Prediction of curing kinetics of resorcinol‐added resole phenolic resins using differential scanning calorimetry for the fabrication of carbon/carbon composites

Cordeiro, Jose C.; Davis, Rachel E.; Ramsurn, Hema; Crunkleton, Daniel W.; Otanicar, Todd P.; Keller, Michael W.

doi:10.1002/app.52949

Title: Prediction of curing kinetics of resorcinol‐added resole phenolic resins using differential scanning calorimetry for the fabrication of carbon/carbon composites

Journal Article · 31 July 2022 · Journal of Applied Polymer Science

DOI: https://doi.org/10.1002/app.52949 · OSTI ID:2418658

^[1]; Davis, Rachel E. ^[2];

^[2]; Crunkleton, Daniel W. ^[2];

^[3];

^[2]

Univ. of Tulsa, Tulsa, OK (United States); OSTI
Univ. of Tulsa, Tulsa, OK (United States)
Boise State Univ., ID (United States)

Phenolic resins are commonly used as carbon precursors for the fabrication of carbon/carbon composites due to their high carbon yield and aromatic nature. To decrease curing times, acid catalysts are generally used, but the addition of resorcinol was found to have a similar effect while being incorporated into the resin matrix with no contamination or corrosion issues. In this work, the curing kinetics of pure, 10, 20, and 30 wt% resorcinol-added phenolic resins were investigated through differential scanning calorimetry. Heating rates of 0.5, 1, 2.5, and 5°C min^-1 were used with several curing models to predict isothermal curing. Averaged mean absolute error (MAE) for the isoconversional mathematical approaches namely Kissinger–Akahira–Sunose (MAE = 12.9 min), Flynn–Wall–Ozawa (15.8 min), and Vyazovkin (14 min) show that these methods provide the best predictions, attributed to their adoption of an activation energy that depends on the extent of cure (E_a(α)). The Kissinger method (MAE = 36 min), which depends only on peak temperature with a constant activation energy assumption, and the data noise sensitive Friedman model (MAE = 1144.7 min) provide the least accurate results. Thermogravimetric analysis revealed that resorcinol decreases the curing times by up to 71% without lowering carbon yield.

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Research Organization:: Univ. of Tulsa, Tulsa, OK (United States)

Sponsoring Organization:: USDOE; USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: EE0008736

OSTI ID:: 2418658

Journal Information:: Journal of Applied Polymer Science, Journal Name: Journal of Applied Polymer Science Journal Issue: 39 Vol. 139; ISSN 0021-8995

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (37)

A unified approach to kinetic processing of nonisothermal data Vyazovkin, Sergey International Journal of Chemical Kinetics, Vol. 28, Issue 2 https://doi.org/10.1002/(SICI)1097-4601(1996)28:2<95::AID-KIN4>3.0.CO;2-G	journal	January 1996
Activation energy and curing behavior of resol- and novolac-type phenolic resins by differential scanning calorimetry and thermogravimetric analysis Lee, Young-Kyu; Kim, Dae-Jun; Kim, Hyun-Joong Journal of Applied Polymer Science, Vol. 89, Issue 10 https://doi.org/10.1002/app.12340	journal	June 2003
Curing behavior of a novolac-type phenolic resin analyzed by differential scanning calorimetry De Medeiros, Eliton S.; Agnelli, Jos� A. M.; Joseph, Kuruvilla Journal of Applied Polymer Science, Vol. 90, Issue 6 https://doi.org/10.1002/app.12838	journal	September 2003
Kinetic analysis of thermogravimetric data Doyle, C. D. Journal of Applied Polymer Science, Vol. 5, Issue 15 https://doi.org/10.1002/app.1961.070051506	journal	May 1961
Estimating isothermal life from thermogravimetric data Doyle, C. D. Journal of Applied Polymer Science, Vol. 6, Issue 24 https://doi.org/10.1002/app.1962.070062406	journal	November 1962
The effects of fillers and extenders on the cure properties of phenol–formaldehyde resin as determined by the application of thermal techniques Waage, S. K.; Gardner, D. J.; Elder, T. J. Journal of Applied Polymer Science, Vol. 42, Issue 1 https://doi.org/10.1002/app.1991.070420131	journal	January 1991
On the chemistry, behavior, and cure acceleration of phenol–formaldehyde resins under very alkaline conditions Pizzi, A.; Stephanou, A. Journal of Applied Polymer Science, Vol. 49, Issue 12 https://doi.org/10.1002/app.1993.070491212	journal	September 1993
Optimizing size and distribution of voids in phenolic resins through the choice of catalyst types Hamad, Sameer F.; Farr, Nicholas; Fei, Teng Journal of Applied Polymer Science, Vol. 136, Issue 47 https://doi.org/10.1002/app.48249	journal	July 2019
Basics and Applications of Solid-State Kinetics: A Pharmaceutical Perspective**The authors dedicate this review to the memory of Dr. David J.W. Grant who passed away on December 9, 2005. Dr. Grant was an internationally known authority at the University of Minnesota on the solid-state properties of drugs. He will be remembered as a kind, humble, and brilliant scholar. Khawam, Ammar; Flanagan, Douglas R. Journal of Pharmaceutical Sciences, Vol. 95, Issue 3 https://doi.org/10.1002/jps.20559	journal	March 2006
Is the Friedman Method Applicable to Transformations with Temperature Dependent Reaction Heat? Sbirrazzuoli, Nicolas Macromolecular Chemistry and Physics, Vol. 208, Issue 14 https://doi.org/10.1002/macp.200700100	journal	July 2007
Kinetics of thermal degradation of char-forming plastics from thermogravimetry. Application to a phenolic plastic Friedman, Henry L. Journal of Polymer Science Part C: Polymer Symposia, Vol. 6, Issue 1 https://doi.org/10.1002/polc.5070060121	journal	January 1964
The Properties of Carbon-carbon Composites Savage, G. Carbon-Carbon Composites https://doi.org/10.1007/978-94-011-1586-5_8	book	January 1993
Kinetics of resorcinol–formaldehyde polycondensation by DSC Kinnertová, Eva; Slovák, Václav Journal of Thermal Analysis and Calorimetry, Vol. 134, Issue 2 https://doi.org/10.1007/s10973-018-7532-0	journal	July 2018
Non-isothermal transformation kinetics: Remarks on the Kissinger method Criado, J. M.; Ortega, A. Journal of Non-Crystalline Solids, Vol. 87, Issue 3 https://doi.org/10.1016/S0022-3093(86)80004-7	journal	November 1986
Differential scanning calorimetry of phenol–formaldehyde resins cure-accelerated by carbonates Park, Byung-Dae; Riedl, Bernard; Hsu, Ernest W. Polymer, Vol. 40, Issue 7 https://doi.org/10.1016/S0032-3861(98)00400-5	journal	March 1999
Simulations for evaluation of kinetic methods in differential scanning calorimetry. Part 3 — Peak maximum evolution methods and isoconversional methods Sbirrazzuoli, N.; Girault, Y.; Elégant, L. Thermochimica Acta, Vol. 293, Issue 1-2 https://doi.org/10.1016/S0040-6031(97)00023-3	journal	June 1997
Densification of two-dimensional carbon/carbon composites by pitch impregnation Tzeng, Shinn-Shyong; Pan, Jiun-Hung Materials Science and Engineering: A, Vol. 316, Issue 1-2 https://doi.org/10.1016/S0921-5093(01)01255-2	journal	November 2001
Injection and stabilization of mesophase pitch in the fabrication of carbon–carbon composites. Part I. Injection process Fathollahi, B.; Chau, P. C.; White, J. L. Carbon, Vol. 43, Issue 1 https://doi.org/10.1016/j.carbon.2004.08.030	journal	January 2005
Inhibition of catalytic oxidation of carbon/carbon composites by phosphorus Wu, Xianxian; Radovic, Ljubisa R. Carbon, Vol. 44, Issue 1 https://doi.org/10.1016/j.carbon.2005.06.038	journal	January 2006
Model-free kinetic analysis of melamine–formaldehyde resin cure Kandelbauer, A.; Wuzella, G.; Mahendran, A. Chemical Engineering Journal, Vol. 152, Issue 2-3 https://doi.org/10.1016/j.cej.2009.05.027	journal	October 2009
Compaction of thick carbon/phenolic fabric composites with autoclave method Kim, Jong Woon; Kim, Hyoung Geun; Lee, Dai Gil Composite Structures, Vol. 66, Issue 1-4 https://doi.org/10.1016/j.compstruct.2004.04.070	journal	October 2004
Effects of production parameters on the structure of resol type phenolic resin/layered silicate nanocomposites Kaynak, Cevdet; Tasan, C. Cem European Polymer Journal, Vol. 42, Issue 8 https://doi.org/10.1016/j.eurpolymj.2006.03.008	journal	August 2006
Bonding performance of melamine-urea–formaldehyde and phenol-resorcinol–formaldehyde adhesive glulams at elevated temperatures Liu, Jian; Yue, Kong; Xu, Liqin International Journal of Adhesion and Adhesives, Vol. 98 https://doi.org/10.1016/j.ijadhadh.2019.102500	journal	April 2020
Advances in addition-cure phenolic resins Nair, C. Progress in Polymer Science, Vol. 29, Issue 5 https://doi.org/10.1016/j.progpolymsci.2004.01.004	journal	May 2004
Phenolic resins: 100Years and still going strong Pilato, Louis Reactive and Functional Polymers, Vol. 73, Issue 2 https://doi.org/10.1016/j.reactfunctpolym.2012.07.008	journal	February 2013
Comparison of model-free kinetic methods for modeling the cure kinetics of commercial phenol–formaldehyde resins Wang, Jinwu; Laborie, Marie-Pierre G.; Wolcott, Michael P. Thermochimica Acta, Vol. 439, Issue 1-2 https://doi.org/10.1016/j.tca.2005.09.001	journal	December 2005
Kinetic study of a phenolic-novolac resin curing process by rheological and DSC analysis Domínguez, J. C.; Alonso, M. V.; Oliet, M. Thermochimica Acta, Vol. 498, Issue 1-2 https://doi.org/10.1016/j.tca.2009.09.010	journal	January 2010
Kinetic study of the novolac resin curing process using model fitting and model-free methods Zhang, Chao; Binienda, Wieslaw K.; Zeng, Liming Thermochimica Acta, Vol. 523, Issue 1-2 https://doi.org/10.1016/j.tca.2011.04.033	journal	August 2011
Estimating Realistic Confidence Intervals for the Activation Energy Determined from Thermoanalytical Measurements Vyazovkin, Sergey; Wight, Charles A. Analytical Chemistry, Vol. 72, Issue 14 https://doi.org/10.1021/ac000210u	journal	June 2000
Reaction Kinetics in Differential Thermal Analysis Kissinger, H. E. Analytical Chemistry, Vol. 29, Issue 11 https://doi.org/10.1021/ac60131a045	journal	November 1957
Linear and Nonlinear Procedures in Isoconversional Computations of the Activation Energy of Nonisothermal Reactions in Solids Vyazovkin, Sergey; Dollimore, David Journal of Chemical Information and Computer Sciences, Vol. 36, Issue 1 https://doi.org/10.1021/ci950062m	journal	January 1996
Kinetic Parameters from Thermogravimetric Data Coats, A. W.; Redfern, J. P. Nature, Vol. 201, Issue 4914 https://doi.org/10.1038/201068a0	journal	January 1964
Processing and Properties of a Phenolic Composite System Hou, T. H.; Bai, J. M.; Baughman, J. M. Journal of Reinforced Plastics and Composites, Vol. 25, Issue 5 https://doi.org/10.1177/0731684405058271	journal	March 2006
A New Method of Analyzing Thermogravimetric Data Ozawa, Takeo Bulletin of the Chemical Society of Japan, Vol. 38, Issue 11 https://doi.org/10.1246/bcsj.38.1881	journal	November 1965
Differential Scanning Calorimetry and Dinamic Mechanical Analysis of Phenol-Resorcinol-Formaldehyde Resins Lisperguer, Justo; Droguett, Cynthia; Ruf, Beatriz Journal of the Chilean Chemical Society, Vol. 50, Issue 2 https://doi.org/10.4067/S0717-97072005000200002	journal	January 2005
Properties of Modified Phenol-Formaldehyde Adhesive for Plywood Panels Manufactured from High Moisture Content Veneer Bekhta, Pavlo; Ortynska, Galyna; Sedliacik, Jan Drvna industrija, Vol. 65, Issue 4 https://doi.org/10.5552/drind.2014.1350	journal	January 2014
General treatment of the thermogravimetry of polymers Flynn, Joseph H.; Wall, Leo A. Journal of Research of the National Bureau of Standards Section A: Physics and Chemistry, Vol. 70A, Issue 6 https://doi.org/10.6028/jres.070A.043	journal	November 1966

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Title: Prediction of curing kinetics of resorcinol‐added resole phenolic resins using differential scanning calorimetry for the fabrication of carbon/carbon composites

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