一种UV光固化树脂固化动力学模型的建立

doi:10.19936/j.cnki.2096-8000.20250628.002

摘要/Abstract

摘要： 光固化动力学是光固化研究中重要的一部分。使用外接UV光源的差示扫描量热仪分别测试在不同光强和温度下的光固化情况,得到树脂固化过程热流曲线、固化度曲线、固化速率曲线。采用自催化模型对固化速率曲线进行拟合,对得到的参数进行线性或非线性拟合,得到曲线函数关系。前人研究较多考虑单一变量对固化动力学模型的影响,具有局限性。本文提出一种假设,在所得固化动力学方程中同时引入固化温度、光强两个变量,通过实际实验与有限元固化仿真模拟对比,验证本文所提出固化动力学模型的可靠性。计算所得仿真与实际测试的最大误差不超过6.5%。这一研究拓展了对于光固化动力学的理解,为优化光固化工艺提供了新的思路和方法。

关键词: 光固化, 差示扫描量热仪, 固化动力学, 自催化模型, 固化仿真

Abstract: The study of photocuring kinetics is an important part of photocuring research. Using an external UV light source coupled with differential scanning calorimetry, the photocuring behavior was tested at different light intensities and temperatures. This investigation provided heat flow curves, curing degree curves, and curing rate curves for the resin during the curing process. The autocatalytic model was used to fit the curing rate curves. The parameters obtained were fitted using linear or nonlinear regression to establish the curve function relationship. Previous studies had limitations as they almost considered the effect of a single variable on the photocuring kinetics model. This paper proposed a hypothesis that simultaneously incorporated curing temperature and light intensity as variables within the derived photocuring kinetic equation. The reliability of the proposed photocuring kinetics model was verified by comparison between actual experiment and finite element curing simulation. The maximum error between simulation and actual experiment is calculated to be no more than 6.5%. This study extends the understanding of photocuring kinetics and provides new perspectives and methods for optimizing the photocuring process.

Key words: photocuring, differential scanning calorimetry, curing kinetics, autocatalytic model, curing simulation

中图分类号:

TB332

彭静璇, 丁安心, 徐秘, 胡雪琴, 杨琳, 郭宁. 一种UV光固化树脂固化动力学模型的建立[J]. 复合材料科学与工程, 2025, 0(6): 10-18.

PENG Jingxuan, DING Anxin, XU Mi, HU Xueqin, YANG Lin, GUO Ning. An establishment of a UV photocuring resin curing kinetic model[J]. COMPOSITES SCIENCE AND ENGINEERING, 2025, 0(6): 10-18.

参考文献

[1] JI L, JIAN C, MA Q, et al. Study on the formation and mechanism of aluminum bulge defect in semiconductor integrated circuit manufacturing[J]. Microelectronic Engineering, 2022, 251: 111661.
[2] ALIM M A, ABDUL AZIZ M S, ABDULLAH M Z, et al. An experimental investigation of shear strength and adhesion on the chip-substrate joint in LED packaging[J]. International Journal of Adhesion and Adhesives, 2022, 119: 103272.
[3] GAO C, ZHANG D, WANG H, et al. Effect of polyhedral oligomeric silsesquioxane on thiol-ene UV curing kinetics of waterborne polyester[J]. Progress in Organic Coatings, 2019, 136: 105231.
[4] LIU F, LIU A, TAO W, et al. Preparation of UV curable organic/inorganic hybrid coatings-a review[J]. Progress in Organic Coatings, 2020, 145: 105685.
[5] CZACHOR-JADACKA D, PILCH-PITERA B. Progress in development of UV curable powder coatings[J]. Progress in Organic Coatings, 2021, 158: 106355.
[6] FU J, WANG L, YU H, et al. Research progress of UV-curable polyurethane acrylate-based hardening coatings[J]. Progress in Organic Coatings, 2019, 131: 82-99.
[7] ZHANG W, WANG R, YANG Z, et al. Synthesis of UV rapid curing silicone coatings via photoinitiated thiol-ene click polymerization for pressure-sensitive adhesive[J]. Polymer, 2023, 283: 126222.
[8] JIANG B, SHI X, ZHANG T, et al. Recent advances in UV/thermal curing silicone polymers[J]. Chemical Engineering Journal, 2022, 435: 134843.
[9] PAN X, TASDELEN M A, LAUN J, et al. Photomediated controlled radical polymerization[J]. Progress in Polymer Science, 2016, 62: 73-125.
[10] XU J, JIANG Y, ZHANG T, et al. Synthesis of UV-curing waterborne polyurethane-acrylate coating and its photopolymerization kinetics using FT-IR and photo-DSC methods[J]. Progress in Organic Coatings, 2018, 122: 10-18.
[11] TAN B, MO H, ZHANG J, et al. Design, synthesis and curing mechanism of two novel photothermal dual-curing adhesives for propellants and explosives[J]. FirePhysChem, 2024, 4(1): 63-71.
[12] BEBER V C, SCHNEIDER B. Fatigue of structural adhesives under stress concentrations: notch effect on fatigue strength, crack initiation and damage evolution[J]. International Journal of Fatigue, 2020, 140: 105824.
[13] YIN W, ZENG X, LI H, et al. Synthesis, photopolymerization kinetics, and thermal properties of UV-curable waterborne hyperbr-anched polyurethane acrylate dispersions[J]. Journal of Coatings Technology and Research, 2011, 8(5): 577-584.
[14] BACHMANN J, GLEIS E, SCHMÖLZER S, et al. Photo-DSC method for liquid samples used in vat photopolymerization[J]. Analytica Chimica Acta, 2021, 1153: 338268.
[15] SCOTT T F, COOK W D, FORSYTHE J S. Photo-DSC cure kinetics of vinyl ester resins. Ⅰ. Influence of temperature[J]. Polymer, 2002, 43(22): 5839-5845.
[16] LECAMP L, PAVILLON C, LEBAUDY P, et al. Influence of temperature and nature of photoinitiator on the formation kinetics of an interpenetrating network photocured from an epoxide/methacrylate system[J]. European Polymer Journal, 2005, 41(1): 169-176.
[17] LEE J H, PRUD’HOMME R K, AKSAY I A. Cure depth in photopolymerization: experiments and theory[J]. Journal of Materials Research, 2001, 16(12): 3536-3544.
[18] SAENZ-DOMINGUEZ I, TENA I, SARRIONANDIA M, et al. An analytical model of through-thickness photopolymerisation of composites: ultraviolet light transmission and curing kinetics[J]. Composites Part B: Engineering, 2020, 191: 107963.
[19] DEROSA M E, BAKER L S, MELOCK T L, et al. Ultraviolet cure kinetics of a low T_g polyurethane acrylate network under varying light intensity and exposure time[J]. Progress in Organic Coatings, 2021, 158: 106353.
[20] ZHANG Y, KRANBUEHL D E, SAUTEREAU H, et al. Study of UV cure kinetics resulting from a changing concentration of mobile and trapped radicals[J]. Macromolecules, 2008, 41(3): 708-715.
[21] VYAZOVKIN S, BURNHAM A K, CRIADO J M, et al. ICTAC Kinetics Committee recommendations for performing kinetic computations on thermal analysis data[J]. Thermochimica Acta, 2011, 520(1-2): 1-19.
[22] LI K, GAN C, ZHANG W, et al. Validity of isothermal kinetic prediction by advanced isoconversional method[J]. Chemical Physics, 2023, 567: 111801.
[23] LIANG Q, HOU X, FENG X, et al. Reaction model and cure kinetics of fiber-reinforced phenolic system[J]. Acta Mechanica Sinica, 2022, 38(6): 422081.
[24] YANG W, LIANG B, TAN W, et al. Rheological study on the cure kinetics of dicyanimidazole resin[J]. Thermochimica Acta, 2020, 694: 178801.
[25] KAMAL M, SOUROUR S. Kinetics and thermal characterization of thermoset cure[J]. Polymer Engineering & Science, 1973, 13(1): 59-64.
[26] WANG Y, WANG Y, SONG X, et al. Rheological properties and curing kinetics of GAP-based propellant slurries[J]. FirePhys-Chem, 2024, 4(1): 80-86.
[27] 胡建华. 含DOPO阻燃环氧树脂的固化动力学研究[D]. 广州: 华南理工大学, 2015.
[28] VYAZOVKIN S, CHRISSAFIS K, DI LORENZO M L, et al. ICTAC Kinetics Committee recommendations for collecting experimental thermal analysis data for kinetic computations[J]. Thermochimica Acta, 2014, 590: 1-23.
[29] PAPPAS S P. Radiation curing: science and technology[M]. Heidelberg, Germany: Springer Science & Business Media, 2013.
[30] ZADE A, SHYAMPRASAD P, KUPPUSAMY R R P. Finite element modelling of non-isothermal curing kinetics for resin transfer moulding process[J]. Materials Today: Proceedings, 2021, 47: 5281-5288.
[31] TENA I, SARRIONANDIA M, TORRE J, et al. The effect of process parameters on ultraviolet cured out of die bent pultrusion process[J]. Composites Part B: Engineering, 2016, 89: 9-17.
[32] DALLE VACCHE S, GEISER V, LETERRIER Y, et al. Time-intensity superposition for photoinitiated polymerization of fluorinated and hyperbranched acrylate nanocomposites[J]. Polymer, 2010, 51(2): 334-341.
[33] LECAMP L, YOUSSEF B, BUNEL C, et al. Photoinitiated polymerization of a dimethacrylate oligomer: 2. Kinetic studies[J]. Polymer, 1999, 40(6): 1403-1409.
[34] SHIM G-S, KIM H-J, BARTKOWIAK M. Curing behavior and impact of crosslinking agent variation in stepwise UV/UV cured acrylic pressure-sensitive adhesives[J]. Journal of Materials Research and Technology, 2021, 15: 1622-1629.
[35] ZHANG L, FENG P, XU J, et al. A piecewise kinetic model consistent with curing cycle of epoxy/amine composite[J]. Journal of Thermal Analysis and Calorimetry, 2023, 148(22): 12781-12793.
[36] 谢占军, 杨喜, 王继辉. 等温DSC法研究风电叶片用环氧树脂固化动力学[J]. 玻璃钢/复合材料, 2018(6): 94-98.
[37] KIM W-S, PARK K-S, NAM J H, et al. Fast cure kinetics of a UV-curable resin for UV nano-imprint lithography: phenomenological model determination based on differential photocalorimetry results[J]. Thermochimica Acta, 2010, 498(1-2): 117-123.
[38] SBIRRAZZUOLI N, MITITELU-MIJA A, VINCENT L, et al. Isoconversional kinetic analysis of stoichiometric and off-stoichiometric epoxy-amine cures[J]. Thermochimica Acta, 2006, 447(2): 167-177.
[39] LECAMP L, YOUSSEF B, BUNEL C, et al. Photoinitiated polymerization of a dimethacrylate oligomer: 1. Influence of photoinitiator concentration, temperature and light intensity[J]. Polymer, 1997, 38(25): 6089-6096.
[40] THOMAS R, DURIX S, SINTUREL C, et al. Cure kinetics, morphology and miscibility of modified DGEBA-based epoxy resin-effects of a liquid rubber inclusion[J]. Polymer, 2007, 48(6): 1695-1710.
[41] LEISTNER C, HARTMANN S, ABLIZ D, et al. Modeling and simulation of the curing process of epoxy resins using finite elements[J]. Continuum Mechanics and Thermodynamics, 2020, 32: 327-350.
[42] LIEBL C, JOHLITZ M, YAGIMLI B, et al. Three-dimensional chemo-thermomechanically coupled simulation of curing adhesives including viscoplasticity and chemical shrinkage[J]. Computational Mechanics, 2011, 49(5): 603-615.