Effect of matrix chemical structure on the thermo‐oxidative stability of addition cure poly(imide siloxane) composites

A series of addition cure poly(imide siloxane) resins were synthesized, incorporating various concentrations of α, ω‐bis(3‐aminopropyl) poly(dimethyl‐diphenylsiloxanes), and α, ω‐bis(p‐aminophenyl) poly(dimethylsiloxane) into the formulated imide oligomer. Both carbon and glass fiber textile laminates were fabricated using amic acid and polymerization of monomer reactants (PMR) approaches. The cured composite laminates were subjected to an accelerated thermo‐oxidative aging environment of 400°C for 100 h in air. Physical, thermal, and mechanical properties were evaluated to determine the structure‐oxidative stability interrelationships. In general, composite mechanical properties were found to increase with increasing siloxane concentration in the matrix. Composite thermo‐oxidative durability (measured via mass loss and mechanical property retention after oxidative aging) was improved through incorporation of diphenyl and diphenyl‐dimethyl siloxane segments into the imide oligomer backbone up to ∼35% by weight aminosiloxane. Oxidative stability was found to be mostly dependent on the degree of phenyl substitution on the silicon atoms in the siloxane blocks, as compared to the moiety attaching the amine groups to the siloxane block. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Novel phosphorus‐containing hardeners with tailored chemical structures for epoxy resins: Synthesis and cured resin properties

A comparative evaluation of systematically tailored chemical structures of various phosphorus‐containing aminic hardeners for epoxy resins was carried out. In particular, the effect of the oxidation state of the phosphorus in the hardener molecule on the curing behavior, the mechanical, thermomechanical, and hot‐wet properties of a cured bifunctional bisphenol‐A based thermoset is discussed. Particular attention is paid to the comparative pyrolysis of neat cured epoxy resins containing phosphine oxide, phosphinate, phosphonate, and phosphate (with a phosphorus content of about 2.6 wt %) and of the fire behavior of their corresponding carbon fiber‐reinforced composites. Comparatively faster curing thermosetting system with an enhanced flame retardancy and adequate processing behavior can be formulated by taking advantage of the higher reactivity of the phosphorus‐modified hardeners. For example, a combination of the high reactivity and of induced secondary crosslinking reactions leads to a comparatively high T_g when curing the epoxy using a substoichiometric amount of the phosphinate‐based hardener. The overall mechanical performance of the materials cured with the phosphorus‐containing hardeners is comparable to that of a 4,4′‐DDS‐cured reference system. While the various phosphorus‐containing hardeners in general provide the epoxy‐based matrix with enhanced flame retardancy properties, it is the flame inhibition in the gas phase especially that determines the improvement in fire retardancy of carbon fiber‐reinforced composites. In summary, the present study provides an important contribution towards developing a better understanding of the potential use of such phosphorus‐containing compounds to provide the composite matrix with sufficient flame retardancy while simultaneously maintaining its overall mechanical performance on a suitable level. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

不同固化剂对环氧树脂玻璃化温度影响的分子动态模拟研究

提出了一个分子动态模拟方法研究环氧树脂玻璃化转变温度(Tg)随固化剂结构变化。首先,建立了固化环氧树脂的一些简单分子模型;然后是一个分子动态模拟(MD)被重复执行。用模拟得到的数据作V-T关系曲线,用曲线上的转折点确定Tg的值。该模拟值与计算值有很好的吻合,尽管与实验值有较大的偏差,固化剂对Tg的影响可以用MD模拟定性得到。所提出的方法对于开发具有提高固化效果的固化剂有潜在的意义。     

UV curing of composites based on modified unsaturated polyester

Synthesis and photocrosslinking of glass fiber-reinforced composites, based on epoxy acrylate-modified unsaturated polyester, have been investigated. The efficiency of the photocrosslinking process for glass fiber laminates of the polyesters that contain different comonomers has been evaluated by measuring mechanical properties. The data show (i) that 2 mm thick laminates, containing 30–40% glass fiber mats, are cured with UV irradiation for 15 sec at room temperature in air; (ii) that multifunctional acrylate or acrylether monomers added to the polyester resin improve the tensile and flexural properties of the photocured product to a greater extent than do added allylic monomers, due to the different photocrosslinking mechanisms; (iii) that the physical properties of the photocrosslinked laminates are well correlated with the molecular weight of the polyester, the amount of multifunctional monomer added, and the glass fiber content. © 1994 John Wiley & Sons, Inc.     

苯并噁嗪和双马来酰亚胺共混树脂性能的研究

将苯并噁嗪(BOZ)和双马来酰亚胺树脂(BMI)按照不同的配比进行共混固化,制备了浇铸体和玻璃纤维增强的层压板。测试结果表明,BOZ和BMI共混的树脂浇铸体线性收缩率为0.85%~0.93%,小于BMI的1.3%略高于BOZ的0.73%。浇铸体和层压板的弯曲强度均随着BOZ含量的增加而上升,并且层压板吸水率还具有不断降低的趋势;其电气绝缘性能较佳。同时该共混树脂体系具有较好的耐热性,其Tg最高达到257℃比单纯BOZ的Tg提高了近50℃。DSC结果表明BOZ/BMI树脂体系的固化反应相对二者各自固化反应向低温移动,使体系中的BMI在相对较低的温度就固化完全。     

Epoxy networks based on solutions of silsesquioxanes functionalized with 3-glycidoxypropyl groups in diglycidylether of bisphenol A (DGEBA)

Summary In previous publications we reported the synthesis and characterization of silsesquioxanes derived from the hydrolytic condensation of (3-glycidoxypropyl) trimethoxysilane (GPMS) using diglycidylether of bisphenol A (DGEBA) as a solvent [1,2]. The reaction product has aliphatic epoxy groups supplied by the silsesquioxane and aromatic epoxy groups supplied by the solvent. Solutions containing 0, 25 and 50% aliphatic epoxy groups, were cured with different hardeners: methyltetrahydrophthalic anhydride (MTHPA), ethylenediamine (EDA) and benzyldimethylamine (BDMA). Silsesquioxane-modified epoxy networks showed a significant increase in the elastic modulus in the rubbery state, the abrasion resistance and the development of strain hardening in uniaxial compression tests. Received: 28 September 2000/Accepted: 27 October 2000     

Nanohole volume dependence on the cure schedule in epoxy thermosetting networks: A PALS study

A systematic study on the dependence of the volumes at nanoscale in epoxy systems cured with two selected aminic hardeners at different pre-cure temperatures is presented. Nanohole volumes were measured by positron annihilation lifetime spectroscopy. Additional information regarding the structure of the thermosets was obtained using dynamic mechanical analysis. Volume results obtained are discussed in terms of the cure schedule applied to the epoxy systems, their characteristic glass transition temperatures and their crosslink density. The pre-cure temperature and the structure of the hardeners govern the packing of the molecular chains of the epoxy network. Using together positron and mechanical experimental techniques allows to conclude that a strong change in the volume and number density of the nanoholes takes place when the pre-cure temperature crosses the glass transition temperature of the systems.     

马来海松酸类环氧树脂固化产物性能

本文研究了马来海松酸类环氧树脂与酸酐及芳香二胺类五种固化剂固化产物的耐热性能和机械性能,并详细讨论了固化后树脂的性能与环氧树脂、固化剂的化学结构及固化反应条件之间的关系。     

Tetraglycidyl epoxy resins and graphite fiber composites cured with flexibilized aromatic diamines

Studies were performed to synthesize new ether modified, flexibilized aromatic diamine hardeners for curing epoxy resins. The effect of moisture absorption on the glass transition temperatures of a tetraglycidyl epoxy, MY 720, cured with flexibilized hardeners and a conventional aromatic diamine was studied. Unidirectional composites, using epoxy-sized Celion 6000 graphite fiber as the reinforcement, were fabricated. The room temperature and 300°F mechanical properties of the composites, before and after moisture exposure, were determined. The Mode I interlaminar fracture toughness of the composites was characterized, using a double cantilever beam technique to calculate the critical strain energy release rate, G_IC.     

Effect of Mercerization on Surface Modification of Henequen (Agave fourcroydes) Fiber by Photo-Curing with 2-Hydroxyethyl Methacrylate (HEMA)

Abstract

Henequen fibers were cured under ultraviolet (UV) radiation with 2-hydroxyethyl methacrylate (HEMA) in order to improve the mechanical properties and reduce the water absorption. A series of solutions of different HEMA concentration in methanol along with photoinitiator Irgacure 907 was prepared. The radiation dose, monomer (HEMA) concentration and soaking time were optimized with respect to grafting of monomer and mechanical properties of cured fiber. 3% HEMA, 5 min soaking time, at the ninth pass of radiation, produced higher tensile strength (190%) and elongation at break (195%), than those of the virgin fiber, as well as the highest grafting value (4.2%). For further improvement of the mechanical properties, the fibers were treated with an alkali (KOH) solution of various concentrations for 1 h before curing. 10% alkali-treated fibers showed increased properties, such as grafting (5.4%), tensile strength (300%), and elongation at break (290%) over raw fiber. The treated fiber showed lower water uptake than the untreated ones. The grafted fibers were also characterized by IR and it was observed that HEMA deposited on the fiber surface may react with the cellulose backbone of the Henequen fibers.     

Epoxide‐terminated hyperbranched polyether sulphone as triple enhancement modifier for DGEBA

Epoxide‐terminated hyperbranched polyether sulphones (EHBPESs) with different backbone structures were synthesized and used as tougheners for diglycidyl ether of bisphenol‐A (DGEBA) curing system, which result in nonphase‐separated cured networks. Effects of backbone structure (at comparable degree of polymerization) and loading contents on the mechanical and thermal properties of cured hybrids were investigated. The hybrid containing EHBPES3, which has the most flexible backbone, shows the best mechanical performance and highest glass transition temperature (T_g). Compared with unmodified system, the impact strength, tensile strength, elongation at break of the hybrid containing 5% EHBPES3 increased by 69.8%, 9.4%, and 60.2%, respectively. The balanced improvements were attributed to the increased crosslink density and fractional free volume as well as the unique inhomogeneous network structure because of incorporation of hyperbranched modifiers with proper structure and loading contents. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41910.     

Effect of carbon nanotube on cured shape of cross-ply polymer matrix nanocomposite laminates: analytical and experimental study

Cured shape of cross-ply [0₂/90₂]_T fiber-reinforced composite laminates and the effect of multi-wall carbon nanotubes (MWCNTs) on the mechanical and thermal properties of laminates have been investigated. The nanocomposite laminate used in this study is composed of three phases: carbon fiber, polymer matrix and MWCNT. The volume fractions of 0%, 1%, 2% and 3% MWCNT were used to prepare nanocomposites. The mechanical and thermal properties of nanocomposites and fiber-reinforced nanocomposite laminates have been calculated by using analytical micromechanical models. Analytical micromechanical models were applied to determine the mechanical and thermal properties for two-phase nanocomposite composed of MWCNT and polymer matrix. The obtained mechanical and thermal data were considered as matrix properties and used in properties calculation of three-phase fiber-reinforced nanocomposite laminates. A developed model was used to determine curvature and the effect of MWCNT on the curvature in different specimens. Nonlinear relations have been considered for non-mid-plane strain equations. The addition of 1% volume fraction of MWCNT led to decreasing curvature and increasing critical size almost 14% and 9%, respectively, in different directions. The results were used to develop model and to compare with those calculated by Hyer model. Finally, unsymmetrical cross-ply [0₂/90₂]_T laminates with different weight fractions of 0, 0.1%, 0.25% and 0.5% MWCNT were fabricated. The curvature of cured composite laminates, obtained by experimental study, was compared with that developed as Hyer models and good agreements were observed between the predicted model and experimental data. The experimentally predicted and developed model for the curvature of cross-ply [0₂/90₂]_T fiber-reinforced nanocomposite laminates is better than the Hyer model.     

Flame retardant polyesters based on bromine derivatives

Unsaturated polyesters containing halogens in the backbone of the polymer chain were synthesized. Derivatives used had brominated functional groups such as tetrabromobisphenol A, tetrabromophthalic anhydride, and dibromoneopentyl glycol. These were compared to chlorine-containing polyesters based on HET acid and tetrachlorophthalic anhydride and an additive exhibiting a synergistic effect of phosphorus and halogen, trichloroethyl phosphate. Optical properties before and after artificial weathering (up to 1650 hr), were determined on cast specimens, and mechanical properties (flexural strength, modulus, and hardness) and flame retardancy were determined on glass fiber laminates. The flammability tests consisted of the “oxygen index” and the “self-extinguishing time” tests, which were correlated for various halogen concentrations and different compositions. The efficiency of bromine in flame retardancy has been found to be much higher than that of chlorine. The minimal concentration of bromine required for self-extinguishing is 10–12%, as compared with 20–25% for chlorine. A general performance index for polyesters has been derived which incorporates both flame and weather resistivity factors of the modified polyesters.     

A structure and property based process window for void free thermoset composites

A process window providing guidelines to minimize internal stress levels and to prevent void formation during cure of thermoset composite materials is presented. A model taking into account the applied pressure and the level of stress borne by the fiber assembly was introduced to calculate the hydrostatic internal stress state in the resin during cure. Based on the fundamental mechanisms of matrix shrinkage and evolution of viscoelastic properties under the given processing conditions, the internal stress in the resin was calculated as a function of fiber volume fraction, fiber stacking sequence, applied pressure and resin conversion. This level of stress is compared to a criterion for void initiation in the resin. A process window was hence constructed for preventing void formation during cure. Composite laminates with different stacking sequences and fiber volume fractions were cured with different applied pressures within and out of the process window boundaries. The composite void contents were measured and correlated perfectly with the process boundaries. This process window construction taking into account the material vis‐coelastic properties and the composite architecture is a unique tool for determining optimum process condition of composite laminates.     

Solid state bonding of graphite/thermoset composites via interchain transesterification reaction (ITR)

Thick section composite laminates are expensive and difficult to manufacture because of problems with porosity, large reaction exotherms from epoxies and residual strains. The copolyester thermosets described here can eliminate these problems. Through interchain transesterification reactions, individually cured prepreg plies of graphite reinforced copolyester can be bonded with each other in the solid state. ITR bonding is shown to produce well‐consolidated laminates with less than 2% void volume and mechanical properties comparable to those of current high‐end polymer matrix composites. DMA testing showed the glass transition to begin at 190°C for a 45% fiber volume fraction composite. Tensile testing of 55% fiber volume composites at room temperature showed modulus, strength and elongation to failure averages of 105.4 GPa, 1.02 GPa and 1.0% respectively.     

Synthesis,characterization, thermal,and viscoelastic properties of an unsaturated epoxy polyester cured with different hardeners

The chemical modification of the structure of the unsaturated polyester obtained in poly condensation process of 1,2,3,6‐tetrahydrophthalic anhydride, maleic anhydride, and ethylene glycol by well known conventional method of epoxidation with peracetic acid in mild conditions has been presented. The new material containing both epoxy groups and unsaturated double bonds in polyester chain was characterized by FTIR and ¹H NMR spectra. The prepared unsaturated epoxy polyester was suitable material for further chemical modification. Both epoxy groups and unsaturated double bonds can be used as cross‐linking sites. Curing behavior, thermal, and visco‐elastic properties of the unsaturated epoxy polyester cured with different hardeners: 1,2,3,6‐tetrahydrophthalic anhydride (THPA), hexahydrophthalic anhydride (HHPA), and/or with vinyl monomer (styrene) using radical initiator—benzoyl peroxide (BPO) were studied by differential scanning calorimetry (DSC), thermo gravimetric analysis (TGA), and dynamic mechanical analysis (DMA). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The comparison of low‐velocity impact resistance of aluminum/carbon and glass fiber metal laminates

This article presents the low‐velocity impact response of fiber metal laminates, based on aluminum with a polymer composite, reinforced with carbon and glass fibers. The influence of fiber orientations as well as analysis of load‐time history, damage area and damage depth in relation to different energy levels is presented and discussed. The obtained results made it possible to determine characteristic points, which may be responsible for particular stages of the laminate structure degradation process: local microcracks and delaminations, leading to a decrease in the stiffness of the laminate, as well as further damage represented by laminate cracks and its perforation. The damage mechanism of fiber metal laminates is rather complex. In case of carbon fiber laminates, a higher tendency to perforation was observed in comparison to laminates containing glass fibers. Delaminations in composite interlayers and at the metal/composite interface constitute a significant damage form of fiber metal laminates resulting from dynamic loads. Fiber metal laminates with glass fibers absorb energy mainly through plastic deformation as well as through delamination initiation and propagation, whereas laminates containing carbon fibers absorb energy for penetration and perforation of the laminate. POLYM. COMPOS. 37:1056–1063, 2016. © 2014 Society of Plastics Engineers     

Properties of carbon fiber composite laminates fabricated by coresin film infusion process for different prepreg materials

A new cocured process called coresin film infusion (co‐RFI) process, which combines RFI process and prepreg/autoclave process, was introduced and four kinds of commercial carbon fiber prepreg material systems and a kind of resin film were applied to fabricate co‐RFI laminates. The compatibility between the resin film and the prepreg matrix and the application of co‐RFI process were investigated based on the resin flowability, glass transition temperature of cured resin, processing quality of laminate, and variation in resin modulus on cocured interphase region measured by nanoindentation. Furthermore, mode I (G_IC), mode II (G_IIC) delamination fracture toughness, and flexural strength and modulus were measured to evaluate the mechanical properties of cocured laminates with different prepreg materials. The experimental results show that thickness and fiber volume fraction of co‐RFI laminates with the four kinds of prepreg materials are similar to those of prepreg laminates and RFI laminate with acceptable differences. In addition, there are no obvious defects in co‐RFI laminates. Moreover, the reduced modulus of resin at cocured interface and glass transition temperature values of the mixed resin reflect good compatibility between prepreg matrix resin and RFI resin. The G_IC, G_IIC values, and flexural performances of cocured laminates lie between and even exceed those of prepreg laminates and RFI laminates, indicating no weakening effect in the cocured interface. Therefore, the co‐RFI process is believed to effectively fabricate composite with low cost and it can be applied using various prepreg systems. POLYM. COMPOS., 34:2008–2018, 2013. © 2013 Society of Plastics Engineers     

Numerical simulation of two‐dimensional flow and compaction during the consolidation of laminated composites

A new special finite element formulation and code are developed to simulate the two‐dimensional flow and compaction process during the autoclave processing of complex fiber‐reinforced thermosetting composite laminates. The numerical model is based on the Biot's consolidation principle, the fluid continuity equation, and Darcy's law. The simulation is performed for Hercules AS4/3501‐6 laminates and the predicted results are in good agreement with the results available in the literature. The laminate thickness and fiber volume fraction distribution of cured laminates are investigated from both the experiments and the simulations for T700S/5228 laminates. The simulations and experimental results are in good agreement for all the studied cases. A significantly uneven degree of consolidation along the laminate thickness direction is observed, and it is necessary to optimize the cure cycle to get uniformly compact and good quality laminates. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Epoxy resin from cardanol as partial replacement of bisphenol-A-based epoxy for coating application

With continuous depletion of petrochemical feedstock and their rising prices, the chemical industry is now looking for alternative renewable and sustainable materials. Such materials could be processed with various chemistries to produce high performance functional materials for a range of applications, such as plastics, coatings, constructions, pharmaceuticals, and food applications. Cardanol derived from cashew nut shell liquid has a reactive phenolic group and aliphatic double bond that could be exploited to produce novel functional materials for polymer and coating applications. It has previously been used for preparation of phenolics, epoxy, and phenalkamine hardeners. In this study, we report on the preparation of novel epoxy resin from cardanol via simple a two-step reaction. The prepared resin with epoxy equivalent weight of 210–220 gm/eq was analyzed using FTIR and NMR spectroscopy. The epoxy resin was then used as binder along with bisphenol-A-based epoxy resin (DGEBPA) at various weight proportions and cured with different amine hardeners. The cured coatings were analyzed for physical, mechanical, and chemical properties for optimization of the coating formulation. The study conducted showed that 40–60% of DGEBPA resulted in comparable properties to that of completely DGEBPA-based system. Further, thermal and anticorrosive properties of the optimized coatings were also evaluated.