Cure Kinetics of DGEBA with Hyperbranched Poly(3-hydroxyphenyl) Phosphate as Curing Agent Studied by Non-isothermal DSC

The cure kinetics of diglycidyl ether of bisphenol A （DGEBA） with hyperbranched poly （3-hydroxyphenyl） phosphate（HHPP） as the curing agent was investigated by means of non-isothermal differential scanning calorimetry （DSC） at various heating rates. The results were compared with the corresponding results by using 1,3-dihydroxybenzene（DHB） as a model compound. The results show that HHPP can enhance the cure reaction of DGEBA, resulting in the decrease of the peak temperature of the curing curve as well as the decrease of the activation energy because of the flexible --P--O-- groups in the backbone of HHPP. However, both the activation energy of the cured polymer and the peak temperature of the curing curve are increased with DHB as a curing agent. The cure kinetics of the DGEBA/HHPP system was calculated by using the isoconversional method given by Malek. It was found that the two-parameter autocatalytic model（Sestak-Berggren equation） is the most adequate one to describe the cure kinetics of the studied System at various heating rates. The obtained non-isothermal DSC curves from the experimental data show the results being accordant with those theoretically calculated.

Rheological Study on the Cure Kinetics of Two-component Addition Cured Silicone Rubber

The cure kinetics for two-component silicone rubber formed by addition reaction was studied by the rheological method. The influence of reaction temperature （7） on the cure kinetics was explored in detail. It was observed that the data of gel time （tgel, i.e. the time when the reaction reaches the gel point） or a specific reaction time （tnc） （defined as the reaction time before which time the influence of confinement of network on the diffusion of reaction components can be neglected） versus T obey certain functional relationship, which was well explained by the cure kinetics model of thermoset network. The cure kinetics for the two-component silicone rubber can be well fitted by the Kamal-Sourour（autocatalyst） reaction model rather than Kissinger model. When the reaction time was before or equal to tnc, the reaction order obtained by the Kamal-Sourour reaction model was 2, which was consistent with the reaction order inferred from the two components chemical reaction when the diffusion of reaction components was not influenced by the formed cross-linked polymer network. When the reaction time was larger than tnc, such as to the end of reaction （re）, the influence of confinement of network on the diffusion of reaction components cannot be neglected, and the reaction order obtained by the Kamal-Sourour reaction model was larger than 2. It was concluded that the confinement effect of network had a greater influence on the cure kinetics of the silicone rubber. The reaction rate constants （kτ） under different temperatures were also determined by Kamal-Sourour reaction model. The activation energy （E） for the two-component silicone rubber was also calculated from the results of lntgcl, lnlnc, and lnkτ versus 1/T, respectively. The three values of E were close, which indicated that above analyses were self-consistent.

CURING KINETICS AND PROPERTIES OF ACRYLIC RESIN CURED WITH AZIRIDINE CROSSLINKER

A kind of aziridine crosslinkers was synthesized and used to crosslink acrylate copolymers. The crosslinking properties and curing kinetics of the resin were studied. It was found that with the increase of the content of crosslinker in the emulsion, the mechanical properties and solvent resistance of the resin will be apparently improved, but its glass transition temperature (T.) is very low. The lowest amount of crosslinker used in the acrylic resin emulsion is 0.25%. Curing kinetics studied by DSC show that this curing reaction occurs readily because the apparent activation energy of the reaction is low (65.1 kJ/mol). These results demonstrate that the aziridine crosslinker is indeed a low temperature crosslinking agent and can be used at room temperature.

Cure Reaction Kinetics of Low Pressure Sheet Molding Compound System Thickened by Crystalline Polymer

Several kinetic models for unsaturated polyester cure reaction and some existing parameter estimation techniques of these models were introduced. Correlated kinetic parameters and kinetic equations of the autocatalytic empirical kinetic model of LPSMC system were determined by using isothermal DSC to scan the system which was thickened by crystalline polymer （PEG-MAH）. Through using a serial curing degree of the system to validate the model, the experimental results were basically identical with the predictions of the autocatalytic empirical kinetic model. This model could provide a theoretical reference to the determination of molding techniques of low pressure SMC.

THE MECHANISM OF CURE REACTION OF 4,4'-DIAMINODIPHENYL METHANE WITH TETRAGLYCIDYL 4,4'-DIAMINODIPHENYL METHANE EPOXY

The cure reaction of tetraglycidyl 4,4'-diaminodiphenyl methane (TGDDM) epoxy resin with 4,4'-diaminodiphenyl methane (DDM) has been studied by using DSC. Instead of one exothermic peak, two exothermic peaks, indicative of a complex reaction mechanism, are shown in the DSC curve of TGDDM-DDM mixtures in nonisothermal cure experiments when the content of DDM is lower than stoichiometric ratio. The result of the kinetic analysis of the cure reaction shows that the activation energy of the lower temperature exotherm peak is about 56 kJ/mol and that of the higher temperature exotherm peak is about 136 kJ/mol. The lower temperature cure reaction peak can be attributed to the primary amine-epoxide and secondary amine-epoxide reactions, and the higher temperature cure reaction peak can be attributed to the epoxide-hydroxy reaction under catalysis of tertiary amine in the TGDDM epoxy resin. Because the network density of the cured epoxy resin is determined by these two reactions, the content of DDM has little effect on the glass transition temperature of cured epoxy resin.

Curing Kinetics of Tannin and Lignin Biobased Adhesives Determined by DSC and ABES

The curing process of two biobased adhesives:pine tanninhexamine(TH)and organosolv lignin non-isocyanate polyurethane(NIPU),suitable for interior nonstructural use,were compared with commercial urea-formaldehyde(UF)adhesive.Changes in chemical structure before and after the curing process were observed with Fouriertransform infrared spectroscopy(FTIR).The process of adhesive curing was monitored with differential scanning calorimetry(DSC)and the automated bonding evaluation system(ABES).Both DSC and ABES measurements confirmed UF as the fastest and NIPU as the slowest curing adhesive observed.Taking into account the ABES results,the optimal pressing parameters for the TH adhesive would be 4 min at 175℃,for the NIPU adhesive 7 min at 200℃and for the UF 1.5 min at 100℃.Strong linear correlation was observed between mechanical and chemical curing for the UF and NIPU adhesives,whereas lower correlation was observed for the TH adhesive.At all observed adhesives,the DSC measurements were underestimating the curing process determined by ABES in the first part and overestimating it at the end.The underestimation was the most evident with the TH adhesive and the less with the UF adhesive.When comparing the uncured and cured FTIR spectra of all three types of adhesives,a drastic decrease in the characteristic band of-OH groups at 3330–3400 cm^(−1)and an increase in the signal intensity at 2920 cm^(−1)of aliphatic-CH2-groups were observed.For the UF adhesive,the C=O stretching frequency has shifted from 1632 cm^(−1)for uncured to three different bands at 1766,1701,and 1655 cm^(−1)for cured UF.The sharp band for phenolic alcohols at 1236 cm^(−1)of C–O stretch and hydroxyl O–H functional group at 1009 cm^(−1)and at 684 cm^(−1)of uncured TH adhesive diminished during curing,which indicates that a crosslinking reaction occurs via-OH groups.The peak of the C=O group of urethane bridges at 1697 cm^(−1)for uncured NIPU shifted to lower wavenumber at 1633 cm^(−1)for cured NIPU.

Rubber Curing Process Simulation Based on Parabola Model

The curing process of rubber fender was investigated. A parabola model was put forward for the first time, which described variation of rubber thermal properties such as heat conduction and specific heat. Based on Kamal and Sourour model, a modified Rafei kinetic model was used to predict the rubber curing kinetics. To compare with experimental data, the fender curing process was simulated by parabola model and linear model respectively. Additionally, the curing craft and structure of the fender were modified and evaluated based on finite element analysis （FEA）. As a result, the curing uniformity and efficiency of the fender was highly improved. It was investigated that, the parabola model correlated the rubber thermal behavior more precisely. The numerical prediction was in good agreement with the experimental evaluation.

Green Composite Material Made from Typha latifolia Fibres Bonded with an Epoxidized Linseed Oil/Tall Oil-Based Polyamide Binder System

Here,we report the mechanical and water sorption properties of a green composite based on Typha latifolia fibres.The composite was prepared either completely binder-less or bonded with 10%(w/w)of a bio-based resin which was a mixture of an epoxidized linseed oil and a tall-oil based polyamide.The flexural modulus of elasticity,the flexural strength and the water absorption of hot pressed Typha panels were measured and the influence of pressing time and panel density on these properties was investigated.The cure kinetics of the biobased resin was analyzed by differential scanning calorimetry(DSC)in combination with the iso-conversional kinetic analysis method of Vyazovkin to derive the curing conditions required for achieving completely cured resin.For the binderless Typha panels the best technological properties were achieved for panels with high density.By adding 10%of the binder resin the flexural strength and especially the water absorption were improved significantly.

MECHANICAL PROPERTIES AND CURING KINETICS OF EPOXY RESINS CURED BY VARIOUS AMINO-TERMINATED POLYETHERS

A high performance thermosetting epoxy resin crosslinkable at room temperature was obtained via directly moulding diglycidyl ether of bisphenol A（DGEBA） and flexibleα,ω-bisamino（n-alkylene）phenyl terminated poly（ethylene glycol）.The influences of the n-alkylene inserted in aminophenyl of flexible amino-terminated polythers（ATPE） on the mechanical properties,fractographs and curing kinetics of the ATPE-DGEBA cured products were studied.The results show that the insertion of n-alkylene group into the aminophenyl group of the ATPE,on one hand,can significantly increase the strain relaxation rate and decrease glass transition temperature of the ATPE-DGEBA cured products,resulting in slight decrease of the Young’s modulus and tensile strength,and significant increase of the toughness and elongation of the ATPE-DGEBA cured products.On the other hand,it can remarkably enhance the reactivity of amine with epoxy,much accelerating the curing rate of the ATPE-DGEBA systems.The activation energy of DGEBA cured by BAPTPE,BAMPTPE and BAEPTPE was 53.1,28.5 and 25.4 kJ·mol;,respectively.The as-obtained ATPE-DGEBA cured products are homogeneous, transparent,and show excellent mechanical properties including tensile strength and toughness.Thus they are promising to have important applications in structure adhesives,casting bulk materials,functional coatings,cryogenic engineering, damping and sound absorbing materials.

CURING KINETICS AND THERMAL STABILITY OF EPOXY BLENDS CONTAINING PHOSPHOROUS-OXIRANE WITH AROMATIC AMIDE-AMINE AS CURING AGENTS

This article describes the synthesis of a series of aromatic amide-amines and their potential use as epoxy hardeners. These amines were synthesized by the reaction of L-phenylalanine （PA） with diamines of different structures i.e. 1,4- phenylene diamine （PD）, 1,5-diamino naphthalene （N）, 4,4＇-（9-fluorenyllidene）-dianiline （F）, 4,4＇-diaminodiphenyl sulphide （DS） and 3,4＇-oxydianiline （O） in a stoichiometric ratio （I ：1）. Structural characterization of synthesized amide-amines was done with the help of elemental analysis and spectroscopic techniques viz. FT-IR, 1H-NMR and 13C-NMR. An epoxy blend was prepared by mixing tris（glycidyloxy） phosphine oxide （TGPO） with conventional epoxy i.e. diglycidyl ether of bisphenol-A （DGEBA） in an equivalent ratio of 2：3 to incorporate phosphorous into the main chain. The curing kinetics of the epoxy blend with synthesized aromatic amide-amines was investigated by non-isothermal DSC technique using multiple heating rate method （5, 10, 15 and 20 K/min.）. The activation energies were determined by fitting the experimental data into Kissinger and Ozawa kinetic models. The activation energies obtained through Ozawa method were slightly higher than those of Kissinger method but were comparable. However, both the energies were found to be dependent on the structure of amines. The thermal stability and weight loss behavior of isothermally cured thermosets were also investigated using thermogravimetric analysis （TGA） in nitrogen atmosphere. All the samples showed improved thermal stability in terms of char yield than using only amines as hardeners.

纤维增强酚醛体系固化机理研究及动力学建模

纤维增强酚醛复合材料以其优异的耐高温和耐烧蚀性能成为固体发动机喷管的理想材料.增强纤维的物理和化学特性会显著影响酚醛树脂(PF)的固化反应,为探究纤维增强酚醛体系固化反应与纯酚醛的区别,并获得高硅氧玻璃纤维/酚醛预浸料和碳纤维/酚醛预浸料的固化模型,本文采用差示扫描量热法(DSC),分别对纯酚醛树脂、高硅氧玻璃纤维/酚醛、碳纤维/酚醛进行了动态DSC实验.针对三种材料的动态DSC测量结果,通过等转变动力学方法,确定了3个反应体系的活化能随固化过程的变化规律,并通过引入动力学补偿效应,获得了3种材料的固化反应机理.结果表明,增强纤维会改变酚醛树脂的固化反应机理,三者的活化能和指前因子都不同,纯酚醛树脂为自催化模型,高硅氧玻璃纤维/酚醛预浸料为由自催化反应转变为N阶反应的两步模型,碳纤维/酚醛预浸料为由自催化反应转变为N阶反应的三步模型.

Study on the curing properties of SBR/La-GDTC/SiO_2 composites

A lanthanum glutamic dithiocarbamate（La-GDTC） was synthesized. The vulcanization kinetic and crosslinking structure of styrene butadiene rubber （SBR）/La-GDTC/silica（SiO2） composites were studied via vulcanization kinetic simulation,swelling equilibrium and differential scanning calorimeter. Simulated curing parameters showed that the curing rate k2 of the SBR/La-GDTC/SiO2 composite was significantly higher than that of the SBR/La-GDTC composite. Also,swelling equilibrium test turned out that crosslinking density of SBR/LaGDTC/SiO2 composite evolved to higher level,compared to that of the SBR/La-GDTC composite. Ammonia modified swelling equilibrium interpreted both lanthanum ions and carboxyl groups could react with silanol groups of silica particles. Finally,vulcanization activation energies of SBR/La-GDTC/SiO2 composite were lower than that of SBR/La-GDTC composite,without respect to different approaches of the DSC measurement or Oscillated Disc Rheometer test. All the results showed that the lanthanum ions of La-GDTC could act as the metal ion catalyzer of sulfur vulcanization during the crosslinking process,which could be attributed to the unoccupied orbital of lanthanum ions. Therefore,a La-GDTC bridged structure between SBR and silica particles for the SBR/La-GDTC/SiO2 composite was suggested according to the experimental results.

Synthesis of hierarchical nanohybrid CNT@Ni-PS and its applications in enhancing the tribological,curing and thermal properties of epoxy nanocomposites

Poor interfacial adhesion and dispersity severely obstruct the continued development of carbon nanotube(CNT)-reinforced epoxy(EP)for potential applications.Herein,hierarchical CNT nanohybrids using nickel phyllosilicate(Ni-PS)as surface decorations(CNT@Ni-PS)were synthesized,and the nanocomposites derived from varied mass fractions of EP and CNT@Ni-PS were prepared.The morphological structures,tribological performances,curing behaviors and thermal properties of EP/CNT@Ni-PS nanocomposites were carefully investigated.Results show that hierarchical CNT nanohybrids with homogeneous dispersion and well-bonded interfacial adhesion in the matrix are successfully obtained,presenting significantly improved thermal and tribological properties.Moreover,analysis on cure kinetics proves the excellent promotion of CNT@Ni-PS on the non-isothermal curing process,lowering the curing energy barrier steadily.

ORGANIC/INORGANIC HYBRID EPOXY NANOCOMPOSITES BASED ON OCTA(AMINOPHENYL)SILSESQUIOXANE

Octa（aminophenyl）silsesquioxane （OAPS） was used as the curing agent of diglycidyl ether of bisphenol-A （DGEBA） epoxy resin. A study on comparison of DGEBA/OAPS with DGEBA/4,4＇-diaminodiphenyl sulfone （DDS） epoxy resins was achieved. Differential scanning calorimetry was used to investigate the curing reaction and its kinetics, and the glass transition of DGEBA/OAPS. Thermogravimetric analysis was used to investigate thermal decomposition of the two kinds of epoxy resins. The reactions between amino groups and epoxy groups were investigated using Fourier transform infrared spectroscopy. Scanning electron microscopy was used to observe morphology of the two epoxy resins. The results indicated that OAPS had very good compatibility with DGEBA in molecular level, and could form a transparent DGEBA/OAPS resin. The curing reaction of the DGEBA/OAPS prepolymer could occur under low temperatures compared with DGEBA/DDS. The DGEBA/OAPS resin didn＇t exhibit glass transition, but the DGEBA/DDS did, which meant that the large cage structure of OAPS limited the motion of chains between the cross-linking points. Measurements of the contact angle indicated that the DGEBA/OAPS showed larger angles with water than the DGEBA/DDS resin. Thermogravimetric analysis indicated that the incorporation of OAPS into epoxy system resulted in low mass loss rate and high char yield, but its initial decomposition temperature seemed to be lowered.

Synthesis and Characterization of Bio-based Epoxy Blends from Renewable Resource Based Epoxidized Soybean Oil as Reactive Diluent

A novel bioresin, epoxidized soybean oil was synthesized by in situ method and was characterized employing FTIR and NMR. The bioresin was blended with epoxy（DGEBA） at different ratios as reactive diluents for improved processibility and toughened nature. The composition with 20 wt% bioresin exhibited improved impact strength to the tune of 60% as compared to virgin epoxy. Fracture toughness parameters critical stress intensity factor（KIC） and critical strain energy release rate（GIC） were evaluated using single edge notch bending test and demonstrated superior enhancement in toughness. Dynamic mechanical, thermal, thermo mechanical and fracture morphological analyses have been studied for bio-based epoxy blends. Curing kinetics has been evaluated through DSC analysis to investigate the effect of bioresin on cross-linking reaction of neat epoxy with triethylenetetramine as curing agent.

Reaction-induced phase separation in rubber-modified epoxy resin

The phase separation mechanism,and structure development during curing of epoxy with a novel liquid rubber-ZR were investigated by time-resolved light scattering,optical microscope and differential scanning calonmetry (DSC) The mixture loaded with curing agent was a single-phase system in the early stage of curing.When the cure reaction proceeded,phase separation took place via the spinodal decomposition induced by polymerization of epoxy resin.This was supported by the characteristic change of light scattering profile with curing time.Cure reaction plays an important role in the progress of phase separation.The bigger the cure reaction rate is,the longer periodic distance will be.The overall two-phase structure was basically locked in when the conversion approached 80% estimated by DSC,and finally the co-continuous two-phase structure was successfully obtained.

Synthesis and characterization of imide modified poly(dimethylsiloxane) with maleopimaric acid as raw material

With the natural rosin derivative （maleopimaric acid, MPA） as the raw material, imide modified vinyl poly（dimethylsiloxane） （MP-VMS） was synthesized and characterized by ^1H NMR and ^13C NMR. The curing kinetic parameters of MP-VMS were determined by differential scanning calorimetry （DSC） at various heating rates （5, 8, 10, 15 ℃/min） from the Kissingner, Ozawa and Crane methods. The activation energy （Ea）, pre-exponential factor （A） and reaction order （n） were respectively 18.6 kJ/mol, 71,108 and 0.902. The low-temperature and high-temperature resistance of its curing product were respectively investigated by DSC and thermogravimetric analysis. The results showed that incorporation of MPA could significantly improve the thermal stability of silicone while had no effect on the low-temperature resistance, and the Tmax （the temperature corresponding to the maximum weight loss rate） increased by 70.7 ℃.