纤维增强环氧树脂基复合材料的研究进展

综述了纤维增强环氧树脂基复合材料的应用及研究进展,其中包括玻璃纤维(GF)增强、碳纤维(CF)增强,芳纶纤维,混杂纤维及植物纤维增强等。     

Curing kinetics study of an epoxy resin system for T800 carbon fiber filament wound composites by dynamic and isothermal DSC

Curing kinetics of DGEAC/DDM/DETDA/DGEB epoxy resin system was studied using dynamic and isothermal differential scanning calorimetry (DSC) for the preparation of T800 carbon fiber filament wound composites. In dynamic experiment, four kinds of epoxy resin systems were studied. Curing characteristics, such as curing range and curing temperatures of the epoxy resin system with mixed hardeners (DGEAC/DDM/DETDA), were found lying within those of the two epoxy resin systems with a single hardener (DGEAC/DDM, DGEAC/DETDA). The addition of reactive diluter (DGEB) caused increase in curing range and exothermic heat. In addition, the activation energies calculated by the isoconversional method of all four resin systems decreased to the minimum value in the early stage due to the autocatalytic role of hydroxyl groups in the curing reaction and then increased due to the increased viscosity and crosslink of epoxy systems. The addition of reactive diluter led to the decrease in activation energies on the initial stage (conversion = 0.1–0.3). In isothermal experiment, a series of isothermal DSC runs provided information about the curing kinetics of the DGEAC/DDM/DETDA/DGEB system over a wide temperature range. The results showed that the isothermal kinetic reaction of the epoxy resin followed an autocatalytic kinetic mechanism. The autocatalytic kinetic expression chosen in this work was suitable to analyze the curing kinetics of this system. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

An impact study of epoxy resin composites reinforced with glass fiber fabrics

The impact properties of epoxy resin composites reinforced with three types of fabrics which are welf-knitted structural fabrics (WKSF), three-dimensional fabrics (3D-3A & 3D-5A) and plain-weave structural fabrics (2D-2A) have been investigated. The results of experiments show that WKSF composite has total impact energy about 1.5 and 3.5 times those of 3D and 2D fabrics composite respectively. The ductility index of WKSF is about 2.2 times of those of 3D and 2D. WKSF composites are very ductile materials and can absorb much more impact energy than 3D and 2D composites. The pushed-out volume of WKSF composites after the impact test was calculated from the photographs and the results show that the volume of the pushed-out zone is proportional to impact energy.     

铜电极与碳纤维/环氧复合材料粘接研究

研究铜电极与碳纤维/环氧复合材料的粘接工艺,比较铜的表面处理方法对于粘接强度和导电性的影响,并验证粘接的可靠性.首先分别用机械打磨、化学表面处理、表面电镀方法对铜片进行处理,然后通过铜粉导电胶与碳纤维/环氧复合材料粘接,测试粘接强度及电阻率,再通过湿热老化实验,对粘接的可靠性进行比较.测试结果表明,经化学表面处理的铜片与碳纤维/环氧复合材料粘接强度达到1.34 MPa,老化后强度保留率为76%;电阻率为4.19 Ω*m,老化后电阻率增加率为4.8%.从而确定化学表面处理方法得到的粘接强度和导电效果较佳.     

Physical aging of polydimethylsiloxane-modified epoxy resin

The thermal expansion coefficient and physical aging behavior of cured epoxy resins modified with amino-terminated polydimethylsiloxane were investigated. The epoxy resin was tetramethyl biphenol diglycidyl ether. Two factors influenced the thermal expansion behavior and the free volume relaxation of the polysiloxane-modified epoxy systems. One was the miscibility between the epoxy resin and the polysiloxane and the flexibility of the chains in the network system. The intrinsic thermal expansion of the network chains and the volume relaxation increased as a result of building polysiloxane molecules into the network structure. The other factor was the size and concentration of the dispersed polysiloxane particles. The increased local free volume at the interface between the epoxy matrix and the polysiloxane particle resulted in a higher thermal expansion coefficient and led to a large driving force for the volume relaxation during annealing. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1291–1300, 1998     

Mechanical properties of glass fiber composites with an epoxy resin modified by a liquid crystalline epoxy

The effect of liquid crystalline networks on epoxy + glass fiber composites is investigated. The matrix obtained from in‐situ curing of liquid crystalline (LC) diglycidyl ether of 4,4‐dihydroxybiphenol (DGE‐DHBP) with diglycidyl ether of bisphenol F (DGEBP‐F) by anhydride curing agent was used as the matrix for polymer composites. Impact, tensile, and flexural testing results are compared between the unmodified and modified systems. The interlaminar fracture toughness of commposites in the shear mode was determined by end notch flexure (ENF) tests. Scanning electron microscopy is used to study the fracture surfaces to understand the mechanism of fracture and interphase formation between the fiber and the matrix.     

Contractive stress of epoxy resin during isothermal curing

The contractive stresses of an amine curing epoxy resin during isothermal curing are studied by photoelastic and bimetallic methods. The increase in elastic modulus during the curing process of the resin is measured by torsional braid analysis (T.B.A.). The contractive stress in composite systems is observed only after gelation of the resin. The volume contraction after gelation is effective in generating contractive stress; the contraction in the fluid state is not effective. The effective contraction is estimated to be one third of the total contraction in this experiment.     

Improved interfacial adhesion in carbon fiber/epoxy composites through a waterborne epoxy resin sizing agent

A series of self‐emulsified waterborne epoxy resin (WEP) emulsions were used as surface sizing for carbon fibers (CFs) to improve the interfacial adhesion between the CF and epoxy matrix. In this work, the hydrogenated bisphenol‐A epoxy resin (HBPAE) was modified by polyethylene glycol (PEG) with molecular weights of 400, 800, 1000, 1500, 2000, 4000, and 6000 g/mol. The properties of the WEP emulsion were examined by Fourier transform infrared spectroscopy, dynamic light scattering, and transmission electron microscopy. The surface characteristics of sized CFs were evaluated using scanning electron microscopy, atomic force microscopy, and X‐ray photoelectron spectroscopy. Afterwards, CF/EP composites were prepared and their fracture surface and interlaminar shear strength (ILSS) were examined. The results indicated that PEG2000 modified HBPAE sizing had the optimum emulsion stability and film‐forming ability. Meanwhile, the results also demonstrated that a continuous and uniform sizing layer was formed on the surface of CFs and the surface sizing was excellent in improving the chemical activity of CFs. Compared with unsized CFs, the O1s/C1s composition ratio was observed to increase from 11.51% to 33.17% and the ILSS of CF/EP composites increased from 81.2 to 89.7 MPa, exhibiting better mechanical property than that of commercial Takemoto S64 sized CFs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44757.     

Synthesis and characterization of chlorinated soy oil based epoxy resin/glass fiber composites

Composites with good toughness properties were prepared from chemically modified soy epoxy resin and glass fiber without additional petroleum based toughening agent. Chlorinated soy epoxy (CSE) resin was prepared from soybean oil. The CSE was characterised by spectral, and titration method. The prepared CSE was blended with commercial epoxy resin in different ratios and cured at 85°C for 3 h, and post cured at 225°C for 2 h using m‐phenylene diamine (MPDA) as curing agent. The cure temperatures of epoxy/CSE/MPDA with different compositions were found to be in the range of (151.2–187.5°C). The composite laminates were fabricated using epoxy /CSE/MPDA‐glass fiber at different compositions. The mechanical properties such as tensile strength (248–299 MPa), tensile modulus (2.4–3.4 GPa), flexural strength (346–379 MPa), flexural modulus (6.3–7.8 GPa) and impact strength (29.7–34.2) were determined. The impact strength increased with the increase in the CSE content. The interlaminor fracture toughness (G_IC) values also increased from 0.6953 KJ/m² for neat epoxy resin to 0.9514 KJ/m² for 15%CSE epoxy‐modified system. Thermogravimetric studies reveal that the thermal stability of the neat epoxy resin was decreased by incorporation of CSE. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Shape memory CTBN/epoxy resin/cyanate ester ternary resin and their carbon fiber reinforced composites

Carboxylated-terminated liquid acrylonitrile rubber (CTBN) and epoxy resin (JEF-0211) were coreacted with cyanate ester (CE) to form CTBN/EP/CE ternary resin systems. Further, the ternary resin system was applied as prepreg for carbon fiber composites with vacuum bag degassing molding process. CTBN/EP/CE ternary shape memory polymer (SMP) exhibited relatively high tensile strength, Young's modulus, impact strength, and excellent shape memory properties. Compared with CTBN/EP/CE ternary SMP, CTBN/EP/CE carbon fiber composites showed much higher mechanical properties, such as their tensile strength and Young's modulus were high to 570 MPa and 36.7 GPa, respectively. Furthermore, CTBN/EP/CE carbon fiber composites exhibited good shape memory properties, their shape fixity ratio and shape recovery ratio were more than 95% after 30 times repeating shape memory tests. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48756.     

Cure-volume-temperature relationships of epoxy resin and graphite/epoxy composites

Taking the material thermal expansion and curing shrinkage in polymer composites into account, this work aims to quantitatively obtain the relationships among the degree of cure, the volumetric change rate and the temperature (CVT) at the atmospheric pressure. According to reaction kinetics and nonlinear deformation theory, the mathematical models are established to implicitly describe the CVT relationships of epoxy resin as well as its unidirectional graphite fiber composites, and then the volumetric change rates of the two types of materials during curing process are obtained via the finite element method. On the basis of the numerical analysis and data fitting, two new explicit CVT expressions are constructed. The numerical analysis of the cure-volume-temperature relationships is helpful not only for the prediction of material warpage and internal stress, but also for the process optimization, such as the shrinkage compensation of polymer composites. By comparing the present results with the results in published articles, the validity of the present results is proven indirectly.     

Liquid diffusion into epoxy resin composites

Dynamic sorption behavior of four epoxy resin matrix composites derived from fly ash, jute, mica, or vermiculite was studied in water and salt solution at 24°, 35°, and 45°C. The mass of water uptake per mass of sample was determined as a function of time. Diffusion coefficients were higher for distilled water than those for salt solution. The diffusion parameters were computed from the Arrhenius plots and the results analyzed in terms of a Fickian model. The results as obtained from weight gain assays are consistent with the view that the activation energy of diffusion is associated with the energy required to produce a space of sufficient cross-section for the diffusing molecule to pass.     

Effects of novolac resin modification on mechanical properties of carbon fiber/epoxy composites

The epoxy resin matrix of carbon fiber (CF)‐reinforced epoxy composites was modified with novolac resin (NR) to improve the matrix‐dominated mechanical properties of composites. Flexural strength, interlaminar shear strength (ILSS), and impact strength were measured with unfilled, 7 wt% NR, 13 wt% NR, and 18 wt% NR filled to epoxy to identify the effect of adding NR on the mechanical properties of composites. The results showed that both interfacial and impact properties of composites were improved except for flexural property. The largest improvement in ILSS and impact strength were obtained with 13 wt% loading of NR. ILSS and impact strength were improved by 7.3% and 38.6%, respectively, compared with the composite without NR. The fracture and surface morphologies of the composite specimens were characterized by scanning electron microscopy. Intimate bonding of the fibers and the matrix was evident with the content of 7–13 wt% NR range. Decrease of crosslinking density and formation of NR transition layer were deduced with adding NR. POLYM. COMPOS., 2011. © 2010 Society of Plastics Engineers     

耐高温高导热环氧树脂／玻纤／BN复合材料的制备

以4,4-二氨基二苯砜（DDS）和内亚甲基四氢邻苯二甲酸酐（NA）为复配固化剂,采用高温模压成型法制备耐高温高导热环氧树脂／玻纤／氮化硼（BN）复合材料。探讨了BN用量和偶联剂处理对复合材料冲击强度、导热性能和电阻率的影响。结果表明：当nDDS：nNA=3：1时,复合材料的耐热性能最佳。当BN质量分数为8％时,复合材料的冲击强度最高;导热性能随BN用量的增加而增加,当BN用量为15％时,热导率为0．7560W／（mk）,此时复合材料仍保持较高的体积、表面电阻率;当BN填充量为一定值时,偶联剂处理使冲击强度和导热性能得到进一步提高。     

PANI-PMN/环氧树脂复合材料的制备

用自制的聚苯胺（PANI）包覆铌镁锫钛酸铅（PMN）粉末为功能相，以环氧树脂为基体，制备了PANI—PMN／环氧树脂复合材料。当w（PANI—PMN）小于60％时，随w（PANI～PMN）的增大复合材料的压缩强度有所提高。当w（PANI-PMN）大于60％时，压缩强度降低。随着w（PANI—PMN）的提高，试样的电导率增大。PANI包覆PMN制备的复合材料的阻尼损耗因子提高。在PANI—PMN／环氧树脂复合材料中，除环氧树脂的黏弹性阻尼、填料与基体的相互作用耗能外，还存在压电阻尼作用，并且具有一定电导率的体系有利于压电阻尼发挥作用。     

Short fiber-reinforced oxide fiber composites

This paper presents a novel fiber spraying process for the manufacturing of short fiber bundle-reinforced Nextel™ 610/Al₂O₃-ZrO₂ oxide fiber composites (SF-OFC) and its characterization. First, the influence of varying fiber lengths (7, 14, and 28 mm, continuous fibers) and fiber orientations (unidirectional 0°, quasi-isotropic, ±45°) was investigated using hand-laid SF-OFC. Due to the weak matrix, the hand-laid material exhibited a strongly fiber-dominated material behavior, that is, variations in fiber length and orientation had a strong influence on the material properties. Second, the automated sprayed SF-OFC, however, exhibited a random orientation of the fiber bundles, which resulted in in-plane isotropic material properties. Average bending strengths of up to 177 MPa, strains of .39%, and a quasi-ductile fracture behavior were achieved. The strain was, therefore, in the range of fabric-reinforced OFC. While the bending strength of the SF-OFC was somewhat lower than that of fabric-reinforced OFC with the fiber orientation parallel to the loading direction, it was more than two times higher than the strength in 45° direction relative to the fabric reinforcement. Combined with good drapability and lower material costs compared to fabric-reinforced OFC, SF-OFC is, therefore, a promising material for industrial applications.     

Rheological study of the isothermal reticulation of an epoxy resin

The complex modulus of shearing G* = G' + jG″ was measured during the isothermal hardening of several epoxy resins. The gelation induces a slowing down of the rate of growth of viscous modulus ν″ = d(log G″)/dt between two zones where this rate is constant. This slowing down of growth rate varies with the temperature and is null for T = T_{C gel}: ν″₂ ?ν″₁ = K(1/T_{C gel} ?1/T). We have shown that the two phenomena of gelation and vitrification stay perfectly distinct at all temperatures and in particular at T_{C gel}. So the decrease of the rate ν″ associated with gelation disappears at this temperature without the vitrification being responsible.