Quantitative Characterization of Microscopic Variations in the Cross-Link Density of Gels
- G. E. Mitchell ,
- L. R. Wilson ,
- M. T. Dineen ,
- S. G. Urquhart ,
- F. Hayes ,
- E. G. Rightor ,
- A. P. Hitchcock , and
- H. Ade
View Author Information
Analytical Sciences Laboratory, The Dow Chemical Company, 1897 Building, Midland, Michigan 48667; Superabsorbent Products R&D, The Dow Chemical Company, 1603 Building, Midland, Michigan 48667; Department of Physics, North Carolina State University, Raleigh, North Carolina 27695; and Brockhouse Institute for Materials Research, McMaster University, Hamilton, Ontario L8S 4M1, Canada
Abstract
We report the visualization and quantitative analysis of the cross-link structure in model core/shell hydrogel polymers on the microscopic scale, in a fully swollen state, using soft X-ray microscopy. The cross-link density in these materials and their microscopic or even nanoscopic variation critically influence materials characteristics, yet the cross-link density is difficult to characterize by conventional methods. By the use of soft X-ray microscopy, one can investigate these materials in a fully swollen state and thus directly visualize and quantitatively determine the cross-link structure on a microscopic scale. Materials that were cross-linked by different methods were shown to give rise to differently shaped profiles. Abrupt and gradient cross-link density profiles have been investigated, and the spatial variation in their cross-link density has been determined quantitatively.
*
To whom correspondence should be addressed.
†
Analytical Sciences Laboratory, The Dow Chemical Company.
‡
Superabsorbent Products R&D, The Dow Chemical Company.
§
North Carolina State University.
#
Present address: Department of Chemistry, Univ. Saskatchewan, Saskatoon, SK, S7N 5C9 Canada.
⊥
McMaster University.
Cited By
This article is cited by 22 publications.
- Syuji Fujii, Damien Dupin, Tohru Araki, Steven P. Armes and Harald Ade . First Direct Imaging of Electrolyte-Induced Deswelling Behavior of pH-Responsive Microgels in Aqueous Media Using Scanning Transmission X-ray Microscopy. Langmuir 2009, 25 (5) , 2588-2592. https://doi.org/10.1021/la804212y
- Syuji Fujii,, Steven P. Armes,, Tohru Araki, and, Harald Ade. Direct Imaging and Spectroscopic Characterization of Stimulus-Responsive Microgels. Journal of the American Chemical Society 2005, 127 (48) , 16808-16809. https://doi.org/10.1021/ja056589p
- Ryan R. Cooney and, Stephen G. Urquhart. Chemical Trends in the Near-Edge X-ray Absorption Fine Structure of Monosubstituted and Para-Bisubstituted Benzenes. The Journal of Physical Chemistry B 2004, 108 (47) , 18185-18191. https://doi.org/10.1021/jp046868j
- Chris Jacobsen. X-ray Microscopy. 2019,,https://doi.org/10.1017/9781139924542
- Jisoo Ha, Minsu Kim, Wooseop Lee, Hoyeon Lee, Changsun Han, Won Gun Koh, Du Yeol Ryu. Direct measurement of crosslinked surface layer in superabsorbent poly(acrylic acid). Materials Letters 2018, 228 , 33-36. https://doi.org/10.1016/j.matlet.2018.05.079
- Valentin V. Lider. X-ray microscopy. Uspekhi Fizicheskih Nauk 2017, 187 (2) , 201-219. https://doi.org/10.3367/UFNr.2016.06.037830
- F. Di Lorenzo, S. Seiffert. Nanostructural heterogeneity in polymer networks and gels. Polymer Chemistry 2015, 6 (31) , 5515-5528. https://doi.org/10.1039/C4PY01677G
- Vincent Lee, Viatcheslav Berejnov, Marcia West, Sumit Kundu, Darija Susac, Jürgen Stumper, Radoslav T. Atanasoski, Mark Debe, Adam P. Hitchcock. Scanning transmission X-ray microscopy of nano structured thin film catalysts for proton-exchange-membrane fuel cells. Journal of Power Sources 2014, 263 , 163-174. https://doi.org/10.1016/j.jpowsour.2014.04.020
- Fátima Rosa, João Bordado, Miguel Casquilho. Synthesis, swelling capacity, and texture of polymers from monomers of sulfonic acid and acrylamide. Polymer Engineering & Science 2013, 53 (8) , 1728-1733. https://doi.org/10.1002/pen.23434
- Adam P. Hitchcock. Soft X-Ray Imaging and Spectromicroscopy. 2012,,, 745-791. https://doi.org/10.1002/9783527641864.ch22
- Ben Watts, Harald Ade. NEXAFS imaging of synthetic organic materials. Materials Today 2012, 15 (4) , 148-157. https://doi.org/10.1016/S1369-7021(12)70068-8
- N. Schmidt, C. Hub, J.-F. Gnichwitz, W. Hieringer, A. Hirsch, R. H. Fink. Structure, morphology and interface properties of ultrathin SnTTBPP(OH)2-films adsorbed on Ag(100). Physical Chemistry Chemical Physics 2011, 13 (20) , 9839. https://doi.org/10.1039/c1cp20340a
- Harald Ade, Cheng Wang, Hongping Yan. The case for soft X-rays: Improved compositional contrast for structure and morphology determination with real and reciprocal space methods. IOP Conference Series: Materials Science and Engineering 2010, 14 , 012020. https://doi.org/10.1088/1757-899X/14/1/012020
- Danielle Covelli, Daniel Hernández-Cruz, Brian M. Haines, Vincente Munoz, Oladipo Omotoso, Randy Mikula, Stephen Urquhart. NEXAFS microscopy studies of the association of hydrocarbon thin films with fine clay particles. Journal of Electron Spectroscopy and Related Phenomena 2009, 173 (1) , 1-6. https://doi.org/10.1016/j.elspec.2009.02.012
- Harald Ade, Herman Stoll. Near-edge X-ray absorption fine-structure microscopy of organic and magnetic materials. Nature Materials 2009, 8 (4) , 281-290. https://doi.org/10.1038/nmat2399
- J. Raabe, G. Tzvetkov, U. Flechsig, M. Böge, A. Jaggi, B. Sarafimov, M. G. C. Vernooij, T. Huthwelker, H. Ade, D. Kilcoyne, T. Tyliszczak, R. H. Fink, C. Quitmann. PolLux: A new facility for soft x-ray spectromicroscopy at the Swiss Light Source. Review of Scientific Instruments 2008, 79 (11) , 113704. https://doi.org/10.1063/1.3021472
- Harald Ade, Adam P. Hitchcock. NEXAFS microscopy and resonant scattering: Composition and orientation probed in real and reciprocal space. Polymer 2008, 49 (3) , 643-675. https://doi.org/10.1016/j.polymer.2007.10.030
- R. Peters, V.M. Litvinov, P. Steeman, A.A. Dias, Y. Mengerink, R. van Benthem, C.G. de Koster, Sj. van der Wal, P. Schoenmakers. Characterisation of UV-cured acrylate networks by means of hydrolysis followed by aqueous size-exclusion combined with reversed-phase chromatography. Journal of Chromatography A 2007, 1156 (1-2) , 111-123. https://doi.org/10.1016/j.chroma.2006.10.071
- Tohru Araki, Harald Ade, Jeffrey M. Stubbs, Donald C. Sundberg, Gary E. Mitchell, Jeffrey B. Kortright, A. L. D. Kilcoyne. Resonant soft x-ray scattering from structured polymer nanoparticles. Applied Physics Letters 2006, 89 (12) , 124106. https://doi.org/10.1063/1.2356306
- Adam P. Hitchcock, Harald D. H. Stöver, Lisa M. Croll, Ronald F. Childs. Chemical Mapping of Polymer Microstructure Using Soft X-ray Spectromicroscopy. Australian Journal of Chemistry 2005, 58 (6) , 423. https://doi.org/10.1071/CH05054
- Markus Plaschke, Jörg Rothe, Melissa A. Denecke, Thomas Fanghänel. Soft X-ray spectromicroscopy of humic acid europium(III) complexation by comparison to model substances. Journal of Electron Spectroscopy and Related Phenomena 2004, 135 (1) , 53-62. https://doi.org/10.1016/j.elspec.2003.12.007
- H. Ade. X-ray Microscopy. 2002,,https://doi.org/10.1002/0471440264.pst403