Effects of the electron‐beam absorption dose on the glass transition,thermal expansion,dynamic mechanical properties,and water uptake of polycardanol containing epoxy groups cured by an electron beam

In this study, the glass transition, thermal expansion, dynamic mechanical properties, and water‐uptake behaviors of diepoxidized polycardanol (DEPC) cured by electron‐beam radiation in the presence of cationic photoinitiators were investigated. How the type and concentration of cationic photoinitiators and the electron‐beam absorption dose influenced the properties of the cured DEPC was also studied. Two types of cationic photoinitiators, triarylsulfonium hexafluorophosphate (simply referred to as phosphate type or P‐type) and triarylsulfonium hexafluoroantimonate (simply referred to as antimonate type or Sb‐type), were used. Electron‐beam absorption doses of 200, 300, 400, and 600 kGy were applied to the uncured diepoxidized cardanol (DEC) samples, respectively. It was revealed that the Sb‐type photoinitiator was preferable to the electron‐beam curing of DEC; this led to a lower photoinitiator concentration and/or a lower electron‐beam absorption dose compared to that in the phosphate‐type photoinitiator. As a result, the variations in the glass‐transition temperature, coefficient of thermal expansion, storage modulus, and water uptake of the cured DEPC were quite consistent with each other. We found that the optimal conditions for the enhanced properties of DEPC by electron‐beam curing were an Sb‐type photoinitiator at 2 wt % and an electron‐beam absorption dose of 600 kGy. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42570.     

Electron beam curing of polymer composites

Electron‐beam (E‐Beam) curing of an epoxy polymer matrix and its composite (reinforced with IM7 Carbon fibers) was studied using a cationic photoinitiator. Photoinitiator concentration, dose, and process temperature were varied to understand their influence on E‐beam curing. Optimal photoinitiator concentration was found to be 5 phr. The curing was due to a primary α reaction with a strong dependence on dose, and a secondary β reaction with a weak dependence on dose and a strong dependence on initiator concentration. The extent of cure increased rapidly with dose until 100 kGy and it approached a plateau value beyond 100 kGy. This plateau value corresponded to incomplete curing by 27% for resin and 22% for composite at a process‐temperature of 22°C. The causes for incomplete curing appear to be the secondary β reaction and diffusional limitation. Increase in process temperature resulted in higher extent of cure at a dose level. The material used in this study was also found to be thermally curable and the reaction onset temperature (measured in a DSC ramp experiment) reduced from about 150°C at 0 kGy to about 50°C at 30 kGy. This indicates that simultaneous thermal curing during E‐beam curing of resin and composite is possible. After thermal post‐curing, the T_g of the E‐beam cured resin increased from 130°C at 200 kGy to a value greater than 370°C and the modulus decreased by 10%. The service temperature and the modulus of the 100% thermally cured resin and the thermally post‐cured (after E‐Beam irradiation) resin were comparable.     

Electron Beam Curing of the System Cycloaliphatic Diepoxide‐Epoxidized Natural Rubber‐Glycidyl Methacrylate in Presence of Cationic Initiators

Electron beam curing of the system cycloaliphatic diepoxide‐epoxidized natural rubber‐glycidyl methacrylate containing a cationic initiator was carried out. Storage modulus, glass transition temperature and pendulum hardness were measured as function of EB dose, photoinitiator concentration, content of epoxidized natural rubber, post cure temperature and post cure time. At electron beam doses larger than 100 kGy a highly cross‐linked polymer network is generated which shows a two phase morphology. Microscale elastomeric domains are incorporated into a continuous epoxy resin phase. Dynamical mechanical analysis and pendulum hardness measurement show that an increase of the ENR ratio leads to a more elastic polymer network. Post curing results in increased glass transition temperatures. This EB cured polymer system is believed to provide both toughness and favorable viscoelastic properties to be used as component of EB curable composites.     

Fabrication and characterization of the mechanical properties of multi-walled carbon nanotube-reinforced epoxy resins by e-beam irradiation

In this study, the multi-walled carbon nanotubes (MWNT) were reinforced to epoxy resin as fabrication of epoxy/MWNT nanocomposites by electron beam (e-beam) curing. An attempt is made to disperse MWNT into diglycidyl ether of bisphenol A (DGEBA) as epoxy resins, using triarylsulfonium hexafluoroantimonate (TASHFA) as an initiator. E-beam irradiation effect on the curing of the epoxy resin was investigated in oxygen and nitrogen atmospheres at room temperature. The flexural modulus was measured by a universal testing machine (UTM). Here, the flexural modulus factor exhibits an upper limit at 0.3 wt% MWNT. The dynamic mechanical and thermal properties of the irradiated epoxy resins were characterized using DMA, DSC and TGA machines. DMA curves of the storage modulus revealed an increase with an increasing MWNT content and radiation dose. However, the T_g curve decreased as a function of the increasing MWNT content and radiation dose. The thermal properties of the TGA and DSC data were improved by increasing the content of the MWNT and the radiation dose. Likewise, the thermal properties were stabilized by increasing the amount of initiator and irradiating the resins in a nitrogen atmosphere.     

Electron‐beam curing of bismaleimide‐reactive diluent resins

Electron‐beam (E‐beam) curing of 4,4′‐bismaleimidodiphenylmethane (BMPM)/BMI‐1,3‐tolyl/o,o′‐diallylbisphenol A (DABPA)–based bismaleimide (BMI) systems and their mixing with various reactive diluents, such as N‐vinylpyrrolidone (NVP) and styrene, were investigated to elucidate how temperature, electron‐beam dosage, and diluent concentration affect the cure extent. The effect of free‐radical initiator on the cure reactions was also studied. It was found that low‐intensity E‐beam exposures cannot cause the polymerization of BMI. High‐intensity E‐beam exposures give high reaction conversion attributed to a high temperature increase, which induced thermal curing. It was shown that the dilution and activation of NVP in BMI cause a more complete BMI cure reaction under E‐beam radiation. BMI/NVP can be initiated easily by low‐intensity E‐beam without thermal curing. FTIR studies indicate that about 70% of the reaction is complete for BMI/NVP with 200 kGy dosage exposure at 10 kGy per pass. The sample temperature only reaches about 75°C. The free‐radical initiator, dicumyl peroxide, can accelerate the reaction rate at the beginning of E‐beam exposure, but does not affect the final reaction conversion. The increase of the concentration of NVP in the BMI/NVP systems increases the reactive conversions almost linearly. © 2004 Wiley Periodicals Inc. J Appl Polym Sci 94: 2407‐2416, 2004     

Investigation of influence factors in electron beam curing of epoxy resins using a calorimetry technique

Because of the complexity of the electron beam (EB) curing process, current understanding of EB curing of polymer resins and composites is limited. This article describes an investigation of different factors affecting EB curing of epoxy resin such as dose rate, time interval between irradiation doses, moisture, and photoinitiator concentration using a calorimetry technique. Results show that higher dose rate resulted in a higher and faster temperature increment in the uncured resin samples, and thus a higher degree of cure. In the multiple‐step EB irradiation, a shorter time interval between irradiation doses resulted in higher temperature in the resin samples and therefore higher degree of cure. Results indicate that moisture could delay crosslinking reaction in the early stages of the cure reaction, but accelerates it later in the curing process. Given a reasonable percentage of photoinitiator, experiments confirmed that samples with higher photoinitiator concentration reach higher degree of cure under same EB irradiation conditions. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Exothermic effect in the process of electron‐beam curing of epoxy resins

Temperature measurements have been performed in the process of electron‐beam curing of EB‐I and EB‐II epoxy resin systems. The influence of initiator content, resin type, and dose rate on the temperature of the systems was studied. Transverse and longitudinal temperatures of samples in the glass vessel were also analyzed. The nature of temperature curves varied with the different epoxy resin systems in the steel mold, but did not change with different contents of the initiator. At the same time, the heat had no effect on the gel fraction of epoxy resin systems. The temperature curve was greatly affected by the dose rate, and its peak value, peak width, and plateau value also increased with it. The transverse temperature of EB‐II glass vessel samples increased as the radiation dose increased and, in the same sample, the temperature reduced as the distance between the radiation center and the test point increased. The longitudinal temperature of EB‐I and EB‐II resin systems in a glass vessel decreased as the radiation depth increased. As the radiation dose increased, the temperature of the EB‐I resin system increased simultaneously, while that of the EB‐II resin system initially increased and then kept constant when the dose reached a certain value. The temperatures of these two resin systems decreased rapidly when the radiation process stopped. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2217–2222, 2004     

采用模型化合物研究环氧树脂电子束固化机理

通过红外光谱、凝胶渗透色谱及核磁共振分析研究了单官能模型化合物苯酚缩水甘油醚在不同辐射剂量、引发剂浓度和羟基化合物掺杂情况下的电子束固化反应特性及机理。结果表明,环氧基团反应完全后,大幅度增加辐射剂量不会导致已经聚合的环氧树脂出现明显的辐射降解,但是引发剂浓度的增加和羟基化合物乙醇使聚合环氧树脂的分子质量下降。     

Effect of curing order on the curing kinetics and morphology of bisGMA/DGEBA interpenetrating polymer networks

The curing kinetics and morphology of an interpenetrating polymer network (IPN) formed from an epoxy resin (DGEBA) cured by an imidazole (1‐MeI) and a dimethacrylate resin (bisGMA), cured by low‐ and high‐temperature peroxide initiators (TBPEH and DHPB, respectively) have been studied by temperature‐ramping DSC, isothermal near‐infrared (NIR), DMTA and small‐angle neutron scattering (SANS). bisGMA and DGEBA are polar and chemically similar thermosetting resins which should enhance the miscibility of their IPNs. The phase structure was controlled by varying the curing procedure: the order of gelation of the components is dependent on the choice of low‐ and high‐temperature initiators for bisGMA and this affects the morphology formation. In the cure of the bisGMA/TBPEH:DGEBA/1‐MeI system, the dimethacrylate cures first. For isothermal cure studies at 80 °C, the final conversion of the epoxy is reduced by high crosslinking of the methacrylate groups in the IPN causing vitrification before full cure. The dimethacrylate conversion is enhanced due to plasticisation with unreacted DGEBA, and its cure rate is increased due to accelerated decomposition of TBPEH initiator by 1‐MeI. SANS revealed that phase separation occurs in these IPNs with domains on the scale of 6–7 nm. In the cure of the bisGMA/DHBP:DGEBA/1‐MeI system, the epoxy cures at a similar rate to that of the methacrylate groups. For isothermal cure studies at 80 °C, similar final conversions of the epoxy have been observed except for the 75:25 IPN. The cure rate of the methacrylate groups in the IPN is increased also due to accelerated decomposition of DHBP initiator by 1‐MeI, and the extent of accelerated decomposition for DHBP is stronger than that in the TBPEH‐based systems. SANS studies revealed that this system is more homogeneous due to the rapid formation of the dimethacrylate gel in the presence of the preformed epoxy network which interlocks the networks at low degrees of methacrylate conversion. Copyright © 2006 Society of Chemical Industry     

基于电子束辅助固化的木塑复合材料的研究

在辐射剂量为56kGy的双面电子束辐照工艺条件下，制备了苯乙烯(St)、苯乙烯与不饱和聚酯树脂(St／UPE)混合物以及苯乙烯与环氧丙烯酸酯树脂(St／EA)混合物浸渍的冬瓜木和松木系列木塑复合材料，研究了木材和浸渍液体种类以及电子束辐射对浸渍液体的聚合和固化程度以及所得木塑复合材料性能的影响。结果表明在电子束辅助固化工艺条件下，浸入木材的St、St/UPE和St／EA的聚合率以及St／UPE和St／EA的固化率均可大于90％。木塑复合材料的硬度和压缩强度较原木材可提高2～6倍，其1昼夜吸水率则从原木材的64．6％和52．8％分别降低到8．9％～12．9％和7．0％～7．9％。     

Investigation of curing characteristics of carbon fiber/epoxy composites cured with low‐energy electron beam

To solve the penetration depth of carbon fiber/epoxy prepreg and irradiation dose uniformity by low‐energy E‐Beam under 125 keV, the both‐side irradiation curing of prepreg was investigated. The results show that there is little thermal effect during the low‐energy electron beam irradiation curing process, even though the irradiation dosage reached 300 kGy, only 46.2°C can be tested on the prepreg surface. Due to the low curing temperature, the degree of cure of prepreg was only 61.8% at 300 kGy level of irradiation, and the glass‐transition temperature (T_g) was only 48.6°C. The degree of cure and T_g can be increased sharply by thermal postcure. After being postcured at 160°C for 30 min, the degree of cure and the T_g of prepreg reached 98.5% and 170.4°C, respectively. Interlaminar shear strength testing result indicate that the fabrication process of the composite layer by layer curing by the low‐ energy E‐Beam is a promising cure approach. POLYM. COMPOS., 36:1731–1737, 2015. © 2014 Society of Plastics Engineers     

FT‐IR studies on the curing behavior of polycardanol from naturally renewable resources

In the present study, the curing behavior of polycardanol prepared by enzymatic oxidative polymerization of thermally treated cashew nut shell liquid, which can be available from naturally renewable resources, was explored in the presence of methyl ethyl ketone peroxide (MEKP) and cobalt naphthenate (Co‐Naph). The curing behavior was monitored varying Co‐Naph concentration and curing temperature by means of Fourier transform infrared (FT‐IR) spectroscopy. The result revealed that the characteristic absorption bands were significantly affected by the given curing condition, resulting mainly from the unsaturated moiety in the polycardanol molecule. The extent of curing of polycardanol strongly depended on curing temperature, showing a typically sigmoidal curve reaching almost 1.0 upon processing at 200°C for 120 min. The thermal curing conditions for preparing polycardanol with an optimal state of cure were provided in the work. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Low‐energy electron beam‐induced cationic polymerization with onium salts

Demand for higher polymer performance with very short cure times has resulted in the development of low energy electron beam processes. This article presents the results of such a process for curing two epoxy systems, namely 3,4‐epoxycyclohexylmethyl‐3′,4′‐epoxycyclohexane carboxylate and di‐glycidyl ether of bisphenol A (DGEBA), using the cationic photoinitiator salts, triarylsulfonium hexafluoroantimonate, and diaryliodonium hexafluoroantimonate, respectively. Glass transition temperature measurements were done using a modulated DSC method while the degree of conversion was measured using FTIR spectroscopy. Results indicate that for both epoxy systems a relatively low dosage of not more than 5 Mrad was sufficient to achieve up to 60% conversion, with up to 80% conversion achievable using 30 Mrad. The diaryliodonium salt appeared to be more effective than the sulphonium salt in the above study. The effect of varying photoinitiator concentration and the resulting glass transition temperature has been studied. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3099–3108, 2001     

含乙烯基有机硅树脂的电子束固化行为研究

以八甲基环四硅氧烷、四甲基四乙烯基环四硅氧烷为单体,六甲基二硅氧烷为封端剂,碱胶为催化剂,合成了含乙烯基有机硅树脂;并研究了电子束辐射剂量对其固化行为的影响和固化涂层的热性能。红外谱图及凝胶率测试结果表明,有机硅树脂中的碳碳双键吸收峰强度随辐射剂量的增加而减弱,辐射诱导交联网络结构的形成导致固化涂层的凝胶率随剂量的增加而显著增加;辐射剂量为30 kGy时,凝胶率为46.2%;辐射剂量增加至60 kGy时为70.1%和100 kGy时为85.9%。差示扫描量热分析和热质分析结果表明,固化涂层具有优良的耐低温性和热稳定性。     

基于变活化能模型的T800/环氧树脂预浸料固化反应动力学研究

为了深入了解某新型高温固化T800/环氧树脂预浸料的固化行为,借助差示扫描量热仪(DSC),采用非等温DSC法研究了T800/环氧树脂预浸料的固化反应过程。基于唯象模型,系统研究了该预浸料的固化反应特征温度及固化动力学参数,确定该预浸料中环氧树脂的固化反应动力学模型为自催化模型。采用等转化率法,分析了预浸料中环氧树脂的反应活化能随固化度的变化情况,结果表明在整个固化反应过程中,树脂固化反应活化能变化较大,传统模型法基于全固化过程活化能不变的假设无法准确描述该固化反应。采用变活化能自催化模型,利用粒子群全局优化算法,得到了T800/环氧树脂预浸料的固化动力学方程,结果表明该模型能较好地描述实验现象,可为进一步研究该预浸料的热力学性能及其成型过程中的质量控制提供理论基础。     

Cure behavior of epoxy resin containing castor oil and cashew nut shell liquid and its derivative

The cure behavior of epoxy resin with a conventional amide‐type hardener (HD) was investigated in the presence of castor oil (CO), cashew nut shell liquid (CNSL), and cashew nut shell liquid–formaldehyde resin (CFR) with dynamic differential scanning calorimetry (DSC). The activation energy of the curing reaction was also calculated on the basis of nonisothermal DSC thermograms at various heating rates. A one‐stage curing was noted in the case of epoxy resin filled with CO, whereas the epoxy resin with CNSL and CFR showed a two‐stage curing process. A competitive cure reaction was noted for the epoxy resin/CNSL(or CFR)/HD blends. In the absence of HD, CFR showed lower values of curing enthalpy than that of CNSL. The activation energy of epoxy resin curing increased with increasing CNSL and CFR loading. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Cationic electron‐beam curing of a high‐functionality epoxy: effect of post‐curing on glass transition and conversion

This paper reports on the cationic electron‐beam curing of a high‐functionality SU8 epoxy resin, which is extensively used as a UV‐curing negative photoresist for micro‐electronics machine systems (MEMS) applications. Results show that elevated post‐curing treatment significantly increased both the conversion and the glass transition. The degree of conversion and the glass transition temperature were measured by using Fourier‐transform infrared (FTIR) spectroscopy and modulated differential scanning calorimetry (MDSC^®), respectively. The glass transition temperature (T_g), which has been observed to be dependent on the degree of conversion, reaches a maximum of 162 °C at 50 Mrad and post‐curing at 90 °C. The degradation pattern of the cured resin does not show much variation for exposure at 5 Mrad, but does show significant variation for 50 Mrad exposure at various post‐curing temperatures. A degree of conversion of more than 0.8 was achieved at a dosage of 30 Mrad with post curing at 80 °C, for the epoxy resin with an average functionality of 8 a feature simply not achievable when using UV‐curing. Copyright © 2004 Society of Chemical Industry     

Curing characteristics of epoxy resin systems that include a biphenyl moiety

The curing characteristics of epoxy resin systems that include a biphenyl moiety were investigated according to the change of curing agents. Their curing kinetics mainly depend on the type of hardener. An autocatalytic kinetic reaction occurs in epoxy resin systems with phenol novolac hardener, regardless of the kinds of epoxy resin and the epoxy resin systems using Xylok and DCPDP (dicyclopentadiene‐type phenol resin) curing agents following an nth‐order kinetic mechanism. The kinetic parameters of all epoxy resin systems were reported in terms of a generalized kinetic equation that considered the diffusion term. The fastest reaction conversion rate among the epoxy resin systems with a phenol novolac curing agent was obtained in the EOCN‐C epoxy resin system, and for systems with Xylok and DCPDP hardeners, the highest reaction rate values were obtained in NC‐3000P and EOCN‐C epoxy resin systems, respectively. The system constants in DiBenedetto's equation of each epoxy resin system with different curing agents were obtained, and their curing characteristics can be interpreted by the curing model using a curing agent as a spacer. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1942–1952, 2002     

Ultraviolet curing kinetics of cycloaliphatic epoxide with real‐time fourier transform infrared spectroscopy

The photo‐induced curing kinetics of cycloaliphatic epoxide coatings were investigated with real‐time Fourier transform infrared spectroscopy with an optical fiber ultraviolet curing system. The consumption of epoxy group as a function of time was obtained by monitoring of the oxirane absorbance in the 789–746‐cm^?1 region. The effect of the type of epoxide, hydroxyl equivalent weight, ratio of oxirane to hydroxyl groups (R), photoinitiator, and exposure time on the curing reaction was investigated. In general, the rate of curing was dependent on the hydroxyl equivalent weight, R, type of epoxide, and photoinitiator. For formulations without polyol, both initiator concentration and exposure time had minimal effects on the curing reaction. However, for formulations with polyol, the curing a reaction was dependent on the initiator concentration. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2485–2499, 2003     

Synthesis and characterization of emulsion‐type curing agent of water‐borne epoxy resin

Self‐emulsified water‐borne epoxy curing agent of nonionic type was prepared using triethylene tetramine (TETA) and derivative of epoxy resin as a capping agent, which was synthesized by liquid epoxy resin (E51) and polyethylene glycol (PEG), and the curing agent possessed emulsification and curing properties at the same time. The curing agent with good property of emulsifying liquid epoxy resin could be obtained under the condition of the molar ratio of PEG : E51 : TETA as 0.8 : 1 : 3.5 at 80°C for 5 h. The mean particle size of the emulsion liquid was about 220 nm with the prepared curing agent and epoxy resin at the mass ratio of 1 : 3. The structure of the emulsion‐type curing agent was confirmed by FTIR and ¹H NMR spectra, and the mechanism of cured film formation was also analyzed by SEM photographs. The cured film prepared by the emulsion‐type curing agent and epoxy resin under ambient cure conditions showed good properties even at high staving temperature. This study provides useful suggestions for the application of the water‐borne epoxy resins in coating industry. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2652–2659, 2013