade, Bützflether Sand, 21683 Stade. [email protected]
Cellulose is a very interesting, abundant and renewable biopolymer provided by nature. By
chemical modification, mainly esterification or etherification, a wide range of semisynthetic
polymers with new properties are obtained. These properties like water solubility, viscosity,
thermoreversible gelation or film formation depend on molecular weight distribution, type of
substituent(s), degree of substitution (DS) and distribution over the polymer chains as well [1].
This lecture will focus on the analysis of various cellulose ethers [2-10]. Beside monomer
analysis [3,11], substituent profiles in oligomeric domains have been studied by (LC)-ESI-IT- or
MALDI-ToF mass spectrometry [4-10] (Figure 1).
Figure 1: MS profiles of obtained from labeled oligomer derivatives of HPMC [10]
The concept comprises quantitative analysis of the molar composition of glucoses with various
numbers and location of substituents, preparation of oligosaccharide mixtures for quantitative
MS analysis and comparison of the experimentally obtained profiles with a calculated random
distribution. For a deeper insight in heterogeneities in the bulk material, fractionation has been
performed prior to further structure analysis [5].
Acknowledgement
Financial support from the Deutsche Forschungsgemeinschaft (DFG, MI 398/11-1) and
Bundesministerium für Bildung und Forschung (BMBF FKZ 0330837A) is gratefully
acknowledged. References [1] – P. Mischnick and D. Momcilovic, Adv. Carbohydr. Chem. Biochem., 64, 117 (2010).
[2] – P. Mischnick and G. Kühn, Carbohydr. Res., 290, 199 (1996).
[3] – K. Voiges, R. Adden, M. Rinken, and P. Mischnick, Cellulose, 19, 993 (2012).
[4] – J. Cuers, I. Unterieser, W. Burchard, R. Adden, M. Rinken, and P. Mischnick, Carbohydr. Res., 348,
55 (2012).
[5] – R. Adden, R. Müller, and P. Mischnick, Macromol. Chem. Phys., 207, 954 (2006). [6] – R. Adden, R. Müller, G. Brinkmalm, R. Ehrler, and P. Mischnick, Macromol. Bioscience, 6, 435
(2006).
[7] – R. Adden, W. Niedner, R. Müller, and P. Mischnick, Anal. Chem., 78, 1146 (2006).
[8] – P. Mischnick, I. Unterieser, K. Voiges, J. Cuers, M. Rinken, and R. Adden, Macromol. Chem. Phys.,
214, 1363 (2013).
[9] – R. Adden, R. Müller, and P. Mischnick, Cellulose, 13, 459 (2006).
[10] – J. Cuers, M. Rinken, R. Adden, and P. Mischnick, Anal. Bioanal Chem., 405, 9021 (2013).
[11] – R. Adden and P. Mischnick, Int. J. Mass Spectrom., 242, 63 (2005).
L7
27
Probing Semi-crystalline and Amorphous Structure in Polymer Systems using
Neutron Scattering, Neutron Imaging, and Neutron Spectroscopy
Ronald L. Jones
Director, NIST nSoft Consortium
Neutron scattering has been applied to the study of semi-crystalline and amorphous polymer
solutions and melts for nearly 50 years. The large contrast between hydrogen and deuterium
provides and opportunity to probe some of the largest issues in polymer science related to
macromolecular topology such as short and long chain branching, structure at hard/soft
interfaces, segregation of polydisperse samples, and others. I will briefly introduce the field of
neutron scattering and related techniques in imaging and spectroscopy. The presentation will
then focus on recent data from our group that highlight our efforts to advance the measurement
of structure in the inter-lamellar amorphous region of semicrystalline polymers, and the
characterization of macromolecules with increasing complexity in chemistry and topology in the
plastics and pharmaceutical industries
L8
28
.In situ Thin Film Processing characterization using X-Rays
Alexander Hexemer
Lawrence Berkeley National Lab
Grazing Incidence Small-Angle Scattering (GISAXS) is a valuable experimental technique in
probing nano structures of thin polymer science. Most of the GISAXS work on thin polymer films so far
has been performed on statics samples. However, understanding the morphology evolution during the
actual polymer processing is extremely crucial. Understanding what happends during e.g. slot die printing
allows to tune the processing parameters to better determine the final properties of thin films. To address
this challenge, we have constructed a miniature slot-die coating system that mimics commercial coaters
and that can be installed directly into the GISAXS beamline 7.3.3 at the ALS, where in situ x-ray
scattering and diffraction can be performed as organic photovoltaics films are being coated onto either
rigid or flexible electrode surfaces. Importantly, this mini-slot-die coater uses very small amounts of
material, allowing the rapid and inexpensive screening of a large number of different materials. With the
mini-slot-die coater in the x-ray beamline, we can watch the development of structures at size scales
ranging from angstroms to thousands of angstroms under different drying conditions, and then can tune
and balance the rate of solvent evaporation, phase separation, and crystallization to optimize performance
on exactly the same devices for which they have the structural data. This represents a tremendous advance
because, using only small amounts of material, we can discover exactly the chemical structure and
processing conditions that will yield the best OPV device.
L9
29
Characterizing Block Copolymer Thin Films with Grazing-Incidence Small
Angle X-ray Scattering
Gila Stein
Ernest J. and Barbara M. Henley Assistant Professor of Chemical and
Biomolecular Engineering
Abstract: Grazing incidence small-angle X-ray scattering (GISAXS) is a powerful method for
quantitative characterization of nanostructured polymer films. This reflection-mode technique
illuminates the sample with a shallow incidence angle and records the off-specular scattering
with an area detector. Analyzing these data is non-trivial, as models must include refraction
corrections and account for multiple scattering events. In this talk, I will provide an overview of
the GISAXS experiment, and then discuss qualitative and quantitative approaches for
interpreting the data. I will present two case studies that illustrate how GISAXS measurements
can detect confinement-induced behavior in block copolymer thin films: First, I will show that
GISAXS detects complex symmetry transitions in thin films of spherical-domain block
copolymers. These transitions (from hexagonal to face-centered orthorhombic to body-centered
cubic) are driven by packing frustration in the confined geometry, and the equilibrium symmetry
depends on the thickness of the film. Second, I will discuss domain orientations in thin films of
lamellar copolymers on “nearly-neutral” substrates. Through detailed analysis of GISAXS data,
we show that lamellae can bend near the bottom of the film. The extent of these deformations is
controlled by film thickness and preferential interactions with the underlying substrate, and such
defects have important implications for microelectronics patterning based on block copolymer
lithography.
L10
30
Understanding the inner morphology of polymeric nanoparticles: expect the
unexpected
Roberto Simonutti
Department of Materials Science, University of Milano-Bicocca, via R. Cozzi 55,
20125 Milan, Italy [email protected]
Nowadays polymer nanoparticles are extensively studied due to their potential applications in
many areas: from drug delivery to cosmetics, from self healing materials to photonics. In order to
completely dominate their properties a detailed characterization of the inner morphology is
necessary. In this contribution I report our multi-technique approach that relies not only on
Transmission Electron Microscopy, but also on solid state NMR, force measurements with
atomic force microscope and time resolved fluorescent spectroscopy of molecular rotors.1 We
applied this approach in the characterization of nanoparticles formed by amphiphilic block
copolymers, poly(N,N -dimethylacrylamide)-block–polystyrene, with different molecular
weights and ratio between the two blocks. In the case of very short hydrophilic block (PDMA10-
b-PS62) we demonstrated an unexpected granular structure of the nanoparticles (Figure 1).2
Figure 1:TEM image of granular PDMA10-b-PS62 nanoparticle with a cartoon describing the
inner morphology.
In the case of core shell poly(n-butylacrylate)/polystyrene nanoparticles (PBA/PS NPs) prepared
via semi-continuous miniemulsion polymerization, the morphology is studied via SEM and
AFM. Composition and local mobility of the system are probed with Solid state NMR (TD-1H-
NMR, CP-MAS and SPE 13
C-NMR). All the data fit a morphological core-shell sharp interface
model, demonstrating the sequestration of the PBA core into the PS shell and probing that the
peculiar mobility of each phase is preserved. Single particle nanomechanics is performed with
AFM force spectroscopy providing clear evidence that the collapse of the NPs is governed by the
baroplastic mixing of the two phases.
References
[1] G. Vaccaro, A. Bianchi, M. Mauri, S. Bonetti, F. Meinardi, A. Sanguineti, R. Simonutti, and
L. Beverina, Chemical Communications 49 (76), 8474 (2013).
[2] A. Bianchi, M. Mauri, S. Bonetti, K. Koynov, M. Kappl, I. Lieberwirth, H.-J. Butt, and R.
Simonutti, Macromolecular rapid communications 35 (23), 1994
L11
31
Nanoscale Molecular Imaging in Polymer Systems
G. F. Meyers, M. A. Rickard, C. W. Reinhardt, J. J. Stanley
The Dow Chemical Company, Corporate R&D-Analytical Sciences, Midland, MI,
48677
[email protected] Scanned probe microscopy (SPM) has had a long history at The Dow Chemical Company,
beginning in the late 1980s when commercial scanning tunneling microscopes were just hitting
the market. Since that time Dow has invested in internal and external collaborative efforts to
drive and develop atomic force microscopy (AFM) based technologies for property
measurements of polymeric materials at nanometer length scales. These capabilities continue to
provide both mechanical spectroscopy and mapping. What these techniques lack, however, is
chemical specificity.
From 2008-2010 Dow worked with Anasys Instruments on the development of an AFM-infrared
(IR) capability (commercialized as the NanoIR in 2010). More recently a top-down version of
the system was commercialized (NanoIR2 in 2013). The AFM-IR method relies on detection of
IR absorption under the AFM tip by rapid photothermal expansion [1]. Such an approach
breaks the diffraction limit enabling IR mapping at <50 nm spatial resolution exceeding that of
confocal Raman by 10X and FTIR by 100X [2].
We will demonstrate the utility and potential of AFM-IR to provide spatially resolved chemical
information in polymer multilayers, phase separated blends, membranes, functionalized resins,
and composites. The method now allows us to ‘see’ where the chemistry goes in the
morphology (Figure 1).
Figure 1: PC\PMMA co-extruded multilayer cross-section showing a) AFM topography; b)
AFM-IR map of carbonate functionality; and c) AFM-IR map of acrylate functionality.
References
[1] A. Dazzi, R. Prazeres, F. Glotin, J. Ortega, Optics Letters 30(18), 2388-2390 (2005).
[2] A. Dazzi, C. Prater, Q. Hu, B. Chase, J. Rabolt, C. Marcott, Applied Spectroscopy 66(12),
1365-1384 (2012).
L12
32
FT-IR Imaging Advances in Polymer Characterization
by Rigoberto C. Advincula
Case Western Reserve University
FT-IR Imaging takes advantage of focal plane array (FPA) detectors for investigating multiple
parameters including spatio-temporal events while enabling resolutions even close to diffraction
limit of optical microscopy. While a number of innovative experiments have been used for
biological and biomedical applications, very few have been applied yet to interesting polymer
characterization problems. In this talk, we will describe the efforts done by our research group in
utilizing FT-IR imaging in investigating degradation of polymers, polymer film composition,
DNA-dendrimer film formation, microfiber differentiation for cell growth, 2-D patterning and
selective polymerization, and other interesting uses that complements AFM, XPS, SEM via
chemical mapping and differentiation. The combination of multiple parameters, high
pixelization, X-Y movement, with the possibility of in-situ measurements renders this chemical
mapping method a powerful addition for any polymer characterization approach and
experimental design.
L13
33
An Interfacial Layer – the Key to Properties of Polymer Nanocomposites
Alexei P. Sokolov
Oak Ridge National Laboratory, and University of Tennessee, Knoxville. Email:
Polymer nanocomposites (PNC) are widely used in different applications. Combination of
nanofillers with polymer matrix provide materials with unique mechanical, optical, electrical and
other properties. However, our understanding of these intrinsically heterogeneous materials
remains limited. This talk focuses on importance of interfacial layer between nanofillers and a
polymer matrix. Extremely high area of the interface is the unique property of PNC. Polymer-
nanoparticle interactions lead to significant change in structure and dynamics of polymers close
to the nanofillers surface. The thickness of this interfacial layer is usually estimated to be several
nm. Thus the interfacial layer occupies significant fraction of the nanocomposite materials and
controls many properties. In this talk we overview recent studies on structure and dynamics of
the interfacial layer in various polymer nanocomposite materials using X-ray and dielectric
relaxation spectroscopy [1], combined with MD-simulations. We discuss the role of polymer
rigidity and molecular weight in structure and dynamics of the interfacial layer. As a conclusion,
we emphasize that fundamental understanding of PNC properties requires explicit account of the
intrinsic heterogeneity in these materials.
References [1] – A. Holt, et al., Macromolecules 47, 1837 (2014).
L14
34
Block Copolymer Bottlebrushes: New Routes to Ever Smaller Microdomain
Sizes
Professor Mahesh K. Mahanthappa
Department of Chemistry, University of Wisconsin–Madison, 1101 University Ave.
Madison, WI 53706
Block copolymer self-assembly at the nanoscale presents tremendous opportunities for the
development of new nanotemplates for advanced lithography applications, wherein the
homopolymer-rich microdomain sizes (~ 10–100 nm) are governed by the total copolymer
degree of polymerization, N. However, this methodology is limited in its smallest achievable
length scale, since AB diblock copolymers self–assemble only above a critical N that depends
inversely on the magnitude of the interaction parameter χAB, which quantifies the energetic
repulsions between the dissimilar homopolymer segments. Numerous recent reports have
focused on developing “high χAB” AB diblocks that self–assemble at low values of N. In this talk
we explore the ability of non-linear polymer architectures to induce block copolymer ordering at
reduced length scales. Thus, we describe the melt and thin film self-assembly behavior of block
copolymer bottlebrushes derived from linking the block junctions of low molecular weight AB
diblocks. We quantitatively demonstrate that increasing the bottlebrush backbone degree of
polymerization (Nbackbone) results in as much as a 75% reduction in the critical copolymer arm
degree of polymerization (Narm) required for self-assembly, thus reducing the length scales at
which these materials self-assemble.
L15
35
Microstructured Polymers
Edwin L. Thomas
Dean of Engineering & Professor in Materials Science and NanoEngineering
Rice University, Houston, Texas, 77030
Periodic structures of polymers can be made by self assembly, directed self assembly and by
photolithography. Such materials provide a versatile platform for 1, 2 and 3D periodic nano-
micro scale composites with either dielectric or impedance contrast or both, and these can serve
for example, as photonic and or phononic crystals for electromagnetic and elastic waves as well
as novel metamechanical materials. Compared to electromagnetic waves, elastic waves are both
less complex (longitudinal modes in fluids) and more complex (longitudinal, transverse in-plane
and transverse out-of-plane modes in solids). Current interest is in our group focuses using
design - modeling, fabrication, characterization and property measurement of polymer-based
periodic materials for various applications. Several examples will be described including the
design of structures for multispectral band gaps for elastic waves, the creation of block polymer
and bicontinuous metal-carbon nanoframes for structures that are robust against ballistic
projectiles and quasi-crystalline solid/fluid structures that can steer shock waves.
Reference:
Periodic Materials and Interference Lithography: For Photonics, Phononics and Mechanics, M.
Maldovan and E.L. Thomas, (Wiley-VCH), 2009.
L16
36
Manipulating Polymers with Light Activated Interfacial Chemistries
Christopher J. Ellison
University of Texas at Austin
Small variations in temperature or composition at a fluid interface, often spontaneously
generated, can cause local changes in surface tension and promote convective motion of fluids
by the Marangoni effect. Given this phenomenon is typically experienced in everyday life as a
macroscopic and seemingly stochastic phenomenon, one might imagine harnessing or directing it
to reproducibly form microscale and nanoscale patterns. The magnitude of surface tension
variations needed to promote Marangoni flow are exceedingly small, which is why it occurs
spontaneously as the “tears of wine” phenomena and can promote development of spin coating
striation defects. In this presentation, we report a photochemical strategy to direct Marangoni
convection as a versatile thin film patterning method. Patterned light exposure on a glassy solid
state polymer film leads to a chemical pattern with associated spatially varying surface energies.
Once this solid film is heated to a melt (liquid) state, Marangoni-flow occurs spontaneously with
polymer migrating from low-to-high surface tension regions. As a consequence, film thickness
variations develop which can be monitored in situ by optical microscopy or on cooled, vitrified
films by atomic force microscopy (AFM) and profilometry. A theoretical model, based on
numerical solutions of equations governing thin film dynamics with Marangoni and capillary
stresses, will also be presented along with comparisons between theoretical predictions and
experimental observations. The model accurately predicts the formation, growth, and eventual
dissipation of topographical features with no adjustable parameters. The quality of agreement
between the model predictions and experimental observations suggests this combined
theory/experimental methodology could be used as a measurement method for subtle surface
energy changes and/or diffusion coefficients of any thin film polymer, using only inexpensive
benchtop equipment and materials.
37
CONTRIBUTED TALKS
O1
38
Size exclusion chromatography of Polyoxymethylene and its polyolefin blends-
possibilities and limitations
BG Umesh1, Wenjie Cao
1, Nasser Al-Harbi
1, Ganesh Bhat
1, Al-Assaf Khalid
Hussein1 Rajendra Singh
2
Affiliation: 1SABIC Regional analytical, STC-Riyadh, Kingdom of Saudi Arabia
2SABIC SPDAC, Riyadh, Kingdom of Saudi Arabia
Polymer blends has always been one of the primary research area in the polymer science and
technology. In the recent past, one of such polymer considered for blends studies by academia
and industry is Polyoxymethylene (POM). POM is a highly crystalline polymer that is most
noted for its high stiffness, mechanical strength, abrasion resistance and good resistance to
chemicals and solvents. Therefore, POM has always been subject of interest for blending with
other polymers to explore new properties. The interest to explore new unique properties has
augmented the pressure on development of analytical methods to evaluate its molecular weight
distribution. Whilst size exclusion chromatography (SEC) has been considered for POM
analysis, however its development and effectiveness for POM polyolefin (PO) blend has been
impaired because of, firstly, the difference in solubility parameter, and secondly, a suitable
solvent that can dissolve both these polymer. Therefore, no significant literatures are available on
POM-PO blends characterization by high temperature SEC (HT-SEC). Hence, we present here
the HT-SEC method for estimating molecular weight averages of POM and its PO blends in an
approach where the mobile phase differed from the solvent in which the polymer dissolved. Use
of a mixed solvent creates a challenging condition for the analysis due to preferential solvation
of macromolecules dispersed in mixed solvents. Therefore, in this work we present, along with a
survey of the existing information, our efforts in optimizing the suitable composition of solvent
mixture of a solubility parameter several Hildebrand units (Mpa1/2) different with respect to
polymer at increasing temperature, that enabled dissolution of the POM and its PO blend. This
article presents practical challenges, our effort to develop a high temperature SEC method,
possibilities, limitations and recommendations to overcome these early difficulties by discussing
the results obtained on the samples analyzed with a commercially available SEC instrument.
O2
39
Spectroscopic Characterization of Plasma Nitrogenation of Polymer Surfaces
at Atmospheric Pressure
Z. Khosravi, S. Kotula, C.-P. Klages
Institute of Surface Technology (IOT), Technische Universität Braunschweig,
Bienroder Weg 54 E, 38108 Braunschweig, Germany. z.khosravi@tu-
braunschweig.de, Polymer surfaces, modified by nitrogen plasmas at atmospheric pressure, have been increasingly
used in numerous applications due to their promising properties [1,2]. Plasma-induced chemical
modifications take place only in the topmost atomic layer of the surface. Hence, a high surface
sensitivity is needed to study the effects of plasma treatment. To achieve the required surface
sensitivity, very thin polyethylene layers with thicknesses of around 80 nm were spun-coated on
ZnS internal reflection elements and surface treated in the flowing-post-discharge region of
dielectric barrier discharges (DBDs) in nitrogen-containing gases. Chemical changes on the
polymer surfaces during plasma exposure were analyzed by in situ attenuated total reflection
(ATR) infrared spectroscopy. FTIR-ATR investigations of treated PE surfaces, derivatized in
situ with vapors of 4-(trifluoromethyl)-benzaldehyde (TFBA), were also performed. In the recent
decades TFBA had been used several times for the derivatization of N-plasma-treated surfaces
because it was thought that it reacts selectively with primary amino groups [3]. However, this
assumption is not justified [4]. Our results show that in spite of the virtual absence of primary
amino groups (< 0.3 nm-2
according to hydrogen-deuterium isotope exchange experiments), a
considerable amount of TFBA reacts with the plasma-treated PE surfaces. Also, ex situ FTIR and
XPS investigations of N-plasma treated PE surfaces, derivatized with vapors of nucleophilic
reagents 4-(trifluoromethyl)phenylhydrazine (TFMPH), 2-mercaptoethanol, 4-
(trifluoromethyl)benzylamine were performed. It was shown that a noticeable amount of these
reagents are able to react with the treated surfaces. Evidently the N-treated surfaces show
nucleophilic as well as electrophilic character. This can be attributed, possibly among other
reasons, to the dual reactivity of imines and other groups with N=C moieties [5]. Interestingly
even more of nucleophilic reagent like TFMPH is bonded to the surface than electrophilic
TFBA. This could be seen not only on the surfaces that were treated using a flowing DBD post
discharge but it is also valid for direct plasma treatment [6]. NEXAFS has been applied to detect
the chemical structural variation of plasma treated LDPE thin films after varying plasma
exposure time in DBD afterglow of N2 + x % H2 (x = 0, 1 and 4) mixtures. Nitrogen and carbon
K-edge spectra confirmed the formation of some chemical functionalities containing remarkable
amounts of nitrogen in N=C or N≡C bonds and carbon in C=C bonds. Because there was a lack
of suitable reference NEXAFS data, some saturated and unsaturated ultra-thin imine films were
investigated too [7].
References
[1] – M. Thomas and K. L. Mittal, (Eds.): Atmospheric Pressure Plasma Treatment of Polymers -
Relevance to Adhesion, Wiley VCH, June 2013.
[2] – N. N. Morgan, International Journal of Physical Sciences. 4 (13), 885 (2009).
[3] – P. Favia, M.V. Stendardo, R. d´Agostino, Plasmas and Polymers 1 (2), 91 (1996).
[4] – C.-P. Klages, A. Hinze, Z. Khosravi, Plasma Process. Polym. 10, 948 (2013).
[5] – Z. Khosravi, C.-P. Klages, Plasma Chem. Plasma Process. 34, 661 (2014)
O3
40
Dissolution and Scattering Behavior of Polyethylenes in Dilute solutions and
Relations between Molecular parameters
J.C.J.F.Tacx1, F.P.H.Schreurs
1, V.Ramakrishnan
2 and H.M.Schoffeleers
1
1Sabic, Technology&Innovation Center, STC Geleen, PO Box 319, 6160 AH
Geleen, The Netherlands. 2Sabic, Technology&Innovation Center, STC Bergen op Zoom, PO Box 117,
4600AC, Bergen op zoom, The Netherlands
It is very difficult to obtain molecularly dispersed and stable solutions of polyethylene (PE). In this
investigation the dissolution and the scattering behavior of PE in various solvents were studied for molar
masses ranging from 50 kg/mol to 3750 kg/mol. Determination of ηsp/c of polyethylene as a function of
dissolution time using an Ubbelohde viscometer is an excellent method to determine the rate of
dissolution and the stability of the solution obtained.
There are two categories of polyethylenes. The first one dissolves easy. In Ubbelohde
viscometry, there is steep rise in specific viscosity as a function of time. The maximum value
reached remains constant as function of time. In Zimm plots an almost straight angular
dependence is observed. This angular dependency is well described with a non-linear scattering
function of Ptytsin. Based on the scattering functions, the value for the non-linear expansion
coefficient (ε) was 0 for diphenylether (theta solvent) and 0.06 for 1-CN. The same value was
obtained from the relationship between molar mass and radius of gyration, indicating that the
state of dissolution for this kind of polymer is good. The expansion coefficient was constant for
the entire range 50-3750 kg/mol. The expansion coefficient calculated from viscometric
measurements seems to be too large. The relations between molar mass and second virial
coefficient show exponents of -0.18 and -0.21 for 1-CN and TCB respectively. Moreover,
experimental data points were in agreement with the Mark-Houwink for polyethylenes. This all
indicates the very good state of dissolution of these kind of materials.
The other category is the difficult dissolving polyethylenes. In this case the rise in specific
viscosity is less and a maximum appears in the specific viscosity with a subsequent decrease
which seems to approach a limiting value. The Zimm-plots and scattering functions show curved
angular dependencies much more than expected on polydispersity. The second virial coefficient
is generally low. These data points often show up below the Mark-Houwink relation. This is
explained by the bad state of dissolution of these materials leading to too low second virial
coefficients, too high radius of gyration and too high molar masses determined from the Zimm-
plot.
It is proposed that the dissolution characteristics are dependent on the morphology of the
material and specific molecular structures hampering proper dissolution. Using preparative
fractionation according to molar mass, these structures were obtained and characterized in detail
using dynamic mechanical spectroscopy.
O4
41
MULTIDIMENSIONAL HIGH TEMPERATURE LIQUID
CHROMATOGRAPHY
Robert Brüll*, Tibor Macko, Frank Malz
Fraunhofer Institute for Structural Durability and System Reliability (LBF),
Division Plastics, Schlossgartenstraße 6, 64289 Darmstadt, Germany
Phone: +49 6151 705 8639, [email protected] Recently, it has been discovered that polyolefins can be reversibly adsorbed from dilute solution
on graphite, and then selectively be desorbed by using gradients of either solvent or temperature.
This paved the way to separate polyolefins and olefin copolymers according to composition or
microstructure by liquid chromatography [1,2]. Subsequently, corresponding multidimensional
chromatographic techniques were developed to further enhance the molecular information which
can be retrieved from a fractionation based approach [3,4].
Liquid chromatography at critical conditions (LCCC) is a key chromatographic technique which
enables, for example, to separate homopolymers according to different end groups. In LCCC the
elution of the chains occurs independent of their molar mass for a given monomer unit
(Fig. 1a) [5].
Fig. 1: a) correlation between elution volume at peak maximum and the average molar
mass (Mp) of PE in ortho dichlorobenzene (ODCB)/1-decanol and b) concentration of PE in
solution in the system graphite/ODCB as monitored by 1H-NMR
The dynamic development of chromatographic techniques for polyolefins also created the need
to understand the mechanism underlying the interaction between polyolefins and graphitic
surfaces in solution. In particular, Nuclear Magnetic Resonance using carefully optimized
experimental parameters has been proven to be a powerful technique to monitor the adsorption of
polyolefin chains of the surface of graphite (Fig. 1b).
The recent progress in HT HPLC of polyolefins will be reviewed, giving particular emphasis to
the development and applications of LCCC for polyolefins. Evidence about the mechanism of
interaction between the graphite and polyolefins will be described. 1 Macko, T.; Pasch, H. Macromolecules 2009, 42(16), 606
2 van Damme, F. W.; Cong, R.; Stokich, T.; Pell, R.; Miller, M.; Roy, A.; deGroot, A.W.; Lyons, J.; Meunier, D. US 8076147 2009
3 Roy, A.; Miller, M. D.; Meunier, D. M.; deGroot, A. W.; Winniford, W. L.; Van Damme, F. A.; Pell, R. J.; Lyons, J. W. Macromolecules 2010,
43(8), 3710
4 Ginzburg, A; Macko, T; Dolle, V; Brüll, R, Eur. Polym. J., 2010, 1217, 6867
5 Mekap, D; Macko, T; Brüll, R; Cong, R; deGroot, A.W; Parrott, A; Cools, P.J.C.H.; Yau, W. Polymer 2013, 54, 5518
a) b)
O5
42
Conversion and Characterization of Agri-based Materials
H. N. Cheng
Southern Regional Research Center
USDA/Agricultural Research Service
1100 Robert E. Lee Blvd.
New Orleans, LA 70124
E-mail: [email protected]
One of the hot research topics today is the use of agri-based materials (e.g., wood, grains,
vegetables, fruits, and seaweeds) as raw materials for further conversion to value-added
products. Indeed most of these natural renewable materials contain useful ingredients, such as
cellulose, hemicellulose, pectin, and triglyceride oils, and they can be modified through
appropriate means to yield a variety of useful derivatives. Different processes have also been
developed to facilitate these conversions, and improved products have been produced. A key
part of these developments is the availability of characterization tools in order to monitor the
reactions, to understand the product structures, to observe the end-use properties, and to derive
structure-property correlations that permit rational product design (Figure 1). In this context, the
use of nuclear magnetic resonance (NMR) is particularly important in structure determination
and in studies of reaction mechanisms. Examples from the speaker’s work will be shown to
illustrate the utility of combining polymer analysis and polymer chemistry to produce new or
improved functional materials.
2
ChemistrySource Structure or Process Product
Natural source Chemical Chemistry - intrinsic(cotton, soybean, - composition - derivatize propertiesnut shells, etc.) - byproducts - hydrolyze - end-use
- MW - crosslink properties- hydrogen bonding - formulate - new- hydrophobicity - stabilize functions- conformation
Process - costPhysical - extract - safety- morphology - separate - efficiency vs.- softening point - purify competition- Tg and Tm - manage cost - patentability- Others - manage waste
Polymer CharacterizationFractionation NMR, IR, mass spec Analysis AnalysisExtraction SEC, HPLC Property testing Property testingAnalysis Compu-chem Process studies Process studies
Microscopy, EDX, XRD Quality controlScattering
Figure 1: Simplified scheme for the conversion and the characterization of agri-based materials
O6
43
DNA-Chitosan Electrostatic Complex Formation:
Stoichiometry and Conformation
L.M. Bravo-Anaya1,2
, Y. Rharbi1, J.F.A. Soltero
2 , M. Rinaudo
3
1Univ. Grenoble Alpes, LRP, F-38000 Grenoble (France)
2Departamento de Ingeniería Química, Universidad de Guadalajara, 44430,
Guadalajara, Jalisco (México) 3Biomaterials Applications, 6 rue Lesdiguières, 38000 Grenoble (France)
e-mail: [email protected], [email protected]
Electrostatic complexes between oppositely charged polyelectrolytes involving natural
biopolymers are being developed for biomedical applications. Up to now, chitosan and DNA
have been investigated for gene delivery due to the advantages that chitosan provides as a
biocompatible and biodegradable non-viral vector which does not produce immunological
reactions, contrary to viral vectors [1]. Chitosan has also been used and studied for its ability to
protect DNA from nuclease degradation and to transfect DNA into several kinds of cells [2]. In
this work, high molecular weight DNA is complexed with chitosan. Different techniques are
used to determine the role of chitosan amount on the formed complex: the obtained data from
conductivity, -potential and dynamic light scattering measurements are combined to determine
the stoichiometry of the complex in dependence of pH. The isoelectric point has found to be
related to the protonation degree of chitosan. The influence of chitosan and DNA concentrations
on the complex formation is discussed and optimized to get stable nanoparticles. The
modification of conformation is presented during complex formation using circular dichroism.
Figure 1 shows -potential evolution for DNA titration at a concentration of 0.03 mg/mL by
chitosan, 1mg/mL, at a pH 6.5 and a temperature of 24 ± 1 ºC.
Our results indicate that the complex is formed between fully ionized phosphates (strong
phosphoric acid) and the fraction of protonated chitosan (NH3+= 0.16 at pH=6.5).
References
[1] – M. Lavertu, S. Méthot, N. Tran-Khanh and M. D. Buschmann, Biomaterials 27 , 4815 -
4824 (2006).
[2] – Z.-X. Liao, S.-F. Peng, Y.-C. Ho, F.-L. Mi, B. Maiti and H.-W. Sung, Biomaterials 33,
3306-3315 (2012).
O7
44
New Approaches in Analysis of Drug Delivery Formulations:
Measuring Domain Sizes in Multi-Component Celluloses Using NMR
Staffan Schantz1, Judith Schlagnitweit
2, Mingxue Tang
2, Maria Baias
2, Aaron J.
Rossini2,3
, Sara Richardson1, Lyndon Emsley
2,3
1AstraZeneca R&D, Pharmaceutical Development, Mölndal, Sweden,
2Centre de RMN à très hauts champs, Université de Lyon (ENS Lyon/CNRS/UCB
Lyon1), France
3Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de
Lausanne (EPFL), CH-1015 Lausanne, Switzerland Pharmaceutical dosage forms of active drugs often include film coatings formed in spray
processes from polymer solutions or suspensions. To develop and fine-tune the formulation in
terms of drug release characteristics, multi-component polymer mixtures are often used.
However, elucidating the morphology of such multi-phase blends remains a formidable
challenge in materials science. Especially for film coatings in controlled drug delivery, to better
understand and control the in-vivo plasma concentration of a drug over time, it is crucial to
determine the structure and the domain size of each coating component.
We have developed a series of new natural abundance NMR methods to determine domain sizes
selectively in mixtures of ethyl cellulose (EC) and hydroxypropyl cellulose (HPC), important
cellulose derivatives used in formulations with widespread applicability in the pharmaceutical
industry, i.e. in tablet or pellet dosage forms as binders or film coatings. We apply these methods
to controlled release formulations originating from an industrial pharmaceutical process without
the need for any advanced sample preparation.
The first method is based on proton detected spin diffusion experiments, previously used in the
characterization of semicrystalline polymer morphologies [1-2]. Here we have developed a
carbon-edited mobility-filtered 1H spin diffusion experiment in which magnetization in well
defined domains is selected an its diffusion over the sample is monitored. Modelling the spin
diffusion process using the diffusion equation then allows us to obtain the domain sizes of the
various components in the film coatings. The second and third method makes use of alternative
ways of introducing a non-equilibrium state of polarization in the solid formulation through
addition of stable radicals, so-called surface enhanced DNP (Dynamic Nuclear Polarization) [3]
and local PRE (Paramagnetic Relaxation Enhancement) [4].
References
[1] - J. Clauss, K. Schmidt-Rohr, H.W. Spiess, Acta Polymer 1993, 44, 1-17.
[2] - D.E. Demco, A. Johansson, J. Tegenfeldt, Solid State Nucl. Magn. Reson. 1995, 4, 13-38.
[3] - A.J. Rossini, A. Zagdoun, F. Hegner, M. Schwarzwalder, D. Gajan, C. Coperet, A. Lesage,
L. Emsley;
J. Am. Chem. Soc. 2012, 134, 16899-16908.
[4] - N. Bloembergen, Physica 1949, 15, 386-426.
O8
45
Preparation and Characterization of microporous hydrogels of cellulose ether
cross-linked with di- or poly functional glycidyl ether made for the delivery of
bioactive substances
O.S Lawal1, M. Yoshimura
2, R. Fukae
2, K. Nishinari
3
1Department of Chemical Sciences, Olabisi Onabanjo University, P.M.B 2002,
Ago-Iwoye, Nigeria. E-mail : [email protected]
2School of Human Science and Environment, University of Hyogo, 1-1-12
Shinzaike-honcho, Himeji, Hyogo 670-0092, Japan
3 Graduate School of Human Life Science, Osaka City University, Sumiyoshi,
Osaka 558-8585, Japan
Abstract
Hydrogels of carboxymethyl biopolymers have wide industrial applications [1]. Hydrogels were
prepared by the cross-linking reactions of carboxymethyl cellulose (CMC) with di-or poly
functional glycidyl ether to investigate the effects of different cross-linker`s chain length and the
number of epoxy groups on the properties of the gels. Fourier transform infrared spectra showed
a new peak at ν =1740 cm-1
. The interior morphology data indicated microporous network
structures which correlated with the swelling of hydrogels. The swelling data in water, urea,
sucrose, urine and aspartame showed increases in swelling with increase in chain length of the
cross-linker but decreased with the number of epoxy groups on the cross-linker. Collectively, the
gels were ionic strength sensitive[2]. The rheology experiments showed that gel point (tgel)
increased with the chain length of the cross-linker but reduced with increase in number of epoxy
groups on the cross-linker. Dynamic oscillatory measurements indicated stronger material
functions in gels prepared with polyfunctional epoxy cross-linkers. The hydrogels prepared with
di-functional epoxy groups had higher loading capacity and faster release of bovine serum
albumin (BSA) compared with hydrogels based on polyfunctional epoxy group cross-linkers.
References
[1]Lawal OS, Storz J, Storz H, Lohmann D, Lechner MD, Kulicke WM (2009) Hydrogels based
on carboxymethyl cassava starch cross-linked with di- or polyfunctional carboxylic acids:
Synthesis, water absorbent behaviour and rheological characterizations. Eur Polym J 45:
3399-3408.
[2].Nishinari K (2009) Some thoughts on the definition of a gel. Progr Colloid Polym Sci 136:
87-94.
O9
46
The Recent Advances and Challenges in Polyolefin Comonomer Distribution
Analysis
Rongjuan Cong & Willem deGroot
Performance Plastics Characterization Group
The Dow Chemical Company
Freeport, TX 77541, USA
Over the last 30 years, several analytical techniques have been developed to analyze the
comonomer distribution of polyolefins. The key techniques include temperature rising elution
fractionation (TREF)1, crystallization analysis fractionation (CRYSTAF)
2, and crystallization
elution fractionation (CEF)3. All of these techniques are based on crystallinity which primarily is
a function of the comonomer composition and its distribution. Two key challenges for
crystallization-based techniques are a narrow comonomer range (up to approximately 8 mol%)
and co-crystallization. Co-crystallization can pose a challenge for complex multiple-component
systems, even with increased analysis time to enhance resolution. Very recently, high
temperature liquid chromatography of polyolefins (using both solvent gradient4,5
and thermal
gradient6,7
) has been developed. These new techniques are able to separate a larger range of
comonomer content and eliminate co-crystallization. This paper is focused on the recent
advancements, understanding of the separation mechanism, and the application of various
techniques to characterize complex polyolefin microstructures.
References
[1] Wild, L. Adv. Polym. Sci. 1990, 98, 1
[2] Monrabal, B. J. Appl. Polym. Sci. 1994, 52, 491
[3] Monrabal, B.; Sancho-Tello, J.; Mayo, N.; Romero, L. Macromolecular Symposia. 2007,
257, 71
[4]van Damme F., Winniford, B., et al. US Patent 8,076,147
[5]Macko, T.; Pasch, H. Macromolecules, 2009, 42, 6063
[6]Cong, R. deGroot, W. et al. Macromolecules, 2011, 44, 302
[7]Winniford, B.; Cong, et al. US Patent 8,318,896
O10
47
New NMR Techniques Developed Recently for Studying Polyolefin
Microstructures
Zhe Zhou ([email protected]),1 R. Kuemmerle,
2 D. Mekap,
3 D. Redwine,
1 R.
Cong,1 F. Malz,
3 R. Brüll,
3 J. C. Stevens,
1 J. Klosin,
1 X. Qiu,
1 Y. He,
1 B.
Winniford,1 M. Miller,
1 P. Chauvel,
1 W. deGroot,
1 M. Cheatham,
1 D. Baugh,
1 M.
Paradkar1
1The Dow Chemical Company, USA;
2Bruker, Switzerland;
3Fraunhofer Institute
for Structural Durability and System Reliability LBF, Germany
Polyolefins, with their excellent cost/performance ratio, are by volume the most produced
synthetic polymers with a global production of 147 million tons in 2011 and a predicted growth
to 170 million tons by 2017.1 Understanding polyolefin molecular structure and property
relationships are a key to improve catalyst systems and process technologies.2 NMR is one of the
best techniques to achieve this goal. New NMR techniques developed recently, such as bi-level
decoupling to remove proton decoupling artifacts in 13
C NMR of polyolefins,3 10 mm high
temperature cryoprobe which brought a revolution to NMR characterization of polyolefins in
chemical industry (Table 1),4-7
unsaturation measurements of polyolefins with the high
temperature cryoprobe8 and temperature gradient NMR with stationary phase in contact with the
analyte solution in the NMR tube (TGNMR)8 for characterizing polyolefins
9 will be presented.
Table 1. 13
C NMR S/N ratios of different 10 mm probes.
References 1. Plastic News 2012, August 30.
2. D. Arriola, E. Carnahan, P. Hustad, R. Kuhlman, T. Wenzel, Science 2006, 312, 714.
3. Z. Zhou, R. Kuemmerle, X. Qiu, D. Redwine, R. Cong, A. Taha, D. Baugh, B. Winniford, Journal of Magnetic Resonance, 2007, 187, 225.
4. Z. Zhou, R. Kuemmerle, J. C. Stevens, D. Redwine, Y. He, X. Qiu, R. Cong, J. Klosin, N. Montañez, G. Roof,
Journal of Magnetic Resonance, 2009, 200, 328.
5. Z. Zhou, J. C. Stevens, J. Klosin, R. Kümmerle, X. Qiu, D. Redwine, R. Cong, A. Taha, J. Mason, B. Winniford,
P. Chauvel, N. Montañez, Macromolecules, 2009, 42, 2291.
6. R. Cong, W. deGroot, A. Parrott, W. Yau, L. Hazlitt, R. Brown, M. Miller, Z. Zhou, Macromolecules, 2011, 44,
3062.
7. K. Frazier, R. Froese, Y. He, J. Klosin, C. Theriault, P. Vosejpka, Z. Zhou, K. Abboud, Organometallics, 2011,
30, 3318.
8. Z. Zhou, R. Cong, Y. He, M. Paradkar, M. Demirors, M. Cheatham, W. deGroot, Macromolecular Symposia,
2012, 312, 88. 9. D. Mekap, F. Malz, R. Brüll, Z. Zhou, R. Cong, A. W. deGroot, A. R. Parrott, Macromolecules, 2014, 47, 7939.
O11
48
Characterization of polypropylene in dibutoxymethane by high temperature
gel permeation chromatography with triple detection
A. Boborodea1, S. J. O’Donohue
2
1Certech ASBL, Rue Jules Bordet, Zone industrielle C, B-7180 Seneffe, Belgium
2Agilent Technologies LDA UK Ltd, Craven Arms, Shropshire SY7 8NR, UK
This study presents the possibility to replace the 1,2,4-trichlorobenzene (TCB) recommended by
ASTM D 6474[1]
for the analysis by gel permeation chromatography (GPC) of polypropylenes
with dibutoxymethane (DBM, butylal), a halogen free and less toxic solvent. The molecular
weight distributions as well as the K and alpha parameters were measured for different types of
commercial polypropylene samples solubilized in TCB, and DBM, using a GPC system fitted
with triple detection (light scattering, differential refractive index and viscometer). For the
analyzed resins, covering typical applications of polypropylene, the GPC method in DBM
provided similar results to those obtained in TCB.
References
[1] - ASTM D 6474 – 12, 2012. Standard Test Method for Determining Molecular Weight
Distribution and Molecular Weight Averages of Polyolefins by High Temperature Gel
Permeation
O12
49
Study of Complex Coacervation of Gelatin A and Pectin for
Microencapsulation of Theophylline
N. Devi, C. Deka, P. Nath, D.K. Kakati
Department of Chemistry, Gauhati University, Guwahati-781014, Assam, India
E-mail:[email protected]
Complex coecervation is gaining importance in the field of drug delivery, agriculture, food and
flavoring systems [1] in the recent years due to its simple and versatile method of preparation. It
involves the electrostatic interaction between the oppositely charged polymers to form a polymer
rich region called the coacervate and a polymer poor region called supernatant [2]. The present
study aims at synthesis and characterization of theophylline-loaded complex coacervate
microcapsules of the biopolymers gelatin A and pectin. Reaction parameters like pH, polymer
ratio and amount of cross-linker, glutaraldehyde were optimized to obtain the maximum yield.
The optimization was based on the relative viscosity, turbidity and UV-visible measurements.
The optimum ratio between gelatin A-pectin and pH for the maximum complex coacervation
was found to be 5.25:1 and pH=3.5, respectively. Theophylline was loaded at the optimized ratio
and pH. The adhesion between the microcapsules was reduced on addition of sodium
carboxymethyl cellulose (SCMC) to the microcapsules. The gelatin A-pectin complex coacervate
and the prepared microcapsules were crosslinked by using glutaraldehyde. The complex
coacervate showed different swelling profiles with changes in pH and glutaraldehyde
crosslinking. The complex coacervate and the prepared microcapsules were characterized by the
Fourier Transform Infrared (FTIR) spectroscopy, UV-visible spectroscopy and scanning electron
microscopy (SEM) study.
Figure 1: SEM images of the neat coacervate (A) and theophylline loaded microcapsules (B)
References
[1] A. Polk, B. Amsden, K. De Yao, T. Peng and M. F. A. Goosen. J. Pharm. Sci. 83, 178 (1994).
[2] E. Tsuchida and K. Abe. Advances in Polymer Science 45, 1-119 (1982).
O13
50
Thermoplastic Elastomer as Toughening Agent for Polylactic acid (PLA):
Effect of blending ratio on morphology and performance
V. Nagarajan1,2
, A.K. Mohanty1,2,*
, M. Misra1,2
1School of Engineering, Thornbrough Building, University of Guelph, Guelph,
Ontario, Canada 2 Bioproducts Discovery and Development centre (BDDC), Department of Plant
Agriculture, University of Guelph, Guelph, Ontario, Canada
Polylactic acid (PLA) is one of the widely studied renewable resource based biopolymer.
Commercial success of PLA in various industrial applications is hindered by its poor resistance
to impact and heat. This study is an attempt to explore the effectiveness of thermoplastic
elastomer (TPE) as a toughening agent for improving the impact strength of PLA. Hytrel®
thermoplastic copolyester of polyether glycol and polybutylene terephthalate was selected as the
TPE of choice for this study. Blends of PLA/TPE at varying weight ratios were prepared using
extrusion followed by injection molding technique. Morphologies, thermal, mechanical and
rheological properties of the blends were systematically evaluated. Scanning electron
microscopy (SEM) and Atomic force microscopy (AFM) revealed a phase separated morphology
indicating PLA/TPE to be an immiscible blend system. Co-continuous morphology was observed
at PLA/TPE-(50/50) blend ratio and phase inversion occurred beyond this ratio. Rheological
determination of phase inversion composition supported the morphological observations.
Thermogravimetric analysis (TGA) showed thermal stability of PLA blends to increase with
increasing weight percentage of TPE in the blend, mainly because of TPE having relatively
higher degradation temperature. Optimal synergies of two polymers were found in the PLA/TPE-
(70/30) blend, showing impact strength of 234 J/m, a 6 fold increase compared to neat PLA.
The authors gratefully acknowledge the financial support from (1) the Ontario Ministry of
Agriculture, Food, and Rural Affairs (OMAFRA); OMAFRA New Directions Research Program
(2) the Ontario Ministry of Economic Development and Innovation (MEDI), Ontario Research
Fund, Research Excellence Round 4 program (ORF-RE04) and (3) the Natural Sciences and
Engineering Research Council (NSERC) Canada Discovery grant (awarded to Mohanty) and
Network of Centres of Excellence (NCE) AUTO21 program.
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51
New Insights on Cellulosic Ether Hydrogels
R.L. Sammler1, R. Adden
2, M. Brackhagen
2, M. Knarr
2, Y. Li
3, C. Mohler
4, J.
Moore5, O.D. Redwine
3, M. Rinken
6, and H. Shen
7
The Dow Chemical Company 1Core R&D, Material Science and Engineering, Midland, MI 48674
[email protected]. 2Dow Pharma & Food Solutions, Products/Characterization R&D, 29699 Bomlitz,
Germany. 3Core R&D, Analytical Sciences, Midland, MI 48674.
4Core R&D, Formulation Science, Midland, MI 48674.
5Core R&D, Material Science and Engineering, Midland, MI 48674
6Deutschland Anlagengesellschaft mbH, Analytical Technology Center, Werk
Stade, Bützflether Sand, 21683 Stade, Germany. 7Core R&D, Formulation Science, Collegeville, PA 19477.
Aqueous hydroxypropylmethylcellulose materials (HPMC) often have much lower hot gel
moduli (< 10 Pa) relative to those (3,000 Pa) of aqueous methylcellulose materials (MC) at end-
use concentrations (< 2 wt.%, 90 °C), and these lower moduli limit their use in applications. The
origin of their lower moduli is suspected to arise from the order of two thermal transitions
occuring when warming. One transition, thought to involve a chain conformation transition
when warming, is referred to here as chain collapse. Another, thought to involve the self-
assembly of chains into a three-dimensional physical network when warming, is referred to as
gelation. Often, chain collapse is thought to precede gelation when slowly warming aqueous
commercial HPMC materials from 5 to 90 °C at 1 °C/min, while the opposite order is thought to
occur for many aqueous commercial MC materials. Chain collapse is identified as a sharp drop
in the solution viscosity at pre-gel temperature as T rises. The insensitivity of the chain collapse
temperature to HPMC concentration is used to argue this thermal event is distinct from gelation.
These concepts are supported with the preparation of two developmental HPMC materials with
similar MW and substitution levels (DS & MS). One HPMC material, prepared by a unique
process, is designed to reverse order of the thermal transitions. This HPMC material is found to
exhibit high hot gel moduli similar to those of aqueous MC materials; moreover, its gel is able to
form synerese fluid as it contracts in size when warmed. The gel contraction is thought to be a
manifestation of chain collape.
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52
In Situ SANS Studies of Semi-Crystalline Polymers Under Tensile
Deformation
J.A. Stull1, D.P. Olds
1, J.T. Mang
2, E.B. Orler
1, V. Hartung
1, T. C. Lin
1, S.L.
Edwards1 and C.F. Welch
1
1Materials Science and Technology Division and
2Weapons Experiments Division,
Los Alamos National Laboratory, Los Alamos, New Mexico, 87545;
Semi-crystalline polymers find application in many areas, including electronics, transportation
and defense. In these materials the crystalline domains serve as physical crosslinks throughout
the material. The interactions between the crystalline and amorphous domains dictate the overall
mechanical properties of the material. Furthermore, exposure to extreme environments, including
mechanical, pressure, tensile strain and radiation, can alter the mechanical behavior of these
materials, which in turn affects their performance. Understanding the correlation between these
properties and the performance of the polymer is very important for determining material
lifetimes.
We are using in situ extreme sample environments coupled with small-angle neutron scattering
(SANS) experiments to monitor any nano-scale changes and/or damage to semi-crystalline
polymers. We have developed a tensile stage for use at the LQD beamline at LANL’s Lujan
Neutron Scattering Center. With this sample environment, we have examined several semi-
crystalline polymers, including a fluorinated copolymer (Kel-F 800) and polyethylene. To
complement the morphological and stress-strain data obtained with these experiments,
differential scanning calorimetry (DSC) measured the percent crystallinity of samples in their
initial states and at each strain examined in the SANS experiments.
In pristine Kel-F 800, we observed that, at low strains, the crystalline domains become slightly
oriented in the perpendicular (to strain) direction. Upon further increases of strain, the original
crystalline domains are destroyed and new crystalline domains are formed, oriented parallel to
the strain. While the SANS signals for the polyethylene samples are affected by the high
hydrogen content, we also observe subtle elongations in the scattering patterns parallel to the
strain axis, revealing contours with an elliptical shape. For both polymers, we see a strong
correlation between the SANS experiments and the changes in cystallinity for different strain
rates.
These experiments have yielded unique insight into the structure of semi-crystalline polymer
molecules under stress. By connecting this morphological evolution to the macroscopic behavior,
we can provide insight into molecular-level polymer physics to aid in the development of
improved macroscopic mechanical models.
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53
Quantifying Tie-Chain Content in Semicrystalline Polyolefins with Vapor-
Flow Small-Angle Neutron Scattering
A. G. McDermott1,2
, C. R. Snyder1, P. J. DesLauriers
3 and R. L. Jones
1,2
1National Institute of Standards and Technology, Materials Science and
Engineering Division, Gaithersburg, MD, USA; 2National Institute of Standards
and Technology, nSoft Consortium, Gaithersburg, MD, USA; 3Chevron Phillips
Chemical Company, Bartlesville, OH, USA; [email protected]
Tie molecules bridging adjacent crystalline lamellae in semicrystalline polymers strongly impact
mechanical properties, but they remain difficult to characterize. We demonstrate a new method
of measuring tie-chain content: applying equilibrium swelling theory [1] to small-angle neutron
scattering patterns from semicrystalline polyethylene films whose interlamellar amorphous
regions are swollen with deuterated organic solvent in a vapor-flow sample environment [2]
(Figure 1). To aid in validating the measurement, measured tie-chain content is compared with a
primary structural parameter (PSP2) that is calculated from molecular architecture and correlates
with slow crack growth behavior [3]. Agreement is favorable for a linear polyethylene and a
series of ethylene-hexene copolymers [4]. Recent applications of the technique are also
discussed.
Figure 1: As the interlamellar amorphous layer in polyethylene is swollen with a deuterated
solvent, the peak associated with the long period L shifts to lower wavevectors, and the SANS
intensity increases as the amorphous-crystalline contrast increases. While the free energy of
mixing drives solvent absorption, the entropic cost of tie-molecule stretching restricts swelling.
Parameters derived from modeling SANS patterns are used in thermodynamic analysis to
quantify the tie-chain content.
References [1] – P. J. Flory and J. Rehner, J. Chem. Phys. 11, 521 (1943).
[2] – M.-H. Kim and C. J. Glinka, J. Appl. Cryst. 38, 734-739 (2005); M.-H. Kim and C. J. Glinka, Macromolecules
42, 2618-2625 (2009).
[3] – P. J. DesLauriers and D. C. Rohlfing, Macromol. Symp. 283, 136-149 (2009).
[4] – A. G. McDermott, C. R. Snyder, P. J. DesLauriers, and R. L. Jones. In preparation.
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Heterogeneous Deuterium Distribution in Commercial Polyolefins:
Measurement and SANS Model
Brian M. Habersberger1, Kyle E. Hart
2, Tianzi Huang
3, David Gillespie
3
Dow Chemical Company: 1Elastomers R&D,
2Performance Plastics
Materials Science R&D, 3Performance Plastics Characterization R&D
Catalytic hydrogen-deuterium exchange provides a facile method for labeling commercially
available polyolefins to create contrast for neutron scattering experiments. Unlike commonly
reported model polymers, which have low dispersity and uniform microstructures, commercial
polyolefins may be composed of a broad range of molecular weights with varying amounts of
comonomer distributed heterogeneously among them. Exchange reactions performed on such
complex resins may result in correspondingly nonuniform distributions of deuterium.
Understanding the relative scattering contribution from different populations of chains can be
essential to interpretation of neutron scattering results. Here, a method is described that allows
for semi-quantitative measurement of the distribution of deuterium across molecular weights
using size exclusion chromatography with infrared detection. The Random Phase Approximation
prediction for scattering from homogeneous polymer blends is adapted to model measured SANS
patterns for a polymer of known deuterium distribution. Additionally, a Monte-Carlo method is
used to calculate the deuterium distribution that corresponds to the experimental SANS
measurements. These methods provide powerful tools for probing the structure of non-ideal
polymer architectures.
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55
Hydrophobically Modified Ethylene Oxide Urethane (HEUR) Based Coatings:
Mesoscale Structure Under Shear and Viscosity
T. Chatterjee1, A.K. VanDyk
2, V.V. Ginzburg
1, A.I. Nakatani
3
The Dow Chemical Company 1Core R&D, Material Science and Engineering, Midland, MI 48674
[email protected]. 2Dow Coatings Materials, Collegeville, PA 19426.
3Core R&D, Analytical Sciences, Collegeville, PA 19426.
Paints are complex formulations of polymeric binders, inorganic pigments, dispersants,
surfactants, colorants, rheology modifiers, and other additives. A commercially successful paint
exhibits a desired viscosity profile over a wide shear rate range from ~10-5
s-1
for settling to > 104
s-1
for brushing, rolling, and spray applications. Understanding paint formulation structure is
critical as it governs the paint viscosity profile. However, probing paint formulation structure
under shear is a challenging task due to the formulation complexity containing structures with
different hierarchical length scales and their alterations under the influence of an external flow
field. In this work mesoscale structures of paint formulations under shear are investigated using
Ultra Small-Angle Neutron Scattering (rheo-USANS). Contrast match conditions were utilized
to independently probe the structure of latex binder particle aggregates and the TiO2 pigment
particle aggregates. Rheo-USANS data revealed that the aggregates are fractal in nature and their
self-similarity dimensions and correlations lengths depend on the chemistry of the binder
particles, the type of rheology modifier present and the shear stress imposed upon the
formulation. These fractal aggregates are the primary structures responsible for coatings
formulation viscosity. Based on these structural parameters, a new model for the viscosity of
coatings formulations has been developed, which is capable of reproducing the observed
viscosity behavior.
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56
FULL MOLECULAR CHARACTERIZATION OF COMPLEX
POLYMERS: MISSION IMPOSSIBLE ?
H. Pasch
SASOL Chair in Analytical Polymer Science, University of Stellenbosch,
Department of Chemistry & Polymer Science, 7602 Stellenbosch, South Africa, e-
mail: [email protected]
Complex polymers are distributed in two or more parameters of molecular heterogeneity, e.g. in
molar mass and chemical composition in the case of copolymers. Liquid chromatographic
techniques are well suited to address the molecular structure of complex polymers. Size
exclusion chromatography (SEC) separates polymers according to molecular size which is not
only a function of chain length but also of chemical composition and molecular topology.
Therefore, the correlation between molecular size and molar mass can only be obtained when
SEC is coupled to molar mass sensitive detectors or when size separation is combined with
chemical composition separation. Similarly, interaction chromatography which is mainly
separating regarding chemical composition is influenced by the molar mass distribution, the
molecular topology and the functionality type distribution.
In the last decade various methods of multidimensional chromatography have been developed
that separate complex polymers regarding chemical composition (or functionality) and molecular
size. In favourable cases fractions are obtained that are very homogeneous regarding molecular
size and chemical composition. The sequence of separations can be adapted to the specifics of
the sample and, thus, the setup is highly flexible. However, detection in multidimensional
chromatography is normally done with a concentration-sensitive detector and, therefore,
information on the chemical composition of the separated species is not obtained.
The present talk discusses strategies for the quantitative analysis of complex polymers by
multidimensional chromatography. It will be shown that spectroscopic detectors can be coupled
directly to multidimensional separations providing chemical composition information. The
application of this approach to the analysis of segmented copolymers will be presented.
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Monitoring the onset and evolution of polymer stimuli responsive behavior
during synthesis
Wayne F. Reed1, Zifu Zhu
1, Colin A. McFaul
1, Michael F. Drenski
2
1Tulane University,
2Advanced Polymer Monitoring Technologies, Inc.,
Polymers with increasingly sophisticated properties are being constantly developed. Some of
these are classified as ‘stimuli responsive polymers’, and have the ability to respond to stimuli
such as heat, light and changing solution conditions, including pH, ionic strength, solvent
polarity, and the presence of specific molecules or agents. The form of response can be a phase
change, conformational transition, micellization, supra-molecular assembly, entrapment or
release of a guest molecule, among others. Numerous potential applications include drug
delivery and other areas of nanomedicine, self-healing materials, sensors, and ‘smart materials’.
The ‘Second Generation Automatic Continuous Online Monitoring of Polymerization reactions’,
or SGA, allows monitoring the onset and evolution of stimuli responsive behavior during
synthesis. This is achieved by coupling a custom-built multi-stage detector train to the highly
dilute, continuous sample stream issuing from the automatic sample extraction and conditioning
stage. Each stage contains a viscometer and light scattering detector and measures the
characteristics of the polymer in the stream under a specific solution condition. The current SGA
embodiment has seven stages. In this presentation results are shown for two types of polymer
stimuli behavior; the first is the response of a copolymer polyelectrolyte at each instant of its
synthesis to ionic strength varying from 0.1mM to 200mM. The response is correlated to both
the comonomer composition and molar mass of the copolymers at any time. The second
example involves the response of copolymers of n-isopropyl acrylamide (NIPAM) to
temperature, and how the Lower Critical Solution Temperature (LCST) varies with copolymer
composition drift during synthesis. This work is the beginning of a larger project that will
involve use of the SGA system by a consortium of polymer synthetic chemists producing novel
stimuli responsive polymers.
This work was supported in part by the U.S. National Science Foundation under the NSF
EPSCoR Cooperative Agreement No. EPS-1430280 with additional support from the Louisiana
Board of Regents
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Synthesis and Characterization of Neem (Azadirachta Indica A.Zuss.) Seed
Oil-based Alkyd Resin
N. Devi, N. Sharma, M. M. Bora, D. K. Kakati
Department of Chemistry, Gauhati University, Assam, India-781014
E-mail: [email protected]
Azadirachta Indica A. Juss., commonly known as the ‘neem’ is a fast growing tree that belongs
to Meliceae family. It is an evergreen tree but under extreme circumstances, such as extended
dry periods, it may become leafless. The neem is native of Indian subcontinent and is widely
distributed by introduction, mainly in the drier (arid) tropical and subtropical zones of Asia,
Africa, the Americas, Australia and the South Pacific islands [1]. The tree produces seeds which
can be extracted to get neem seed oil (NSO) [2,3]. Mature neem seed gives upto 50% of NSO.
Three different alkyd resins (Figure1) based on purified NSO were synthesized by two-stage
alcoholysis–polyesterification reaction of this oil with phthalic and maleic anhydride. The
synthesized alkyd resins were characterized by the FTIR and 1H NMR spectroscopic analysis.
Resins were cured by blending with epoxy resin. The surface characteristic of the cured resins
was studied by SEM analysis. Further characterizations of NSO and resins were carried out by
using the GPC analysis and measurement of physico-chemical properties. The coating
performance of the cured resins was tested by measuring chemical resistance, thermal stability,
pencil hardness, gloss and adhesion. The study revealed that NSO is a good source of renewable
raw material having the potential to synthesize alkyd resins for the coating industry.
Figure 1: Neem seed oil (A) and neem seed oil-based alkyd resins (B,C,D)
References
[1] www.neemfoundation.org
[2] A. M. Dave, M.H. Mehta, T.M. Aminabhavi, A.R. Kulkarni, K..S.Soppimath, Polym Plast
Technol Eng. 38, 673(1999).
[3] N.Devi and T.K.Maji, J Appl Polym Sci.113,1576(2009).
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Characterization of a new high temperature thermoplastic elastomer
synthesized by living anionic polymerization in hydrocarbon solvent at room
temperature
Weiyu Wang1, Ralf Schlegel
2, Tyler White
1, Nam-Goo Kang
1, Mario Beiner
2,
Jimmy Mays1*
1Department of Chemistry, University of Tennessee, Knoxville, TN 37996, USA
2LB Polymerbas. Materialdesign, Fraunhofer-Institut für Werkstoffmechanik
IWM, 06120 Halle, Germany
[email protected], [email protected]
High temperature application of styrenic thermoplastic elastomers (S-TPEs) is largely limited by
the glass transition temperature (Tg) of polystyrene (Tg = 100 °C) [1, 2]. In order to improve the
upper service temperature of S-TPEs, three requirements need to be fulfilled for the interest of
both scientific research and industrial application. These requirements are: 1) polymers is
synthesized in hydrocarbon solvent at room temperature by anionic polymerization, 2) polymer
has a glass transition higher than 120 °C for high temperature application but lower than 180 °C
for the purpose of processing, 3) polymer undergoes micro-phase separation with either
polyisoprene or polybutadiene to form strong physical crosslinks. Here we present the
characterization of a new high temperature thermoplastic elastomer based on polybenzofulvene-
b-polyisoprene-b-polybenzofulvene (FIF) triblock copolymers, which was synthesized in
hydrocarbon solvent at room temperature by living anionic polymerization (Figure 1). For FIF-
20 with 15 vol% of polybenzofulvene, tensile test showed maximum tensile stress of 15 MPa
with 1500% strain at break. Dynamic mechanical analysis indicates that the storage modulus of
FIF copolymers starts to drop when temperature approaches 150°C. Phase separation of
polybenzofulvene and polyisoprene was confirmed by AFM at cross-section with cryo-
microtomed FIF samples.
Figure 1. Polybenzofulvene-b-polyisoprene-b-polybenzofulvene (FIF) triblock copolymers
References
[1] - J. Drobny, Handbook of thermoplastic elastomers, William Andrew Publishing, 2014
[2] - Henry Hsieh, Anionic Polymerization: Principles and Practical Applications, CRC Press,
1996
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Characterization of a Polyethylene – Polyamide Multilayer Film Using
Nanoscale Infrared Spectroscopy and Imaging
C. Marcott1, M. Lo
2, E. Dillon
2, K. Kjoller
2, C. Prater
2, M. Kelchermans
3
1Light Light Solutions, LLC., P. O. Box 81486, Athens, GA 30608-1484, USA,
2Anasys Instruments, Inc., 325 Chapala Street, Santa Barbara, CA 93101, USA, 3ExxonMobile Chemical Europe, Hermeslaan 2, B-1831 Machelen, Belgium,
Atomic force microscopy (AFM) and infrared (IR) spectroscopy have been combined in a single
instrument (AFM-IR) capable of producing IR spectra and absorption images at sub-micrometer
spatial resolution [1]. This new device enables cross sections of multilayer films to be
spectroscopically characterized at levels not previously possible. In particular, it was possible to
observe nanoscale IR spectroscopic differences, as well as thermal and mechanical property
differences, in the tie layers located between the individual polyethylene and polyamide layers of
a multilayer film of unknown structure. It also appears that a two-µm-thick barrier layer
between two polyamide layers near the center of the multilayer film consist of an ethylene (vinyl
alcohol) copolymer. Mechanical stiffness and thermal property differences are also observed
between the various layers in the film. This powerful capability should prove generally useful
for reverse engineering complex unknown multilayer film materials, as well as in aiding the
intelligent design of superior multilayer film materials.
References
[1] – A. Dazzi, C. B. Prater, Q. Hu, D. B. Chase, J. F. Rabolt, and C. Marcott, Appl. Spectrosc.
66, 1365 (2012).
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Solid-State NMR in Industrial Polymer Research
V. Litvinov
DSM Resolve, P.O. Box 18, 6160 MD, Geleen, The Netherlands,
NMR is very versatile technique both in the methodology and the type of information can be
obtained (Figure 1). Using different NMR methods detailed information about physical
structures, molecular mobility and nano- and micrometer scales heterogeneity of materials can be
gained. Several applications were also established for quality control of industrial products. The
use of complimentary techniques, such as WAXD, SAXS, DSC, light scattering and mechanical
experiments provides solid base for establishing structure – processing - property relationships
for the variety of polymeric materials, and solving complex problems of practical importance.
Industrial applications of solid-state NMR methods for various types of polymeric materials
(viscoelastic materials, semicrystalline polymers, fibres, coatings, multi-phase materials and
polymers for biomedical applications) are reviewed.
Figure 1: Different NMR methods for material research. A combination of high-field NMR
spectroscopy with the other NMR methods allows chemical structure selective characterization
of physical structures and molecular dynamics in multi-phase/component materials [1].
References
[1] – V.Litvinov, NMR on Elastomers, in Ëncyclopedia of Polymeric Nanomaterials”, Eds.
S.Kobayashi, K.Müllen, Springer-Verlas, Berlin, Heidelberg, 2014, DOI 10.1007/978-3-642-
36199-9_303-1.
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Conformational, Crystallinity and Orientation Changes in Poly (trimethylene
terephthalate) (PTT) During Crystallization Studied by FTIR Spectroscopy
N. Vasanthan
Department of Chemistry, Long Island University, One University Plaza,
Brooklyn, NY 11201, [email protected]
This paper presents conformational, crystallinity and molecular orientation changes during
thermally-induced and strain-induced-crystallization of Poly (trimethylene terephthalate) (PTT)
by combination of DSC and FTIR spectroscopy. Infrared spectra of amorphous and
semicrystalline PTT were obtained, and digital subtraction of the amorphous contribution from
the semicrystalline PTT spectra provided characteristic spectra of amorphous and crystalline
PTT. The normalized absorbance of 1577, 1173, and 976 cm-1
were plotted against the
crystallinity showing that these bands can be used unambiguously to represent the trans
conformation while the band at 1358 cm-1
can be used to represent gauche conformation of
methylene segment. The presence of a weak band at 1358 cm-1
in the amorphous spectrum
suggested that a small amount of gauche conformation is present in the amorphous phase. The
bands at 1358 and 976 cm-1
were chosen to determine the gauche and trans conformations of
methylene segments during crystallization. It has been shown that the amorphous and crystalline
gauche conformation increases at the expense of amorphous trans conformation during
thermally-induced crystallization of PTT. On the other hand, crystalline gauche conformation
increases at the expense of the amorphous trans conformation during the strain-induced
crystallization of PTT. The conversion of the amorphous trans conformation into the crystalline
gauche conformation was delayed at lower strain rate. Polarized IR spectroscopy was used to
measure the crystalline and the amorphous orientation functions separately with draw ratios and
strain rates, and it was demonstrated that the crystalline orientation develops rapidly with strain-
induced crystallization and that the amorphous orientation stays constant up to draw ratio of 2.5
and increases slowly above a draw ratio of 2.5, which is typical behavior for flexible chain
polymers. The effect of molecular orientation on cold crystallization of amorphous PTT was
examined. The cold crystallization temperature (Tc), cold crystallization exotherm ( c), and
subsequent melting temperature (Tm) were carefully correlated to the overall molecular
orientation. For the first time, the overall molecular orientation was shown to have an inverse
relationship to the cold crystallization temperature, as well as the cold crystallization exotherm.
It was demonstrated that non isothermal cold crystallization does not occur when the overall
orientation exceeds the critical value of 0.43.
References
1. N. Vasanthan and M. Yamen, J. Polym. Sci, PartB: Polym Phys. 45, 1675 (2007).
2. H. H. Chuah, J. Polym. Sci, Part B: Polym Phys. 40, 1513 (2002).
3. M. Yaman, S. Ozkaya and N. Vasanthan. J. Polym. Sci, PartB: Polym Phys, 46,1497 (2008).
4. N. Vasanthan, S. Ozkaya and M. Yaman . J Phy Chem B. 114, 13069 (2010).
5. N. Vasanthan and N. Manne. Ind Eng Chem Res, 52, 12596 (2013)
6.. N. Vasanthan, N. Manne and A. Krishnama. Ind Eng Chem Res, 52, 17920 (2013)
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Field-Flow Fractionation: Solving the Challenges where Size Exclusion
Chromatography meets its Limitations and Now Complementing Size
Exclusion in Applications that Were not Expected
aTrevor Havard,
aSoheyl Tajiki,
bFlorian Meier and
bThorsten Klein
aPostnova Analytics, Inc., 230 South 500 East Suite 120, Salt Lake City, UT
84102, USA,
bPostnova Analytics GmbH, Max-
Planck-Str. 14, 86899 Landsberg, Lech,
Germany,
Cal Giddings at the University of Utah conceived the technique of Field-Flow Fractionation
almost 50 years ago. Wherever there is a problem due to the size of a macromolecule or if there
are column interactions between the polymer and the packing material, a form of field-flow
fractionation is available to solve the problem. Field-Flow Fractionation or FFF works on a
principle where the separation is achieved by applying a force perpendicular to the direction of
an eluent flow through a usually ribbon-like channel in which the respective sample, e.g.,
macromolecules or polymers, is transported. These forces may be generated by gravitation,
centrifugation, heat or the application of another force. Currently, there are four versions of FFF
available to separate macromolecules and particles based on aforementioned forces, namely
Asymmetrical Flow-, Thermal-, Centrifugal-, and Gravitational-FFF. This study shall give a
general overview on the application of field forces in FFF, how they work and how they can be
applied in the separation of macromolecules and polymers. This Paper will also identify some
new areas where FFF has been considered in the past, to be limited and explain how new
innovations have expanded the use of the technology
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Unique Three-Phase Self-Assembly and Order-Disorder Transition of
Poly(cyclohexadiene)-Based Copolymers
K. Misichronis1,2
, J. Chen2, A. Imel
1, R. Kumar
2,3, M. Dadmun
1, J. Kennemur
4,5, F.
S. Bates5, K. Hong
2, J. Thostenson
6, B. G. Sumpter
2,3, J. W. Mays
1, A.
Avgeropoulos*7
1Dept of Chemistry, University of Tennessee, Knoxville, TN,
2Center for
Nanophase Materials Sciences, Oak Ridge National Lab, Oak Ridge, TN, 3Computer Science and Mathematics Division, Oak Ridge National Lab, Oak
Ridge, TN, 4Dept of Chemistry & Biochemistry, Florida State University,
Tallahassee, FL, 5Dept of Chemical Engineering and Materials Science, University
of Minnesota, Minneapolis, MN, 6Shared Materials Instrumentation Facility, Duke
University, Durham, NC, 7Dept of Materials Science and Engineering, University
of Ioannina, Greece, [email protected]
A series of linear diblock copolymers containing polystyrene (PS) and poly(1,3-cyclohexadiene)
(PCHD) with high 1,4-microstructure (>87%) was synthesized and their morphologies in bulk
were characterized using transmission electron microscopy (TEM), small angle X-ray scattering
(SAXS) and rheology[1]
. Computational methods were employed to predict the morphological
diagram of the system[2]
. The results show that these materials can self-assemble driven from the
high conformational asymmetry, forming not only well-known structures but also several unique
ones (Figure 1). Rheological measurements performed for the first time on this type of block
copolymers verify our morphological characterization results and they reveal order-to-order and
order-disorder transition temperatures (TODT) for several samples, while our theoretical
predictions come in agreement with the experimental results.
Figure 1: Schematic representation of a core-shell cylinder morphology for a PS-PCHD diblock
copolymer.
References
[1] – K. Misichronis et al., Polymer 54, 1480 (2013).
[2] – R. Kumar et al., Langmuir 29, 1995 (2013).
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Use of ACOMP to monitor residual monomer concentration and polymer
intrinsic viscosity throughout industrial scale polymerization reactions
Michael F. Drenski1, Alex W. Reed
1, Wayne F. Reed
2
1 Advanced Polymer Monitoring Technologies, Inc.,
2 Tulane University,
We have been using our new Industrial Automatic Continuous Online Monitoring of
Polymerization Reactions (ACOMP) platform to monitor industrial scale polymerization
reactions to determine reaction properties; conversion, kinetics, residual monomer concentration
and onset of gelation as well as polymer product properties; polymer concentration, intrinsic
viscosity, and polymer molar mass. Among the challenges in moving this technology from the
laboratory to the industrial environment has been the engineering and implementation of wide
scale onboard sensors and automation into the platform so that the system can run and monitor
itself without human intervention. Remote access has also been a critically important in the
successful adaptation to intensive polymer manufacturing operations.
The particular industrial scale ACOMP system presented here monitors ultraviolet (UV)
absorption of monomer and dilute solution viscosity to directly calculate the conversion of
monomer to polymer and determine the Intrinsic Viscosity of the polymer product throughout
the reaction. A critical feature is to measure residual monomer down to a setpoint below 1000
ppm as the reaction nears completion. The increasing amount of polymer in the reactor, and
hence also in the continuous, dilute sample stream, leads to significant UV scattering so that the
UV signal will not return to its initial solvent baseline value even when 100% of monomer has
been consumed. Hence, it is not possible to simply use monomer extinction coefficients of the
UV signal for determining residual monomer. Instead, we have developed a dynamic approach
to ppm determination in which accurate fits to the online data, performed each second, allow
elimination of the growing, interfering UV scattering signal from polymer and hence recovery of
the true monomer concentration and accurate prediction of the time when the desired ppm level
will be reached. This capability, which was cross-validated with traditional HPLC methods in the
early R&D phase, eliminates the need for inefficient and labor intensive manual sample
extraction, preparation and offline residual monomer measurements. This approach also sets the
stage for active online control of polymer manufacturing.
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High temperature AFM imaging and nanoindentation during the
transformation of isotactic poly(propylene)
D. Tranchida , W. Schaffer
Borealis Polyolefine GmbH, St. Peter Straße 21, Linz 4021, Austria
[email protected] High resolution imaging at high temperatures is prohibitive for many microscopy techniques, yet
relatively easily achieved by Atomic Force Microscopy (AFM). In this work, the evolution of
morphology and local mechanical properties during the phase transformation at ~150°C of
isotactic polypropylene (iPP) was explored by both standard imaging and nanoindentation by
AFM.
Since an accurate temperature control is one of the most demanding parts of this kind of
experiments, the phase transformation of one particular iPP with one particular
nucleating agent was first studied with temperature-resolved wide angle x-ray diffraction
(WAXD), dynamic mechanical thermal analysis (DMTA), and temperature modulated
differential scanning calorimetry (TM-DSC). The transformation was located in the range
of temperature 145-150°C, and the coexistence of and phases was proved while heating with
heating rates similar to the ones used by AFM analysis.
The change of elastic modulus with increasing temperature as measured by DMTA was
compared to the trend obtained by nanoindentation. This comparison showed that the trend
measured by both techniques was identical, however a temperature correction was required for
the nanoindentation to match the DMTA measurements.
After this correction, melting of phase lamellae both edge-on and flat-on was observed in
temperature ranges in agreement with the other techniques. Only the initially very thick
lamellae were visible up to temperature of ca. 145°C. AFM allowed the visualization of “ phase
patches”, as shown in Figure 1. Small areas with edge-on lamellae with crosshatching, typical of
phase, were indeed observed.
Nanoindentation performed at ca. 150°C showed that the local elastic modulus was the same and
in the order of 50 MPa when measured in different areas, suggesting a spatially homogeneous
occurrence of the transformation
Figure 1: AFM phase image collected at 149°C, showing areas with crosshatched lamellae. Scale
bar is 2 µm.
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Design of Interpenetrating Networks for the Formation of Tough Epoxy
Resins
B.J. Rohde, M.L. Robertson, R. Krishnamoorti
University of Houston, [email protected]
Interpenetrating polymer networks (IPNs), in which macroscopically homogeneous mixtures are
formed containing two distinct network-forming polymers, provide a route to producing
mechanically superior thermoset materials. Such materials can be useful in a wide variety of
applications, including composites for wind energy, structural applications, and adhesives,
among others. In this study, IPNs were prepared consisting of polydicyclopentadiene
(polyDCPD), contributing enhanced toughness and impact strength, and an epoxy resin (the
diglycidyl ether of bisphenol A cured with nadic methyl anhydride), contributing high tensile
strength and modulus. The concurrent curing of the networks resulted in macroscopically phase
separated blends. In situ Fourier transform infrared spectroscopy was used to explore the reaction
kinetics in neat systems and diluted mixtures of epoxy resin and polyDCPD. A sequential curing
protocol was developed, in which the polyDCPD was first cured in the presence of the epoxy
resin components, followed by curing of the epoxy resin at an elevated temperature. These
results provide the kinetic basis for future studies to prepare interpenetrating polymer networks
which employ thermodynamic control of phase separation such as through the addition of
compatibilizing molecules.
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68
Sample Preparation in Polymer Mass Spectrometry
C. Schwarzinger1, S. Gabriel
1,2, U. Panne
2, S. Weidner
2
1Institute for Chemical Technology of Organic Materials, Johannes Kepler
University Linz, 2Federal Institute of Materials Research and Testing (BAM),
Berlin, [email protected] Polymer mass spectrometry, especially MALDI-ToF MS, has gained a lot of attention in the last
years because of the high amount of information that can be gained, such as molar mass
distribution, repeat units, end groups, etc. But care must be taken when it comes to sample
preparation, especially when the simple and fast “dried droplet” technique is used.
As most people have already experienced dried droplet preparation tends to from rings of higher
concentration at the outer rim, the so called “coffee rings”, which results in inhomogeneous
distribution of the compounds and therefore questionable results. We will show that several
rather simples steps can be used to circumvent this phenomenon and how to produce reliable
high quality data using dried droplets, as there are the use of ionic liquids as matrices [1] or
higher matrix concentration [2]. The results were monitored with imaging techniques such as
FTIR or mass spectrometric imaging to understand the processes necessary for a perfect sample
preparation.
Figure 1: Influence of matrix concentration on the coffee ring formation, resolution and intensity
of spectra.
When it comes to copolymers things are getting even worse. In this case it is mostly necessary to
separate the polymer into fractions either by precipitation or by SEC. We have found that a
modified Electrospray interface coupled to the SEC is a very efficient and elegant way yielding
best results in terms of polymer separation and MALDI sample preparation.
References
[1] – S. Gabriel, D. Pfeifer, C. Schwarzinger, U. Panne, S.Weidner, Rapid Commun. Mass
Spectrom. 28, 489-498 (2014).
[2] – S. Gabriel, C. Schwarzinger, B. Schwarzinger, U. Panne, S. Weidner, J. Am. Soc. Mass
Spectrom. 25, 1356 (2014).
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Characterization of Polyelectrolyte Multilayers by Temperature-Controlled
Quartz Crystal Microbalance with Dissipation
Jodie L. Lutkenhaus, Ajay Vidyasagar, Joe Puhr, Dariya Reid, Yanpu Zhang
Affiliation: Artie McFerrin Department of Chemical Engineering, Texas A&M
University, [email protected] Quartz crystal microbalance with dissipation (QCM-D) is a powerful tool to assess the physical
properties of an ultra thin polymer film under various stimuli (pH, temperature,
adsorption/desorption of small molecules, ionic strength). It provides unparalleled detail of a thin
film’s hydrated thickness and mass, shear modulus, and shear viscosity for thicknesses on the
order of 100 nm. This technique also provides this information for varying penetration depths,
giving a qualitative “depth profile” of phenomena occurring within the film. Here we provide an
overview of the characterization of polyelectrolyte multilayers via QCM-D. Polyelectrolyte
multilayers are constructed by the alternate adsorption of oppositely charged polyelectrolytes and
have been explored in a wide range of applications ranging from energy to health.
In our lab, we have recently demonstrated the application of temperature-controlled QCM-D, in
which temperature is systematically varied1-3
. We observe distinct changes in the film’s
properties associated with an LCST-type transition. This transition is also observed by
differential scanning calorimetry, but it is extremely weak. However, in QCM-D the transition
may be easily resolved because of its sensitivity to small-scale changes. While the raw data is
reliable and yields valuable information, it is desired to apply a viscoelastic model to glean
further detail. Modelling of QCM-D data, however, continues to be a challenge.
Figure 1: A polyelectrolyte multilayer assembled at different pH values exhibits varying
transition temperatures as measured by QCM-D.
References
[1] Vidyasagar A, Sung C, Losensky K, Lutkenhaus JL. pH-Dependent Thermal Transitions in Hydrated Layer-by-
Layer Assemblies Containing Weak Polyelectrolytes. Macromolecules. 2012;45:9169-76.
[2] Vidyasagar A, Sung C, Gamble R, Lutkenhaus JL. Thermal Transitions in Dry and Hydrated Layer-by-Layer Assemblies Exhibiting Linear and Exponential Growth. Acs Nano. 2012;6:6174-84.
[3] Puhr JT, Swerdlow BE, Reid DK, Lutkenhaus JL. The effect of nanoparticle location and shape on thermal
transitions observed in hydrated layer-by-layer assemblies. Soft Matter. 2014;10:8107-15.
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EIS in Characterization of Polmer based Hydrogel Support for Biomimetic
Membrane Applications
A. Mech-Dorosz, A. Heiskanen, C. Helix-Nielsen1, Jenny Emneus
Department of Micro and Nanotechnology, Technical University of Denmark (DTU),
Productionstorvet 423, room 118, 2800 Lyngby, Denmark 2Department of Environmental Engineering, Technical University of Denmark (DTU)
Bygninstorvet 115, room 140, 2800 Lyngby, Denmark
[email protected]; [email protected]; [email protected];
Hydrogels, polymeric networks capable of absorbing water up to thousands of times their dry
weight have been of great interest in pharmaceutical and biomedical applications due to their
excellent hydrophilic properties and potential to be biocompatible. The constantly increasing
spectrum of hydrogel applications forces the researchers to perform detailed chemical and
physical analysis of the hydrogels to obtain desirable properties in potential applications.
Hydrogel composed of copolymerized poly(ethylene glycol)dimethacrylate (PEG-DMA) and 2-
hydroxyethylene methacrylate (HEMA) in molar ratio 1:200 greatly stabilizes biomimetic
membranes suitable for membrane protein incorporation [1] In this work, we present
electrochemical impedance spectroscopy (EIS) characterization of PEG-DMA/HEMA (1:200)
hydrogel covalently immobilized on a modified gold electrode microchip in PBS buffer
containing electroactive probe. Characterization was performed immediately after
polymerization and after 24 h to verify the relation of electroactive probe flux through the
hydrogel bulk with respect to the hydration time. Two other molar ratios of PEG-DMA/HEMA
monomers: 1:100; 1:400 were tested with respect to EIS response 24 h after polymerization.
Non-faradaic and faradaic responses were studied based on devised equivalent circuit models.
The swelling properties of hydrogels with different monomer ratios were also investigated by dry
and wet weight determination.
We show that change of the PEG-DMA/HEMA molar ratio in the hydrogel structure
significantly affects the behavior at the electrode/hydrogel interface but not in the bulk of the
hydrogel. The increase of PEG-DMA amount promotes an access of electroactive probe to the
electrode surface, hence, considerably influencing the electrochemical response in biomimetic
applications.
Figure 1: Impedance spectra acquired on a modified gold electrode microchip with covalently
attached hydrogel containing PEG-DMA/HEMA monomers: molar ratio 1:200 (A), 1:400 (B),
and 1:100 (C).
References
[1] – A.Mech-Dorosz, A.Heiskanen, S.Bäckström, M.Perry, H.B. Muhammad, C.Hélix-Nielsen,
J.Emnéus, Biomed. Microdevices 17, 21 (2015).
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71
Strain-Induced Phenomena in Multi-Phase Polymers
V. Litvinov
DSM Resolve, P.O. Box 18, 6160 MD, Geleen, The Netherlands,
Mechanical properties belong to one of the most important parameters of polymers largely
determining many of their application areas. Much research has been devoted to understanding
the mechanical properties. Despite these efforts, the deformation process in multi-phase
materials is not well understood largely due to the lack of information about phenomena that
occur at the molecular and nanometric length scales in different phases during deformation.
Solid-state NMR methods offer very high selectivity to different phases/components in multi-
phase polymers. Strain-induced changes in soft phases are of special interest since NMR is
highly sensitive to even minor effects and NMR results are complimentary to those by X-ray
studies. A short overeview of strain-induced phenomena in viscoelastic materials, block-
copolymers and polyolefines is provided [1- 4].
References
[1] - V.M. Litvinov, Macromolecules 34, 8468 (2001).
[2] - A. Schmidt, W.S. Veeman, V.M. Litvinov and W. Gabriëlse, Macromolecules 31, 1652
(1998).
[3] - C. Hedesiu, D. Demco, K. Remerie, B. Blümich and V. Litvinov, Macromol. Chem. Phys.
209, 734 (2008).
[4] - V.M. Litvinov and L. Kurelek, Polymer 55, 620 (2014).
73
POSTERS
P1
74
Vectorization Dynamics Between Amphiphilic Block Copolymer Micelles and
Liposomes: Role of Chitosan Interactions
L.M. Bravo-Anaya1,2
, M. Rinaudo3, J.F.A. Soltero
2 ,Y. Rharbi
1
1Univ. Grenoble Alpes, LRP, F-38000 Grenoble (France)
2Departamento de Ingeniería Química, Universidad de Guadalajara, 44430,
Guadalajara, Jalisco (México) 3Biomaterials Applications, 6 rue Lesdiguières, 38000 Grenoble (France)
e-mail: [email protected], [email protected] Over the last few years, vectorization has experienced an important development. It has been
used to control the distribution of active ingredients such as proteins, genes for gene therapy and
drugs, to a target by associating it with a vector [1]. Molecules for chemotherapy are frequently
hydrophobic and require vectorization to be transported to the target cell. Nevertheless, this
controlled drug delivery suffers from a phenomenon called “burst release” as the drugs are
released before their target [2]. In this manner, our main objective is to understand the exchange
dynamics between vectors and cells via collective mechanisms, such as fusion/adhesion and
exchange/separation. Understanding these dynamics becomes essential for the design and the
control of new materials and new processes effective in drug delivery. The used model is the
following: liposomes representing cells, amphiphilic block copolymer micelles modeling the
encapsulating and transporting vehicles and highly hydrophobic alkylated pyrene representing
the active ingredient introduced into the micelles. Different techniques such as dynamic light
scattering (DLS), pH and zeta potential were used to characterize liposomes and micelles and to
identify their interactions. Fluorescence time-scan study allows monitoring the monomer and
excimer intensities of the alkylated pyrene, used as a fluorescent probe, to quantify the exchange
rate of the dynamics [3]. With this technique we can distinguish the individual mechanisms, i.e.
exit-entry of the probe molecule, from collective ones involving adhesion-fusion. Firstly, we
studied the role of the addition of chitosan (positively charged polymer) on liposomes, on the
interactions between the amphiphilic block copolymer micelles and liposomes through DLS and
zeta potential [4]. Secondly, we investigated the role of chitosan in controlling the collective
mechanism through fluorescence.
References
[1] - Y. Liu, T.-S. Niu, L. Zhang and J.-S. Yang, Natural Science 2, 41-48 (2010).
[2] - X. Huang and C. S. Brazel, Journal of Controlled Release 73, 121–136 (2001).
[3] - Y. Rharbi, Macromolecules 45, 9823−9826 (2012).
[4] - F. Quemeneur, M. Rinaudo, G. Maret and B. Pépin-Donat, Soft Matter 6, 4471-4481
(2010).
P2
75
Analytical Development for γ-PGA, γ-PGA-PAE and nanoparticle
Mayumi Ikeda1, Tatsuya Yasuoka
1, Masao Nagao
1, Takami Akagi
2, Mitsuru
Akashi2
1 Takeda Pharmaceutical Company Limited, Japan
2 Graduate School of Engineering, Osaka University, Japan
[email protected] Takeda Pharmaceutical Company Limited and Osaka University developed a platform for the
practical application using biodegradable nanoparticles (NPs) consisting of hydrophilic poly(γ-
glutamic acid) (γ-PGA) substituted hydrophobic L-phenylalanine ethylester side chain (γ-PGA-
PAE).
We established the analytical methods of quality of γ-PGA, amphiphilic γ-PGA-PAE and γ-
PGA-PAE NPs. Quantitative evaluations of them were first accomplished in the field of NPs
based delivery system.
SEC (Size Exclusion Chromatography)-RI (Refractive Index) /MALS (Multi Angle Light
Scattering) system was developed for physicochemical properties of various types of polymers
and for formulation study. By this method, the characterization differences of each vender's
polymer were evaluated on molecular weight (MW) and grafting degree of PAE.
A gradient reversed phase HPLC (RP-HPLC) method was developed and validated for
content and impurity of γ-PGA-PAE and γ-PGA-PAE NPs. The dissociation of γ-PGA-PAE NPs
to intact γ-PGA-PAE by sodium dodecyl sulfate (SDS) was one of the critical key elements for
the quantitative evaluation at RP-HPLC and SEC-RI/MALS. The newly developed analytical
methods indicated robustness evaluation could be performed for their quality. Additionally, the
degradation mechanism of γ-PGA-PAE was also identified as cleavage of main-chain of γ-PGA-
PAE based on the pH stability of γ-PGA-PAE in buffer solution.
Above success in analytical methods establishment will be an important implication not only
for characterization of polymers and NPs but also for the formulation design.
Figure : Establishment of quantitative Analytical Method for NPs.
P3
76
Nanostructuration of PVDF based polymer fuel cell membranes investigated
by scattering and microscopy techniques
P. Ricou, D. Mountz, L. Fang, J. Fang, W. He, J. Goldbach
Arkema Inc., KOP Research Center, 900 First Avenue, King of Prussia, PA 19406,
A polymer electrolyte membrane (PEM) based on a polymer blend is seen as an advantageous
alternative to a single phase polymer as it allows one to decouple transport from mechanical
properties. Significant efforts have been devoted by Arkema towards developing a PEM
membrane based on blends of Kynar® polyvinylidene fluoride (PVDF) and polyelectrolytes.
Though the two phase approach offers technical and economic advantages it also brings
challenges of its own, one of which is the understanding of the blend morphology and its impact
on transport properties.
The present work focuses on the characterization of a blend of a Kynar® copolymer grade
(vinylidene fluoride, VDF and hexafluoropropylene, HFP) with a sulfonated based
polyelectrolyte. Miscibility of the various phases was engineered to such a high degree that
common imaging approaches could not achieve satisfactory results. The PVDF-HFP copolymer
also shows reduced crystallinity compared to PVDF homopolymer, further increasing the
difficulty of resolving the various phases. Wide and small angle X-ray scattering (WAXS,
SAXS) were used in conjunction to define the crystalline domain size. This approach facilitated
imaging efforts, in particular for resolving small crystalline domains from artifacts and image
noise. Dark field scanning Transmission Electron Microscopy (STEM) eventually yielded a
morphology representation of the membrane in its dry state.
Characterization of ionomer size domain in hydrated perfluoro-sulfonated membranes such as
Nafion® has previously been successfully reported in the literature [1,2]. We followed a similar
approach to study the Kynar® based membrane in its hydrated state by using the environmental
chamber developed at the University of Pennsylvania and the multiple angle X-ray scattering
bench (MAXS). The ionomer signal from a neat polyelectrolyte membrane was observed at
around 0.26 Å-1
when relative humidity reached 85%. This result is in agreement with the higher
proton conductivities seen in high humidity environment for Fuel Cell devices assembled with
this membrane. However, the ionomer peak could not be observed once the polyelectrolyte was
diluted in its host fluoropolymer matrix. We therefore turned to neutron scattering and
deuterated water experiments to increase contrast between hydrated ionomer domains and the
fluoropolymer matrix. The ionomer cluster size in the Kynar® matrix obtained from neutron
scattering results was found to be in agreement with SAXS results on neat polyelectrolyte.
References
[1] - G. Gebel, Polymer, 2000, 41, 5829-5838.
[2] - K.A. Mauritz, R.B. Moore, Chemical Reviews, 2004, 104, 4535-4585.
Nafion is a registered trademark of E.I. DuPont. Kynar is a registered trademark of Arkema Inc.
P4
77
Title: Analysis of PLGA molecular weight and structure by the latest
advanced multi-detector GPC systems
Mark R. Pothecary1, Stephen Ball
2
1Malvern Instruments Inc., 4802 North Sam Houston Parkway, Ste 100, Houston
Texas, 77086, [email protected]
2Malvern Instruments Ltd, Enigma Business Park, Malvern, Worcestershire, WR14
1XZ
Poly(D,L-lactide-co-glycolic acid), PLGA, is a copolymer of polylactic acid and polyglycolide.
As a biodegradable and biocompatible polymer, it is has found use in a number of medical
devices such as grafts and sutures as well as in drug delivery applications. The principle of drug
delivery applications with PLGA is that as the polymer degrades, it releases drug molecules in a
controlled timed-release profile which can be tailored to the requirements of the particular drug
being delivered. The degradation process and subsequent drug release is dependent on the
distribution of molecular weight, molecular structure and composition of the copolymer being
used.
Gel-permeation chromatography (GPC) is the most widely used tool for the measurement of
molecular weight and molecular weight distribution of natural and synthetic polymers.
Historically, the elution volume of an unknown sample was compared with that of known
standards to estimate molecular weight and distribution. However, this ‘conventional
calibration’ is limited by the structural differences between standards and samples, meaning that
the measured molecular weight is only a relative value if the standards and samples are different
polymers. This is particularly true for PLGA where both structure and composition will affect
the elution volume of different products of similar molecular weight.
Static light scattering detectors measure the intensity of light scattered by the sample as it elutes
from the column. Since the intensity of the scattered light is proportional to the sample’s
molecular weight and concentration, they allow the direct measurement of the sample molecular
weight independent of its elution volume. A viscosity detector can also be used as part of a GPC
system to measure the parameter of intrinsic viscosity which can be combined with molecular
weight data to calculate hydrodynamic radius. In combination these data allow detailed
structural information of a polymer to be generated in a single GPC measurement which can be
compared with other samples in Mark-Houwink plots.
In this paper, we analysed different samples of commercially available PLGA to compare their
absolute molecular weight from light scattering to those quoted with the product. Additionally,
we compared the Mark-Houwink plots of different examples containing different ratios of the
two co-monomers. Structural and molecular weight differences are clearly visible which will
result in changes in drug release and delivery profile. More detailed analysis of these parameters
can be used to better control the end-properties of the PLGA and its release rate of drugs in
delivery applications.
P5
78
Analysis of monomer sequences of copolymers prepared by various polymer
reactions of poly(benzyl methacrylate)
Yuchin Hsu, Mingyeh Chuang, Miyuki Oshimura, Tomohiro Hirano, Koichi Ute
Department of Chemical Science and Technology, Tokushima University, Japan
E-mail: [email protected]
Abstract
NMR technology have afforded us with detailed information on polymer structure in decades.
However, copolymer structure is still perplexing when the chemical shifts of the signals are
sensitive to both configurational sequences and monomer sequences. To extract quantitative
information about microstructure of copolymers from those complicated resonances, statistical
(multivariate) analysis of the NMR spectra was recently found useful [1,2]. We have here
focused our attention to multivariate analysis that performed for the 13
C NMR spectra of
methacrylate copolymers derived from catalytic reduction of poly(benzyl methacrylate)
(PBnMA), or from partial hydrolysis of PBnMA under acidic or alkaline conditions to
investigate monomer sequence distribution in those copolymers. The resultant copolymers of
BnMA and methacrylic acid were converted to BnMA-MMA copolymers by methylation with
diazomethane prior to the analysis.
Fig. 1 shows the 13
C NMR spectra of the poly(BnMA-co-MMA)s. The spectrum of the
copolymer (Fig.1b and c) shows overlapped splitting and is complicated than that of a
homopolymer blend (Fig. 1e). Fig. 2 showed the principal component score plots for the 13
C
NMR spectra of those BnMA-MMA series. The variances for the first (PC1) and second
principal components (PC2) reflected chemical composition and heterogeneity of monomer
sequence, respectively. The plots indicate that the monomer sequence in the copolymers derived
from acidic hydrolysis resembles to the sequence in radical copolymers (nearly random) while
the sequence in the copolymers derived from catalytic reduction resembles to the sequence in
homopolymer blends (blocky). Furthermore, the sequence in the copolymers derived from basic
hydrolysis is suggested to have a somewhat alternating tendency.
References
[1] Momose, H. et al. J. Polym. 44, 808 (2012).
[2] Ute, K. The 13th Pacific Polymer Conference (PPC-13), Kaohsiung, Taiwan, Nov., 2013.
Fig. 1: 13C NMR resonances due to the carbonyl groups of various poly(BnMA-co-MMA)s
Fig. 2: Principal component score plots for the 13C NMR spectra of benzyl methacrylate (BnMA) - MMA copolymers prepared by copolymerization or various polymer reactions of poly(BnMA).
P6
79
Dielectric Relaxation Spectroscopy
of Polypropylene Organoclay Nanocomposites
Jesper Bøgelund, Rasmus Klitkou1, Jesper de Claville Christiansen
1
Novo Nordisk A/S, Device Research and Development, 20C Brennum Park, DK-
3400 Hillerød, Denmark, [email protected] 1Department of Mechanical and Manufacturing Engineering, Aalborg University,
16 Fibigerstraede, DK-9220 Aalborg, Denmark
Dispersion of nanoparticles in polymers is a challenging task, but believed to be of crucial
importance for realizing the potential properties of polymer nanocomposites. Indirect
measurements of the dispersion level can be made by melt rheometry and dielectric relaxation
spectroscopy (DRS).
Composites of polypropylene and organophilic montmorillonite (OMMT) were prepared by melt
extrusion. Different dispersion states were obtained by successive extrusions.
Dielectric Spectroscopy revealed a Maxwell-Wagner relaxation in the composites. The strength
of the relaxation was found to correlate to the dispersion state of the nanoclay.
Figure 1: Change of the low-frequency dielectric relaxation of the surfactant in the PP/OMMT
nanocomposite system due to increased dispersion and exfoliation of the organoclay.
P7
80
The Effect of Processing Conditions and Thermal History on Physical Phases
and Chain Dynamics in Nylons
V.M. Litvinov
DSM Resolve, P.O. Box 18, 6160 MD, Geleen, The Netherlands,
The effect of processing conditions, thermal history and annealing on the phase composition,
molecular mobility, water absorption and oxygen permeability in Nylons is studied by NMR
methods. The NMR relaxation data are interpreted using a three-phase model which is proposed
on the basis of distinct differences in chain mobility in crystalline phase(s), a semi-rigid crystal-
amorphous interface and soft fraction of the amorphous phase. It is shown that chain mobility in
the amorphous phase plays very important role in water uptake and diffusivity of small
molecules in Nylons. The following topics are addressed.
(1) The role of fibre spinning conditions, annealing and absorbed water on physical phases in
PA6 fibres. 1H NMR T2 relaxation method was established to provide a fast and accurate
technique to analyse the phase composition in Nylon 6 fibres [1].
(2) The effect of branching and annealing of PA46 on the amount of absorbed water, crystallinity
and chain dynamics in the amorphous phase [2]. Water uptake by PA46 is mainly
determined by the strength of hydrogen bonds between amide groups in the amorphous
phase which is largely affected by crystallization rate and annealing at elevated
temperatures.
(3) Quantitative MRI and NMR relaxation experiments are used to study the role of chemical
structure of Nylons and their annealing on water uptake by injection moulded samples [3].
Fast crystallization of PA46 causes less ordered structures both in the crystalline and the
amorphous phases. The effect is especially large in a skin layer which absorbs more water.
Annealing causes densification of the amorphous phase. As result of that water uptake
decreases and becomes similar to that in PA6 and PA66 taking into account crystallinity and
the molar fraction of amide groups.
(4) The effect of phase composition and molecular mobility on oxygen permeability is studied
for stretched films prepared from PA6 and a blend of PA6 with amorphous semi-aromatic
polyamide (aPA) [4]. Molecular mobility in the amorphous phase of stretched films is
largely restricted upon stretching of films. The immobilization of the amorphous phase has a
large influence on the permeability of the films. Despite lower oxygen solubility in PA6
films, the permeability of all PA6/aPA films is significantly lower than that of PA6 films. It
is suggested that the lower permeability of PA6/aPA films is due to complex formation
between oxygen molecules and aromatic rings of aPA. As result of that oxygen diffusivity
decreases whereas oxygen solubility increases.
References
[1] - V.M. Litvinov and J.P. Penning, Macromol. Chem. Phys. 205, 1721 (2004).
[2] – V.M. Litvinov, C.E. Koning and J. Tijssen, Polymer 56, 406 (2015).
[3] - P. Adriaensens, A. Pollaris, R. Carleer, D. Vanderzande, J. Gelan, V.M. Litvinov and J.
Tijssen, Polymer 42, 7943 (2001).
[4] - V.M. Litvinov, O. Persyn, V. Miri and J.M. Lefebvre, Macromolecules 43, 7668 (2010).
P8
81
Structural Determination of Novel Polyamine by Correlation Analysis of 1H
NMR and Mass Spectra
M. Oshimura1, K. Motoyama
1, H. Kitayama
2, Y. Ikeda
2, T. Hirano
1, K. Ute
1
1Department of Chemical Science and Technology, Tokushima University,
2Solvay
Japan,
E-mail: [email protected]
Novel synthetic method of polyamine by
polycondensation of diamine and dinitrile with
transition metal catalysts were developed recently
(Scheme).[1, 2]
Determination of molecular weight and
structure of the polyamine is difficult because of a
strong interaction with column filler for SEC, and
existence of different structural polyamines having
identical mass number.
In this study, structural determination of the polyamine
was investigated.[3]
Polymer structure and molecular
weight were analyzed by 1H NMR and DOSY,
respectively. Polymer chain end was analyzed by
MALDI-TOFMS. In addition, conformity or
nonconformity of the charge in signal intensity of each
signal in the 1H NMR spectra and the mass-to-charge
ratio was investigated by correlation analysis of 1H
NMR and MALDI-TOFMS spectra. The difference was
shown by the slice data which differs in a mass-to-
charge ratio and the NMR spectra (Figure). These
results indicate that the polyamine have various
structures, such as linear and branched chains.
Structural determination of novel polyamine was
achieved by estimation of molecular weight using
DOSY method and correlation analysis of 1H NMR and
mass spectra. This method enabled not only structural
determination, but also preparation of polymers having
object structures (linear or branched etc.) by analyzing a
polymerization mechanism and feedback the results to
polymerization condition.
References
[1] T. Ikawa, Y. Fujita, T. Mizusaki, S. Betsuin, H.
Takamatsu, T. Maegawa, Y. Monguchi, and H.
Sajiki, Org. Biomol. Chem., 10, 293-304 (2012).
[2] H. Kitayama, H. Sajiki, and Y. Monguchi, PCT Int.
Appl., WO 2011-081038 (2011).
[3] K. Motoyama, H. Kitayama, Y. Ikeda, M. Oshimura, K. Ute, The 13th Pacific Polymer
Conference, Poster-S1-059 (2013).
Figure: NMR spectra of polyamines in the different mass-to-charge ratio.
Scheme: Synthesis of polyamine using transition metal catalysts.
P9
82
Independent Quality Assessment Of Matrix Assisted Laser
Desorption/Ionization Mass Spectrometry Sample Preparation For Synthetic
Polymers
Pieter Kooijmana, Sander Kok
b, Jos Weusten
b and Maarten Honing
a, b
aVrije Universiteit, Division of BioAnalytical Chemistry, Amsterdam, The Netherlands;
bDSM
Resolve, Urmonderbaan 22, Geleen, The Netherlands, [email protected]
Matrix assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS)
has firmly positioned itself as one of the key techniques for the molecular characterization of
synthetic polymers. Over the last years, the instrument hardware has improved like an increased
mass resolution, detector linearity and laser speed. However, choosing the right sample
preparation factors is still crucial to determine accurately the characteristics of polymer samples
by MALDI-TOF-MS analysis. Sample preparation conditions such as matrix choice,
cationization agent, deposition technique or even the deposition volume should be chosen to suit
both the sample of interest and the information that needs to be obtained. Deposition patterns
such as coffee-stains [1], matrix crystals [2] and mass-dependent distribution differences [3]
hamper high measurement precision for polymer sample analysis and should be avoided. Many
successful sample preparation protocols have been developed and employed [4, 5] but for new
and challenging applications the process of finding the optimal sample preparation protocol is
often difficult. Because objective comparisons between the results of diverse protocols is not
possible, often “gut-feeling” or “good enough” is decisive in the search for an optimum.
To address this problem we have drafted eight parameters to objectively quantify the quality of
sample deposition and MALDI matrix composition. These parameters can be established in a
fully automated way using commercially available mass spectrometry imaging instruments
without any hardware adjustments. A synthetic polymer sample is imaged using two different
sample preparation protocols with DCTB and CHCA as matrix as a proof of principle. Our
method enables an objective comparison of sample preparation protocols for any analyte and
opens up new fields of investigation by presenting MALDI performance data in a clear and
concise way.
References
[1] S. M. Weidner et al., MALDI-TOF imaging mass spectrometry of artifacts in "dried droplet"
polymer samples, Analytical and Bioanalytical Chemistry 401 (2011) 127
[2] S.D. Hanton et al., Investigations of matrix-assisted laser desorption/ionization sample
preparation by time-of-flight secondary ion mass spectrometry, Journal of the American Society
for Mass Spectrometry 10 (1999) 104.
[3] S. M. Weidner et al., Imaging mass spectrometry for examining localization of polymeric
composition in matrix-assisted laser desorption/ionization samples,Rapid Communications in
Mass Spectrometry 23 (2009) 653
[4] M.W. Nielen, MALDI time-of-flight mass spectrometry of synthetic polymers, Mass
Spectrometry Reviews 18 (1999) 309
[5] G. Montaudo et al., Characterization of synthetic polymers by MALDI-MS, Progress in
Polymer Science 31 (2006) 277.
P10
83
Characterization and Determination of Irganox 1076 and 1010 in
Polyethylene using Thermal Desorption and Reactive Pyrolysis – GC/MS
Dave Randle1, Itsuko Iwai
2
1Frontier Laboratories USA, Antioch, CA, [email protected],
2Diablo
Analytical, Antioch, CA
Two of the more commonly used antioxidants, Irganox® 1076 and 1010, are sterically hindered
phenolic antioxidants used to ensure processing stability (color and viscosity retention) and the
long term thermal stability and durability of many substrates including polyolefins, synthetic
fibers and elastomers. Analysis of 1076 and 1010 is difficult using gas chromatography (GC)
because they are difficult isolate and concentrate using conventional solvent-based extraction
techniques. Both of these antioxidants have a very low vapor pressure which implies that high
injection port and column temperatures are needed and that any cold spots in the GC system have
to be eliminated.
This report details a GC/MS-based analytical method for the qualitative and quantitative
determination of Irganox 1076 and 1010 in polyethylene. 1076 is thermally desorbed from
polyethylene at 320⁰C [1]. Both 1076 and 1010 have an ester linkage which can be thermally
hydrolyzed and methylated using tetramethylammonium hydroxide (TMAH)[2,3].
Factors affecting the accuracy and precision of each technique will be discussed. Calibration is
performed using standard addition which eliminates the need for in-matrix (additive in polymer)
primary standards and takes in account both instrument changes and matrix interference. The
precision of the method for both compounds is on the order of 5%RSD and the %error is <10%.
References
[1] - Rapid and Simple Determination of phthalates in plastic toys by a thermal desorption-
GC/MS method, T. Yuzawa, C. Watanabe, R. Freeman and S. Tsuge, Anal.Sci., Vol. 25, pages 1-
2.
[2] - Review: the development and applications of thermally assisted hydrolysis and methylation
reactions, J.M. Challinor, J. Anal. and Appl Pyrolysis, 61(2001), 3-34.
[3] - Characterization of Condensation Polymers by pyrolysis-GC in the presence of organic
alkali, H. Ohtani and S. Tsuge, Applied Pyrolysis Handbook, Second Edition, pages 249-269.
P11
84
The Effect of Aging of Polyolefines on Physical Structures in the Relation to
Some Mechanical Properties
V.M. Litvinov1, K. Remerie
2
1 DSM Resolve, P.O. Box 18, 6160 MD, Geleen, The Netherlands, [email protected]
2 SABIC T&I , Address: P.O. Box 319, 6160 AH Geleen, The Netherlands,
Molecular mobility, phase composition and morphology of various types of polyethylenes (PE),
polypropylenes (PP) and random poly(ethylene propylene) copolymers (PPR) were studied by
solid-state NMR, X-Ray, DSC and microscopy methods. A three-phase model, which consists of
a crystalline phase, a semi-rigid crystal amorphous-interface, and a soft fraction of the
amorphous phase, is the most suitable for describing the phase composition in PE and PP
homopolymers as studied by solid-state NMR relaxometry [1]. In addition to these three phases,
a fourth rubbery-like phase is present in PPR and polypropylene impact copolymer [2]. NMR
relaxometry provides information about the phase composition as well as molecular mobility in
these phases. Influence of the following factors on the phase composition and molecular mobility
is discussed [1].
(1) The effect of aging (annealing) conditions on phase composition and chain dynamics in
HDPE, iPP and PPR.
(2) The effect of the amount of comonomer units in HDPE on chain dynamics in the amorphous
phase.
(3) The role of physical phases on several mechanical properties and fracture behavior. It is
shown that even small changes in the chemical composition and thermal history can largely
influence molecular mobility in the amorphous phase. Prolonged storage of PPR pipes at
hydrostatic pressures and elevated temperatures causes large immobilization of the
amorphous phase without significant increase in crystallinity. This immobilization increases
sensitivity of the material for brittle failure of pipes. Another example is the effect of short-
chain branching in high density HDPE on molecular mobility in the amorphous phase. A
small change in the amount of branching largely affects molecular mobility and has large
impact on the environmental stress crack resistance (ESCR) response. This suggests that
there may be a positive correlation between chain mobility and ESCR.
These studies show that solid-state NMR provides an unique and complimentary tool to
traditional methods for obtaining information about physical structures and local dynamics in
polyolefines. This information is useful to achieve a better understanding of yield and
deformation behaviour of polyolefines and establishing structure – processing – property
relationships.
References
[1] - V.M. Litvinov, in “NMR Spectroscopy of Polymers: Innovative Strategies for Complex
Macromolecules”, ACS Symposium Series, Vol. 1077, Eds.: H. N. Cheng, T. Asakura and
A.D. English, Chapter 11, pp 179–190 (2011).
[2] - V. Agarwal, T. B. van Erp, L. Balzano, M. Gahleitner, M. Parkinson, L.E. Govaert, V.
Litvinov and A. P.M. Kentgens, Polymer 55, 896 (2014).
P12
85
Crystallite Reorganization in Thin Multi-layered
Polyethylene/polypropylene Films Undergoing Thermal Ageing M. Mauri, R. Simonutti , F. Pisciotti
1
Dept. of Material Science, University of Milan-Bicocca, Via R. Cozzi 55, 20125 Milan, Italy, 1Tetra Pak Packaging Solutions AB, Ruben Rausings gata, 22186 Lund, Sweden,
Recent generations of commercial polyolefins are engineered to enable the control of the
defectivity of the polymer chains, and this has a strong influence not only on their processability
but also on the performance of the final product. We used advanced NMR techniques to
characterize samples of films produced with varying number of polypropylene (PP) and
polyethylene (PE) alternating layers. For fixed thickness (25 μm) and PP content (50%),
mechanical properties can depend on the number of layers. Solid State NMR indicates for all
samples a partially disordered PP phase seldom reported in literature, except for a PP/ODCB gel
[1]. Time Domain NMR confirms and quantifies the presence of low mobility phases,
compatible with the polycrystalline nature of the samples.
Figure 1: (left), comparison of CP-MAS spectra of pristine films with 65 and 3 layers. The
methyl signal, zoomed in the inset, does not present the splitting that is typically present in well
formed α phases, and is more intense in the 65 layer sample; (right) ageing of a 3 layer sample
produces an increase of rigid fraction even at very mild annealing conditions, as detected by time
domain NMR.
By ageing at 60 °C for 16 hours in air, a mild condition for PP, mechanical properties of 3 layer
samples tend towards values displayed by pristine 65 layer samples, which in turn remain
unaffected by the thermal ageing conditions used. TD-NMR and DSC indicate a small but
significant (3-4%) increase of crystallinity of the sample, and SS-NMR confirms increased order
in the PP phase. Thus, defective PP forms a mesophase composed of small and easily
reorganized crystals. The increase of local polymer mobility provided by interfaces is sufficient
to allow reorganization of PP in the 65 layer system during or immediately after production.
Where layer thickness is in the order of microns the same reorganization can be achieved by mild
thermal treatment.
References
[1] - T. Nakaoki and Y. Inaji, Polym. J. 34, 539 (2002).
P13
86
Revealing the Microstructure of Chemically Modified Polyolefins
Tianzi Huang
The Dow Chemical Company, Freeport, TX 77541, [email protected]
Polyolefin resins were chemically modified in order to adjust their performance to expand their
applications in businesses such as automotive, adhesive, wire and cable. These resins typically
are made from chemical reactions with polyolefin base resins. Widely performed chemical
reactions include substitution, grafting, addition, esterification, etc., in order to introduce
functional groups.
Detailed structural information of these resins and correlations between structure and
performance are keys to business success. Besides molecular weight and molecular weight
distribution, the overall content, and their distribution along with molecular weight of functional
groups, are of strong interest. Composition-sensitive detectors, infrared detectors with fixed
wave number bands or with a full IR spectrum range, have been added onto traditional triple
detector, high temperature gel permeation chromatography (HT GPC) instruments in order to
generate accurate resin MW/MWD and functional group distribution information.
Selected polyolefin base resins, such as maleic anhydride-grafted polyethylene, deuterated
polyethylene, chlorinated polyethylene, are discussed. Research results prove that HT GPC, with
infrared detection, is a powerful tool to reveal the structural information of chemically-modified
polymer resins.
P14
87
Use of band filter based GPC-IR to determine the extent of
isotope substitution in deuterium-labeled polyolefins
Shuhui Kang1, Carlos Lopez-Barron
1, Pat Brant
1, Yiming Zeng
2,
Frank Bates2, Tim Lodge
2,3
1ExxonMobil Chemical Company;
2Department of Chemical Engineering and Materials Science, and
3Chemistry,
University of Minnesota
Abstract
A band filter based GPC-IR method has been used to characterize the extent of isotope
substitution in deuterium-labeled polyolefins through a recently developed catalytic hydrogen-
deuterium (H/D) exchange process [1]. A similar method using high temperature size exclusion
chromatography with infrared detection was recently reported by Habersberger [2]. The
catalytic H/D exchange process, which does not alter the molecular structure, permits deuterium
labeling of polymers prepared using any synthetic approach, a major advantage over the
traditional method of polymerizing deuterated monomers. However one complication is that H/D
exchange is not complete, and may vary with molecular weight or comonomer content. The
resulting heterogeneity in deuterium distribution has repercussions in the neutron scattering
measurements, and therefore this effect needs to be accurately characterized. The band-filter
based GPC-IR method provides a simple but precise measurement for establishing the
deuteration level as a function of MW. Commercial LLDPE, HDPE and lab-prepared atactic PP
samples have been evaluated. The deuteration level has been found to increase with MW for PE
but barely change for aPP. This unusual behavior has been further confirmed with an
independent measurement on a series of samples fractionated by MW. The results have been
compared with measurements based on other techniques. This study provides a promising
strategy for exploring hydrogen-deuterium exchange using heterogeneous catalysts.
[1] Habersberger B. M., Lodge T. P., Bates F. S., Macromolecules, 45, 19, 7778-7782, (2012).
[2] B. Habersberger, T. Huang, K. Hart, D. Gillespie, D. Baugh III , Joint PMSE/POLY Poster Session at 249th ACS National
Meeting, Denver, CO (2015).
P15
88
Contributions of Polymer Chain Configuration to Solvation Thermodynamics
of Polymer Thin Films
Sara V. Orski, Richard J. Sheridan, Edwin P. Chan and Kathryn L. Beers
Materials Science & Engineering Division, National Institute of Standards &
Technology,
Gaithersburg, Maryland, 20899, [email protected]
Solvation effects in confined polymer thin films are not well understood, as macromolecular
chains are no longer in their native random-walk configuration and thermodynamic contributions
from inter- and intra-chain interactions may be significant. To address this question, a series of
model thin films were made on substrates with varying chain confinement and chain
configuration. A series of poly(methyl methacrylate) (PMMA) crosslinked thin films of various
thicknesses and crosslink densities were synthesized to generate networks with comparable
random chain configuration, but differing response to solvent, as the average number of
monomer units between crosslinks is systematically varied. Polymer brushes of PMMA were
also synthesized using controlled surface initiated polymerization, generating high grafting
density, and therefore highly extended chains. The brush films were of equal thicknesses to the
crosslinked network films to control for thickness effects. In-situ x-ray reflectivity
measurements were conducted on both systems to measure film thickness as a function of
solvent activity. Crosslinked films demonstrated increased solvent uptake at lower activities,
indicating plasticization of the network, which was not observed in brushes. Different degrees of
swelling are observed between polymer crosslinked thin films and polymer brushes of equal
thicknesses, indicating the orientation and configuration of confined polymer chains may play a
substantial role in solvation behavior. The solvation difference indicates that the concentration
dependent polymer-solvent interacti
macromolecular chains of the same chemistry are not equivalent. Swelling data was fit to
modified Flory-
Figure 1: Polymer thin film systems where film thickness change is measured as a function of
solvent activity.
P16
89
Interfacial behaviour of polymer coated nanoparticles
L. Qi1, J. Mann
2, H. ShamsiJazeyi
1, M Puerto
1, J. M. Tour
2, R. Verduzco
1, G. J. Hirasaki
1
1Department of Chemical and Biomolecular Engineering, email: [email protected]
2Department of Chemistry
Surfactants are kwon to form micro-emulsions. On the contrary to the macro-emulsions that are
only kinetically stable dispersions of one phase into another one with domain sizes in the range
of micron, micro-emulsions are thermodynamically stable and can form nanoscopic bi-
continuous structures. [1] In this work, it will be shown for the first time that amphiphilic
nanoparticles are able to migrate to the micro-emulsion nanostructures in the absence of
Pickering macro-emulsions.
Figure 1: The figure caption is written in Times 10 and aligned with the picture.
Oxidized carbon black (OCB) nanoparticle is functionalized with different
hydrophilic/hydrophobic coatings, i.e. alkyl group, polyvinyl alcohol (PVA) and partially
sulfonated polyvinyl alcohol (sPVA). In oil and water systems, the functionalized nanoparticle is
found to have a versatile dispersion i.e. in lower aqueous phase, in upper oil phase, or in middle
phase microemulsion. Series of commercially available surfactant, C12-4,5 orthoxylene
sulfonate(OXS), i-C13-(PO)7 –SO4Na (S13B) etc have been test as additive to help with the
OCB dispersion. It is found that the OCB with only sulfonated polyvinyl alcohol attachment
(sPVA-OCB) stays in microemulsion; with the increase of salinity, it follows the microemulsion
to go from lower phase, to middle phase, and to upper phase. And the dispersion of sPVA and
alkyl functionalized OCB (Cn-OCB-sPVA) is the balance of the length of alkyl and sPVA group
and the degree of sulfonation of PVA, depending on which, it can either disperse into
microemulsion or form a separate layer. The sPVA-OCB also indicates a tolerance of high
salinity. The study of different functionality on OCB dispersion can help design appropriate
modified nanoparticle as additive for enhanced oil recovery either to reduce the interfacial
tension between oil and water phase, or to stabilize the microemulsion.
References
[1] Lukas Wolf, Heinz Hoffmann, Yeshayahu Talmon, Takashi Teshigawara, Kei Watanabe,
Cryo-TEM imaging of a novel microemulsion system of silicone oil with an anionic/nonionic
surfactant mixture, Soft Matter, 2010,6, 5367-5374.
P17
90
Synthesis of bottlebrush copolymers based on poly(dimethylsiloxane) for
surface active additives
Stacy L. Pesek
1, Yen-Hao Lin
1, Will Kasper
1, Bo Chen
2, Brian J. Rohde
3, Megan Robertson
3,
Gila E. Stein3, Rafael Verduzco
1.
1 Department of Chemical and Biomolecular Engineering Department, Rice University, Houston,
Texas 77005. [email protected] 2Smalley Institute for Nanoscale Sciences & Technology, Rice University, Houston, Texas
77005. 3Department of Chemical and Biomolecular Engineering, University of Houston, Houston, Texas
77204. 4
Department of Material Science and Nanoengineering, Rice University, Houston, Texas 77005.
Bottlebrush polymers have been used as surface-active additives for chemically-identical linear
polymers because they spontaneously accumulate at surfaces through an entropy-mediated
process [1]. In this work, we introduce enthalpic contributions by designing bottlebrush polymer
additives with mixed side-chain chemistries. First, we report the synthesis of low surface energy
bottlebrush poly(dimethylsiloxane) (PDMS) and bottlebrush copolymers with mixed PDMS and
poly(lactic acid) (PLA) side-chains. Bottlebrush PDMS has either 2 or 5 kg/mol side-chains
with backbone degrees of polymerization up to 139 and molecular weights of 699
kg/mol. PDMS/PLA bottlebrush copolymers have 2 kg/mol side-chains, 75, 50 and 25 mol %
PDMS, with molecular weights in the range of 132 – 162 kg/mol. Blends of PDMS/PLA
bottlebrush copolymers (1 and 5 wt %) and linear PLA (18 kg/mol) were cast in thin films, and
surface analysis based on water contact angle, X-ray photoelectron spectroscopy, and atomic
force microscopy confirmed that low-energy bottlebrush copolymers preferentially segregate to
the top surface without lateral phase separation. This work demonstrates that low-energy
bottlebrush copolymer additives can introduce new surface properties in polymer films.
Figure 1: Schematic for the modification of polymer thin films through the addition of
bottlebrush copolymers, which segregate to the film surface due to enthalpic and entropic effects.
References
[1] – I.Mitra, X.Li, S.L.Pesek, B.Makarenko, B.S.Lokitz, D.Uhrig, J.F.Ankner, R.Verduzco,
G.E.Stein, Macromolecules 47 (2014).
P18
91
Ionic Conductivity and Characterization Study on Gel Electrolytes Based on
Hydroxyethyl Cellulose
S. Çavuş and M. Yıldıran
Department of Chemical Engineering, Faculty of Engineering, Istanbul University,
Avcilar, 34320, Istanbul, Turkey. E-mail: [email protected]
Many polymer electrolyte systems traditionally use poly(ethylene glycol) and poly(ethylene
oxide) as polymer matrix.[1] Compared to these polymers, polysaccharides, environmentally
friendly polymers, offer many advantages especially in terms of ionic conductivity. Crystallinity
of polysaccharide is much lower at ambient condition and polysaccharide-based electrolytes
show superior thermal and chemical stability.[2] However, there are very few studies on the
ionic conductivity and characterization of these sytems.
In the present work, a novel gel electrolyte based on hydroxyethyl cellulose (HEC) was prepared
using potassium iodide/iodine (KI/I2) as redox couple and 1-Methyl-2-pyrrolidone (NMP) and γ-
Butyrolactone (GBL) as solvents. While KI concentration is varied from 0.4 to 1.8 mol/L, equal
volume ratio of NMP and GBL is preferred. Required amounts of KI and I2 (10 mol % of KI)
were dissolved in the binary organic solvent mixture to obtain liquid electrolyte, and then HEC
(3 wt%) was added into the liquid electrolyte. The final mixture was stirred at 50 °C under
vigorous stirring up to homogen and stagnant polymer gel electrolyte was attained. Small times
(less than an hour) are needed for this form of the gel electrolytes. The highest ionic conductivity
at room temperature (25 oC) is 9.46 mScm
-1.
The ion transport mechanism for the HEC-based gel electrolyte system is investigated, and the
best fit with respect to the temperature dependence of the ionic conductivity is determined with
the Arrhenius equation. Detailed characterizations of the gel electrolytes were performed
systematically by FT-IR, TGA, DSC and XRD.
References
[1] – Y. Wang, Solar EnergyMaterials&SolarCells 93, 1167 (2009).
[2] – Y. Yang, H. Hub, C-H. Zhouc, S. Xub, B. Sebob, X-Z. Zhao, Journal of Power Sources
196, 2410 (2011).
P19
92
Micro-heterogeneity of corn hulls cellulosic fiber biopolymer studied by
multiple-particle tracking (MPT)
J. Xu, Y. Tseng1
National Center for Agricultural Utilization Research, Agricultural Research Service, US
Department of Agriculture, 1815 North University Street, Peoria, Illinois 61604, USA.
[email protected] 1Department of Chemical Engineering, University of Florida,
Gainesville, Florida 32611, USA. A novel technique named multiple-particle tracking (MPT) was used to investigate the micro-structural
heterogeneities of Z-trim, a zero calorie cellulosic fiber biopolymer produced from corn hulls. The
Multiple-Particle Tracking (MPT) method was used in this study, which was originally described by
Apgar et al. [1]
. The principle of this technique is to monitor the thermally driven motion of inert micro-spheres, which are evenly distributed within the samples, and to statistically analyze their displacement
distributions. From the data of MPT measurements, information about the extent of heterogeneity can be
-spheres (0.1 volume percent) was gently mixed with the Z-trim biopolymer. Images of the fluorescent
beads were recorded onto the random-access memory of a computer via a cascade 1 k camera mounted on
an inverted epifluorescence microscope. Movies were analyzed by a custom MPT routine analysis
program from Tseng’s lab. The displacements of the microspheres’ centroids were simultaneously monitored in the focal plane of the microscope for 21.5 seconds at a rate of 30 fps, and the last 20 seconds
(total 600 frames) of the movie was taken for particle tracking to avoid the unstable acquisition time in
initialization. For each sample of Z-trim, we tracked a total of ~200 microspheres. Individual time-2
-x(t)]2 + -y(t)]
2
the time lag and t is the elapsed time, were calculated from the two-dimensional trajectories [2]
. From 2
-lag-dependent ensemble-2
computed. The ensemble-averaged diffusion coefficient of the microspheres can be calculated as 2 [3]
.
This work indicated a relatively rapid concentration-induced transition of the properties of the Z-trim.
Pre-transitional effects were apparent at low concentrations as clearly detected by the shape of the MSD
distribution of imbedded particles. At lower concentration of 0.5% of Z-trim, the overall ensemble-averaged MSDs were very similar to that of a viscous homogenous liquid glycerol with a slope of unity.
The diffusion coefficient for the 0.5% Z-trim was independent of time just like glycerol. The
contributions of the 10%, 25%, 50% highest MSD values to the ensemble-averaged MSD for the 0.5% Z-trim were also similar to those for homogeneous solution of glycerol. Therefore, 0.5% Z-trim mostly
behaved like a homogeneous viscous fluid. However, the time-dependence and asymmetry profiles of the
MSD distributions and higher standard deviation of the normalized MSD distribution implied that even at
0.5% concentration, Z-trim showed a symptom of trend of heterogeneity. For the 1% Z-trim colloidal dispersion, though it behaved like a liquid from a relatively macroscopic standpoint because of its close to
unity slope of ensemble-averaged MSD trace. It exhibited more heterogeneity as evidenced by the
slightly time-dependence diffusion coefficient, time-dependence and asymmetry profiles of the MSD distributions, higher standard deviation of the normalized MSD distribution, and higher contributions of
the 10%, 25%, 50% highest MSD values to the ensemble-averaged MSD. At higher concentration of 2%
Z-trim, the heterogeneity became more evident.
References
[1] - J.Apgar, Y.Tseng, E.Federov, M.B.Herwig, S.C.Almo, D.Wirtz, Biophys. J. 79, 1095 (2000).
[2] - J.Xu, Y.Tseng, C.J.Carriere, D.Wirtz, Biomacromolecules. 3, 92 (2002).
[3] - J.Xu, W.Cheng, G.E.Inglett, P.Wu, S.Kim, S.X.Liu, Y.Tseng, LWT – Food Sci. Tech. 43, 977 (2010).
P20
93
Rapid, Simplified Analysis and Data Interpretation of Polymer Mixtures
using MALDI-IMMS
M.J. O’Leary1, K.G. Craven
2
1Waters Corporation, Milford, MA, USA, [email protected];
2Waters
Corporation, Wilmslow, UK
Polymeric materials are abundant in our modern societies and the associated applications are
becoming increasingly diverse and sophisticated.
Mixtures of polymers are difficult to analyse due to the complexity of the sample. Many of the
more traditional techniques, such as size exclusion chromatography and nuclear magnetic
resonance spectroscopy, are averaging techniques which is not ideal for polymer mixtures. Mass
spectrometry allows polymer chemists to be able to make measurements on a molecular level.
With Ion Mobility Mass Spectrometry (IMMS) complex mixtures can be separated and measured
in more detail.
Preliminary Data
Polymers are complex materials, producing complex mass spectral data. When the polymers are
present as a mixture or as copolymers the complexity increases. For these types of analyses
MALDI-IMMS is a well placed technique as it generates predominantly singly charged ions that
are separated by their size and shape. Related polymeric ions form lines within the mobility plot
making confident identification quicker and easier.
Mixtures of biodegradable polymers and copolymers were ionized by MALDI and separated by
ion mobility. The results were viewed in DriftScope and clearly separated series of ions were
observed in the mobility plots.
DriftScope software was then used to interpret the mobility data. Singly charged polymeric ions
increase in molecular weight, size and shape in a predictable manner and as a consequence form
series across a mobility plot. The ability to perform spectral clean-up within DriftScope
simplifies data interpretation, and as a consequence makes the process of characterisation that
much quicker. The software allows selected aspects of the data to be viewed in isolation from
the whole data set, and as a consequence the polymers can be interpreted as if they had been
analysed as a single polymer or copolymer.
P21
94
Use of High Speed/High Resolution Size Based Chromatographic Separation
of Polymeric Materials with Micro Viscometric Detection
M.J. OLeary1, M. Möller
2, and D. Lohmann
3
1Waters Corporation, USA, [email protected];
2Polymer Standards
Services, GmbH, Germany; 3Polymer Standards Services USA, Inc, USA
Recent developments in polymerization processes have utilized a wide array of strategies. The
development has evolved from simple polymer chains to complex polymers capable of
performing multiple functions within a single molecular chains. As these new materials evolve
their control and understanding has come under intense scrutiny utilizing a wide range of
analytical technology ranging from chromatographic separation to advance mass spectrometry.
Addressing the challenges of material characterization has often been focused on hyphenated
detection techniques such as so called triple detection. This approach utilizes a concentration
detector such as a refractive index (RI) detector as well as a viscosity detector and a multi angle
light scattering detector.
With the introduction of the Waters Advanced Polymer Chromatography system (APC) a break
though was achieved in high speed high resolution size based separation. This approach
delivered a novel approach to the separation equipment including the separation column as well
as the entire flow path to yield a high speed / resolution separation maintained from injection to
detection with traditional detector options such as RI and UV detection. The use of conventional
viscometer detectors and multi angle detectors with APC has been limited due to the optical path
and associated band broadening of the viscometer and light scattering detectors available to the
polymer scientist.
In this study the expansion of the APC approach is presented. A new high resolution micro
viscometer is evaluated and shown to match the optical requirements and chromatographic
dispersion control needs enabling high speed high resolution multi detector analysis.
P22
95
Mechanical Properties of All-Acrylic Graft Copolymers Synthesized via the
Grafting-Through Approach
Andrew Goodwin1, Weiyu Wang
1, Nam-Goo Kang
1, Yangyang Wang
2, Kunlun
Hong2, Jimmy Mays
1, 3
1Department of Chemistry, University of Tennessee, Knoxville, Tennessee 37996
2Center for Nanophase Material Sciences, Oak Ridge National Laboratory, Oak
Ridge, Tennessee 37831
3Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge,
Tennessee 37831
Email: [email protected]; [email protected]
A thermoplastic elastomer (TPE) based on an all-acrylic multiblock branched architecture has
been synthesized by the controlled radical polymerization of n-butyl acrylate and anionically
polymerized poly(methyl methacrylate) macromonomer in a ‘grafting-through’ approach. The
synthetic procedure yields high molecular weight (> 200 kg/mol) materials with tuneable volume
fractions of the randomly spaced PMMA branchpoints. The physical properties were investigated
by rheology and dynamic mechanical analysis and compared to that of commercially available
TPEs based on MAM and SIS linear triblock copolymers. Additionally, atomic force microscopy
was employed to observe the influence of both branching and molecular weight of the grafted
chains on the materials morphology in order to gain insight into the structure-property
relationship of our materials.
P23
96
Investigating miniaturization in GPC/SEC
Authors are cited first and underlined, in Times 12, centred, as in the following:
Stephen Luke1, Graham Cleaver
1
1Agilent Technologies, UK, [email protected]
GPC/SEC is an important liquid chromatographic technique for determining the molecular
weight distribution and averages of a polymer and for comparing batch-to-batch polymer quality.
Miniaturization, the use of smaller column dimensions, has been a popular approach in many
liquid chromatographic techniques. The benefits of miniaturization include reduced solvent
costs, higher throughput, increased detector response and taking full advantage of the latest
advances in liquid chromatography instrument design.
In this work we investigate how miniaturization can be applied to gel permeation
chromatography, discuss critical considerations and determine what benefits the approach brings
for size based separations.
P24
97
Molecular Linker Effect on Charge Separation in Organic Photovoltaics
J.W. Mok1, Y-H. Lin
1, K. G. Yager
2, A. D. Mohite
3, W. Nie
3, S. B. Darling
4, Y.
Lee5, E. Gomez
5, D. Gosztola
4, R. D. Schaller
4,6, and R. Verduzco
1
Affiliation: 1Rice University,
2Brookhaven National Laboratory,
3Los Alamos
National Laboratory, 4Argonne National Laboratory,
5The Pennsylvania State
University, and 6Northwestern University.
All-conjugated block copolymers are promising materials for organic photovoltaics, but it
remains uncertain how morphology, molecular structure, and optical and electronic properties of
conjugated block copolymers affect device performance. We demonstrate the effect of a molecular linker between donor and acceptor polymers on photovoltaic performance and optoelectronic properties. We
synthesized two poly(3-hexylthiophene)-poly(2,7-diyl-alt-[4,7-bis(thiophen-5-yl)-2,1,3-
benzothiadiazole]-2′,2″-diyl-(9,9-dioctylfluorene)) (P3HT-PTBTF) block copolymers which only
differ by molecular linker. Power conversion efficiencies decrease by a factor of 40 times, from
2.2% to 0.05%, when the molecular linker is switched. X-ray scattering profiles and TEM
images indicate that morphology is virtually identical independent of molecular linker, as
expected. In contrast, ultrafast transient absorption data reveals charge separation is affected by
the molecular linker. We also show that the molecular linker can influence on electronic
properties at the donor-acceptor interface and kinetics for charge separation and recombination.
In our studies, we find the rate of charge recombination is faster than in polymer-polymer and
polymer-fullerene blends, suggesting further improvement is possible through optimization of
the linking group. This work demonstrates that the molecular linker chemistry influences charge
separation in all-conjugated block copolymer systems, and also suggests that all-conjugated
block copolymers can be used as model systems for the donor-acceptor interface in bulk
heterojunction blends.
Figure 1. Schematics of charge separation on both block-copolymers. Top: charge separation is
suppressed by the TBT molecule. Bottom: charge separation occurs.
P25
98
- Implementation of a post cure at different period of time for nitrile
rubber to improved mechanical properties.
M.G. Orozco1, M. Hinojosa
1, N. Gonzalez
2, A.A. Naranjo
1,2
[email protected], [email protected], [email protected],
Affiliation: (1)Universidad Autonoma de Nuevo León , (2) Discover Integral
Solutions
Rubber-based materials have been commonly used in the oil industry for over 70 years; this is
due to their cost-effective balance between mechanical and chemical properties which results in
good performance. Nevertheless, it is always desirable to obtain better properties through
innovation in the manufacturing processes. In this work we describe the implementation of a
post-curing treatment for high nitrile-rubber components. To this purpose, specimens of a special
mixture of high nitrile-rubber were subjected to immersion in a 3.5% saline solution, at different
periods of time ranging from 72 to 168 hours at 70 °C, the post-cured specimen were then
mechanically tested. We have found a significally increase in mechanical strength without an
undesirable increase in hardness.
Maximum stress
(psi)
Displacement at
break. (in)
Modulus of
elasticity.
Maximum load Die
(Lbf)
3342 12.54 323 23.08
Table 1.1. Results of High Nitrile-Rubber without post-cured.
References
[1] P.H Mott, C.M Roland, Aiging of Natural Rubber In Air and Seawater, Naval Research
Laboratory.
[2] P.Y. Le Gac, V. Le Saux, M. Paris, Y. Marco, Archimer March 2012, volumen 97, Issue 3,
Pages 288-286.
[3] D.L.Hertz Jr. H. Bussem. Seals Esterm, Inc. and T.W. Ray Halliburton Energy Services, Inc.
October 1994.
P26
99
Malvern Polyacrylonitrile Characterization
Technology Package
Wei Sen Wong
Malvern Instruments, [email protected]
Gel Permeation Chromatography (GPC) also known as Size Exclusion Chromatography (SEC),
is a very popular analytical tool for characterizing natural and synthetic polymers. This seminar
will show excellent results possible with our Triple Detection GPC systems for various
polyacrylonitrile (PAN) samples. Molecular weight distribution and structural information are of
special interest to PAN research as well as product and process specifications. This presentation
will show GPC data that differentiated PAN samples with copolymer and/or branching features.
In addition, we will show that FIPA can be a fast and reliable tool for process control activities.
Finally, we will review our well established Dilute Solution Viscometry (DSV) technology
which is often used for product release specifications. DSV, when coupled with GPC and FIPA
form a significant single vendor Polyolefin Characterization Capability Suite.
P27
100
Chemical and molar mass detection in GPC by online detection with specialty
detectors
D. Lohmann1, M. Cudaj
2, G. Guthausen
2, T. Hofe
3, J. McConville
1, M. Wilhelm
2
1 PSS USA Inc., 160 Old Farm Road, Amherst, MA 01002, USA, dlohmann@pss-
polymer.com 2 Karlsruhe Institute of Technology (KIT), Karlsruhe, Germany
3 PSS Polymer Standards Service GmbH, Mainz, Germany
In liquid chromatography, challenges exist when it comes to chemically sensitive detectors
and/or convoluted molar mass distributions.
Hyphenation of size exclusion chromatography with medium resolution nuclear magnetic
resonance (SEC-MR-NMR) is one solution to solving the problem of chemically sensitive
detection in liquid polymer chromatography. Use of a specially designed table-top 20MHz NMR
spectrometer with a permanent magnet coupled to SEC, enables the acquisition of online 1H
NMR spectra of the individual SEC fractions.
A substantial increase in sensitivity and chemical selectivity could be achieved through digital
and mechanical improvements. Online collection of 1H NMR spectra of PMMA and PS homo-
polymers as well as PS-PMMA block-copolymers during SEC fractionation were of sufficient
quality to enable detection and deformulation of unknown polymer compounds.
In addition, coupling GPC to ESI-MS enables generation of absolute molar mass and distribution
data for polymers up to 10 kDa.
Deconvolution via a sophisticated software algorithm enables direct access to calibration curves
and molar mass distribution data, allowing for the reconstruction of the molar mass distribution
of polymer mixtures.
We will present methods and challenges, as well as data generated utilizing the coupling
techniques.
101
ISPAC 2015 List of Participants
102
Rigoberto Advincula
Case Western Reserve University
Peter Alden
Waters Corp
Meshaal Almarzouq
Petro Rabigh
Ronald Andrekanic
Braskem
Guy Berry
Carnegie Melon University
Jesper Bogelund
Novo Nordisk
Amber Bordelon
Albemarle
Hillary Bradshaw
ExxonMobil
Pat Brant
ExxonMobil
Robert Bruell
Fraunhofer Institute
Jeff Butler
ExxonMobil
Tony Carpenter
FEI
Selva Cavus
Istanbul University
Zibin Chai
Sinopec Yangzi Petrochemical Co. Ltd.
Tirtha Chatterjee
Dow Chemical
Chun-Yu Chen
Formosa Plastics Corporation
103
H.N. Cheng
USDA
Oscar Chiantore
University of Torino
Graham Cleaver
Agilent Technologies
Rongjuan Cong
Dow Chemical
Newton Davis
Agilent Technologies
A. Willem deGroot
Dow Chemical
Steven Dell
Afton Chemical
Paul DesLauriers
Chevron Phillips
Nirmala Devi
Gauhati University
Michael F. Drenski
Center for Polymer Reaction Monitoring and
Characterization
Cary Ellis
Bruker AXS
Chris Ellison
University of Texas
Clay Enos
UL Consumer
Casandra Gallaschun
Braskem
Andrew Goodwin
University of Tennessee
Brian Goolsby
Hitachi
104
Brian Habersberger
Dow Chemical Company
Trevor Havard
Postnova Analytics
Alexander Hexemer
Lawrence Berkeley National Laboratory
Maarton Honing
DSM Resolve
Yuchin Hsu
Tokushima University
Zhiqi Hu
Rice University
Tianzi Huang
Dow Chemical
Emma Ibarra
CIP Comex-ppg
Mayumi Ikeda
Takeda Pharmaceutical Company
Abdul Jangda
ExxonMobil
Joerg Jinshek
FEI
Lili Johnson
ExxonMobil
Ron Jones
NIST
Shuhui Kang
ExxonMobil
Zohreh Khosravi
Technische Universitat Braunschweig
Chanda Klinker
Dow Chemical
105
Yeng Ming Lam
Nanyang Technological University
Olayide Samuel Lawal
Olabisi Onabanjo University
Koyau Lee
Formosa Plastics Corp. Texas
Arturo Leyva
ExxonMobil
Chuanfeng Li
Sinopec Yangzi Petrochemical Co. Ltd.
Xiaoyi Li
Rice University
Rongti Li
Formosa Plastics Corp. Texas
Matthew Libera
Stevens Institute of Technology
Yen-Hao Lin
Rice University
Victor Litvinov
DSM Resolve
Lizhi Liu
Sinopec
Derek Lohmann
PSS
Stephen Luke
Agilent Technologies
Jodie Lutkenhaus
Texas A&M University
Mahesh Mahanthappa
University of Wisconsin
Curtis Marcott
Anasys Instruments, Inc.
106
Anna Masek
Lodz University of Technology
Michele Mauri
University of Milan-Bicocca
Jimmy Mays
University of Tennessee
John McConville
PSS Polymer Standards
Amanda McDermott
NIST
Agnieszka Mech-Dorosz
Technical University of Denmark
Debbie Mercer
Dow Chemical
Andy Meyer
Wyatt Technology
Greg Meyers
Dow Chemical
Scott Milner
Penn State University
Petra Mischnick
TU Braunschweig
Konstantinos Misichronis
University of Tennessee
Nolan Mitchell
University of Tennessee
Pornwilard M-M
SCG Chemical
Jorge Mok
Rice University
Benjamin Monrabal
PolymerChar
107
Vidhya Nagarajan
University of Guelph
Martin Nosowitz
Arkema, Inc.
Steve O'Donohue
Agilent Technologies
Michael J. O'Leary
Waters Corp
Marilu Orozco
Universidad Autonoma de Nuevo León
Sara V. Orski
NIST
Miyuki Oshimura
Tokushima University
Steve Page
TA Instruments
Rajesh Paradkar
Dow Chemical
Harald Pasch
University of Stellenbosch
Jayme Paullin
DuPont
Stacy L. Pesek
Rice University
Mark R. Pothecary
Malvern Instruments Inc.
Luqing Qi
Rice University
Dave Randle
Frontier Laboratories
Alex Reed
Advanced Polymer Monitoring Technologies
108
Wayne Reed
Tulane University
Pierre Ricou
Arkema Inc.
Marguerite Rinaudo
CERMAV-CNRS
Megan Robertson
University of Houston
Wonchalerm Rungswang
SCG Chemical
Paul Russo
Georgia Tech University
Bob Sammler
Dow Chemical
Juan Sancho-Tello
Polymer Char
Dan Savin
University of Florida
James Scanlan
Eastman Chemical Company
Staffan Schantz
AstraZeneca R&D
Carrie Schindler
Malvern Instruments Inc.
Clemens Schwarzinger
Johannes Kepler University Linz
Peter Shang
Eastman Chemical Company
YeoOol Shin
LSCNS (South Korea)
Roberto Simonutti
University of Milan
109
Lloyd Smith
University of Wisconsin
Joao Soares
University of Alberta
Alexei Sokolov
University of Tennessee
Dave Soules
Chevron Phillips
Gila Stein
University of Houston
Joe Strukl
Afton Chemical
Jamie Stull
Los Alamos National Laboratory
Jacques Tacx
Sabic
Ned Thomas
Rice University
Davide Tranchida
Borealis
David Ulfik
Hitachi
Gadgoli Umesh
SABIC
Julius Vansco
University of Twente
Nadarajah Vasanthan
Long Island University
Rafael Verduzco
Rice University
Weiyu Wang
University of Tennessee
110
Chrys Wesdemiotis
University of Akron
Wei Sen Wong
Malvern Instruments Inc.
Jingyuan Xu
US Department of Agriculture
Dalia Yablon
SurfaceChar
Wale Zawal
Rice University
Zhe Zhou
Dow Chemical
Yonghua Zhou
Kraton
111
MAPS
112
Hotel ZaZa First Floor
113
Hotel ZaZa 11th
Floor
114
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