Cure behaviour of epoxy resin matrices for carbon fibre composites

The cure behaviour of two resin formulations (with high and low curing agent content respectively) of an epoxy resin system, used as matrix for carbon fibre composites, was studied through calorimetric analysis. The aim of this work is to investigate the kinetics of this specific epoxy system in order to be able to choose a proper set of processing parameters which will give good composite material properties. The shape of the conversion curves gives evidence of the differences in the cure kinetics of the two systems. Furthermore, the values of the activation energies were determined both for formulation in the conversion range where vitrification occurs, following a phenomenological approach. These values give an indication of the differences in the curing mechanisms, when varying the content of curing agent. In particular, for both systems, the same reaction represents the onset of the cure process, ie the autocatalytic epoxy ring opening through addition reaction to the primary amine. This reaction dominates the entire cure process of the epoxy formulation at high curing agent content. Conversely, in the formulations with a low curing agent content, after depletion of the primary amines, different reactions may take place (with secondary amines and hydroxyl groups), depending on the cure temperature and the resin viscosity. © 1999 Society of Chemical Industry     

Influence of carbon fibre orientation on reaction‐to‐fire properties of polymer matrix composites

The influence of the orientation of carbon fibres on the reaction‐to‐fire characteristics of a layered composite has been investigated in detail. 8552/IM7 prepregs were laid up to give unidirectional and quasi‐isotropic laminates. Specimen thickness (0.25 to 8.0 mm) and heat flux (15 to 80 kW/m²) were varied for irradiation. Fundamental reaction‐to‐fire properties of this composite are interpreted on the basis of the matrix components: epoxy resin and polyethersulfone. Cone calorimetry and temperature distributions through the laminate showed that the velocity and degree of combustion are dominated by fibre orientation for a given resin. In general, a quasi‐isotropic fibre orientation leads to faster ignition, because of preferred delaminations, but retards combustion processes more effectively than a unidirectional lay‐up. Migration velocities of the pyrolysis zone were measured. Copyright © 2011 John Wiley & Sons, Ltd.     

Carbon fibre reinforced epoxy composites

Carbon fibre reinforced epoxy composites were fabricated from the matrix resin diglycidyl ether of bisphenol-A and novel tetrafunctional epoxy resins N,N,N′,N′-tetraglycidyl-2,2-bis[4-(4-aminophenoxy)phenyl]propane and N,N,N′N′-tetraglycidyl-1,1 ′-bis[4-(4-aminophenoxy)phenyl]cyclohexane using diaminodiphenyl methane as curing agent. Mechanical properties and chemical resistance of the composites were determined. Significant improvements in the mechanical properties were observed by adding epoxy fortifier to the resin-curing agent mixtures before fabrication of composites.     

Mechanical and viscoelastic properties of butadiene–styrene thermoplastic and oxidized carbon fibre composites

The mechanical and dynamic properties of oxidized carbon fibre and butadiene–styrene thermoplastic elastomer (SBS) composites were studied as a function of the level of fibre oxidation and in comparison with the properties of composites reinforced with untreated commercial carbon fibre. As a general rule, fibre oxidation gives rise to materials with improved mechanical properties—greater tensile and tear strengths. The improvements accomplished depend on the degree of fibre oxidation. The effects of long exposure times to oxidizing agents were tested on the experimental samples, i.e. increase in the number of functional surface groups and loss in mechanical strength due to a decrease in the L/d ratio, properties which act in opposite directions in the composite. Storage modulus retention with increasing strain amplitude is directly proportional to the number of functional groups incorporated into the fibre surface, whereas at low strain amplitude it is proportional to fibre strength, measured in terms of the L/d ratio after processing. It is suggested that improved adhesion at the matrix–fibre interface is obtained through the functional groups of the oxidized fibre. As a consequence of fibre–matrix interface and at any frequency, the damping peak temperature is shifted towards higher ranges and at the same time the apparent activation energy of the relaxation process is observed to increase.     

Preparation of polyetherimide/carbon fibre composites by a cataphoresis process

Preliminary results in this study show that it is possible to achieve a good Ultem 1000/carbon fibres covering by means of electrophoretical deposition. The expected amount of deposited polymer is well controlled and the deposited films have a good appearance. In this way a variety of carbon fibre composite materials can be manufactured. © 1999 Society of Chemical Industry     

Characterization of epoxy–clay hybrid composite prepared by emulsion polymerization

This article demonstrates the direct intercalation of an epoxy polymer in the interlayer of Na⁺–montmorillonite (MMT) by a step type of polymerization in an aqueous emulsion media. The synthesis and the results of structural and thermal characterizations for this hybrid composite are described. Equimolar quantities of bisphenol A and an epoxy prepolymer (n = 0.2) in an emulsion media were polymerized in the presence of Na⁺–MMT. X-ray diffraction (XRD) data obtained from the acetone-extracted products show that the basal spacing of the MMT is expanded from 0.96 to 1.64 nm. Thermal characterization for the postcured products by TGA and DSC gave evidence of enhanced thermal stabilities. SEM examination of the uncured products revealed that a disordered phase begins to appear with increasing polymer loading. However, the XRD profile supported that an overwhelming fraction of the nanocomposite contains intercalated clay. Also, the possibility of intercalation by the emulsion technique is proposed on the basis of the swelling characteristics of MMT in aqueous media and the sizes of micelles containing a monomer. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1997–2005, 1998     

Glass fibre reinforced composites of triglycidyl-p-aminophenol

Glass fibre reinforced epoxy composites were fabricated from the matrix resins diglycidyl ether of bisphenol A (DGEBA) and triglycidyl-p-aminophenol (TGAP) using diethylene triamine as curing agent. The epoxy laminates were evaluated for their mechanical properties, dielectrical properties and chemical resistance. Significant improvement in fiexural strength but a slight deterioration in dielectrical properties were observed on incorporation of an epoxy fortifier into the resin system before fabricating the composites.     

Preparation and properties of multiwalled carbon nanotube/epoxy‐amine composites

Different amounts of multiwalled carbon tubes (MWCNTs) were incorporated into an epoxy resin based on diglycidyl ether of bisphenol A and both epoxy precursor and composite were cured with 4,4′‐diamino diphenyl sulfone. Transmission and scanning electron microscopy demonstrated that the carbon nanotubes are dispersed well in the epoxy matrix. Differential scanning calorimetry measurements confirmed the decrease in overall cure by the addition of MWCNTs. A decrease in volume shrinkage of the epoxy matrix caused by the addition of MWCNTs was observed by pressure–volume–temperature measurements. Thermomechanical and dynamic mechanical analysis were performed for the MWCNT/epoxy composites, showing that the T_g was slightly affected, whereas the dimensional stability and stiffness are improved by the addition of MWCNTs. Electrical conductivity measurements of the composite samples showed that an insulator to conductor transition takes place between 0.019 and 0.037 wt % MWCNTs. The addition of MWCNTs induces an increase in both impact strength (18%) and fracture toughness (38%) of the epoxy matrix with very low filler content. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Surface‐initiated atom‐transfer radical polymerization (SI‐ATRP) of methyl methacrylate from carbon fibre

Surface modification of carbon fibre (CF) by well‐defined polymer brushes was carried out using the ‘grafting from’ method. Poly(methyl methacrylate)‐grafted carbon fibre (CF‐PMMA) was successfully prepared by surface‐initiated atom‐transfer radical polymerization (SI‐ATRP) of methyl methacrylate (MMA) from the macro‐initiator, bromo‐acetic ester‐modified carbon fibre (CF‐BrA), with the complex of 1,10‐phenanthroline and Cu(I)Br as catalyst. The percentage of grafting (PG%) and the conversion of monomer (C%) increased linearly with increasing of polymerization time, and reached 24.0 % and 6.7 %, respectively, after a polymerization time of 6 h, calculated from the elemental analyses (EA). The structural and surface morphological analyses were conducted with Fourier‐transform infrared (FTIR) spectroscopy, X‐ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Copyright © 2005 Society of Chemical Industry     

热引发前线聚合法固化脂环族环氧树脂

采用热引发前线聚合（TFP） 方法固化了脂环族环氧树脂（221树脂）,研究了固化剂用量、预热温度和反应器倾斜角度等因素对聚合前线的推动速率和前线温度的影响,并利用FTIR、DSC、TG等手段对固化物结构和热性能进行了表征。研究结果表明,固化剂用量越大或预热温度越高,引发前线聚合反应所需的时间越短,前线推动速率V_f 越快,前线最高温度T_max 越高,达到最高前线温度所需时间越短;试管倾斜一定角度后,下行前线方向发生偏离,V_f有所下降;FTIR测试结果表明,采用TFP法得到的环氧固化物与采用传统热固化工艺得到的固化物有相似的红外吸收,DSC和TG测试结果表明前线聚合产物具有更高的玻璃化温度和更好的热稳定性。     

Study on spatial–temporal kinetics of photo‐initiated frontal polymerization in stacked reaction cells

The spatial–temporal kinetics for photo‐initiated frontal polymerization(PFP) of isobornyl acrylate with 2,4,6‐trimethylbenzoyldiphenyl phosphine oxide (TPO) as photobleaching initiator was studied experimentally in stacked reaction cells. FTIR and NMR spectroscopy were employed to measure the polymerization conversion, which is dependent on the exposure time, sample depth, light intensity and photo‐initiator concentration. The experimental results are consistent with the theoretical model prediction and show that prolonged irradiation time, higher light intensity and lower photo‐initiator concentration are favorable in enhancing the advance of the polymerization front. The depth‐resolved GPC analysis shows that the average molecular weight of the PFP product dramatically increases with sample depth, while the molecular weight polydispersity reduces steadily with increase in sample depth. Copyright © 2006 Society of Chemical Industry     

Surface modification of single‐walled carbon nanotubes with polyethylene via in situ Ziegler–Natta polymerization

Single‐walled carbon nanotubes (SWNTs) were modified with polyethylene (PE) prepared by in situ Ziegler–Natta polymerization. Because of the catalyst pretreated on the surface of the SWNTs, the ethylene was expected to polymerize there. Scanning electron microscopy images and solubility measurements showed that the surface of the SWNTs was covered with a PE layer, and a crosslink may have formed between the SWNTs and PE. When the SWNTs covered with a PE layer were mixed with commercialized PE by melt blending, the resulting composite had better mechanical properties than the composite from the SWNTs without a PE layer. The yield strength, the tensile strength and modulus, the strain at break, and the fracture energy of the modified‐SWNT/PE composites were improved by 25, 15.2, 25.4, 21, and 38% in comparison with those of the raw‐SWNT/PE composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3697–3700, 2004     

The effect of hydroxyl‐terminated polybutadiene‐grafted carbon fiber on the impact performance of carbon fiber–epoxy resin composites

Carbon fiber (CF) containing 1.4 and 2.1 mmol/g of —COOH and —OH groups, respectively, was functionalized by using an excess of tolylene‐2,4‐diisocyanate. The NCO‐modified CF was submitted to a graft reaction with hydroxyl‐terminated polybutadiene (HTPB). The HTPB‐grafted carbon fiber was employed as reinforcing agent for epoxy resin‐based composites. The presence of the flexible HTPB at the interface between the fiber and the matrix resulted in a substantial improvement on impact strength. Additional improvement on toughness was achieved by using epoxy matrix containing dispersed phase of HTPB. The composite morphology was also studied by scanning electron microscopy. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1424–1431, 1999     

Electrical and electromagnetic shielding behavior of laminated epoxy–carbon fiber composite

This paper reports results on the electrical properties of laminated epoxy composite containing 25 layers of carbon fibers in the form of mats. The dependence of the activation energy (calculated from DC resistivity measurements) on temperature reveals two independent conduction processes. The AC impedance is independent of the applied frequency below 75°C, and the real componet of the dielectric constant is also independent of temperature at high frequencies. The determined shielding effectiveness is dominated by the insertion loss. The observed optimum shielding effectiveness occurs at 30 mm spacing and applied frequency 9 GHz.     

Sensing behaviors of polymer/carbon nanotubes composites prepared in reversed microemulsion polymerization

Polystyrene/carbon nanotubes composites were readily prepared by reversed microemulsion polymerization. Compared with the composites prepared by solution mixing, the uniform dispersion of carbon nanotubes in polymer matrix could be obtained more easily and the thermal and electrical properties of the as‐prepared composites were also enhanced. The as‐prepared composites were deposited onto a microelectrode array to fabricate a vapor sensor. The response for different organic vapors was evaluated by monitoring the change in the resistance of the composites upon exposure to various gases. The change in resistance was of the order of about 10³ for the composites prepared by reversed microemulsion polymerization. The chemical sensors based on the composites prepared by reversed microemulsion polymerization presented excellent reproducibility and reversibility in response. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Mechanical and anticorrosion properties of furan/epoxy‐based basalt fiber‐reinforced composites

A furan/epoxy blend applicable to composite manufacture was studied and corresponding basalt fiber‐reinforced composites were prepared. The processability, mechanical properties, and reasons for the improved mechanical properties of this blend were investigated by rheology machine, mechanical testing machine, and scanning electron microscopy. With excellent processability, furan/epoxy was suitable for manufacturing composites. Furan/epoxy with the ratio of 5/5 showed the best properties, and the impact strength, flexural strength and flexural modulus were 15.43 kJ/m², 102.81 MPa, and 3209.40 MPa, respectively. The river‐like fracture surface of the furan/epoxy system was well consistent with the mechanical properties. The mechanical and anti‐corrosive properties of basalt fiber‐reinforced furan/epoxy composites were also studied. The mechanical properties of composites changed the same as those of furan/epoxy matrix did. Furan resin effectively improved the anti‐acid but not anti‐alkali property of composites, probably because furan could be cured in acidic condition and basalt fiber was resistant to acid and alkali. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44799.     

Reaction‐to‐fire properties of polymer matrix composites with integrated intumescent barriers

The integration of an intumescent barrier between the plies of prepreg based polymer matrix composite and sandwich panels is investigated in detail with regard to reaction‐to‐fire properties. Incident heat flux, panel thickness and insertion depth within the panel were varied systematically. Fire retarding effects are compared to the application of an intumescent and top coating on the surface. All tests were carried out with a commercial material: HexPly® 8552/IM7 by Hexcel. Design rules for an effective improvement of reaction‐to‐fire properties are derived. Two practical applications were identified not interfering with mechanical properties: A metal mesh as support for the intumescent material underneath a single top ply and the one‐sided integration in a sandwich with the possibility to expand into the honeycomb. Degradation mechanisms are characterized by cone calorimetry and temperature development throughout the specimens. Copyright © 2014 John Wiley & Sons, Ltd.     

Bistability of propagating front with spin‐mode in a frontal polymerization of trimethylopropane triacrylate

We have studied a nonlinear dynamic behaviour in a frontal polymerization process. Frontal polymerization is a mode of converting a monomer into a polymer via a localized reaction zone that propagates as a front. Interest in studying the dynamic behaviour of such propagating fronts is growing. Many studies focus on the spin‐mode front propagation characterized by a nonplanar front having one or more high temperature regions which move in a helical path along the axis of the reaction vessel. In this study, the bistable character of the spin‐mode induced by reaction vessel diameter has been analyzed. First, a reactor with a discontinuously varying diameter for preliminary tests, and second, a conical reactor with a continuously varying diameter have been used. We have obtained evidence of bistability of the spin‐mode front in the frontal polymerization of trimethylopropane triacrylate under certain reaction conditions. Copyright © 2003 Society of Chemical Industry     

Protective coatings for carbon bonded carbon fibre composites

Carbon bonded carbon fibre composites (CBCF) were modified by direct reaction with molten silicon in order to obtain a silicon carbide layer on the composite surface. Subsequently, the Si-infiltrated CBCF material was coated with a silica-based glass containing yttria and alumina by means of a slurry-dipping technique. On heat treatment the glass yielded a glass-ceramic layer thus giving a multi-layered oxidation and erosion protection system. The microstructural characterisation of the coating was conducted by standard microscopy techniques and by X-ray diffraction. The controlled crystallization of the glass-produced cristobalite, yttrium silicate (Y₂Si₂O₇, keiviite, β-form) and mullite as main crystalline phases. These are excellent ceramic materials for oxidation and erosion protection of SiC-coated carbon-based composites since their coefficients of thermal expansion (CTE) closely match that of SiC. The possibility of healing (closure) of micro cracks by a thermal treatment at 1375 °C, thus exploiting the viscous flow of the residual glass in the glass-ceramic, was explored in order to extend the service life of the protection system.     

前端聚合的研究进展

前端聚合因具有简易、节能、反应速度快和独特的产物形貌等优点而受到越来越广泛的关注。本论文将前端聚合按照聚合方法分为3类：热前端聚合,光前端聚合和等温前端聚合,讨论了前端聚合的组成,综述了前端聚合的应用,前端聚合在功能材料、有机无机纳米复合材料和工业生产上将会得到广泛的应用。