Preparation and characterization of 3,3′‐bis (maleimidophenyl)phenylphosphine oxide (BMI)/polysulfone modified epoxy intercrosslinked matrices

An intercrosslinked network of polysulfone (PSF)—bismaleimide (BMI) modified epoxy matrix system was made by using diglycidyl ether of bisphenol A (DGEBA) epoxy resin, hydroxyl terminated polysulfone and bismaleimide (3,3′‐bis(maleimidophenyl) phenylphosphine oxide) with diaminodiphenylmethane (DDM) as curing agent. BMI–PSF–epoxy matrices were characterized using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and heat deflection temperature (HDT) analysis. The matrices, in the form of castings, were characterized for their mechanical properties such as tensile strength, flexural strength, and unnotched Izod impact test as per ASTM methods. Mechanical studies indicated that the introduction of polysulfone into epoxy resin improves the toughness to an appreciable extent with insignificant increase in stress–strain properties. DSC studies indicated that the introduction of polysulfone decreases the glass transition temperature, whereas the incorporation of bismaleimide into epoxy resin influences the mechanical and thermal properties according to its percentage content. DSC thermograms of polysulfone as well as BMI modified epoxy resin show a unimodal reaction exotherm. The thermal stability and flame retardant properties of cured epoxy resins were improved with the introduction of bismaleimide and polysulfone. Water absorption characteristics were studied as per ASTM method and the morphology of the BMI modified epoxy and PSF‐epoxy systems were studied by scanning electron microscope. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Multi-component nanocomposites of epoxy/silsesquioxane reinforced with carbon fibers and carbon nanotubes processed by resin transfer molding

ABSTRACT

In this work, an epoxy resin modified by silsesquioxane oligomers was used to produce multi-component nanocomposites reinforced with carbon fiber (CF) and multi-walled carbon nanotubes (CNT) by resin transfer molding (RTM). The combination of sonication process with the incorporation of silsesquioxane domains (i.e. increasing the degree of crosslinking of the epoxy matrix), improved the mechanical strength of the hybrid matrix and hybrid/CF/CNT nanocomposites. The multi-component nanocomposites produced by RTM presented Young modulus of 35 ± 8 GPa, tensile strength of 303 ± 41 MPa and impact strength of 1.0 ± 0.3 kJ m^?1. The results showed a significant increase in the tensile strength and impact resistance of the epoxy matrix by the incorporation of silsesquioxanes and sonication before curing of the matrices, showing the promising potential of this multi-component nanocomposite for pipelines and other structural applications.     

Rheology,morphological evolution,thermal, and mechanical properties of epoxy modified with polysulfone and cellulose nanofibers

In this work, the epoxy systems modified with polysulfone (PSF) and cellulose nanofiber (CNF) cured at different temperatures are prepared to investigate the effect of CNF on curing reaction, morphology evolution, rheology, thermal, and mechanical performance of composites. The reaction rate is increased and the activation energy is decreased with CNF incorporation, implying an accelerating effect of CNF on the epoxy-amine reaction. The phase separation and gelation of the epoxy/PSF/CNF system start earlier compared with the binary system of epoxy/PSF. While it is displayed by rheology that both the system viscosity and relaxation time are elevated with CNF, presenting an inhibiting effect on phase evolution. Morphologies with smaller domain size are finally freezed by the epoxy gelation. The enhancement of impact performance for the epoxy/PSF/CNF composites is indicated by 40.2% increase in the impact strength, which is attributed to the finer phase-separated morphology, the uniformly distributed CNF within the polymer matrix and the good load transfer between phases. In addition, the thermal stability of composites is improved as the CNFs existed in the phase-separated polymer matrix can restrict the thermal motion of molecules during decomposition process. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48628.     

Modification of epoxy resin by polysulfone to improve the interfacial and mechanical properties in glass fibre composites. III. Properties of the cured blends and their structures in the polymer/fibre interphase

Thermal and mechanical properties (linear expansion coefficient, glass transition temperatures, Young's modulus, tensile and bending strengths, and failure energies under quasistatic and impact loadings) of cured epoxy-polysulfone (PSF) blends, as well as their structures have been studied. It was shown that PSF incorporation did not lead to appreciable changes in the linear thermal expansion coefficients and glass transition temperatures of the cured blends. According to this observation, incorporation of PSF into the epoxy matrix should not result in a significant increase in the internal stresses in the system. No drop in the modulus and strength of the bulk blends was observed when compared with unmodified epoxy matrix. The failure energy of the epoxy-PSF matrices increased as the PSF content increased under all loading conditions, whereas the strength of the polymer blend matrices increased only under impact loading. Optimal PSF content was found to be 10 wt%. It was shown that all the blends investigated were homogeneous before curing and became heterogeneous after curing. For epoxy-PSF/fibre joints a mixed (interfacial-cohesive) failure mode was observed for all the samples investigated. The results from the rheology, wetting, thermal, mechanical and structural tests, described in a set of papers, are compared with each other to explain the reasons for the adhesion strength behaviour of epoxy-PSF/glass fibre joints. Based on the finding here, an epoxy-10% PSF matrix is recommended for composite production.     

新型环氧大豆油增韧酚醛树脂的合成与性质

A novel epoxidized soybean oil-toughened-phenolic resin（ESO-T-PR）has been synthesized by etheri- fication graft and multi-amine curing ESO.Fourier transform infrared spectroscopy（FTIR）was adopted to investi- gate its molecular structure and scan electron microscope（SEM）was used to observe the micro morphology of its impact fracture surface.This ESO-T-PR was adopted as the matrix resin to prepare paper copper clad laminate （P-CCL）and the properties of resulting P-CCL are found superior to the related Chinese National Standard.The toughing mechanism was investigated by comparing the impact strength,solderleaching resistance,flexural strength, peeling strength and morphology of this ESO-T-PR with those of other two ESO modified phenolic resins.It is demonstrated that during the synthesizing process of ESO-T-PR,the phenol hydroxyl is etherified by ESO or ESO epoxy resin prepolymer（ESO chain extension polymer）and the long ESO epoxy resin chain segments enhance the crosslink density of ESO-T-PR and consequently improve the impact toughness and solderleaching resistance of P-CCL made of ESO-T-PR.The ESO-T-PR is a cheap matrix resin with excellent properties to make P-CCL（elec- tric guide board）.     

Effect of Xylene Formaldehyde Resins on Epoxy Resin Adhesive

The effect of some types of xylene formaldehyde on epoxy resin adhesive is studied. Xylene formaldehyde resin or modified xylene formaldehyde resins are mixed into liquid epoxy resin and curing properties of the blends, their adhesive properties and the dispersion state of xylene formaldehyde resin in cured adhesive film are examined. The results obtained are as follows.

1) Generally, by the addition of xylene formaldehyde resins, the degree of curing of blends are decreased, but pot life is prolonged, and tensile shear strength of steel bonds is increased.

2) It is observed that effects of the amount of xylene formaldehyde resins and curing condition on tensile shear strength vary with the kind of xylene formaldehyde resin, because of the difference in chemical structure of xylene formaldehyde resins and their reactivity to epoxy resin.

3) It is found that a limited region of compatibility, between 80 and 100 phr, exists for 100% xylene formaldehyde resin in epoxy resin. It is also found that joint strength is reduced with higher viscosity and molecular weight of 100% xylene formaldehyde resin in the case of 80 phr blends, and that these results have some relation to the dispersion state of xylene formaldehyde resin in epoxy resin, judging from the cured adhesive film observed under a phase contrast microscope.     

The Role of the Interface in Carbon Fibre-Epoxy Composites

The final performance of a composite material depends strongly on the quality of the fibre-matrix interface. The interactions developed at the interface were studied using the acid-base or acceptor-donor concept.

The surface characteristics of the carbon fibres and the epoxy matrix were studied using a tensiometric method and the inverse gas chromatography technique. Acid-base surface characters could be determined allowing the interactions at the interface to be described by a specific interaction parameter.

It was shown that the shear strength of the interface, as measured by a fragmentation test, is strongly correlated to this specific interaction parameter, demonstrating the importance of acid-base interactions in the fibre-matrix adhesion.     

The Compatibilizing Effects of Epoxy Oligomers on Blends of Thermoplastics and Thermotropic Liquid Crystalline Polymer

Abstract:

Several epoxy oligomers, A-X-A series, in which the A represents epoxy group, and the X is molecular block between epoxy groups, were synthesized or selected to compatibilize the blends of polysulfone (PSF)/a semiaromatic Thermotropic Liquid Crystalline Polymer (TLCPA1) and the blends of polycarbonate (PC)/TLCPA1. The results of Differential Scanning Calorimetry (DSC), Scanning Electronic Microscopy (SEM), and mechanical properties measurement of these compatibilized blends showed that the compatibilizing effects of these epoxy oligomers relied on the structure and the spacing block length of X. Among them, one new epoxy oligomer, which was made from allyl bisphenol-A and E-44 (a bisphenol-A epoxy resin, epoxy equivalent: 230), has been demonstrated to be a highly efficient compatibilizer for PSF/TLCPA1 blends. Adding 2% of this compatibilizer to PSF/TLCPA1 blend led to a 6.7% and 9.7% increase of bending strength and tensile strength, respectively.     

Aging Process of Metal/Epoxy Laminates Investigated with X-ray Photoelectron Microscopy and Spectroscopy

In this article we describe the application of X-ray photoelectron spectroscopy to epoxy/dicyandiamide laminates on zinc galvanized steel which were aged under different environmental conditions involving high humidity and temperatures.

X-ray photoelectron microscopy allows us to identify the distribution of chemical elements with a lateral resolution of 10μm. Areas selected in the microscopy mode were then analyzed in the spectroscopy mode in order to get information on the local chemical composition.

We compared the spectroscopic features of the aged but freshly delaminated surfaces of samples stored under ambient conditions at room temperature with samples exposed to the “Kataplasmann” and the “KWT” test, respectively. Furthermore, a comparison was made with a model sample which was prepared in vacuum and on which the curing process was investigated.

Though there is no substantial loss in the lap-shear strength of the samples, we find drastic spectroscopic changes in the Kataplasma and KWT treated samples compared with the sample kept at room temperature. We conclude that the chemical changes induced by these tests cause an internal interphase boundary between the epoxy/metal interface and the bulk adhesive along which delamination occurs. Comparison with the behavior of the water-vapor-treated model sample gives evidence that hydrolysis is the main reaction in these tests.

The results described here complement our former study.¹     

Unit Cell Evolution in Structurally Damageable Particulate-Filled Elastomeric Composites under Simple Extension

A special form of the unit cell is offered for investigation of matrix separation in particulate composites. The threshold tear strength of the matrix is used as a basis for the strength-of-cell estimations. Numerical experiments have been performed within the bounds of large deformation theory.

A weak dependence of the ultimate strength on the filler content as well as the extensive plateaus on tensile elongation have been revealed. The latter are due to the slow and stable character of matrix detachment from filler particles.

These results have proved to be in a good agreement with the available experience.     

Room Temperature Curing Epoxy Adhesives for Elevated Temperature Service

Room Temperature curing compositions of epoxy resins with high temperature service capability (95-120°C) were formulated and evaluated. The compositions were based on selected high functionality atomatic epoxy polymers and multicomponent poly amine curing agent systems. Toughening was achieved by addition of a rubbery phase either by prereaction of the epoxy resin with carboxyl terminated (CTBN) or by amine terminated (ATBN) poly butadiene acrylonitrile. The latter elastomeric component served as a part of the poly amine curing agent.

Best results were achieved with an adhesive formulation comprising tetra glycidyl-4-4'-diaminodiphenylmethane (TGDDM) and triglycidyl ether of p-aminophenol with triethylenetetramine and addition of ATBN with a felt carrier.

Lap shear strengths of aluminum/aluminum specimens primed by silane coupling agent in the order of 22 MPa at 25°C and 11 MPa at 120°C with T-Peel strengths of 1.6N/mm at 25°C and 0.52 N/mm at 120°C, were obtained.

The thermal behaviour and transitions, the chemical and mechanical properties, the microstructure and morphology of the selected adhesive formulation were studied, using DSC, Gehman, FTIR, mechanical testing and SEM analysis, respectively.

Experimental results showed that the selected compositions could develop good high temperature (120°C) properties while cured at room temperature. Furthermore, their high temperature performance compares favorably or even exceeds that of commercially available room-temperature-curing adhesive compounds, and are competitive with elevated temperature cured film adhesives.     

Morphology,thermal and mechanical performance of epoxy/polysulfone composites improved by curing with two different aromatic diamines

Epoxy/polysufone (PSF) composites cured with 4,4'-diaminodiphenyl sulfone (DDS) and 4,4'-diaminodiphenyl methane (DDM) were fabricated, and the effect of dual curing reaction of diamines with epoxy on morphology, mechanical, and thermal performance was investigated. DSC results indicated that DDM was more reactive than DDS and the activation energy decreased with the rising of DDM content. Structures with small domain size at the early stage of phase separation were fixed by the fast epoxy-DDM reaction. When the DDM content was elevated to a high level, large dual structures were changed to fine bicontinuous structures, which was favorable to improve the mechanical property. The mechanical performance of epoxy composites was enhanced and the maximum values were achieved when the DDM/DDS ratio was located at 75/25 (PSF/DDS0.25-DDM0.75). The flexural and tensile strength relative to epoxy/DDM system were enhanced more than those relative to epoxy/DDS, while the increase in toughness was the opposite. TGA measurement showed that thermal stability of epoxy/PSF composites was improved because of the restricting effect of continuous PSF domains on thermal motion of epoxy. DMA analysis exhibited two relaxation peaks for PSF/DDS0.25-DDM0.75, which could be attributed to the formation of phase separated morphology and epoxy network with different cross-link density.     

Application of Adhesive Joining Technology for Manufacturing of the Composite Flexspline for a Harmonic Drive

A new manufacturing method for the cup-type composite flexspline for a harmonic drive was developed using adhesive joining technology to obviate the manufacturing difficulty of the conventional one-piece cup-type steel flexspline and to improve the dynamic characteristics of the flexspline.

In this method, the boss, tube and tooth sections of the flexspline were designed and manufactured separately, and adhesively bonded. The tube section was manufactured with high strength carbon fiber epoxy composite material and its dynamic properties were compared with those of the conventional steel flexspline.

The torque transmission capability of the adhesively-bonded joint was numerically calculated using the nonlinear shear stress-strain relationship which was represented by an exponential form.

From the test results of the manufactured composite flexspline and the conventional steel flexspline, it was found that the manufactured composite flexspline had better torque transmission characteristics. Also, it was found that the damping capacity of the composite flexspline was considerably improved.     

Adhesive Joining Technology for Manufacturing of the Composite Flexspline for a Harmonic Drive

A new manufacturing method for the cup-type composite flexsplinc drive was developed using adhesive joining technology to obviate the manufacturing difficulty of the conventional one-piece cup-type steel flexspline and to improve the dynamic characteristics of the flexspline.

In this method, the boss, tube and tooth sections of the flexspline were designed and manufactured separately, and adhesively bonded. The tube section was manufactured with high strength carbon fiber epoxy composite material and its dynamic properties were compared with those of the conventional steel flexspline.

The torque transmission capability of the adhesively-bonded joint was numerically calculated using the nonlinear shear stress-strain relationship which was represented by an exponential form.

From the test results of the manufactured composite flexspline and the conventional flexspline, it was found that the manufactured composite flexspline had better torque transmission characteristics. Also, it was found that the damping capacity of the composite flexspline was considerable improved.     

Effect of epoxy resin on morphology and physical properties of PVC/organophilic montmorillonite nanocomposites

Poly(vinyl chloride)/organophilic montmorillonite (PVC/OMMT) nanocomposites were prepared by means of melt blending. A liquid epoxy resin was used to aid PVC chains in intercalating into silicate layers. The effects of the preparation methods and epoxy resin contents on the melt intercalation of PVC were investigated. The morphology development, mechanical properties and optical properties of the PVC/OMMT composites were tested as functions of epoxy resin content and OMMT content. Wide‐angle X‐ray diffraction, transmission electron microscopy and scanning electron microscopy were used to characterize the morphology of the resulting composites. After being pretreated by the epoxy resin, the OMMT layers were largely intercalated into the PVC matrix, and even exfoliated at high epoxy resin content. The addition of epoxy resin led to a decrease in optical clarity of the composites but improved the processing stability, as indicated by yellowness index and haze measurement. However, the optical clarity of the composites containing 4 phr of epoxy resin (PVC/E‐OMMT) was improved by increasing the OMMT content, as shown by light transmission. Both the tensile strength and notched Izod impact strength of the PVC/E‐OMMT composites reached their maximum values when the OMMT content was 0.5 phr and the epoxy resin content was 2 phr. With further increase of the OMMT content and the epoxy resin content, the tensile strength decreased but was still higher than that of original PVC. The method of addition of epoxy resin had little effect on the physical properties but mainly influenced the morphology of PVC/OMMT nanocomposites. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2184–2191, 2003     

Mechanical Properties of Bismaleimides Modified Polysulfone Epoxy Matrices

Epoxy resin has been chemically modified using 4, 8, and 12% of bisphenol-A based polysulphone along with three types of bismaleimides, namely [N, N′-bismaleimido-4,4′-diphenylmethane (BMI-1), 1,3-bis (maleimido) benzene (BMI-2) and 1,1′-bis (4-maleimidophenyl) cyclohexane (BMI-3)]. The epoxy hybrid matrices developed, in the form of castings, were used to characterize their mechanical properties like tensile strength, tensile modulus, flexural strength, flexural modulus, impact strength, hardness, and dynamic mechanical analysis as per ASTM standards. Data obtained from mechanical studies indicate that the introduction of hydroxyl terminated polysulfone into epoxy resin enhanced the value of impact strength to the extent of 48% due to the formation of flexible graft structures. Similarly, the incorporation of bismaleimides into epoxy resin also improved both tensile and flexural behavior of epoxy resin. Further, the introduction of combination of both polysulfone and bismaleimides into epoxy resin improved the mechanical properties according to their percentage content. Among the bismaleimides-modified polysulfone epoxy matrices, the epoxy matrix modified with 8% polysulfone and 8% BMI-2 exhibited better mechanical properties than other modified epoxy matrices.     

聚砜改性环氧树脂复合材料热老化性能研究

以聚砜(PSF)改性环氧树脂(EP)为基体树脂,玻璃纤维为增强材料,采用高温模压成型法制备出PSF改性EP/玻璃纤维复合材料。结果表明:PSF能有效提高EP基体的热稳定性能;经200℃热老化72 h后,PSF改性EP/玻璃纤维复合材料的热失重率<1%,其冲击强度和弯曲强度呈先升后降态势,电绝缘性能仍然较好(其体积电阻率和表面电阻率的数量级仍保持在1012左右);该复合材料在高温绝缘场合中具有良好的应用前景。     

Porous epoxy monolith prepared via chemically induced phase separation

Macroporous epoxy monolith was prepared via chemically induced phase separation using diglycidyl ether of bisphenol A (DGEBA) as a monomer, 4,4′-diaminodiphenylmethane (DDM) as a curing agent, and epoxy soybean oil (ESO) as a solvent. The morphology of the cured systems after removal of ESO was examined using scanning electron microscopy, and the composition of epoxy precursors/solvent for phase inversion was determined. The phase-separation mechanism was deduced from the optic microscopic images to be spinodal decomposition. The pore structure of the cured monolith was controlled by a competition between the rates of curing and phase separation. The ESO concentration, content of curing agent, and the curing temperature constituted the influencing factors on the porous morphology. The average pore size increased with increasing ESO concentration, increasing curing temperature, and decreasing the content of curing agent.     

The Temperature Dependence of Interfacial Shear Strength for Various Polymeric Matrices Reinforced with Carbon Fibers

The influence of temperature on the interfacial shear strength between epoxy thermoset matrices and surface treated, carbon AS4 as well as with surface treated and sized AS4-C carbon fibers was investigated. The thermoset matrices all consisted of DGEBA epoxy resin cured with different amine curing agents resulting in matrices with a range of behavior from brittle, elastic to ductile, plastic. For all systems, the results indicate that the interfacial shear strength (ISS) decreases with increasing temperature and as the T_g of the matrix is approached, a large corresponding decrease in the interfacial shear strength is seen. Moreover, the AS4-C (epoxy sized) system revealed a distinct decrease in interfacial shear strength at temperatures lower than the bulk matrix T_g indicating the formation of an interphase layer of composition different from the bulk matrix. Linear superposition methods were used to generate a master curve for the different matrix materials reinforced with the AS4 fibers. These results allow the prediction of ISS at any temperature.     

茶粉/聚乳酸复合材料的增韧改性

为高值化利用茶产业剩余物资源,以茶粉（TD）为生物质填料,聚乳酸（PLA）为基体,以甘油（GL）、聚乙二醇400（PEG400）、环氧大豆油（ESO）和乙酰柠檬酸丁酯（ATBC）为增塑剂,制备了可降解TD/PLA增韧复合材料,并采用红外吸收光谱、热重分析、转矩流变仪、扫描电镜及力学性能测试等考察了增塑剂对TD/PLA复合材料结构与性能的影响。结果表明：4种增塑剂都可改善TD/PLA复合材料的加工流变性,GL的添加不利于复合材料韧性,PEG、ATBC及ESO的添加提高了复合材料韧性,其中ESO增韧效果最佳,其添加制备的复合材料断裂伸长率及缺口冲击强度分别提高了154.23%和65.53%,GL增韧效果最差,ATBC增韧后复合材料力学强度和模量最高。FTIR分析表明,ATBC和ESO可与PLA发生一定相互作用,使C-O键红外吸收峰位增大,其增韧后复合材料吸水率下降。ESO添加提高了TD/PLA复合材料的维卡软化点和热稳定性。SEM图片显示,TD/PLA/ESO复合材料断面粗糙,ESO分散较均匀,与PLA部分相容,而TD/PLA/GL复合材料断面出现严重相分离结构。该研究结果可为进一步探索聚乳酸基茶塑复合材料制备及应用提供试验数据和理论参考。