Abstract
In this study, polyhedral oligomeric silsesquioxane glycidylisobutyl–POSS was dispersed in an epoxy resin (DGEBA) using ultrasound, and the thermal degradation was investigated by the Flynn–Wall–Ozawa and Criado methods using thermogravimetric analysis. The TEM analysis indicated higher polyhedral oligomeric silsesquioxane (POSS) dispersion in spherical shape. The POSS dispersion was associated with the formation of micelles as a result of their hybrid character. The addition of POSS did not change the degradation of the resin until ~380 °C, and above this temperature, increase in the thermal stability was observed. The kinetic results revealed that the addition of POSS decreased E a values primarily to 10 % POSS and did not affect the mechanism of degradation for all contents. The reduction in E a was associated with the easier breaking of bonds at the interface of the DGEBA/POSS nanocomposite. The thermodynamic parameters suggested an increased “degree of arrangement” for the formation of an active complex during the degradation process and corroborate the lower E a values. The results suggest that the addition of POSS is able to cause an effect of thermal barrier at higher temperatures without affecting the homogeneity of the microstructure of the cured resin.
Similar content being viewed by others
References
Fu BX, Namani M, Lee A (2003) Influence of phenyl-trisilanol polyhedral silsesquioxane on properties of epoxy network glasses. Polymer 44:7739–7747
Liu Y, Zheng S, Nie K (2005) Epoxy nanocomposites with octa(propylglycidyl ether) polyhedral oligomeric silsesquioxane. Polymer 46:12016–12025
Ni Y, Zheng S (2005) Epoxy Resin Containing Octamaleimidophenyl Polyhedral Oligomeric Silsesquioxane. Macromol Chem Phys 206:2075–2083
Marini A, Alzari V, Monticelli O, Pojman JA, Caria G (2007) Polymeric Nanocomposites Containing Polyhedral Oligomeric Silsesquioxanes Prepared via Frontal Polymerization. J Polym Sci, Part A: Polym Chem 45:4514–4521
Zhang Z, Gu A, Liang G, Ren P, Xie J, Wang X (2007) Thermo-oxygen degradation mechanisms of POSS/epoxy nanocomposites. Polym Deg Stab 92:1986–1993
Pellice SA, Fasce DP, Williams RJ (2003) Properties of epoxy networks derived from the reaction of diglycidyl ether of bisphenol A with polyhedral oligomeric silsesquioxanes bearing OH-functionalized organic substituents. J Polym Sci, Part B: Polym Phys 41:1451–1461
Pistor V, Barbosa LG, Soares BG, Mauler RS (2012) Relaxation phenomena in the glass transition of epoxy/N-phenylaminopropyl e POSS nanocomposites. Polymer 53:5798–5805
Liu H, Zheng S, Nie K (2005) Morphology and Thermomechanical Properties of Organic–Inorganic Hybrid Composites Involving Epoxy Resin and an Incompletely Condensed Polyhedral Oligomeric Silsesquioxane. Macromolecules 38:5088–5097
Ni Y, Zheng S, Nie K (2004) Morphology and thermal properties of inorganic–organic hybrids involving epoxy resin and polyhedral oligomeric silsesquioxanes. Polymer 45:5557–5568
Pistor V, Soares BG, Mauler RS (2012) Influence of Different Percentages of N-Phenylaminopropyl—POSS on the Degradation Kinetic of Epoxy Resin. Polym Comp 33:1437–1444
Pistor V, Ornaghi FG, Ornaghi HL Jr, Zattera AJ (2012) Degradation Kinetic of Epoxy Nanocomposites Containing Different Percentage of Epoxycyclohexyl—POSS. Polym Comp 33:1224–1232
Deng J, Polidan JT, Hottle JR, Farmer-Creely CE, Viers BD, Esker AR (2002) Polyhedral Oligomeric Silsesquioxanes: A New Class of Amphiphiles at the Air/Water Interface. J Am Chem Soc 124:15194–15195
Deng J, Hottle JR, Polidan JT, Kim H-J, Farmer-Creely CE, Viers BD, Esker AR (2004) Polyhedral Oligomeric Silsesquioxane Amphiphiles: isotherm and Brewster Angle Microscopy Studies of Trisilanolisobutyl-POSS at the Air/Water Interface. Langmuir 20:109–115
Zeng K, Zheng S (2007) Nanostructures and Surface Dewettability of Epoxy Thermosets Containing Hepta(3,3,3-trifluoropropyl) Polyhedral Oligomeric Silsesquioxane-Capped Poly(ethylene Oxide). J Phys Chem B 111:13919–13928
Ozawa TA (1965) New Method of Analyzing Thermogravimetric Data. Soc Jpn 38:1881–1886
Ozawa TA (1966) A New Method of Quantitative Differential Thermal Analysis. Bull Chem Soc Jpn 39:2071–2085
Flynn JH, Wall LA (1966) General Treatment of the Thermogravimetry of Polymers. J Res Natl Bur Stand 70A:487–523
Poletto M, Pistor V, Zeni M, Zattera AJ (2011) Crystalline properties and decomposition kinetics of cellulose fibers in wood pulp obtained by two pulping processes. Polym Deg Stab 96:679–685
Doyle CD (1961) Kinetic analysis of thermogravimetric data. J Appl Polym Sci 5:285–292
Criado JM, Malek J, Ortega A (1989) Applicability of the master plots in kinetic analysis of non-isothermal data. Thermochim Acta 147:377–385
Núñez L, Fraga F, Núñez MR, Villanueva M (2000) Thermogravimetric study of the decomposition process of the system BADGE (n = 0)/1,2 DCH. Polymer 41:4635–4641
Núñez L, Villanueva M, Núñez MR, Rial BJ (2004) Influence of an Epoxy Reactive Diluent on the Thermal Degradation Process of the System DGEBA n = 0/1,2 DCH. J App Polym Sci 92:1199–1207
Pérez-maqueda LA, Criado JMJ (2000) The Accuracy of Senum and Yang’s Approximations to the Arrhenius Integral. J Therm Anal Calorim 60:909–915
Eyring H (1935) The Activated Complex in Chemical Reactions. J Chem Phys 3:107–115
Vlaev LT, Markovska IG, Lyubchev LA (2003) Non-isothermal kinetics of pyrolysis of rice husk. Thermochim Acta 406:1–7
Genieva SD, Vlaev LT, Atanassov AN (2010) Atanassov, Study of the thermooxidative degradation kinetics of poly(tetrafluoroethene) using iso-conversional calculation procedure. J Therm Anal Calorim 99:551–561
Turmanova S, Genieva S, Vlaev L (2011) Kinetics of Nonisothermal Degradation of Some Polymer Composites: change of Entropy at the Formation of the Activated Complex from the Reagents. J. Thermodynamics 2011:1–10
Pistor V, Puziski L, Zattera AJ (2014) Influence of Different Concentrations of Glycidylisobutyl-POSS on the Glass Transition of the Cured Epoxy Resin. J App Polym Sci 132:41453–41461
Montserrat S, Málek J, Colomer P (1999) Thermal degradation kinetics of epoxy-anhydride resins: II. Influence of a reactive diluents. Thermochim Acta 336:65–71
Pistor V, Ornaghi FG, Ornaghi HL Jr, Zattera AJ (2012) Dynamic mechanical characterization of epoxy/epoxycyclohexyl–POSS nanocomposites. Mater Sci Eng, A 532:339–345
Ornaghi HL Jr, Pistor V, Zattera AJ (2012) Effect of the epoxycyclohexyl polyhedral oligomeric silsesquioxane content on the dynamic fragility of an epoxy resin. J Non-Cryst Solids 358:427–432
Acknowledgements
The authors gratefully acknowledge UCS, CAPES, and CNPq for providing scholarships and financial support.
Author information
Authors and Affiliations
Corresponding authors
Rights and permissions
About this article
Cite this article
Pistor, V., Puziski, L. & Zattera, A.J. Effect of glycidylisobutyl–POSS on the thermal degradation of the epoxy resin. J Mater Sci 50, 3697–3705 (2015). https://doi.org/10.1007/s10853-015-8930-3
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10853-015-8930-3