Hostname: page-component-586b7cd67f-2plfb Total loading time: 0 Render date: 2024-11-23T05:31:20.413Z Has data issue: false hasContentIssue false
  • English
  • Français

Modification of Montmorillonite with Alkyl Silanes and Fluorosurfactant for Clay/fluoroelastomer (FKM) Nanocomposites

Published online by Cambridge University Press:  01 January 2024

Maryam Khajehpour ,
Genaro A. Gelves  and
Uttandaraman Sundararaj
Maryam Khajehpour
Affiliation:
Department of Chemical and Petroleum Engineering, University of Calgary, Calgary, Canada, T2N 1N4
Genaro A. Gelves
Affiliation:
Department of Chemical and Petroleum Engineering, University of Calgary, Calgary, Canada, T2N 1N4
Uttandaraman Sundararaj*
Affiliation:
Department of Chemical and Petroleum Engineering, University of Calgary, Calgary, Canada, T2N 1N4
*
*E-mail address of corresponding author: u.sundararaj@ucalgary.ca
Rights & Permissions [Opens in a new window]

Abstract

Core share and HTML view are not available for this content. However, as you have access to this content, a full PDF is available via the ‘Save PDF’ action button.

The main objective of the present work was to functionalize nanoclays with organosilanes and surfactant in order to facilitate the dispersion of the nanofillers in the host fluoroelastomer (FKM) polymer matrix. Better dispersion was achieved by improving interaction between the clay polymer nanocomposite (CPN) constituents. The first part of this study investigated modification of montmorillonite (Mnt) using different saturated and unsaturated alkyl silanes and an alkyl hydrocarbon ammonium quaternary surfactant. Silicon magic angle spinning nuclear magnetic resonance spectroscopy, thermal gravimetric analysis (TGA), elemental analysis, X-ray diffraction (XRD), and Fourier transform infrared spectroscopy were used to characterize the silane-grafted clays. Results indicated that the amount of silane grafted depended on the specific structure of the silane. Silane-grafted Mnt was also modified with ionic surfactants intercalated between the clay layers. A 169% increase in the clay basal spacing (from initial spacing of 10.0 Å to 26.9 Å) was achieved. The second part of the study successfully synthesized FKM nanocomposites containing custom-functionalized Mnt, with the aim of producing reinforced high-performance materials. The effects of clay modification on the morphology and thermal properties of the CPN were studied using XRD, TGA, scanning electron microscopy, and transmission electron microscopy. The CPN made with the modified clay exhibited greater thermal stability than the CPN of the commercially available modified Mnt, with a degradation onset point ~ 40°C higher.

Keywords

ClayFluoroelastomerMontmorilloniteNanocompositeSilane Grafting
Type
Research Article
Information
Clays and Clay Minerals , Volume 63 , Issue 1 , February 2015 , pp. 1 - 14
Copyright
Copyright © Clay Minerals Society 2015

References

Abbehausen, C. Formiga, A.L.B. Sabadini, E. and Yoshid, I.V.P., 2010 A β-cyclodextrin/siloxane hybrid polymer: synthesis, characterization and inclusion complexes Journal of Brazilian Chemical Society 21 1867–1876.CrossRefGoogle Scholar
Akelah, A. and Moet, A., 1996 Polymer-clay nanocomposites: Free-radical grafting of polystyrene on to organophilic montmorillonite interlayers Journal of Materials Science 31 3589–3596.CrossRefGoogle Scholar
Al-haj Ali, M. and Elleithy, R.H., 2011 Viscoelastic properties of polypropylene/organo-clay nano-composites prepared using miniature lab mixing extruder from masterbatch Journal of Applied Polymer Science 121 27–36.Google Scholar
Ameduri, B. Boutevin, B. and Kostov, G., 2001 Fluoroelastomers: synthesis, properties and applications Progress in Polymer Science 26 105–187.CrossRefGoogle Scholar
Bergaya, F. and Lagaly, G., 2001 Surface modification of clay minerals Applied Clay Science 19 1–3.CrossRefGoogle Scholar
Bergaya, F. Jaber, M. Lambert, J.F., Galimberti, M., 2011 Clays and clay minerals Rubber-Clay Nanocomposites, Science, Technology and Applications Hoboken, New Jersey Wiley.Google Scholar
Bergaya, F. Detellier, C. Lambert, J.-F. and Lagaly, G., 2013 Introduction to clay polymer nanocomposites Handbook of Clay Science 2nd edition Amsterdam Elsevier.Google Scholar
Borse, N.K. and Kamal, M.R., 2006 Melt processing effects on the structure and mechanical properties of PA-6/clay nanocomposites Polymer Engineering and Science 46 1094–1103.CrossRefGoogle Scholar
Bukka, K. and Miller, J.D., 1992 FTIR study of deuterated montmorillonites: Structural features relevant to pillared clay stability Clays and Clay Minerals 40 92–102.CrossRefGoogle Scholar
Chen, G.X. Choi, J.B. and Yoon, J.S., 2005 The role of functional group on the exfoliation of clay in poly(L-lactide) Macromolecular Rapid Communication 26 183–187.CrossRefGoogle Scholar
Coates, J., 2000 Interpretation of infrared spectra, a practical approach Encyclopedia of Analytical Chemistry 10815–10837.CrossRefGoogle Scholar
Daniel, L.M. Frost, R.L. and Zhu, H.Y., 2008 Edge-modification of Laponite with dimethyl-octylmethoxysilane Journal of Colloid Interface Science 321 302–309.CrossRefGoogle ScholarPubMed
Das, A. Stöckelhuber, K.W. Jurk, R. Jehnichen, D. and Heinrich, G., 2011 A general approach to rubber—montmorillonite nanocomposites: Intercalation of stearic acid Applied Clay Science 51 117–125.CrossRefGoogle Scholar
Dennis, H.R. Hunter, D.L. Chang, D. White, J.L. Cho, J.W. and Paul, D.R., 2001 Effect of melt processing conditions on the extent of exfoliation in organoclay-based nanocomposites Polymer 42 9513–9522.CrossRefGoogle Scholar
Dong, J. Ozaki, Y. and Nakashima, K., 1997 Infrared, Raman, and near-infrared spectroscopic evidence for the coexistence of various hydrogen-bond forms in poly(acrylic acid) Macromolecules 30 1111–1117.CrossRefGoogle Scholar
El Rassy, H. and Pierre, A.C., 2005 NMR and IR spectroscopy of silica aerogels with different hydrophobic characteristics Journal of Non-Crystalline Solids 351 1603–1610.CrossRefGoogle Scholar
He, H. Frost, L.R. and Zhu, J., 2004 Infrared study of HDTMA+ intercalated montmorillonite Spectrochimica Acta Part A 60 2853–2859.Google Scholar
He, H. Duchet, J. Galy, J. and Gerard, J.F., 2005 Grafting of swelling clay materials with 3-aminopropyltriethoxysilane Journal of Colloid and Interface Science 288 171–176.CrossRefGoogle ScholarPubMed
Heinz, H., 2012 Clay minerals for nanocomposites and biotechnology: surface modification, dynamics and responses to stimuli Clay Minerals 47 205–230.CrossRefGoogle Scholar
Hermosin, M.C. and Cornejo, J., 1986 Methylation of sepiolite and palygorskite with diazomethane Clays and Clay Minerals 34 591–596.CrossRefGoogle Scholar
Herrera, N.N. Letoffe, J.M. Putaux, J.L. David, L. and Bourgeat-Lami, E., 2004 Aqueous dispersions of silane-functionalized Laponite clay platelets. A first step toward the elaboration of water-based polymer/clay nanocomposites Langmuir 20 1564–1571.Google Scholar
Hrachová, J. Komadel, P. and Chodák, I., 2008 Effect of montmorillonite modification on mechanical properties of vulcanized natural rubber composites Journal of Materials Science 43 2012–2017.CrossRefGoogle Scholar
Hussain, F. Hojjati, M. Okamoto, M. and Gorga, R.E., 2006 Polymer-matrix nanocomposites, processing, manufacturing, and application: An overview Journal of Composite Materials 43 3107–3123.Google Scholar
Huskic, M. Zigon, M. and Ivanković, M., 2013 Comparison of the properties of clay polymer nanocomposites prepared by montmorillonite modified by silane and by quaternary ammonium salts Applied Clay Science 85 109–115.CrossRefGoogle Scholar
Joo, J.H. Shim, J.H. Choi, J.H. Choi, C.H. Kim, D.S. and Yoon, J.S., 2008 Effect of the silane modification of an organoclay on the properties of polypropylene/clay composites Journal of Applied Polymer Science 109 3645–3650.CrossRefGoogle Scholar
Lakshminarayanan, S. Lin, B. and Sundararaj, U., 2009 Effect of clay surfactant type and clay content on the rheology and morphology of uncured fluoroelastomer/clay nanocomposites prepared by melt-mixing Journal of Applied Polymer Science 112 3597–3604.CrossRefGoogle Scholar
Lambert, J.-F. and Bergaya, F., 2013 Smectite-polymer nanocomposites Handbook of Clay Science 2nd edition Amsterdam Elsevier.Google Scholar
Marynick, D.S. and Dixon, D.A., 1977 Electron affinity of the methyl radical: Structures of CH3 and CH3− Proceedings of the National Academy of Sciences of the United States of America 74 410–413.CrossRefGoogle ScholarPubMed
Mingliang, G. and Demin, J., 2008 Influence of organoclay prepared by solid state method on the morphology and properties of polyvinyl chloride/organoclay nanocomposites Journal of Elastomers and Plastics 40 223–235.CrossRefGoogle Scholar
Mittal, V. Kim, J.K. and Pal, K., 2011 Recent Advances in Elastomeric Nanocomposites Berlin, Heidelberg Springer-Verlag.CrossRefGoogle Scholar
Modesti, M. Lorenzetti, A. Bon, D. and Besco, S., 2005 Effect of processing conditions on morphology and mechanical properties of compatibilized polypropylene nanocomposite Polymer 46 10237–10245.CrossRefGoogle Scholar
Monasterio, F.E., 2010 Effect of the organic groups of difunctional silanes on the preparation of coated clays for olefin polymer modification Clay Minerals 45 489–502.CrossRefGoogle Scholar
Morrison, R.T. and Boyd, R.N., 1983 Organic Chemistry 4th edition New York New York University.Google Scholar
Norrish, K., 1954 The Swelling of Montmorillonite Adelaide, Australia Division of Soils, C.S.I.R.O..CrossRefGoogle Scholar
Orprecio, R. and Evans, C.H., 2003 Polymer-immobilized cyclodextrin trapping of model organic pollutants in flowing water streams Journal of Applied Polymer Science 90 2103–2110.CrossRefGoogle Scholar
Park, M. Shim, I.K. Jung, E.Y. and Choy, J.H., 2004 Modification of external surface of Laponite by silane grafting Journal of Physical Chemistry of Solids 65 499–501.CrossRefGoogle Scholar
Paul, D.R. and Robeson, L.M., 2008 Polymer nanotechnology: Nanocomposites Polymer 49 3187–3204.CrossRefGoogle Scholar
Pramanik, S. Das, G. and Karak, N., 2013 Facile preparation of polyaniline nanofibers modified bentonite nanohybrid for gas sensor application The Royal Society of Chemistry Advances 3 4574–4581.Google Scholar
Qian, Z. Zhou, H. Xu, X. Ding, Y. Zhang, S. and Yang, M., 2009 Effect of the grafted silane on the dispersion and orientation of clay in polyethylene nanocomposites Polymer Composite 30 1234–1242.CrossRefGoogle Scholar
Shanmugharaj, A.M. Rhee, K.Y. and Ryu, S.H., 2006 Influence of dispersing medium on grafting of aminopropyltriethoxysilane in swelling clay materials Journal of Colloid and Interface Science 298 854–859.CrossRefGoogle ScholarPubMed
Shen, W. He, H. Zhu, J. Yuan, P. and Frost, R.L., 2007 Grafting of montmorillonite with different functional silanes via two different reaction systems Journal of Colloid and Interface Science 313 268–273.CrossRefGoogle ScholarPubMed
Stuart, B.H., 2004 Infrared Spectroscopy: Fundamentals and Applications New Jersey Wiley.CrossRefGoogle Scholar
Smidt, E. Bhm, K. Schwanninger, M., Nikolic, G., 2011 The application of FT-IR spectroscopy in waste management Fourier Transforms — New Analytical Approaches and FTIR Strategies Rijeka, Croatia InTech.Google Scholar
Tian, R. Sitez, O. Li, M. Hu, W. Chabal, Y.J. and Gao, J., 2010 Infrared characterization of interfacial Si-O bond formation on silanized flat SiO2/Si surfaces Langmuir 26 4563–4566.CrossRefGoogle ScholarPubMed
Valsecchi, R. Torlaj, L. Turri, S. Tonelli, C. and Levi, M., 2011 Barrier properties in hydrogenated acrylonitrile butadiene rubber compounds containing organoclays and perfluoropolyether additives Journal of Applied Polymer Science 119 3476–3482.CrossRefGoogle Scholar
Wang, Y. Wang, X. Duan, Y. Liu, Y. and Du, S., 2011 Modification of montmorillonite with poly(oxypropylene) amine hydrochlorides: Basal spacing, amount intercalated, and thermal stability Clays and Clay Minerals 59 507–517.CrossRefGoogle Scholar
Wu, Y.P. Jia, Q.X. Yu, D.S. and Zhang, L.Q., 2004 Modeling Young’s modulus of rubber—clay nanocomposites using composite theories Polymer Testing 23 903–909.CrossRefGoogle Scholar
Xie, W. Gao, Z. Pan, W.P. Hunter, D. Singh, A. and Vaia, R., 2001 Thermal degradation chemistry of alkyl quaternary ammonium montmorillonite Chemistry of Materials 13 2979–2990.CrossRefGoogle Scholar
Xu, X. Ding, Y. Wang, F. Wen, B. Zhang, J. Zhang, S. and Yang, M., 2009 Effects of silane grafting on the morphology and thermal stability of poly(ethylene terephthalate)/clay nanocomposites Polymer Composite 31 825–834.CrossRefGoogle Scholar
Zhu, L. and Xanthos, M., 2004 Effects of process conditions and mixing protocols on structure of extruded polypropylene nanocomposites Journal of Applied Polymer Science 93 1891–1899.CrossRefGoogle Scholar
Zumdahl, S.S., 1999 Chemistry 5th edition Boston, Massachusetts, USA Houghton Mifflin Harcourt.Google Scholar