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NMR Analysis of Solution
Polymers in Industrial R&D
Brian Antalek
Eastman Kodak Company
PANIC Conference
La Jolla, CA Feb 9 2015
‹#›
© Eastman Kodak Company, 2015
Kodak’s Materials Research Fields
Polymer Design and Synthesis
Ink and Media Technology
Dispersions and Formulations
Microfluidic Applications
Modeling of Complex Fluids
Stimulus-Responsive and Self-Assembling Materials
Surface and Colloid Chemistry and Physics
Molecular Semiconductors
Inorganic Nanomaterials
‹#›
© Eastman Kodak Company, 2015
Analytical Science
NMR/EPR
Mass Spectrometry
Liquid and Ion Chromatography
Gas Chromatography GC/MS
Polymer Dilute Solution GPC
Rheology and Thermal Analysis
Particle Characterization
Atomic Spectroscopy
Electronic Spectroscopy
Surface Science
Micromechanical Characterization
Optical Microscopy
Electron Microscopy
Vibrational Spectroscopy
X-Ray Spectroscopy
Walkup Facilities
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© Eastman Kodak Company, 2015
Techniques
Structure Characterization
Quantitative Analysis
Diffusion Methods
Mixture Analysis
Materials Partitioning
Size Estimation
Solid-State Methods
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© Eastman Kodak Company, 2015
Applications
Polymer Analysis
Solution Structure
Solution Components
Surface Adsorption
Multi-Point Contact
Single-Point Contact
Diffusion Methods
Optical Film Characterization
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© Eastman Kodak Company, 2015
Automated Analysis
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© Eastman Kodak Company, 2015
Application
+
HO(CH2)nCH3
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© Eastman Kodak Company, 2015
Application
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© Eastman Kodak Company, 2015
PGSE (diffusion) NMR
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© Eastman Kodak Company, 2015
PGSE (diffusion) NMR
© Eastman Kodak Company, 2015
‹#›
© Eastman Kodak Company, 2015
11
PGSE (diffusion) NMR
© Eastman Kodak Company, 2015
D is related to
Molecular size (RH, hydrodynamic radius)
Solution viscosity (η)
Temperature (T)
Stokes-Einstein equation
‹#›
© Eastman Kodak Company, 2015
12
PGSE (diffusion) NMR
time = 0
time = Δ
© Eastman Kodak Company, 2015
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© Eastman Kodak Company, 2015
PGSE (diffusion) NMR
© Eastman Kodak Company, 2015
‹#›
© Eastman Kodak Company, 2015
14
PGSE (diffusion) NMR
g
© Eastman Kodak Company, 2015
-
‹#›
© Eastman Kodak Company, 2015
Mixture Analysis
PGSE NMR data set
how do we analyze?
Concept. Magnet. Reson. 14(4) 225–258 (2002)
g signal ~ g2Δ
‹#›
© Eastman Kodak Company, 2015
Mixture Analysis
DOSY – diffusion-ordered spectroscopy
J. Am. Chem. Soc. 114, 3139–3141 (1992)
‹#›
© Eastman Kodak Company, 2015
Mixture Analysis
DECRA – direct exponential curve resolution algorithm
J. Am. Chem. Soc. 118, 10331-10332 (1996)
A = CP
mixture spectra = conc profiles x pure spectra
GRAM
A = CβP
‹#›
© Eastman Kodak Company, 2015
DOSY Toolbox J Magn Reson, 200, 296-302 (2009)
Pc
Linux
Mac
Free for
download
Mathias Nilsson, Univ of Manchester
‹#›
© Eastman Kodak Company, 2015
Application
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© Eastman Kodak Company, 2015
Application
‹#›
© Eastman Kodak Company, 2015
polyurethanes
‹#›
© Eastman Kodak Company, 2015
polyurethanes
CD3OD D2O
Mw ~ 32500 DH ~ 22nm, 5nm
‹#›
© Eastman Kodak Company, 2015
Polyurethanes – PDMS incorporation
‹#›
© Eastman Kodak Company, 2015
Polyurethanes – PDMS incorporation
‹#›
© Eastman Kodak Company, 2015
Polymer chain adsorbs at
multiple points
Chain experiences
significantly reduced
molecular mobility
NMR resonances broaden
and are therefore not
detected (by solution
methods)
Surface Adsorption
‹#›
© Eastman Kodak Company, 2015
Molecular Dynamics and NMR
as tc increases, T2 decreases, linewidth increases
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© Eastman Kodak Company, 2015
Molecular Dynamics and NMR
as tc increases, T2 decreases, linewidth increases
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© Eastman Kodak Company, 2015
Quantitative Analysis
Surface adsorption
multiple point attachment
Langmuir, 22(9), 4198-4207 (2006)
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© Eastman Kodak Company, 2015
Surface Adsorption
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© Eastman Kodak Company, 2015
External Reference
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© Eastman Kodak Company, 2015
10 kDa PEI on 15 nm Silica
‹#›
© Eastman Kodak Company, 2015
with
crosslinking
10 kDa PEI on 15 nm Silica
‹#›
© Eastman Kodak Company, 2015
Quantitative Analysis
Surface adsorption
single point attachmentLangmuir, 22(9), 4198-4207 (2006)
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© Eastman Kodak Company, 2015
PEG on Surface
R-NH2
silica core
PEI shell
mPEG periphery
unreacted mPEG
‹#›
© Eastman Kodak Company, 2015
PEG Adsorption on PEI/Silica Composite
‹#›
© Eastman Kodak Company, 2015
PEG Adsorption on PEI/Silica Composite
‹#›
© Eastman Kodak Company, 2015
redispersed solids
bound
free
NMR signal decay
PEG Adsorption on PEI/Silica Composite
‹#›
© Eastman Kodak Company, 2015
PEG Adsorption on PEI/Silica Composite
‹#›
© Eastman Kodak Company, 2015
Application
Surface-modified titania for optical coatings
Multidisciplinary approach
Langmuir, 25(21), 12713–12720 (2009)
‹#›
© Eastman Kodak Company, 2015
Surface-Modified Titania
‹#›
© Eastman Kodak Company, 2015
Surface-Modified Titania
‹#›
© Eastman Kodak Company, 2015
Surface-Modified Titania
‹#›
© Eastman Kodak Company, 2015
Surface-Modified Titania
‹#›
© Eastman Kodak Company, 2015
Surface-Modified Titania
‹#›
© Eastman Kodak Company, 2015
Surface-Modified Titania
Atomic Force Microscopy (AFM)
‹#›
© Eastman Kodak Company, 2015
Surface-Modified Titania
‹#›
© Eastman Kodak Company, 2015
43
Acknowledgments
Thomas Blanton Mark Mis
Joseph Bringley Hwei-Ling Yau
Ken Baptiste Brian Cleary
Michael Hewitt Barbara Lussier
John Minter Gary Slater
Thomas Mourey Lisa Slater
YuanQiao Rao Cathy Falkner
© Eastman Kodak Company, 2015
‹#›

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Antalek_PANIC_Feb2015

Editor's Notes

  1. Added “Eastman Kodak Company” below your name
  2. Slide title – added apostrophe “s” after Kodak Bulleted items – applied initial caps to main words (consistency) Added copyright notification at bottom left
  3. Applied initial caps to main words in each bulleted item I tried applying sub-bullets to “Mixture Analysis” etc., but it looked better this way Last bullet – inserted the hyphen
  4. Initial caps Although the tint of the yellow bullets differs from that on previous slides, I wasn’t able to access the bullet to adjust the color. Don’t be concerned.
  5. For this and the next several slides, I changed the font of the titles from Times to Arial and increased font size for consistency I noticed that for this and several other slides onward, everything below the yellow line is grouped, and I’m unable to ungroup them in order to perform edits on the text; if I find a problem, I’ll call it to your attention and ask that you make the change yourself if possible
  6. Do you have permission to use this figure?
  7. I was unable to add the copyright notification on this slide, although it does appear when I view its slide master; somehow a black background seems to have been added to the entire slide and it obliterates the copyright notification (maybe the black is on “top” of the slide master?), whereas the Kodak logo and yellow lines at the top are okay. I tried to add the notification to the slide itself but was unable to do so and didn’t want to “monkey” with it too much. Don’t know what you did to this and some future slides, but if it was necessary for some reason, it’s okay Also, if you can put an initial cap on the first letter of the three items that follow “D is related to” that would be fine
  8. If possible, please put an initial cap on “components” near top of slide
  9. If possible, please insert a hyphen between “Diffusion” and “dependent” and if you can change that line from Times to Arial (Body), please do
  10. Do you have permission to use this graphic, or is the article one of yours? I’m unable to find it online to verify I’ve noticed that most of the text on this slide (labels) is in Times rather than Arial, but that is not a big issue; if I’d had access to the slide (and some that follow) I probably would have changed it, but it is not worth the time for you to do it at this point, unless you wanted to Changed format of reference for greater consistency with the other references that appear on the presentation
  11. Permission? I don’t think this is one of your articles Inserted hyphen in “diffusion-ordered” Reference – changed font to Arial – is this one of your articles?
  12. Nudged the “GRAM” and “A = C(Beta)P” up so they wouldn’t obliterate “A = CP” I see that this is one of your articles
  13. Do this and the following two images belong to Kodak?
  14. Slide title – changed from Times 24 to Arial Heading 30 and lined up consistently with other slide titles I’m not sure why you have “Eastman Kodak Company” on the top right of this slide (and two following slides) but I didn’t delete it Text at bottom – changed from Arial to times
  15. Slide title – changed from Times 24 to Arial Heading 30 and lined up consistently with other slide titles I’m not sure why you have “Eastman Kodak Company” on the top right of this slide (and two following slides) but I didn’t delete it Text at bottom – changed from Arial to times
  16. I see that this is one of your articles and I gather than the slides that follow are from that article
  17. Moved title up a bit to be on same plane as other slide titles.
  18. Same changes as previous slide.
  19. I see this is one of your articles so I gather that the slides that follow are from it?
  20. Title – put an initial cap on “Surface”
  21. I see that this is one of your articles – following slides are from it?
  22. Nudged the graphic down a bit
  23. Increased line spacing between the names from 0 to 4 points