Effect of nanoclay on shrinkage control of low profile unsaturated polyester (UP) resin cured at room temperature

The addition of a small amount of nanoclay (1-3 wt%) can provide excellent volume shrinkage control of unsaturated polyester (UP)/styrene (St)/poly(vinyl acetate) (PVAc) systems cured at room temperature. PVAc serves as the low profile additive (LPA). In this study, both temperature-induced phase separation of the uncured resin mixture and transmission electron microscopy (TEM) of the cured sample revealed that nanoclay resided in the LPA-rich phase, leading to a higher reaction rate and earlier onset of micro-cracking in the LPA-rich phase or at the interface of the LPA-rich and UP-rich phases. Consequently, an earlier volume expansion during curing was observed in reactive dilatometry, resulting in better shrinkage control. On-line measurement of the composite thickness change during vacuum-infusion liquid composite molding [e.g. the Seemann Composite Resin Infusion Molding Process (SCRIMP)] further proved excellent volume shrinkage control of nanoclay filled systems, leading to a smoother composite surface.     

Low temperature cure of vinyl ester resins

Vinyl ester resins are well known for their versatility as a composite matrix. With the development of a promising room temperature molding technology, vacuum-assisted resin transfer molding, e.g. Seemann Composite Resin Infusion Molding Process (SCRIMP), the processability of vinyl ester resins at low temperatures has attracted considerable attention from the composite industry. The objective of this paper is to provide a better understanding of the reaction kinetics of this resin system at low temperatures. In this study, a differential scanning calorimeter (DSC) coupled with a Fourier transform infrared (FTIR) spectrometer was employed to measure the reaction profile of a vinyl ester resin with different promoter and styrene contents. A kinetic model based on the free radical co-polymerization mechanism was developed for simulating the reaction rates and conversions of styrene vinyl and vinyl ester vinylene groups. The model parameters were determined from several FTIR experiments under isothermal conditions. This model, in conjunction with heat transfer analysis, was able to successfully predict the temperature profiles during curing in two SCRIMP molding cases based on groove type resin distribution system.     

Effects of inhibitors and retarders on low temperature free radical crosslinking polymerization between styrene and vinyl ester resin

Many composite manufacturing methods are room temperature processes, which require the resins to be cured at low temperatures. Examples are Seemann Composite Resin Infusion Molding Process (SCRIMP)—a vacuum assisted resin transfer molding (VARTM) process, hand lay‐up and spray‐up. Vinyl ester resins have been widely used in this type of processes because of their versatility as a composite matrix. Low temperature polymerization between styrene and vinyl ester tends to be complex because of the presence of different curing agents. This paper reports on (1) the effects of a promoter (cobalt naphthenate) on the initiatin at low temperatures, and (2) the effects fo a retarder (2,4‐pentanedione) and an inhibitor (1,4‐benzoquinone) on the pot life, gel time, and cure kinetics. A differntial scanning calorimeter (DSC) and a Fourier transform infrared (FTIR) spectrometer were used to investigate the reaction kinetics of vinyl ester resins. The influence of the retarders and inhibitors on the rheological changes of the resin during curing was also studied using a Rheometris Dynamic Analyzer (RDA).     

Control of volume shrinkage and residual styrene of unsaturated polyester resins cured at low temperatures. II. Effect of comonomer

The effect of a comonomer, methyl methacrylate (MMA), on volume shrinkage and residual styrene content of an unsaturated polyester (UP) resin with low profile additives (LPAs) cured at low temperature was investigated by an integrated reaction kinetics-morphology-property analysis. MMA affects the volume shrinkage and residual styrene content differently depending on MMA to styrene (St) CC bond molar ratio. At low MMA/St ratio, residual styrene decreases and the volume shrinkage of the resin system remains unchanged. At high MMA/St ratio, residual styrene can be substantially reduced, but the resin system suffers poor volume shrinkage control. Reactivity of the comonomer MMA and its compatibility to other components in the resin system can explain the observed results. A series of Seemann composites resin infusion molding process (SCRIMP) were conducted to study the relationship among materials, processing, and properties of molded composites in low temperature curing processes.     

A kinetic model for free‐radical crosslinking co‐polymerization of styrene/vinylester resin

Vinylester resin is a major thermoset polymer used In low temperature composite manufacturing processes, such as the Seemann Composite Resin Infusion Molding Process (SCRIMP). In this study, the effect of temperature on the cure kinetics of vinylester resin in the range of 35 to 90°C was investigated using a differential scanning calorimeter (DSC) and a Fourier transform infrared spectrometer (FTIR). A mechanistic kinetic model was developed to simulate the reaction rate and conversion profiles of vinylester vinylene and styrene vinyl groups, as well as the total reaction action rate and conversion. Experimental results from DSC and FUR at different temperatures were compared with model predictions. The glass transition temperature of the vinylester resin cured at different temperatures was identified and used to monitor the final conversion change. A series of SCRIMP molding experiments were conducted. The developed kinetic model in conjunction with a heat transfer model was used to simulate the temperature and conversion changes inside the SCRIMP‐molded composites.     

Vacuum‐assisted resin transfer molding using tackified fiber preforms

A low cost composite fabrication process—tackified SCRIMP—is described for fabricating aerospace‐grade composites based on tackification and vacuum‐assisted resin transfer molding (VARTM). Tackification based on a commercial tackifier (FT 500 from 3M) was used to make the net‐shape fiber preform. It was found that tackifier concentration and application conditions play important roles in governing the moldability of tackified fiber preforms. An epoxy resin (PR 500 from 3M) was used in the VARTM process‐SCRIMP at high temperatures. Experimental results show that composites with high fiber content (> 60% by volume) can be manufactured at low cost using tackification. Effects of tackification methods on composite dimension control, void content and mechanical properties were investigated and compared in both RTM and SCRIMP.     

SCRIMP用原位分相增韧中温环氧树脂体系制备及复合材料性能

针对复合材料真空辅助树脂浸渍模塑技术(SCRIMP)对树脂体系要求进行配方设计及性能测试。采用动态差示扫描量热(DSC)法,运用Kissinger动力学方程研究了基础树脂的固化反应动力学。通过添加QS-VA-3型原位分相型增韧剂,改善了基础树脂脆性,依据力学性能测试结果确定最佳添加量。对增韧环氧树脂体系进行等温/非等温黏度特性研究,确定了SCRIM P灌注成型过程的适用期,并使用该技术成型了增韧环氧树脂体系/单向玻璃纤维布复合材料试样,发现与玻璃纤维复合后具有强度高、界面性能好及低电压绝缘性能良好特点,但牺牲了高电压环境下绝缘性能。     

酚醛环氧乙烯基酯树脂碳纤维复合材料的制备及性能研究

把酚醛环氧乙烯基酯树脂分别与固化剂过氧化氢异丙苯(CHP)、过氧化苯甲酸叔丁酯(TBPB)、过氧化二异丙苯(DCP)进行混溶,模压成型,碳纤维层合板,进行了力学性能和热稳定性的研究。结果表明,研究的碳纤维-酚醛环氧基乙烯基酯树脂复合材料具有非常好的力学性能及热稳定性,弯曲强度达到1 400～1 900 MPa。     

Comparison of unsaturated polyester and vinylester resins in low temperature polymerization

Many composite products are produced at low temperatures in processes such as resin transfer molding (RTM), vacuum infusion molding (e.g., Seemann Composite Resin Infusion Molding Process—SCRIMP), and hand lay‐up. These processes are widely used for marine, civil infrastructure, transportation and defense applications. Unsaturated polyester and vinylester resins are two major resins used in these processes due to their low cost, good performance, and processibility. In this study, the reaction kinetics and rheological changes of these two resins cured at low temperatures were studied. Effects of resin type, initiator, promoter, inhibitor and retarder on the reaction kinetics and rheological behaviors were examined using a Differential Scanning Calorimeter (DSC) and a Rheometrics Dynamic Analyzer (RDA). A model was developed to quantify the effects of resin type, temperature, and different curing agents on the gel time for both polyester and vinylester resins cured at low temperatures. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1230–1242, 2001     

Poly(methyl methacrylate)‐modified vinyl ester thermosets: Morphology,volume shrinkage,and mechanical properties

Thermoset materials obtained from styrene/vinyl ester resins of different molecular weights modified with poly(methyl methacrylate) (PMMA) were prepared and studied. Scanning electron microscopy and transmission electron microscopy micrographs of the fracture surfaces allowed the determination of a two‐phase morphology of the modified networks. Depending on the molecular weight of the vinyl ester oligomer, the initial content of the PMMA additive, and the selected curing temperature, different morphologies were obtained, including the dispersion of thermoplastic‐rich particles in a thermoset‐rich matrix, cocontinuous structures, and the dispersion of thermoset‐rich particles in a thermoplastic‐rich matrix (phase‐inverted structure). Density measurements were performed to determine the effect of the PMMA‐modifier concentration and curing temperature on the volume shrinkage of the final materials. The development of cocontinuous or thermoplastic‐rich matrices was not too effective in controlling the volume shrinkage of the studied vinyl ester systems. The evaluation of the dynamic mechanical behavior, flexural modulus, compressive yield stress, and fracture toughness showed that the addition of PMMA increased the fracture resistance without significantly compromising the thermal or mechanical properties of the vinyl ester networks. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Effects of a chelating agent - 2,4-pentanedione on low temperature composite molding of vinyl ester and unsaturated polyester resins

A major concern in low temperature composite manufacturing processes is how to design and control the mold filling and curing time. Inhibitors or retarders are often used to prevent premature gelation and provide a sufficiently long time to fill the mold completely. However, the addition of these chemical species tends to result in a low mold curing rate and a low final resin conversion. In this study, a chelating agent 2,4-pentanedione (2,4-P) was used to manipulate resin gelation and curing. This agent is known to affect the catalytic activity of the promoters (i.e. metal compounds such as cobalt carboxylates) in the decomposition of initiators. It can function as either a retarder or a co-promoter in the co-polymerization of styrene/polyester and styrene/vinyl ester resins depending on the acidity of the resin system. Based on this observation, an improved room temperature vacuum-assisted resin transfer molding process was designed. This design allows 2,4-P to serve first as a retarder during mold filling to achieve a long gel time, it then as a co-promoter during curing to increase the curing rate. The 2,4-P also increases the resin conversion as the acidity of the resin increases.     

Resin transfer molding of natural fiber reinforced polybenzoxazine composities

Kenaf fiber is incorporated in a polybenzoxazine (PBZX) resin matrix to form a unidirectionally reinforced composite containing 20 wt% fiber by a resin transfer molding technique. Two types of benzoxazine monomer are synthesized and used as resin mixtures: Benzozazines based on bisphenol‐A/aniline (BA‐a) and phenol/aniline (Ph‐a). The effects of varying BA‐a:Ph‐a ratio in the resin mixture and curing conditions on mechanical properties of pure PBZX resin and kenaf/PBZX composites are studies. The Flexural strength of the pure PBZX resin increases with increasing ratio of BA‐a:Ph‐a, curing temperature and curing time, but the impact strength increases only slightly. PBZX resin has lower water absorption and higher flexural modulus, when compared with unsaturated polyester (UPE) resin. PBZX composites with 20 wt% fiber content have lower flexural and impact strengths, but higher moduli compared with UPE composites with the same fiber content.     

Silicone‐Organic Resin Hybrid Matrix Composites

Summary: Glass fabric reinforced hybrid matrix composites of a toughened silicone resin and a vinyl ester resin were fabricated and their properties investigated. The hybrid composites consisted of multi‐layers of fiber reinforced silicone resins and vinyl ester resins. The toughened silicone resin, a crosslinkable phenylsilsesquioxane resin with high thermal and thermal oxidation resistance but relatively low T_g, was chosen to be the outer layers. The vinyl ester resin, with better strength, toughness and a much higher T_g than the toughened silicone resin, was used as the inner layers. A co‐cure process proved to establish a strong interface between the two in a hybrid composite. The hybrid composites had better flammability properties and much lower short term moisture absorption than the vinyl ester composites. The strength and modulus retention of the hybrid composites at elevated temperatures was higher than the composites using any single resin as the matrix. For example, when tested at 150 °C the flexural modulus and strength values of a twelve layer composite, with eight inner vinyl ester resin layers and four silicone outer layers, were almost an order of magnitude higher than the composite using the silicone resin alone, and were significantly higher than the one using vinyl ester resin alone. The room temperature short beam shear strength of the hybrid composites was also higher. DMA revealed that the inter‐diffusion of reactive components between the two resins was probably responsible for this synergistic effect, resulting in an α transition temperature of 182 °C for the hybrid composite, higher than that of either the silicone resin (85 °C) or the vinyl ester resin (162 °C).

     

Simultaneous effects of silanized coal fly ash and nano/micro glass fiber on fracture toughness and mechanical properties of carbon fiber‐reinforced vinyl ester resin composites

In this study, the simultaneous effects of both silanized coal fly ash (S‐CFA) and nano/micro glass fiber (nGF) on fracture toughness and mechanical properties of vinyl ester (VE) resin filled with carbon fiber‐based composite materials were investigated. The CFA was treated with (3‐trimethoxysilyl) propyl methacrylate to introduce the methacryloxy groups into the surface of CFA, and was confirmed by using FTIR technique. The nGF and S‐CFA with different weight ratios were well mixed with VE resin by using of high‐speed mechanical stirrer, and ultrasonic technique before using as matrices for fabrication of carbon fiber‐based composite materials via sheet molding compound (SMC) method and hot curing processing. Many characteristics of both cured VE resin composites and carbon fiber‐based composite were examined such as mechanical properties, fracture toughness, and morphology. The results showed that by adding of both 0.1 wt% nGF and 1 wt% S‐CFA into VE resin the tensile strength, tensile modulus, flexural strength, K_IC, impact strength as well as the Mode I interlaminar fracture toughness (G_IC) of VE composites and carbon fiber based composites get optimum values and increased about 61.39%; 39.83%; 36.21%; 103.1%; 81.79%; 48.61%, respectively when compared with pristine materials. POLYM. ENG. SCI., 59:584–591, 2019. © 2018 Society of Plastics Engineers     

后处理温度对EP/CF复合材料拉伸性能影响

采用模压成型工艺和拉挤工艺制备了加捻碳纤维增强环氧树脂(EP/CF)复合材料,利用微机控制电液伺服万能试验机和扫描电子显微镜研究了不同后处理温度对EP/CF复合材料的拉伸性能和断面微观形貌的影响。研究表明,相对于高温后处理下的EP/CF复合材料,室温后处理下的EP/CF复合材料的拉伸强度较优,其拉伸强度接近890 MPa;而随着后处理温度的升高,EP/CF复合材料的截面和表面显微硬度值呈先上升后下降趋势,当后处理温度为150℃时,其硬度值最优。随着后处理温度的上升,样品的断面形态由撕拉态变为剪切状态,整个断面转变为脆性断面,EP与CF之间的界面变差。较优后处理工艺为低温后处理;同时,常温固化剂下的EP和CF体系选择后处理工艺优化时,后固化温度应接近固化体系温度进行优化处理。     

Flow and cure phenomena in liquid composite molding

Liquid molding processes including resin transfer molding (RTM) and structural reaction injection molding (SRIM) continue to attract attention due to their potential for high volume manufacture. This paper examines and compares the pressuare and temperature histories observed in mold cavities during impregnation, heating, and polymerization for both RTM and SRIM using polyester, vinyl ester, and polyurethane resins in combination with continuous strand mats. Experimental results are related to thermal, chemical and rheological effects. Factors which influence materials behavior and process control and the implications for mold design are discussed.     

The influence of post‐cure on properties of carbon/phenolic resin cured composites and their final carbon/carbon composites

Two‐dimensional (2D) carbon/carbon (C/C) composites were prepared with phenol‐formaldehyde resin and graphite fabric. After curing, polymer composites were post‐cured in air at 160°C and 230°C for several hours and then all polymer composites were carbonized up to 1500°C. The effect of post‐cure on the microstructure and fracture behavior of the resultant carbon/carbon composites was studied. The post‐cure process was characterized by weight loss. This process promoted the crosslinking and condensation reactions and led to the formation of long‐chain, cross‐linked polymeric structures in the matrix. The post‐cured composites had a greater density than the unpost‐cured composite. This study indicates that a longer post‐curing time and higher post‐curing temperature would limit the shrinkage for the post‐cured composites during carbonization. The improvement in linear shrinkage was 22% to 44%. This process also limited the formation of open pores and decreased the weight loss of the resultant C/C composites. The resultant C/C composites developed from post‐cured composites had a greater flexural strength by 7 to 26% over that developed from unpost‐cured composite.     

Apparent volumetric shrinkage study of RTM6 resin during the curing process and its effect on the residual stresses in a composite

A comprehensive characterization of the volumetric shrinkage of a commercially important aerospace resin (RTM6) during the various stages of the curing process was studied. The apparent volumetric shrinkage, evaluated from density measurements at room temperature, was correlated with the progress of epoxide conversion. During the entire curing process, the apparent volume shrinkage was found to be less than 3% and occurred before vitrification. A slight re‐expansion of the resin, attributed to self‐antiplasticization effects, was observed during postcuring at 180°C. It was concluded that residual stresses were not generated due to chemical cross‐linking during curing but rather from thermal contraction occurring during the cooling stage after cure. A photo‐elastic method was used to characterize residual stresses during cooling in a deliberately engineered resin rich hole of a carbon fiber/RTM6 composite. The residual stress was found to reach approximately 28 MPa, which is in good agreement with the value calculated from the shrinkage and elastic moduli. It is proposed that this simple method can be provide insights useful to the design and materials selection processes by measuring and localizing residual stresses from resin during curing and or thermal cycling. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

High‐performance thermosets with tailored properties derived from methacrylated eugenol and epoxy‐based vinyl ester

A renewable chemical, eugenol, is methacrylated to produce methacrylated eugenol (ME) employing the Steglich esterification reaction without any solvent. The resulting ME is used as a low‐viscosity co‐monomer to replace styrene in a commercial epoxy‐based vinyl ester resin (VE). The volatility and viscosity of ME and styrene are compared. The effect of ME loading and temperature on the viscosity of the VE–ME resin is investigated. Moreover, the thermomechanical properties, curing extent and thermal stability of the fully cured VE–ME thermosets are systematically examined. The results indicate that ME is a monomer with low volatility and low viscosity, and therefore the incorporation of ME monomer in VE resins allows significant reduction of viscosity. Moreover, the viscosity of the VE–ME resin can be tailored by adjusting the ME loadings and processing temperature to meet commercial liquid molding technology requirements. The glass transition temperatures of VE–ME thermosets range from 139 to 199 °C. In addition, more than 95% of the monomer is incorporated and fixed in the crosslinked network structure of VE–ME thermosets. Overall, the developed ME monomer exhibits promising potential for replacing styrene as an effective low‐viscosity co‐monomer. The VE–ME resins show great advantages for use in polymer matrices for high‐performance fiber‐reinforced composites. This work is of great significance to the vinyl ester industry by providing detailed experimental support. © 2018 Society of Chemical Industry     

Mechanical performance of vinyl ester—polyurethane interpenetrating polymer network composites

In this study, a carbon fiber/vinyl ester-polyurethane interpenetrating polymer network (IPN) laminate composite was fabricated and characterized for the first time. The IPN matrix, consisting of a commercially available vinyl ester and polyurethane, was synthesized via a sequential method with vinyl ester as the rigid phase and polyurethane as the flexible phase. Good compatibility between the two phases in the matrix was achieved and confirmed via differential scanning calorimetry and dynamic mechanical analysis. The thermomechanical response of the IPN matrix was compared with that of an unmodified vinyl ester resin. The presence of the more ductile polyurethane in the IPN matrix depressed the glass transition temperature (from 94 to 84°C), but also served to improve damping response at all frequencies studied. Tensile and flexural tests were performed on the carbon fiber/IPN and carbon fiber/vinyl ester composites to determine their mechanical response. The IPN composite exhibited lower tensile properties than the vinyl ester composite. However, its flexural properties were on par with those of the vinyl ester composite.