固化条件对热塑增韧环氧树脂的固化动力学和相分离的影响EI

采用砂型和金属型两种不同铸造方法对铸态、固溶态和时效态ZL210A合金性能及断口形貌的影响进行研究.结果表明:对ZL210A铸造合金而言,金属型铸造方法优于砂型铸造方法,其常规力学性能σb,σ0.2和δ5均高于砂型铸造,从断口形貌上看,试样断口形貌均呈现典型的穿晶断裂,且韧窝较深.其中,金属型固溶态试样的断口韧窝最为明显,呈现出较好的韧性.     

固化条件对热塑增韧环氧树脂的固化动力学和相分离的影响

Thermoplastic toughened epoxy resins are widely used as matrices in modern prepreg systems.Different curing conditions play a great role in affecting the cure kinetics and phase behaviour of thermoplastic modified epoxies which further result in different mechanical properties of polymer matrix composites.Since the morphology of the cured thermoplastic/epoxy blends is directly related to the mechanical properties,it is essential to control processing conditions for obtaining desirable morphology.A polyethersulphone (PES) modified multifunctional epoxies,triglycidylaminophenol (TGAP) and tetraglycidyldiaminodiphenylmethane (TGDDM),was used for investigation.The cure kinetics and cured morphology of polymer blends heated at different heating rates and cured at different temperature were studied.It is shown that higher cure temperature and higher heating rate display similar effects in the epoxy conversion and the domain size of phase separated structure.     

Prestressed double network thermoset: preparation and characterization

An innovative scheme to prepare Prestressed double network (PDN) epoxies is presented using a judicious combination of tetrafunctional curatives that have similar molecular weights but different reaction kinetics. A diglycidyl ether of bisphenol A epoxy monomer was reacted stoichiometrically and sequentially with various molar ratios of an aliphatic polyetheramine curing agent and an aromatic curing agent. Deformation was imposed on the partially cured resins after the formation of the first network, and postcuring was conducted at 50% compressive strain. Physical properties of the resulting PDN epoxies were examined using thermomechanical analysis, dynamic mechanical analysis, uniaxial tensile test, and plane-strain fracture toughness test. The application of prestress resulted in no changes in glass transition temperature, coefficient of linear thermal expansion, and Young’s modulus. However, a marked increase in fracture toughness is observed, accompanied by strong birefringence and visible roughness on the fracture surface.     

Micro-crack behavior of carbon fiber reinforced thermoplastic modified epoxy composites for cryogenic applications

Three different types of thermoplastics, poly(ether imide) (PEI), polycarbonate (PC), and poly(butylene terephthalate) (PBT) were used to modify epoxy for cryogenic applications. Carbon fiber reinforced thermoplastic modified epoxy composites were also prepared through vacuum-assisted resin transfer molding (RTM). Dynamic mechanical analysis (DMA) shows that the storage moduli of PEI, PC, and PBT modified epoxies are 30%, 21%, and 17% higher than that of the neat epoxy respectively. The impact strength of the modified epoxies at cryogenic temperature increases with increasing thermoplastic content up to 1.5 wt.% and then decreases for further loading (2.0 wt.%). The coefficient of thermal expansion (CTE) values of the PBT, PEI, and PC modified epoxies also decreased by 17.76%, 25.42%, and 30.15%, respectively, as compared with that of the neat epoxy. Optical microscopy image analysis suggests that the presence of PEI and PC in the carbon fiber reinforced epoxy composites can prevent the formation of micro-cracks. Therefore, both the PEI and PC were very effective in preventing micro-crack formation in the composites during thermal cycles at cryogenic condition due to their low CTE values and high impact strength.     

Effect of DOP-based compounds on fire retardancy, thermal stability, and mechanical properties of DGEBA cured with 4,4′-DDS

The structure-property-relationships, thermal stability and flame retardancy of a DGEBA-DDS system containing various organo-phosphorus compounds as flame retardants is investigated. Three non-reactive (DOP-ethyl, DOP-ethylhexyl and DOP-cyanur) and one reactive (DOP-glycidyl) phosphorous compounds are added separately to the epoxy resin and the mixtures are cured with 4,4′-DDS in a substoichiometric ratio. The addition of such DOPO-compounds leads to improved flame retardancy at low phosphorus contents of about 2 wt.% (about 20 wt.% of additive) without significantly affecting other important properties such as fracture toughness (K_lc) and glass transition temperature (T_g) of the matrix. Neither the type nor the amount of additive affects the fracture toughness of cured epoxies up to additive concentrations of between 18 and 24 wt.%. Furthermore, the loss in glass transition temperature of the cured resin can be correlated with the amount and chemical reactivity of the organo-phosphorus additive. The reactive DOP-glycidyl and the non-reactive DOP-cyanur additive are observed to maintain the highest glass transition temperature of the epoxy system mainly due to a higher extent of the cross-linking reaction. The results presented in this study highlight the potential of optimising the flame retardancy and the resulting physical and mechanical properties of epoxy systems for liquid composite moulding applications by varying the chemical structure of the organo-phosphorus compounds.     

Morphology, dynamic mechanical and thermal studies on poly(styrene-co-acrylonitrile) modified epoxy resin/glass fibre composites

Poly(styrene-co-acrylonitrile) (SAN) was used to modify diglycidyl ether of bisphenol-A (DGEBA) type epoxy resin cured with diamino diphenyl sulfone (DDS) and the modified epoxy resin was used as the matrix for fibre reinforced composites (FRPs) in order to get improved mechanical and thermal properties. E-glass fibre was used as the fibre reinforcement. The morphology, dynamic mechanical and thermal characteristics of the systems were analyzed. Morphological analysis revealed heterogeneous dispersed morphology. There was good adhesion between the matrix polymer and the glass fibre. The dynamic moduli, mechanical loss and damping behaviour as a function of temperature of the systems were studied using dynamic mechanical analysis (DMA). DMA studies showed that DDS cured epoxy resin/SAN/glass fibre composite systems have two T_gs corresponding to epoxy rich and SAN rich phases. The effect of thermoplastic modification and fibre loading on the dynamic mechanical properties of the composites were also analyzed. Thermogravimetric analysis (TGA) revealed the superior thermal stability of composite system.     

Role of rigid nanoparticles and CTBN rubber in the toughening of epoxies with different cross-linking densities

Experimental investigations were conducted to characterize the fracture behaviours of Bisphenol A diglycidyl ether (DGEBA) epoxies modified with rigid nanoparticles (nanosilica or halloysite) and a reactive liquid carboxylterminated butadiene–acrylonitrile (CTBN) liquid rubber to identify toughening mechanisms and toughenability in the cured epoxies with different cross-linking densities. The epoxy was cured using three different hardeners, a heterocyclic amine (piperidine), a cycloaliphatic polyamine (Aradur 2954) and an aromatic amine [4,4′-Diaminodiphenyl sulfone (DDS)] to form nanocomposites with different cross-linking densities. It was found that both the hybrid particles, nanosilica with CTBN rubber and halloysite with CTBN rubber, were effective additives that clearly increased the fracture toughness of the three epoxy composites. In particular, the use of halloysite nanoparticles as additives for the epoxies showed greater potential than nanosilica to increase strength and modulus due to the reinforcing effect of the halloysite nanotubes (HNTs). The epoxy systems cured with the hardeners (Aradur 2954 and DDS), which generated relatively high cross-linking densities, evidenced inferior toughenability of the hybrid particles, compared with the epoxy systems cured using the hardener (piperidine), which produced lower cross-linking densities. The CTBN rubber formed dissimilar domains in different epoxy systems, features which were attributed to the different toughenability of the hybrid particles in the systems due to variations in the dominant toughening mechanisms involved.     

Water vapor transport in liquid crystalline and non-liquid crystalline epoxies

This paper presents a comparison of moisture permeation in liquid crystalline and non-liquid crystalline epoxy systems. The permeability is obtained using a dynamic method. It is found that diffusion in both epoxy systems is Fickian. The liquid crystalline epoxy network exhibits higher barrier properties to moisture transport than the conventional epoxy network. The efficient chain packing of the smectic mesophase of the liquid crystalline epoxy is the main factor for this difference. The stoichiometry has a large effect on the moisture permeation. The diffusion coefficient decreases monotonically with increasing amine/epoxide functional ratio. The permeability (P) and solubility coefficient (S) reach a minimum for a functional ratio of one. The results are described on the basis of hydrogen bonding of water to the epoxy network and the two phase morphology of cured epoxies.     

氧化石墨烯有序排列对碳纤维增强环氧树脂复合材料低温性能影响

为了提高碳纤维增强环氧树脂复合材料在低温(77 K)循环条件下的微裂纹抗性,文中采用共沉淀法制备了具有良好顺磁性的四氧化三铁/氧化石墨烯(Fe_3O_4/GO),采用红外光谱、X射线衍射、扫描电镜、透射电镜等手段研究了Fe_3O_4/GO在环氧树脂基体中的有序排列对环氧树脂及碳纤维增强环氧树脂复合材料低温性能的影响。结果表明,Fe_3O_4/GO的有序排列可有效提高环氧树脂基体的低温力学性能及降低环氧树脂基体的热膨胀系数,并可明显改善碳纤维增强环氧树脂(CF/EP)复合材料的低温微裂纹抗性;相对于纯环氧树脂,改性环氧树脂的热膨胀系数和低温环境下的微裂纹密度分别降低了36.5%和37.5%。     

Mechanisches Verhalten von kohlenstoffaserverstärkten Duromeren im Tieftemperaturbereich

Investigations on the suitability of carbon fiber reinforced epoxy for using at cryogenic temperatures The following investigations show the mechanical properties of some carbon fiber reinforced epoxies under quasistatic load. Both prepregs and wet laminates are tested to get a suitable fiber/matrix-combination for using at cryogenic temperatures. Therefore the material research is done at room temperatures. Therefore the material research is done at room temperature and at liquid nitrogen atmosphere. The characteristics, which serve for the basis of valuation are ultimate strength, elongation at fracture and modulus of elasticity. At liquid nitrogen temperature ultimate tensile strength and elongation at fracture show a decrease in comparison to room temperature, but Young's Modulus increases insignificantly with tensile loading. In the compression test all the characteristics grow larger. Furthermore the influence of the testing temperature on the mechanical characteristics of prepregs and wet laminates is pronounced differently. The experiments also show, that the dependence of the temperature on the mechanical properties may be influenced by the kind of the reinforcing fibers. This statement applies especially to the value of the obtainable interlaminar shear strength.     

Synergistic effects of oxidized CNTs and reactive oligomer on the fracture toughness and mechanical properties of epoxy

The soft modifiers added to improve the fracture toughness of epoxies generally deteriorate their mechanical properties. Hence, oxidized multi-walled carbon nanotubes (O-CNTs) were added to the epoxy modified with reactive oligomer. The NCO terminated reactive oligomer acts as a cross-linker between the O-CNTs and the OH groups of the epoxies. The impact strengths of the 15 wt.% oligomer modified epoxy containing 0.5 wt.% of O-CNTs at room temperature (RT) and cryogenic temperature (CT) are enhanced by 23.6% and 69.5% compared to that of the unmodified epoxy. In addition to increasing fracture toughness, the tensile strength (TS) of the modified epoxy/O-CNTs at CT is found to be 91.7 MPa, which is comparable to that of the unmodified epoxy (92.1 MPa). Hence, the attachment of O-CNTs to the reactive oligomer modified epoxy can be an efficient approach to toughen epoxy resins without compromising their tensile properties.     

石墨烯-多壁碳纳米管协同增强环氧树脂复合材料的低温力学性能

为了提高环氧树脂的低温力学性能,采用石墨烯与多壁碳纳米管(MWCNTs)协同改性环氧树脂,系统研究了石墨烯-MWCNTs/环氧树脂复合材料的室温(RT)和低温(77K)力学性能。结果表明:当石墨烯的质量分数为0.1wt%,MWCNTs的质量分数为0.5wt%时,纳米填料的加入可同时改善环氧树脂的低温拉伸强度、弹性模量和冲击强度;在此最佳含量下,石墨烯-MWCNTs/环氧树脂复合材料在RT和77K时的拉伸强度皆达到最大值,比纯环氧树脂的拉伸强度分别提高了11.04%和43.78%。石墨烯和MWCNTs能协同提高环氧树脂的低温力学性能。     

Simultaneously Enhanced Cryogenic Tensile Strength,Ductility and Impact Resistance of Epoxy Resins by Polyethylene Glycol简

Rubbers have been well accepted for modifying brittle epoxies but rubber modified epoxies usually posses lowered tensile strength though enhanced ductility and fracture resistance. In this work, a polyethylene glycol （PEG-4000） is used to modify diglycidyl ether of bisphenol A/methyltetrahydrophthalic anhydride system for enhancing cryogenic tensile strength, ductility and impact resistance. The results display that the cryogenic tensile strength, ductility （failure strain） and fracture resistance （impact strength） are all enhanced for the modified epoxy system at proper PEG contents. The maximum tensile strength （127.8 MPa） at the cryogenic temperature （77 K） with an improvement of 30.1% is observed for the modified system with the 15 wt% PEG content. The ductility and impact resistance at both room temperature and cryogenic temperature are all improved for the modified epoxy system with proper PEG-4000 contents. These observations are explained by the positron annihilation lifetime spectroscopy results and scanning electron microscopy results. Moreover, the glass transition temperature decreases slightly with increasing PEG content.     

有机硅改性双酚F环氧树脂的性能

合成了脂肪族二官能度端环氧基聚二甲基硅氧烷、含酚羟基烷氧基硅烷及3,3′,3″-三羟基苯氧基硅烷三缩水甘油醚,研究了有机硅对环氧树脂力学性能的影响,并用TMA及化学分析方法研究了改性固化物的热性能和树脂/玻璃纤维复合材料的耐酸性。研究结果表明,3,3′,3″-三羟基苯氧基硅烷三缩水甘油醚可使环氧树脂的拉伸强度、弯曲强度分别提高10.4%及53.6%,线胀系数降低18.8%,抗开裂指数提高52.2%,同时保持固化物较高的玻璃化温度,提高耐酸性,是一种理想的环氧树脂新型改性剂。     

The cryogenic thermal expansion and mechanical properties of plasma modified ZrW2O8 reinforced epoxy

In this article, epoxy resin reinforced by negative thermal expansion material, ZrW₂O₈, was fabricated. The surface modification of ZrW₂O₈ particles was performed via plasma enhanced chemical vapor deposition (PECVD) process. As a result, a thin film was uniformly deposited on the surfaces of the ZrW₂O₈ particles, leading to an improvement of compatibility and dispersion of ZrW₂O₈ fillers inside epoxy matrix. Moreover, the coefficients of thermal expansion (CTEs) of the composite material containing 0-40 vol.% fillers were studied under cryogenic temperatures. The results showed a significant reduction in thermal expansion with increasing ZrW₂O₈ content. The cryogenic mechanical properties of ZrW₂O₈/epoxy composites were also investigated, showing the properties were improved by adding ZrW₂O₈ to certain content. In addition, the mechanical strength and modulus of the composite were observed significantly higher at cryogenic temperature than that at room temperature because of the thermal shrink effect and the frozen epoxy matrix.     

混合型固化剂对环氧树脂室温和低温力学性能的影响

研究了一种刚性和柔性胺混合型固化剂（芳香胺DETD和聚醚胺D-400）固化环氧树脂浇铸体的力学性能、材料断裂表面的微观形貌和玻璃化转变温度等性能。结果表明:当D-400加入量占固化剂总量的40%时,其室温拉伸强度呈现最大值,为82.52 MPa,弹性模量为2.30 GPa,与未加D-400的体系相比分别提高了6.3%和14.4%,其低温冲击强度提高了14%。对冲击断面形貌进行扫描电子显微分析表明:D-400的加入致使断口形貌变得粗糙,抗开裂能力得到提高。热分析实验结果显示,体系的玻璃化转变温度随着D-400含量的增加而降低。此外,还探讨了环氧树脂体系低温增韧机制。      

A COMPARATIVE STUDY OF THE PREPARATION AND CHARACTERIZATION OF AROMATIC AND ALIPHATIC BISMALEIMIDES TO PRODUCE MODIFIED SILICONIZED EPOXY INTERCROSSLINKED MATRICES FOR ENGINEERING APPLICATIONS

A novel hybrid intercrosslinked network of hydroxyl-terminated polydimethylsiloxane modified epoxy and bismaleimides [N,N'-bismaleimido-4,4'-diphenylmethane and 1,6-bis(maleimido)hexane] matrix systems were developed. Epoxy resin was modified with 5, 10, and 15% (wt%) of hydroxyl-terminated polydimethylsiloxane using γ-aminopropyltriethoxysilane as crosslinking agent and dibutyltindilaurate as catalyst. The reaction between hydroxyl-terminated polydimethylsiloxane and epoxy resin was confirmed by IR spectral studies. The siliconized epoxy systems were further modified with 5, 10, and 15% (wt%) of both aromatic and aliphatic bismaleimides separately. The castings and E-glass fiber-reinforced composites prepared were characterized for their mechanical properties. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) of the matrix samples were also performed to determine the glass transition temperature (T_g) and thermal degradation temperature of the hybrid intercrosslinked systems. Data obtained from mechanical studies and thermal characterization indicate that the introduction of siloxane into epoxy resin improves the toughness and thermal stability, with reduction in strength and modulus values. The incorporation of aromatic bismaleimide into epoxy resin improved both tensile strength and thermal properties, whereas it was observed that the incorporation up to 5% of aliphatic bismaleimide into epoxy resin decreased the stress-strain value and above 5% increased the strength properties. However, the introduction of both aromatic and aliphatic bismaleimides (aromatic and aliphatic) into siliconized epoxy resin influenced both mechanical and thermal properties according to the percentage content.     

可控交联聚芳醚酮改性电子束固化环氧树脂结构与性能的研究

报道了一种可控交联聚芳醚酮(CCPAEK)的电子束辐照交联行为，研究了CCPAEK改性电子束固化EB-3环氧树脂体系的结构和性能。DMTA分析表明，150kGy EB辐照剂量固化后的改性EB-3树脂体系具有介于两单纯组分之间的单一玻璃化转变温度。改性前后EB-3树脂基体断口形貌发生很大变化，改性体系呈现韧性断裂的特征，其力学性能及抗冲击性能均有较大提高。TGA分析表明，CCPAEK的加入对EB-3树脂基体的耐热性能影响较小。     

高导热环氧/有机硅杂化封装胶的制备与性能

以γ-缩水甘油醚氧丙基三甲氧基硅烷为原料,通过水解缩聚制备出有机硅树脂,采用不同尺寸的改性氧化铝填充环氧/有机硅树脂基体以改善其耐热性能,并考察其力学性能、导热性能。结果表明,合成的有机硅树脂能提高封装胶的热分解温度,其热分解温度比环氧树脂高35.66℃。所制备封装胶的导热系数为1.01 W/(m.K),相比单一环氧树脂其导热性能提高了约5倍,其粘接强度为10.27 MPa,该导热封装胶表现出良好的的综合性能,可用于微电子器件封装领域。     

The reinforcing effect of graphene nanosheets on the cryogenic mechanical properties of epoxy resins

The reinforcing effect of graphene in enhancing the cryogenic tensile and impact properties of epoxy composites is examined at a weight fraction of 0.05–0.50%. The micro-structure and cryogenic mechanical properties of the graphene/epoxy composites are investigated using scanning electron microscopy, transmission electron microscopy, small-angle X-ray scattering and mechanical testing techniques. The results show that the graphene dispersion in the epoxy matrix is good at low contents while its aggregation takes place and becomes severer as its content increases. And the cryogenic tensile and impact strength at liquid nitrogen temperature (77 K) of the composites are effectively improved by the graphene addition at proper contents. The cryogenic Young’s modulus increases almost linearly with increasing the graphene content. Moreover, the results for the mechanical properties at room temperature (298 K) of the graphene/epoxy composites are also presented for the purpose of comparison.