Pultrusion is a highly efficient composite manufacturing process. To accurately describe pultrusion, an appropriate model of resin cure kinetics is required. In this study, we investigated cure kinetics modeling of a vinyl ester pultrusion resin (Atlac 430) in the presence of aluminum hydroxide (Al(OH)3) and zinc stearate (Zn(C18H35O2)2) as processing additives. Herein, four different resin compositions were studied: neat resin composition, composition with Al(OH)3, composition comprising Zn(C18H35O2)2, and composition containing both Al(OH)3 and Zn(C18H35O2)2. To analyze each composition, we performed differential scanning calorimetry at the heating rates of 5, 7.5, and 10 K/min. To characterize the cure kinetics of Atlac 430, 16 kinetic models were tested, and their performances were compared. The model based on the th-order autocatalytic reaction demonstrated the best results, with a 4.5% mean squared error (MSE) between the experimental and predicted data. This study proposes a method to reduce the MSE resulting from the simultaneous melting of Zn(C18H35O2)2. We were able to reduce the MSE by approximately 34%. Numerical simulations conducted at different temperatures and pulling speeds demonstrated a significant influence of resin composition on the pultrusion of a flat laminate profile. Simulation results obtained for the 600 mm long die block at different die temperatures (115, 120, 125, and 130 °C) showed that for a resin with a final degree of cure exceeding 95% at the die exit, the maximum difference between the predicted values of pulling speed for a specified set of compositions may exceed 1.7 times.
BakisCEBankLCBrownVL, et al.
Fiber-reinforced polymer composites for construction – state-of-the-art review. J Compos Constr2002;
6: 73–87.
2.
BankLC.Composites for construction: structural design with FRP materials, 2007. Epub ahead of print. DOI: 10.1002/9780470121429.
3.
LionettoFMontagnaFNataliD, et al.
Correlation between elastic properties and morphology in short fiber composites by X-ray computed micro-tomography. Compos Part A Appl Sci Manuf2021;
140: 106169.
4.
CascardiADell'AnnaRMicelliF, et al.
Reversible techniques for FRP-confinement of masonry columns. Constr Build Mater2019;
225: 415–428.
5.
MinchenkovKVedernikovASafonovA, et al.
Thermoplastic pultrusion: a review. Polymers2021;
13: 180–136.
6.
VedernikovASafonovATucciF, et al.
Pultruded materials and structures: a review. J Compos Mater2020;
54: 4081–4117.
7.
XiongZLiuYZuoY, et al.
Experimental evaluation of shear behavior of pultruded GFRP perforated connectors embedded in concrete. Compos Struct2019;
222: 110938.
8.
ParmarHKhanTTucciF, et al.
Advanced robotics and additive manufacturing of composites: towards a new era in industry 4.0. Mater Manuf Process2021; 36: 1–35.
9.
Zhu, R., Li, F., Zhao, Z., Zhang, D., & Chen, Y. Compression Behavior of Square Pyramid Substructure of Novel Pultruded FRP-Aluminum Space Truss. J Compo Constr 2020; 24(6): 04020062. DOI: 10.1061/(ASCE)CC.1943-5614.0001074.
10.
Li, C., Yin, X., Wang, Y., Zhang, L., Zhang, Z., Liu, Y., & Xian, G. Mechanical property evolution and service life prediction of pultruded carbon/glass hybrid rod exposed in harsh oil-well condition. Compos Struct 2020; 246: 112418. DOI: 10.1016/j.compstruct.2020.112418.
11.
LiuTFengPWuY, et al.
Developing an innovative curved-pultruded large-scale GFRP arch beam. Compos Struct2021;
256: 113111.
12.
LiuTLiuXFengP.A comprehensive review on mechanical properties of pultruded FRP composites subjected to long-term environmental effects. Compos Part B Eng2020;
191: 107958.
13.
IrfanMSHarrisDPagetMA, et al.
On-site evaluation of a modified pultrusion process: fibre spreading and resin injection-based impregnation. J Compos Mater2020. Epub ahead of print. DOI: 10.1177/0021998320943268.
14.
IrfanMSShotton-GaleNPagetMA, et al.
A modified pultrusion process. J Compos Mater2017;
51: 1925–1941.
15.
VedernikovATucciFSafonovA, et al.
Investigation on the shape distortions of pultruded profiles at different pulling speed. Procedia Manuf2020;
47: 1–5.
16.
MadenciEÖzkılıçYOGemiL.Experimental and theoretical investigation on flexure performance of pultruded GFRP composite beams with damage analyses. Compos Struct2020;
242: 112162.
17.
SafonovAACarlonePAkhatovI.Mathematical simulation of pultrusion processes: a review. Compos Struct2018;
184. Epub ahead of print DOI: 10.1016/j.compstruct.2017.09.093.
18.
HeJXianGZhangYX.Numerical modelling of bond behaviour between steel and CFRP laminates with a ductile adhesive. Int J Adhes Adhes2021;
104: 102753.
19.
LionettoFMoscatelloATotaroG, et al.
Experimental and numerical study of vacuum resin infusion of stiffened carbon fiber reinforced panels. Materials2020;
13: 4800–4817.
20.
LionettoFPappadàSBuccolieroG, et al.
Finite element modeling of continuous induction welding of thermoplastic matrix composites. Mater Des2017;
120: 212–221.
21.
VedernikovATucciFCarloneP, et al.
Effects of pulling speed on structural performance of L-shaped pultruded profiles. Compos Struct2021;
255: 112967.
22.
VedernikovANSafonovAAGusevSA, et al.
Spring-in experimental evaluation of L-shaped pultruded profiles. IOP Conf Ser: Mater Sci Eng2020;
747: 012013.
23.
JoshiSCLamYC.Integrated approach for modelling cure and crystallization kinetics of different polymers in 3D pultrusion simulation. J Mater Process Technol2006;
174: 178–182.
24.
PrimeRBMichalskiCNeagCM.Kinetic analysis of a fast reacting thermoset system. Thermochim Acta2005;
429: 213–217.
25.
MoschiarSMReboredoMMLarrondoH, et al.
Pultrusion of epoxy matrix composites: pulling force model and thermal stress analysis. Polym Compos1996;
17: 850–858.
26.
BarkanovEAkishinPMiazzaNL, et al.
ANSYS-based algorithms for a simulation of pultrusion processes. Mech Adv Mater Struct2017;
24: 377–384.
27.
CarlonePPalazzoGSPasquinoR.Pultrusion manufacturing process development: cure optimization by hybrid computational methods. Comput Math with Appl2007;
53: 1464–1471.
28.
ChachadYRRouxJAVaughanJG, et al.
Three-dimensional characterization of pultruded fiberglass-epoxy composite materials. J Reinf Plast Compos1995;
14: 495–512.
29.
GorthalaRRouxJAVaughanJG.Resin flow, cure and heat transfer analysis for pultrusion process. J Compos Mater1994;
28: 486–506.
30.
SafonovAASuvorovaYV.Optimization of the pultrusion process for a rod with a large diameter. J Mach Manuf Reliab2009;
38: 572–578.
31.
SafonovAGusevMSaratovA, et al.
Modeling of cracking during pultrusion of large-size profiles. Compos Struct2020;
235: 111801.
32.
BadrinarayananPLuYLarockRC, et al.
Cure characterization of soybean oil-styrene- divinylbenzene thermosetting copolymers. J Appl Polym Sci2009;
113: 1042–1049.
33.
LueJChenCYenC.In situ pultrusion of urea-formaldehyde matrix composites. I. Processability, kinetic analysis, and dynamic mechanical properties. J Appl Polym Sci2002;
83. Epub ahead of print. DOI: 10.1002/app.2291.
34.
MaCMChenCH.The development of a mathematical model for the pultrusion of blocked polyurethane composites. J Appl Polym Sci1993;
50: 759–764.
35.
SunY-YChenC-H.Process feasibility and kinetic analysis of glass fiber-reinforced vinyl ester/nano-Al 2O 3 matrix composites for pultrusion. J Appl Polym Sci2012;
125: E429–E434.
36.
AkishinPBarkanovEMiazzaN, et al.
Curing kinetic models of resins for microwave assisted pultrusion. Key Eng Mater201;
721: 92–96.
37.
YousefiALafleurPGGauvinR.Kinetic studies of thermoset cure reactions: a review. Polym Compos1997;
18: 157–168.
38.
KamalMRSourourS.Kinetics and thermal characterization of thermoset cure. Polym Eng Sci1973;
13: 59–64.
39.
HanCDChinHB.Development of a mathematical model for the pultrusion of unsaturated polyester resin. Polym Eng Sci1988;
28: 321–332.
40.
NgHManas-ZloczowerI.Kinetic studies of a composite thermoset cure reaction—application in pultrusion simulations. Polym Eng Sci1989;
29: 302–307.
41.
TrivisanoAMaffezzoliAKennyJM, et al.
Mathematical modeling of the pultrusion of epoxy based composites. Adv Polym Technol1990;
10: 251–264.
42.
ValliappanMRouxJAVaughanJG.Temperature and cure in pultruded composites using multi-step reaction model for resin. J Reinf Plast Compos1996;
15: 295–320.
43.
SuratnoBRYeLMaiY-W.Simulation of temperature and curing profiles in pultruded composite rods. Compos Sci Technol1998;
58: 191–197.
44.
RouxJAVaughanJGShankuR, et al.
Comparison of measurements and modeling for pultrusion of a fiberglass/epoxy I-beam. J Reinf Plast Compos1998;
17: 1557–1578.
45.
AtarsiaABoukhiliR.Relationship between isothermal and dynamic cure of thermosets via the isoconversion representation. Polym Eng Sci2000;
40: 607–620.
46.
Lin LiuXCrouchIGLamYC.Simulation of heat transfer and cure in pultrusion with a general-purpose finite element package. Compos Sci Technol2000;
60: 857–864.
PantaleãoAVDeAndradeCRZaparoliEL.The effect of anisotropic thermal conductivity on the pultrusion process simulation. Int Commun Heat Mass Transf2002;
29: 611–621.
49.
SarrionandiaMMondragónIMoschiarSM, et al.
Heat transfer for pultrusion of a modified acrylic/glass reinforced composite. Polym Compos2002;
23: 21–27.
50.
CalabreseLValenzaA.Effect of CTBN rubber inclusions on the curing kinetic of DGEBA-DGEBF epoxy resin. Eur Polym J2003;
39: 1355–1363.
51.
SamarasZIPartridgeIK.Effects of styrene evaporation on the cure kinetics behaviour of a vinylester resin system suitable for composite pultrusion. Polym Polym Compos2003;
11: 623–632.
52.
LiangGGargAChandrashekharaK, et al.
Cure characterization of pultruded soy-based composites. J Reinf Plast Compos2005;
24: 1509–1520.
53.
BaiYValléeTKellerT.Modeling of thermo-physical properties for FRP composites under elevated and high temperature. Compos Sci Technol2007;
67: 3098–3109.
54.
ChenXXieHChenH, et al.
Optimization for CFRP pultrusion process based on genetic algorithm-neural network. Int J Mater Form2010;
3: 1391–1399.
55.
ZhouZLiABaiR, et al.
Thermal analysis and gelation property of multifunctional epoxy resins used for pultruded composite ropes. J Therm Anal Calorim2014;
115: 1601–1608.
56.
ZhengYXiaoJDuanM, et al.
Experimental study of partially-cured Z-pins reinforced foam core composites: K-Cor sandwich structures. Chin J Aeronaut2014;
27: 153–159.
57.
BaranIAkkermanRHattelJH.Material characterization of a polyester resin system for the pultrusion process. Compos Part B Eng2014;
64: 194–201.
58.
BaranITutumCCHattelJH.Probabilistic analysis of a thermosetting pultrusion process. Sci Eng Compos Mater2016;
23: 67–76.
59.
TenaISarrionandiaMTorreJ, et al.
The effect of process parameters on ultraviolet cured out of die bent pultrusion process. Compos Part B Eng2016;
89: 9–17.
60.
Saenz-DominguezITenaISarrionandiaM, et al.
Effect of ultraviolet curing kinetics on the mechanical properties of out of die pultruded vinyl ester composites. Compos Part A Appl Sci Manuf2018;
109: 280–289.
61.
WangY-WZhuBYuanX-M, et al.
Investigation of facile strategy for eliminating internal cracks of pultruded carbon fiber composites. Mater Res Express2019;
6. Epub ahead of print. DOI: 10.1088/2053-1591/ab448e.
62.
de Cassia Costa DiasRCostaMLde Sousa SantosL, et al.
Kinetic parameter estimation and simulation of pultrusion process of an epoxy-glass fiber system. Thermochim Acta2020;
690: 178636.
63.
CorreiaJRBaiYKellerT.A review of the fire behaviour of pultruded GFRP structural profiles for civil engineering applications. Compos Struct2015;
127: 267–287.
64.
StarrTF.Pultrusion for engineers. 2000. Epub ahead of print 2000. DOI: 10.1533/9781855738881.97.
65.
HowardRDSayersDR.Development of new methacrylate resins for use in pultrusion. Sampe Q1985;
16: 22–26.
66.
HowardRDHollandSJSayersDR. Methacrylate resins in pultrusion: factors affecting pulling force. In: Society of the plastics industry, reinforced plastics/composites institute, annual conference—proceedings. Publ by SPI, Washington, DC, United States, pp. 2B.1–2B.7.
WinklerM. Automotive under-the-hood applications in vinyl ester resin SMC/BMC. SAE Tech Pap. Epub ahead of print 1990. DOI: 10.4271/900633.
69.
Kicko-WalczakE.Study on flame retardant unsaturated polyester resins—an overview of past and new developments. Polimery/Polym1999;
44: 724–729.
70.
Le LayFGutierrezJ.Improvement of the fire behaviour of composite materials for naval application. Polym Degrad Stab1999;
64: 397–401.
71.
MalikMChoudharyVVarmaIK.Effect of non-halogen flame retardant additives on the properties of vinyl ester resins and their composites. J Fire Sci2002;
20: 329–342.
WeilEDLevchikSV.Commercial flame retardancy of unsaturated polyester and vinyl resins: review. J Fire Sci2004;
22: 293–303.
74.
KandolaBKPornwannachaiW.Enhancement of passive fire protection ability of inorganic fire retardants in vinyl ester resin using glass frit synergists. J Fire Sci2010;
28: 357–381.
75.
MaheshKVMurthyHNNSwamyBEK, et al.
Organomodified clay and its influence on thermal and fire behaviors of clay/fire retardant/poly vinyl ester composites. Key Eng Mater2015;
659: 468–473.
76.
de Freitas RochaMALandesmannAda Silva RibeiroSP, et al.
Enhancement of fire retardancy properties of glass fibre–reinforced polyesters composites. Fire Mater2019;
43: 734–746.
77.
DaiLWangXZhangJ, et al.
Effects of lubricants on the rheological and mechanical properties of wood flour/polypropylene composites. J Appl Polym Sci2019;
136: 47667.
78.
CapekIBartonJ.Photoinitiation. IV. The effect of Lewis acid on the vinyl monomer polymerization photoinitiated by aromatic hydrocarbons. J Polym Sci Polym Chem Ed1979;
17: 937–942.
79.
RabagliatiFMPérezMASotoMA, et al.
Copolymerization of styrene by diphenylzinc-additive systems I. Copolymerization of styrene/p-tert-butylstyrene by Ph2Zn–metallocene–MAO systems. Eur Polym J2001;
37: 1001–1006.
80.
AsandeiADMoranIW.TiCp2Cl-catalyzed living radical polymerization of styrene initiated by oxirane radical ring opening. J Am Chem Soc2004;
126: 15932–15933.
81.
ShihY-FJengR-J.Carbon black-containing interpenetrating polymer networks based on unsaturated polyester/epoxy II. Thermal degradation behavior and kinetic analysis. Polym Degrad Stab2002;
77: 67–76.
ZhangCLiuSHuangJ.Synthesis and curing kinetics of phosphorus-containing unsaturated polyester with reactive flame retardant. Shiyou Huagong/Petrochemical Technol2009;
38: 515–520.
84.
Ittner MazaliCAFelisbertiMI.Vinyl ester resin modified with silicone-based additives: III. Curing kinetics. Eur Polym J2009;
45: 2222–2233.
85.
GaoWCaoJ-ZLiJ-Z.Effect of ammonium pentaborate on curing of aqueous phenol formaldehyde resin. Iran Polym J2010;
19: 255–264.
86.
JinxueJYonglinYChengL, et al.
Effect of three boron flame retardants on thermal curing behavior of urea formaldehyde resin. J Therm Anal Calorim2011;
105: 223–228.
87.
TanYShaoZ-BChenX-F, et al.
Novel multifunctional organic-inorganic hybrid curing agent with high flame-retardant efficiency for epoxy resin. ACS Appl Mater Interfaces2015;
7: 17919–17928.
88.
HamciucCVlad-BubulacTSerbezeanuD, et al.
Environmentally friendly fire-resistant epoxy resins based on a new oligophosphonate with high flame retardant efficiency. RSC Adv2016;
6: 22764–22776.
89.
LuTChenTLiangG.Synthesis, thermal properties, and flame retardance of the epoxy-silsesquioxane hybrid resins. Polym Eng Sci2007;
47: 225–234.
90.
International Organization for Standardization (ISO) 2016. Plastics – Differential scanning calorimetry (DSC) – Part 1: General principles, ISO 11357-1:2016 (Switzerland: International Organization for Standardization). Retrieved 15 November 2020, https://www.iso.org/standard/70024.html
91.
Satoh, K., Fujiki, Y., Uchiyama, M., & Kamigaito, M. (2018). Vinyl ether/vinyl ester copolymerization by cationic and radical interconvertible simultaneous polymerization. In Reversible Deactivation Radical Polymerization: Mechanisms and Synthetic Methodologies (pp. 323–334). American Chemical Society.
92.
KrauklisAEDreyerI.A simplistic preliminary assessment of Ginstling-Brounstein model for solid spherical particles in the context of a diffusion-controlled synthesis. Open Chem2018;
16: 64–72.
93.
StrømmeKO.On the application of the Avrami-Erofeev equation in non-isothermal reaction kinetics. Thermochim Acta1986;
97: 363–368.
94.
ZhangKHongJCaoG, et al.
The kinetics of thermal dehydration of copper(II) acetate monohydrate in air. Thermochim Acta2005;
437: 145–149.
95.
BurnhamAK.Application of the Sestak-Berggren equation to organic and inorganic materials of practical interest. J Therm Anal Calorim2000;
60: 895–908.
96.
JanowskiBPielichowskiK.A kinetic analysis of the thermo-oxidative degradation of PU/POSS nanohybrid elastomers. Silicon2016;
8: 65–74.
97.
MontserratSMálekJ.A kinetic analysis of the curing reaction of an epoxy resin. Thermochim Acta1993;
228: 47–60.
98.
CriadoJMMálekJOrtegaA.Applicability of the master plots in kinetic analysis of non-isothermal data. Thermochim Acta1989;
147: 377–385.
99.
MálekJCriadoJMŠestákJ, et al.
The boundary conditions for kinetic models. Thermochim Acta1989;
153: 429–432.
100.
ArasaMRamisXSallaJM, et al.
Kinetic study by FTIR and DSC on the cationic curing of a DGEBA/γ-valerolactone mixture with ytterbium triflate as an initiator. Thermochim Acta2008;
479: 37–44.
101.
PérezJSánchezGGarcı́aJ, et al.
Thermal and kinetic analysis of ortho-palladated complexes with pyridines. Thermochim Acta2000;
362: 59–70.
102.
RamisXSallaJMCadenatoA, et al.
Simulation of isothermal cure of a powder coating non-isothermal DSC experiments. J Therm Anal Calorim2003;
72: 707–718.
103.
OthmanMBHKhanAAhmadZ, et al.
Kinetic investigation and lifetime prediction of Cs-NIPAM-MBA-based thermo-responsive hydrogels. Carbohydr Polym2016;
136: 1182–1193.
104.
XieQXieYLiuW, et al.
Thermal decomposition behaviour and kinetics of a mixed solution: n-propyl nitrate and nitric acid solution. J Therm Anal Calorim2020;
140: 1801–1810.
105.
RamisXSallaJMMasC, et al.
Kinetic study by FTIR, TMA, and DSC of the curing of a mixture of DGEBA resin and γ-butyrolactone catalyzed by ytterbium triflate. J Appl Polym Sci2004;
92: 381–393.
106.
MálekJ.A computer program for kinetic analysis of non-isothermal thermoanalytical data. Thermochim Acta1989;
138: 337–346.
107.
WorzakowskaM.Kinetics of the curing reaction of unsaturated polyester resins catalyzed with new initiators and a promoter. J Appl Polym Sci2006;
102: 1870–1876.
