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1.
Yongsung Eom Louis Boogh Vronique Michaud Paul Sunderland Jan‐Anders Mnson 《Polymer Engineering and Science》2001,41(3):492-503
During cure of epoxy resins, polymerization induces an increase in mechanical properties, which is accompanied by a volumetric shrinkage. When the resin is cured in a constrained mold to which it adheres, tensile stresses will hence develop, which may exceed the stremgth of the resin at a given curing stage. Voids will then form. The origin and governing parameters of void formation are studied using an epoxy resin cured in a three‐dimensionally constrained glass mold following isothermal cure cycles. Two types of voids are shown to appear during cure, one early in the process and a second around the gelation point. A viscoelastic analysis of the material stress state over the whole range of cure is performed. Both the viscoelastic modulus obtained from a time‐cure‐temperature superposition and the volumetric shrinkage, which was continuously measured by density change, are taken into account. A value for the critical internal stress at void initiation is thus proposed. This criterion can be used to provide guidelines for tailoring the material properties toward an increase of the critical stress for void initiation. Also, since during theprocessing of composite materials, cases may arise where the resin cures within the interstices left between consolidated fibres that do not move, this critical stress failure criterion can be of use in the eastablishment of a process window providing guidelines for the production of void free composites. 相似文献
2.
Bhaskar Patham 《应用聚合物科学杂志》2013,129(3):983-998
Simulations of evolution of cure‐induced stresses in a viscoelastic thermoset resin are presented. The phenomenology involves evolution of resin modulus with degree of cure and temperature, the development of stresses due to crosslink induced shrinkage, and the viscoelastic relaxation of these stresses. For the simulations, the detailed kinetic and chemo‐thermo‐rheological models for an epoxy‐amine thermoset resin system, described in Eom et al. (Polym. Eng. Sci. 2000, 40, 1281) are employed. The implementation of this model into the simulation is facilitated by multiphysics simulation strategies. The trends in simulated cure‐induced stresses obtained using the full‐fledged viscoelastic model are compared with those obtained from two other equivalent material models, one involving a constant elastic modulus, and the other involving a cure‐dependent (but time‐invariant) elastic modulus. It is observed that the viscoelastic model not only results in lower estimates of cure‐induced stresses, but also provides subtle details of the springback behavior. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013 相似文献
3.
A manufacturing process is described that builds complex composite parts using a layered building process in which each layer of pre‐preg composite is laid and cured as the build progresses. In order to employ on‐line curing without molds, resin technologies that provide fast curing at room temperature—ultraviolet curable and epoxy/polyamide—were investigated. UV‐curable resins were tested for their ability to “shadow” cure by exposing carbon fiber composites to ultraviolet light to determine if the cure propagated from areas directly exposed to areas under fibers. Though ultraviolet curing showed advantages in cure time and low volatile production, very minimal “shadow” curing was achieved. A low temperature curing epoxy/polyamide mixture was tested for the effects of cure temperature, cure time, and mix ratio on the final degree of cure (%DOC) and glass transition temperature (Tg). Layers were made using different resin mixtures, partially cured, and used to build layered parts to determine curing characteristics during the lay‐up process. In the epoxy/polyamide mixtures, mix ratio had little effect on the reaction rate but did affect the Tg. A kinetic model was established for the resin epoxy/polyamide system for optimizing processing conditions during fabrication. However, the model failed to correctly predict the fabrication. The reaction of the material was different during the fabrication process than during the isothermal cure due to the presence of oxygen. During the build process, the degree of cure in each layer increased significantly over the prestaged degree of cure in less time than theoretically predicted. However, the final resin properties, such as Tg, were still below the specifications for high performance parts. 相似文献
4.
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. 相似文献
5.
A study of viscoelastic properties and gelation in epoxy/phenol‐novolac blend system initiated with 1 wt % of N‐benzylpyrazinium hexafluoroantimonate (BPH) as a latent cationic thermal initiator was performed by analysis of rheological properties using a rheometer. Latent behavior was investigated by measuring the conversion as a function of curing temperature using traditional curing agents, such as ethylene diamine (EDA) and nadic methyl anhydride (NMA) in comparison to BPH. In the relationship between viscoelastic properties and gelation of epoxy/phenol‐novolac blend system, the time of modulus crossover was dependent on high frequency and cure temperature. The activation energy (Ec) for crosslinking from rheometric analysis increased within the composition range of 20–40 wt % phenol‐novolac resin. The 40 wt % phenol‐novolac (N40) to epoxy resin showed the highest value in the blend system, due to the three‐dimensional crosslinking that can take place between hydroxyl groups within the phenol resin or epoxides within the epoxy resin involving polyaddition of the initiator with BPH. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2299–2308, 2001 相似文献
6.
In this study, we aimed to reduce the cure time, and to lower the cure temperature of the benzoxazine compound. Therefore, curing reaction of benzoxazine with bisoxazoline or epoxy resin using the latent curing agent and the properties of the cured resins were investigated. The cure behavior of benzoxazine with bisoxazoline or epoxy resin using the latent curing agent was monitored by differential scanning calorimetry and measurements for storage modulus (G′). The properties of the cured resin were estimated by mechanical properties, electrical insulation, water resistance, heat resistance, and flame resistance. As a result, it was confirmed that by using the latent curing agent, cure time of benzoxazine and bisoxazoline or epoxy resin was reduced, and cure temperature was lowered. And it was found that the curing reaction using phenol‐novolac based benzoxazine (Na) as the benzoxazine compound could proceed more rapidly than that using bisphenol‐A based benzoxazine (Ba) as the benzoxazine compound. However, the cured resins from Ba and bisoxazoline or epoxy resin using the latent curing agent showed good heat resistance, flame resistance, and mechanical properties compared with those from Na and bisoxazoline or epoxy resin using the latent curing agent. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 相似文献
7.
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 相似文献
8.
In this work, epoxy resin viscosity was calculated by using reference viscosity and “viscosity‐cure” shift factor which was established to research the dependence of viscosity on curing degree. The predicted results were compared with experimental data and the agreements between them were better than those in reference. Generalized Maxwell model was used to characterize the viscoelastic behavior of epoxy resin and the relaxation modulus was modeled by Prony series. A simple model of stress relaxation times was derived as functions of viscosity and stiffness. The stress relaxation times at different curing degrees were calculated after acquiring the stress relaxation times at the reference curing degree. The relaxation modulus predicted by this method agreed well with experimental data. The above results showed that these models could well be used to predict the viscosity and relaxation modulus of thermosetting resin during cure. POLYM. ENG. SCI., 56:617–621, 2016. © 2016 Society of Plastics Engineers 相似文献
9.
Haixiang Sun Weiliang Ni Bingbing Yuan Tiantian Wang Peng Li Yunqi Liu Lintong Wang 《应用聚合物科学杂志》2013,130(4):2652-2659
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 相似文献
10.
Epoxy resin is widely used for coatings, adhesives, castings, electrical insulation materials, and other applications. However, unsolved problems still remain in its applications. The main problem is low toughness: cured epoxy resin is rather brittle, with poor resistance to the propagation of cracks derived from the internal stress generated by shrinkage in the cooling process from cure temperature to room temperature. The objective of this study was to improve the flexibility and toughness of diglycidyl ether of bisphenol A based epoxy resin with a liquid rubber. For this purpose, amine‐terminated polybutadiene (ATPB) was synthesized. The product was characterized by Fourier transform infrared and NMR spectroscopy and elemental analysis. ATPB‐modified epoxy networks were made by curing with an ambient‐temperature curing agent, triethylene tetramine. We varied the epoxy/liquid rubber compositions to study the effect of toughener concentration on the impact and thermal properties. Higher mechanical properties were obtained for epoxy resins toughened with 1 phr ATPB. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2446–2453, 2005 相似文献
11.
Hongfeng Xie Binghua Liu Hu Yang Zhiliu Wang Jianyi Shen Rongshi Cheng 《应用聚合物科学杂志》2006,100(1):295-298
The thermal properties of carbon nanofibers (CNF)/epoxy composites, composed of tetraglycidyl‐4,4′‐diaminodiphenylmethane (TGDDM) resin and 4,4′‐diaminodiphenylsulfone (DDS) as a curing agent, were investigated with differential scanning calorimetry (DSC), thermogravimetric analysis, and dynamic mechanical thermal analysis. DSC results showed that the presence of CNF had no pronounced influence on the heat of the cure reaction. However, the incorporation of CNF slightly improved the thermal stability of the epoxy. Furthermore, the storage modulus of the TGDDM/DDS epoxy was significantly enhanced, whereas the glass‐transition temperature was not significantly affected, upon the incorporation of CNFs. The storage modulus of 5 wt % CNF/epoxy composites at 25°C was increased by 35% in comparison with that of the pure epoxy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 295–298, 2006 相似文献
12.
Naoya Saiki Sayaka Kainou Hironori Shizuhata Hideo Seno Kazuyoshi Ebe 《应用聚合物科学杂志》2010,117(6):3466-3472
To facilitate the fabrication of a reliable semiconductor package, the UV/heat dual curing of film adhesives was investigated. The curing system of the epoxy resin affected the film adhesive properties. As the UV/heat dual‐curable epoxy resin, a modified o‐cresol novolak epoxy resin, in which half of the glycidyl groups were substituted by acryloyl groups (OCN‐AE), was applied to the film adhesive. The formulated film adhesive contained acrylic copolymer, OCN‐AE, phenolic aralkyl resin as a heat‐curing agent of the glycidyl groups, and 1‐hydroxycyclohexyl phenyl ketone as a photoinitiator of the acryloyl groups. The formulated reference film adhesive contained unmodified o‐cresol novolak epoxy resin (OCN‐E) in place of OCN‐AE. Formulated film adhesives containing a mixture of OCN‐E and o‐cresol novolak epoxy acrylate were also used as references. The morphology and the film adhesive properties were investigated. In these investigations, the film adhesive of OCN‐AE showed better adhesive properties, lower modulus, and a better stress‐relaxation ability than the referenced adhesives. As a result, a reliable film adhesive for semiconductor packages was successfully developed. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 相似文献
13.
The curing kinetics and the resulting viscosity change of a two‐part epoxy/amine resin during the mold‐filling process of resin‐transfer molding (RTM) of composites was investigated. The curing kinetics of the epoxy/amine resin was analyzed in both the dynamic and the isothermal modes with differential scanning calorimetry (DSC). The dynamic viscosity of the resin at the same temperature as in the mold‐filling process was measured. The curing kinetics of the resin was described by a modified Kamal kinetic model, accounting for the autocatalytic and the diffusion‐control effect. An empirical model correlated the resin viscosity with temperature and the degree of cure was obtained. Predictions of the rate of reaction and the resulting viscosity change by the modified Kamal model and by the empirical model agreed well with the experimental data, respectively, over the temperature range 50–80°C and up to the degree of cure α = 0.4, which are suitable for the mold‐filling stage in the RTM process. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2139–2148, 2000 相似文献
14.
The curing reaction of an epoxy–phenolic resin under different conditions was monitored using rheological measurements. The evolution of viscoelastic properties, such as storage modulus, G′, and loss modulus, G″, was recorded. Several experiments were performed to confidently compare the rheological data obtained under varied curing conditions of temperature, catalyst concentration, and reactive ratios. The values of G′ measured at the end of the reactions (at maximum conversion) were independent of the frequency and temperature of the tests in the range of high temperatures investigated. The overall curing process was described by a second‐order phenomenological rheokinetic equation based on the model of Kamal. The effects of the epoxy‐to‐phenolic ratio as well as the curing temperature and the catalyst concentration were also investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4430–4439, 2006 相似文献
15.
Fabrication of thermosetting‐matrix composites is based on a critical step of cure, which involves applying a predefined temperature cycle to a fiber‐resin mixture. Several temperature‐dependent mass transport processes occur in the vicinity of the reinforcement fiber, leading to the formation of an interphase region with different chemical and physical properties from the bulk resin. The cure cycles applied on the macroscopic boundaries of the composite govern the microscopic cure kinetics near the fiber surface, which in turn determines the interphase and composite properties. A predictive approach to directly linking the cure cycles and final composite properties is not presently available and is established for the first time in this paper. A multiscale thermochemical model is developed to predict the concentration profile evolution with time near fiber surfaces at various locations across the composite thickness. The concentration profiles at the gelation time are mapped to modulus profiles within the interphase region, and a finite element analysis is used to determine the overall composite modulus in terms of the constituent interphase, fiber, and matrix properties. Relevant numerical results are presented for the first time where the composite modulus is directly linked to the cure cycle and interphase formation parameters without assumed structures or properties of the interphase. The results provide useful information for selecting material components and cure cycles parameters to achieve desired interphase and composite properties. POLYM. COMPOS., 26:193–208, 2005. © 2005 Society of Plastics Engineers 相似文献
16.
The objective of this research is to understand the influence of the thermochemical and thermomechanical material response of low temperature cured vinyl ester resin (Dow Derakane 411‐C‐50) on the development of residual stress and warpage during processing. The primary experimental technique is the bimaterial specimen experiment, in which the warpage of a bimaterial beam is used as a measure of residual stress. The bimaterial specimen experiment was developed to isolate the chemical and thermal contributions to curvature. Existing material models for shrinkage, modulus, and glass transition temperature as a function of cure were evaluated. These material models were used as input into the bimaterial equation for curvature prediction. The predicted curvatures were used along with the experimental curvatures to evaluate the material models and their ability to accurately describe the material response of the vinyl ester resin. Results showed that the model captured the overall experimental trend in curvature buildup during processing but overestimated the curvature from chemical effects during isothermal cure. Improved correlation was achieved by incorporating a time shift in the model to account for viscoelastic stress relaxation of the resin. 相似文献
17.
Judith Moosburger‐Will Michael Greisel Markus G. R. Sause Robert Horny Siegfried Horn 《应用聚合物科学杂志》2013,130(6):4338-4346
Thermo‐physical and mechanical properties of partially and completely cross‐linked RTM6 epoxy resin samples in the glassy state have been investigated. A significant dependence of glass transition temperature, density, and modulus on the curing history and the curing degree is found. Density and modulus decrease with increasing curing degree and show a step‐like irregularity in the so called transition region, which is related to the transition from rubber to glassy state during cross‐linking and the starting of structural relaxation processes. The relationship between the thermo‐physical and mechanical properties, which is important for the development of new processing routes for fiber reinforced polymers, is addressed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4338–4346, 2013 相似文献
18.
Hong-Bing Wang Yu-Geng Yang Hui-Hong Yu Wei-Ming Sun Ying-Hua Zhang Hong-Wei Zhou 《Polymer Engineering and Science》1995,35(23):1895-1898
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. 相似文献
19.
Three experimental techniques were used to characterize the cure state of an epoxy resin system of DGEBA epoxide and DDS diamine curing agent. Samples were prepared from non‐stoichiometric monomer mixtures designed so as to simulate various stages of cure of a stoichiometrically prepared epoxy. Such an approach allows for variable temperature characterization of specimens without concern for ongoing chemical reactions that would cloud interpretation of results. Additional experiments were performed on stoichiometric samples that were isothermally cured. Differential scanning calorimetry (DSC) was used to measure the heat of reaction and glass transition temperature. Dynamic mechanical analysis (DMA) was used to measure complex modulus, while ultrasonic cure monitoring (UCM) was used to measure longitudinal velocity throughout cure. DSC analysis was found to be insensitive to changes occurring at the latter stage of polymer network development, especially after vitrification. DMA characterization, however, was found to be quite sensitive to the rubbery modulus (and as such, the cure state), but is limited to cure states above gelation. Only the UCM technique was robust enough to accommodate all cure states while providing highly sensitive measurements of mechanical property development. 相似文献
20.
Yongsung Eom Louis Boogh Véronique Michaud Jan-Anders Månson 《Polymer Composites》2002,23(6):1044-1056
The development of internal stress during cure of epoxy and hyperbranched polymer-modified epoxy resins was characterized, taking into account the evolving viscoelastic properties, the volumetric shrinkage due to the chemical reaction, and the thermal expansion. A criterion for void formation during cure in a constrained mold was proposed, providing guidelines for the construction of a process window for manufacturing of void-free composites. It was shown that the internal stress development in epoxy resins during cure is strongly influenced by the presence of hyperbranched polymer modifiers. The role of these modifiers was illustrated for the case of autoclave processing of glass fiber/epoxy composites. This study showed that higher fiber volume fractions could be used with hyperbranched polymer-modified resins than with unmodified resins, for producing void-free laminates. It also appeared that by suitable tailoring of the process cycle, a fully stress-free laminate could be obtained after cure, using the modified resin. 相似文献