Avoidance of fabricational thermal residual stresses in co-cure bonded metal-composite hybrid structures

In this work, a smart cure cycle with cooling, polymerization and reheating was devised to nearly completely eliminate thermal residual stresses in the bonding layer of the co-cure bonded hybrid structure. In situ dielectrometry cure monitoring, DSC experiments and rheometric measurements were performed to investigate the physical state and the cure kinetics of the neat epoxy resin in the carbon fiber/epoxy composite materials. From the experimental results, an optimal cooling point in the cure cycle was obtained. Also, process parameters such as cooling rate, polymerization temperature and polymerization time in the curing process were investigated. Then, the thermal residual stresses were estimated by measuring the curvatures of co-cure bonded steel/composite strips and their effects on the static lap-shear strengths of co-cure bonded steel/composite lap joints were measured. Also, the effects of thermal residual stresses on the tensile strength, the interlaminar shear strength and the interlaminar fracture toughness of the composite material itself were measured using tensile, short beam shear and double cantilever beam tests. From these results, it was found that the smart cure cycle with cooling, polymerization and reheating eliminated the thermal residual stresses completely and improved the interfacial strength of the co-cure bonded hybrid structures, as well as the tensile strength of the composite structures.     

Mechanical properties of graphene nanoplatelet/epoxy composites

Because of their high‐specific stiffness, carbon‐filled epoxy composites can be used in structural components in fixed‐wing aircraft. Graphene nanoplatelets (GNPs) are short stacks of individual layers of graphite that are a newly developed, lower cost material that often increases the composite tensile modulus. In this work, researchers fabricated neat epoxy (EPON 862 with Curing Agent W) and 1–6 wt % GNP in epoxy composites. The cure cycle used for this aerospace epoxy resin was 2 h at 121°C followed by 2 h at 177°C. These materials were tested for tensile properties using typical macroscopic measurements. Nanoindentation was also used to determine modulus and creep compliance. These macroscopic results showed that the tensile modulus increased from 2.72 GPa for the neat epoxy to 3.36 GPa for 6 wt % (3.7 vol %) GNP in epoxy composite. The modulus results from nanoindentation followed this same trend. For loadings from 10 to 45 mN, the creep compliance for the neat epoxy and GNP/epoxy composites was similar. The GNP aspect ratio in the composite samples was confirmed to be similar to that of the as‐received material by using the percolation threshold measured from electrical resistivity measurements. Using this GNP aspect ratio, the two‐dimensional randomly oriented filler Halpin–Tsai model adjusted for platelet filler shape predicts the tensile modulus well for the GNP/epoxy composites. Per the authors' knowledge, mechanical properties and modeling for this GNP/epoxy system have never been reported in the open literature. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Cure kinetic study of carbon nanofibers/epoxy composites by isothermal DSC

An investigation was carried out into the cure kinetics of carbon nanofibers (CNF)/epoxy composites, composed of tetraglycidyl‐4,4′‐diaminodiphenylmethane (TGDDM) resin and 4,4′‐diaminodiphenylsulfone (DDS) as a curing agent. The experimental data for both neat system and CNF/epoxy composites revealed an autocatalytic behavior. Analysis of DSC data indicated that the presence of carbon nanofibers had only a negligible effect on the cure kinetics of the epoxy. Kinetic analysis was performed using the phenomenological model of Kamal and two diffusion factors were introduced to describe the cure reaction in the latter stage. Activation energies and kinetic parameters were determined by fitting experimental data. Comparison between the two diffusion factors was performed, showing that the modified factor was successfully applied to the experimental data over the whole curing temperature range. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 329–335, 2005     

The sonication effect on CNT‐epoxy composites finally clarified

Carbon nanotube‐epoxy composites were prepared using amino‐functionalized CNTs and sonication as a mixing process. Different times and sonication powers were used for preparing composites in order to study how the sonication process may influence the curing reaction of both systems: neat epoxy resin and amino‐CNT/epoxy composite.The curing reaction was investigated with differential scanning calorimetry and the results were associated with analysis of gel permeation chromatography. The results showed that the effect of CNTs on the cure behavior of the epoxy resin depends on the sonication power. The sonication of neat resin with a 150 W powered device led to a molar mass reduction of the resin and an increase in the cure enthalpy. The CNT addition to this system reduced the cure enthalpy. However, when neat epoxy resin was sonicated with a 200 W powered device, the molar mass did not decrease (i.e., it was increased or was not changed) and the cure enthalpy did not increase (essentially it decreased or did not change). The CNT addition to such solutions did not reduce (i.e., it was increased or did not change) the cure enthalpy, which is a contrary result from that obtained with a 150 W powered device. POLYM. COMPOS., 38:1964–1973, 2017. © 2015 Society of Plastics Engineers     

Effects of carbon nanotube fillers on the curing processes of epoxy resin‐based composites

The effects of different grades of carbon nanotubes on the curing of a typical epoxy resin (EPIKOTE? resin 862 and EPIKURE? curing agent W) were examined via differential scanning calorimetry. It was found that nanotubes could initiate cure at lower temperatures, while the overall curing process was slowed as evidenced by lower total heat of reaction and lower glass transition temperatures of the cured nanocomposites compared to neat epoxy. This finding is practically important as it is essential to have a consistent degree of cure when the properties of thermosets with nanoinclusions are compared to neat resins. It was also found that the inclusion of carbon nanotubes might induce the thermal degradation of epoxy composites at lower temperatures. Morphological analysis done with scanning electron microscopy revealed good dispersion of nanotubes within the epoxy matrix. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:5248–5254, 2006     

Phthalonitrile‐epoxy blends: Cure behavior and copolymer properties

Binary blends composed of 4,4′‐bis(3,4‐dicyanophenoxy)biphenyl (biphenyl PN) and diglycidyl ether of bisphenol A (epoxy resin) and oligomeric n = 4 phthalonitrile (n = 4 PN) and epoxy resin were prepared. The cure behavior of the blends was studied under dynamic and isothermal curing conditions using differential scanning calorimetry, simultaneous thermogravimetric/differential thermal analysis, infrared spectroscopy, and rheological analysis. The studies revealed that phthalonitrile‐epoxy blends exhibited good processability and that they copolymerized with or without the addition of curing additive. In the absence of curing additive, the blends required higher temperatures and longer cure times. The thermal and dynamic viscoelastic properties of amine‐cured phthalonitrile‐epoxy copolymers were examined and compared with those of the neat epoxy resin. The properties of the epoxy resin improved with increasing biphenyl PN content and with n = 4 PN addition. Specifically, the copolymers exhibited higher glass transition temperatures, increased thermal and thermo‐oxidative stabililty, and enhanced dynamic mechanical properties relative to the commercially available epoxy resin. The results showed that the phthalonitrile‐epoxy blends and copolymers have an attractive combination of processability and high temperature properties. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Analysis of the cure reaction of carbon nanotubes/epoxy resin composites through thermal analysis and Raman spectroscopy

The effect of the incorporation of single‐walled carbon nanotubes (SWNTs) onto a diglycidyl ether of bisphenol A‐based (DGEBA) epoxy resin cure reaction was investigated by thermal analysis and Raman spectroscopy. The results of the investigation show that SWNTs act as a strong catalyst. A shift of the exothermic reaction peak to lower temperatures is, in fact, observed in the presence of SWNTs. Moreover, these effects are already noticeable at the lowest SWNT content investigated (5%) with slight further effects at higher concentrations, suggesting a saturation of the catalyzing action at the higher concentrations studied. The curves obtained under isothermal conditions confirm the results obtained in nonisothermal tests showing that the cure reaction takes less time with respect to the neat epoxy. The thermal degradation of cured DGEBA and DGEBA/SWNT composites was examined by thermogravimetry, showing a faster thermal degradation for DGEBA–SWNT composites. Raman spectroscopy was successfully applied to demonstrate that the observed changes in the cure reaction of the composites lead to a different residual strain on the SWNT bundles following a different intercalation of the epoxy matrix. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 452–458, 2003     

Utilization of flyash as filler for polybutyleneterepthalate‐toughened epoxy resin

Flyash, a waste product generated in large quantities in thermal power plants, has been posing problems of disposal. The purpose of the present work was to make a meaningful utilization of flyash as filler in neat epoxy resin matrix and 2% Polybutyleneterepthalate (PBT)/epoxy blend matrix. For this purpose, the tensile, flexural, compression, impact, chemical resistance, and water absorption properties were studied. Composites were made with varying proportion of flyash in epoxy resin and 2% PBT/epoxy blend matrix. Tensile, flexural, and compression properties were measured on a computerized universal testing machine, according to ASTM procedures. Impact strength was determined using izod impact tester for un‐notched specimens. PBT (2%)/epoxy blend matrix composites showed improved mechanical properties over neat epoxy flyash composites. All the composites were found to have good chemical resistance toward acids, solvents, and alkalies. These composites showed better water resistance over neat epoxy flyash composites. POLYM. ENG. SCI. 46:946–953, 2006. © 2006 Society of Plastics Engineers     

Effect of cyanate ester on the cure behavior and thermal stability of epoxy resin

Epoxy resin (diglycidyl ether of bisphenol A, DGEBA)/cyanate ester mixtures were cured with a curing agent, 4,4′-diaminodiphenylsulfone, and the effect of cyanate ester resin on the cure behavior and thermal stability in the epoxy resin was investigated with a Fourier transform infrared spectrometer, a rheometer, a dynamic mechanical analyzer, and a thermogravimetric analyzer. Cure reactions in the epoxy/cyanate ester mixture were faster than that of the neat epoxy system. The cure reaction was accelerated by increasing the cyanate ester resin component. Glass transition temperature and thermal stability in the cured resins were increased with increasing cyanate ester resin component. This may be caused by the increase of crosslinking density due to the polycyclotrimerization of the cyanate ester monomer to form triazine rings and the reaction of cyanate ester resin with the epoxy network. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 85–90, 1997     

Carbon fiber cardanol-epoxy composites

Carbon fiber composites based on tetrafunctional epoxy resin N,N,N′,N′-tetraglycidyl-2,2-bis[4-(4-aminophenoxy)phenyl]propane modified with cardanol were investigated. The differential scanning calorimetric technique was used to study the curing reaction of the neat resins. The dielectric properties of the composites were compared. The use of cardanol in epoxy resins at cardanol/epoxy molar ratios less than 0.3/1 improved the chemical resistance as well as the mechanical properties of the composites, such as the flexural strength and modulus, tensile strength and modulus, and interlaminar shear strength. Higher cardanol contents decreased such properties. The highest properties of the composites were observed with the epoxy-cardanol resin having a cardanol/epoxy molar ratio of 0.3/1. © 1996 John Wiley & Sons, Inc.     

Low-temperature fast curable behavior and properties of bio-based carbon fiber composites based on resveratrol

Environmentally friendly materials are an integral part of sustainable chemistry, and bio-based polymer composites are an important class of materials. The manufacture of composites is expected to reduce or even eliminate the use of adjuvants, considering the importance of reducing energy consumption and avoiding health and environmental risks. In this study, a phenyl-containing, polyfunctional, bio-based epoxy resin (TGER) was synthesized, and carbon fiber-reinforced, bio-based epoxy resin composites were fabricated by vacuum-assisted resin infusion using two aromatic amine curing agents, 4,4′-diaminodiphenylmethane (DDM) and 3,3′-diethyl-4,4′-diaminodiphenylmethane (DEDDM). Curing reactions and rheological behavior studies showed that TGER had higher curing reactivity toward DDM and DEDDM than to diglycidyl ether of bisphenol A (DGEBA) and possessed good processability. The results indicated that the resveratrol-based epoxy resin displayed low-temperature fast curing properties. The evaluation of the mechanical properties of the carbon fiber composites showed that the flexural strengths of CF/TGER/DDM and CF/TGER/DEDDM were 520 and 628 MPa, respectively. The initial decomposition temperature of CF/TGER composites is above 200°C. Furthermore, the carbon fiber–reinforced biopolymers possess excellent heat resistance. Therefore, carbon fiber-reinforced, resveratrol-based epoxy resin composites are promising candidates as alternatives to petroleum-based high-performance carbon fiber composites.     

四氨酯化合物的合成及其对液体双酚A环氧树脂的流变控制及固化性能的影响

利用羟基(-OH)和异氰酸酯基(-NCO)的简易反应合成了含4个氨酯键(-NHCOO-),两端基为十六碳烷链(-C16H33)的四氨酯化合物,并用作液体双酚A环氧的流变改性剂。利用傅里叶红外(FTIR)、差示量热扫描仪(DSC)、偏光显微镜和扫描电镜(SEM)对四氨酯化合物及其环氧复配物进行了表征分析。通过流变仪、动态力学分析仪(DMA)及万能试验机等对环氧复配物的流变性及其固化物性能进行了研究。结果表明,四氨酯化合物借助氢键作用和范德华力可在液体环氧基体中自组装形成合适及可控的分子聚集体形态,从而实现对液体环氧复配物流变性的有效控制。5%的四氨酯化合物可使环氧复配物拥有与含10%工业用气相二氧化硅(RY200)的环氧复配物一样的触变性。同时,四氨酯化合物的相变特性使其环氧复配物的流变性具有热可逆性。另外,环氧固化性能受四氨酯化合物影响较小。     

Wavelength‐shift fluorescent probes for monitoring of polymerization

The feasibility of using wavelength‐shift fluorescent probes for cure monitoring of an epoxy resin and an acrylic resin was evaluated. 4‐(N,N‐dihexylaminostyryl)‐4′‐pyridinium propylsulfonate (DHASP‐PS), as well as each of other wavelength‐shift fluorescent probes, was dissolved in the epoxy resin, a stoichiometric mixture of diglycidyl ether of bisphenol A and 4,4′‐methylene‐bis(cyclohexylamine). The fluorescence and the excitation spectra of each of the probes dissolved in the epoxy resin were then measured at various times during the cure of the epoxy resin at 60°C. The fluorescence and the excitation spectra of the probe DHASP‐PS dissolved in methyl methacrylate (MMA) were also measured at various times during the cure of the acrylic resin at 55°C. Since the peak fluorescence wavelength of each of the wavelength‐shift fluorescent probes decreased during the cure of the epoxy resin or MMA, these fluorescent probes can be used for monitoring the polymerization reactions of epoxy resins and vinyl resins. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 747–750, 2006     

Bisphenol A dicyanate–novolac epoxy blend: Cure characteristics,physical and mechanical properties,and application in composites

Reactive blends of bisphenol A dicyanate (BACY) and a novolac epoxy resin (EPN) were investigated for their cure behavior and the mechanical, thermal, and physical properties of the cocured neat resin and glass‐laminate composites. Contrary to the apparent observation in DSC, the dynamic mechanical analysis confirmed a multistep cure reaction of the blend, in league with an established reaction path for similar systems. The cured matrix was found to contain both polycyanurate and oxazolidinone networks that existed in discrete phases exhibiting independent glass transitions in dynamic mechanical analysis (DMA). The flexible and less crosslinked oxazolidinone network contributed to enhanced flexural strength at the cost of the tensile strength of the neat resin. The increased resin flexibility was, however, not translated to the glass‐laminate composite for which the flexural strength decreased with the oxazolidinone content, although the latter was conducive for rendering a stronger interphase. The presence of oxazolidinone adversely affected the thermal stability of the cured resin and the high‐temperature performance of both neat resin and the composites. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1675–1685, 1999     

Experimental characterization of a curing thermoset epoxy‐anhydride system—Isothermal and nonisothermal cure kinetics

This work describes in detail the kinetic model for the cure of an epoxy‐anhydride thermoset matrix resin system. The cure kinetics in both nonisothermal and isothermal modes has been characterized using differential scanning calorimetry. The Sestak–Berggren two‐parameter autocatalytic model was used to describe the nonisothermal cure behavior of the resin satisfactorily. The isothermal cure data was fitted with Kamal's four‐parameter autocatalytic model, coupled with a diffusion factor. These characterization data will form material property inputs for a multiscale modeling framework for the estimation of cure‐induced residual stresses in thick thermoset matrix composites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Microstructural effects and the toughening of thermoplastic modified epoxy resins

We have studied an epoxy resin formulation consisting of the diglycidyl ether of bisphenol-A (DGEBA), modified with phenolic hydroxyl-terminated polysulfone (PSF) and cured with an aromatic amine curing agent, diaminodiphenyl sulfone (DDS). A range of microstructures and fracture properties have been obtained by controlling the formulation cure conditions (cure temperature and cure cycle in an isothermal mode). The chemical conversion of the cured resins has been monitored by near-infrared spectroscopy (NIR). Although only a single material formulation was used, three distinct types of microstructure were identified by scanning electron microscope (SEM) observations on samples prepared at different cure temperatures. Surprisingly, the thermal and fracture properties of the cured samples did not vary noticeably, in spite of the significant microstructure variations. The consistency of these fracture toughness results with cure temperature changes was an unexpected result in the light of our earlier observations of a strong dependence of fracture toughness on cure temperature in neat resin systems. The difference in behavior between neat and modified resins reveals that the fracture toughness of the latter is dependent on a combination of the microstructure and the matrix resin properties. This hypothesis was also supported by an observation of high fracture thoughness in a sample cured in a two-step process, which we believe is due to the optimum microstructure and matrix resin properties, being achieved separately during precure and postcure, respectively. The increase in fracture toughness values caused by the modification (ΔG_IC) was calculated from the fracture toughness values of neat and modified resins, prepared under the same cure conditions, using a proposed theoretical equation. © 1993 John Wiley & Sons, Inc.     

Effects of resin storage aging on rheological property and consolidation of composite laminates

The ability to predict the viscosity of thermoset resin is important to understand the manufacturing process of composites and optimize the processing parameters. During resin or prepreg storage course, the cure reaction may happen and the degree of cure increases gradually. The storage aging effect reduces the fluidity of resin, and hence alters the processability of resin. In this article, the rheological properties of an epoxy resin and a bismaleimide resin used in composite autoclave process were measured and a viscosity model was established, which can predict the viscosity progression during cure for different aging degree of resin. Moreover, a computer simulation method was used to study the effects of aging degree on the composite consolidation and the processing operations. It is found that the viscosity model of aged resin can be obtained by modified dual Arrhenius model of fresh resin with the dynamic rheological measurement. The resin aging strongly alters the flowability, so influences composite consolidation. According to the simulated results, the processing parameters need to be adjusted to achieve cured composites with appropriate fiber content. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

New tetrafunctional epoxy resin system with increased shelf life

Chlorine‐ and methyl‐substituted aromatic diamines based on diaminodiphenylmethane were epoxidized and characterized. The effect of different substituents on epoxidation was studied. The cure studies of the two new tetrafunctional resins in comparison with unsubstituted resin N,N,N′,N′‐tetraglycidyl‐4,4′‐diaminodiphenylmethane (TGDDM) was carried out by DSC with 3,3′‐dichloro‐4,4′diaminodiphenylmethane (o‐DCDDM; 30% w/w) as a common curing agent. The mechanical properties such as flexural, Izod impact, heat distortion temperature (HDT), of such cured neat resins were also studied. The results of the cure studies indicate that the substitution of the α‐hydrogen of the resin by chlorine or methyl group decreases the reactivity of the resin leading to an increase in the shelf life. This study also indicates that the functionality of the resin plays a pivotal role in the reactivity and thus the shelf life of an epoxy resin system. The results of the mechanical properties of the neat resin casts obtained by subjecting to a common cure schedule when compared with the unsubstituted resin showed a decrease in impact strength, which is obvious because of the presence of a bulky pendant group but the impact strength was higher than that of the TGOS30 resin system. Results of flexural strength of the different substituted neat resin casts did not show much of a deviation from that of the unsubstituted resin system. The HDT results indicate no significant difference in the values of the unsubstituted resin vis‐a‐vis with substituted resin systems. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2790–2801, 2004     

Cure kinetics of neat and graphite-fiber-reinforced epoxy formulations

An investigation was carried out into the cure kinetics of neat and graphite fiber-reinforced epoxy formulation, composed of tetraglycidyl 4,4′-diaminodiphenyl methane (TGDDM) resin and diaminodiphenyl sulfone (DDS) curing agent. Two experimental techniques were employed: isothermal differential scanning calorimetry (IDSC) and dynamic differential scanning calorimetry (DDSC). An autocatalytic mechanism with the overall reaction rate order of 2 was found to describe adequately the cure kinetics, of the neat resin and the composite. All kinetic parameters, including reaction rate constants, activation energies and preexponential factors, were calculated and reported. The presence of graphite fibers in the composite had only a very small initial effect on the kinetics of cure.     

Assessment of residual stresses during cure and cooling of epoxy resins

A new stress monitoring technique, a stress-tracking device, is described here. It has been used to study some important properties of epoxy resin. Residual stresses, including a curing shrinkage stress and a cooling shrinkage stress, were measured automatically and continuously during curing and cooling. Simultaneously, information such as an apparent gelation time and glass transition temperature were obtained directly during the experiment. These epoxy resin properties were related to the extent of cure. Varying cure temperature produced changes of cure behavior, which resulted in different residual stresses.