Design of the phthalonitrile‐based composite laminates by improving the interfacial compatibility and their enhanced properties

Phthalonitrile containing benzoxazine (BA‐ph) and cyanate ester (CE) were chosen as the thermosetting matrix and the glass fiber (GF) reinforced laminates formed at low temperature were designed. The polyarylene ether nitriles containing pendent carboxyl groups (CPEN) was selected to modify the interfacial interaction between the resin matrix and GFs. Two methods of introducing CPEN were compared and the effects of CPEN on curing behaviors and properties of the composites were investigated. Results showed that with the CPEN, exothermic peaks shifted to lower temperature and curing temperatures of BA‐ph/CE decreased slightly. The mechanical and thermal properties of GF‐reinforced composites were discussed and the results indicated that the composites of modified GFs with CPEN exhibited outstanding mechanical properties, higher glass transition temperature (T_g > 290 °C) than that of composites composed of CPEN mixed with BA‐ph/CE. Moreover, GF‐reinforced composites showed stable dielectric constants (3.8–4.5) and low dielectric loss (0.005–0.01), which were independent of the frequency. In sum, the various methods of the introduction of CPEN in the GF‐reinforced composites may provide a new route to prepare improved composites, meanwhile, composites with outstanding processability and excellent mechanical and thermal properties are expected to be widely applied in the fields of high‐performance structural materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45881.     

New composites with high thermal conductivity and low dielectric constant for microelectronic packaging

Three composites based on cyanate (CE) resin, aluminum nitride (AlN), surface‐treated aluminum nitride [AlN(KH560)], and silicon dioxide (SiO₂) for microelectronic packaging, coded as AlN/CE, AlN(KH560)‐SiO₂(KH560)/CE, and AlN‐SiO₂/CE composite, respectively, were developed for the first time. The thermal conductivity and dielectric constant of all composites were investigated in detail. Results show that properties of fillers in composites have great influence on the thermal conductivity and dielectric constant of composites. Surface treatment of fillers is beneficial to increase the thermal conductivity or reduce dielectric constant of the composites. Comparing with binary composite, when the filler content is high, ternary composites possess lower thermal conductivity and dielectric constant. The reasons leading to these outcomes are discussed intensively. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Effect of processing conditions on physical properties of 3‐aminophenoxyphthalonitrile/epoxy laminates

To develop high performances of polymer composite laminates, differential scanning calorimetry and dynamic rheological analysis studies were conducted to show curing behaviors of 3‐aminophenoxyphthalonitrile/epoxy resin (3‐APN/EP) matrix and define cure parameters of manufacturing processes. Glass fiber reinforced 3‐APN/EP (GF/3‐APN/EP) composite laminates were successfully prepared through different processing conditions with three parameters such as pressures, temperatures, and time. Based on flexure tests, dynamic mechanical analysis, thermal gravimetric analysis, and scanning electron microscope, the complementary catalytic effect of the three processing parameters is investigated by studying mechanical behavior, thermomechanical behavior, thermal behavior, and fracture morphology of GF/3‐APN/EP laminates. The 50/50 GF/3‐APN/EP laminates showed a significant improvement in flexural strength, glass transition temperature (T_g), and thermal stability with favorable processing parameters. It was also found that the T_g and thermal stability were significantly improved by the postheated treatment method. The effect of manufacturing process provides a new and simple route for the polymer–matrix composites application, which indicates that the composites can be manufactured at low temperatures. But, they can be used in a high temperature environment. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39746.     

Investigation on thermal stability and tribological properties of ZrB2 particles filling cyanate ester resin composites by experiments and numerical simulation

The thermal stability and tribological properties of cyanate ester (CE) composites filled with Zirconium boride (ZrB₂) particles were investigated by experimental and numerical simulation. The results of thermogravimetric analysis and differential scanning calorimetry showed that the thermal stability of composites was improved by introduction of ZrB₂ particles. The tribological properties of composites including friction coefficient and wear rate measured by pin‐on‐disk friction and wear tester were enhanced. Friction coefficient and wear rate of composites were decreased significantly with an increase of ZrB₂ particles content under dry and oil sliding conditions. The 5 wt% ZrB₂ particles reinforced CE resin composite presented optimal thermal stability and tribological performance due to good dispersion of ZrB₂ particles. The worn surfaces of composites were observed by scanning electron microscopy to explore wear mechanism, indicating that the dominant wear mechanism of composites was transformed from adhesive wear to abrasive wear after incorporation of ZrB₂ particles. Finite element model was established to study the distribution of friction stress. The results revealed that filling ZrB₂ particles in the friction process of composites could bear more friction stress than CE resin matrix, which further illustrated that abrasive wear is main wear mechanism of ZrB₂/CE resin composites. POLYM. ENG. SCI., 59:602–607, 2019. © 2018 Society of Plastics Engineers     

Dynamic mechanical properties of three‐component composites (acrylic polymer/epoxy/SiO2) in the glass‐transition region

In previous studies, we reported the linear and nonlinear rheological properties of three‐component composites consisting of acrylic polymer (AP), epoxy resin (EP), and various SiO₂ contents (AP/EP/SiO₂) in the molten state. In this study, the dynamic mechanical properties of AP/EP/SiO₂ composites with different particle sizes (0.5 and 8 μm) were investigated in the glass‐transition region. The EP consisted of three kinds of EP components. The α relaxation due to the glass transition shifted to a higher temperature with an increase in the volume fraction (?) for the AP/EP/SiO₂ composites having a particle size of 0.5 μm, but the α relaxation scarcely shifted for the composite having a particle size of 8 μm as a general result. This result suggested that the SiO₂ nanoparticles that were 0.5 μm in size adsorbed a lot of the low‐glass‐transition‐temperature (T_g) component because of their large surface area. The AP/SiO₂ composites did not exhibit a shift in T_g; this indicated that the composite did not adsorb any component. The modulus in the glassy state (E′_g) exhibited a very weak &phis; dependence for the AP/EP/SiO₂ composites having particle sizes of 0.5 and 8 μm, although E′_g of the AP/SiO₂ composites increased with &phis;. The AP/EP/SiO₂ composites exhibited a peculiar dynamic mechanical behavior, although the AP/SiO₂ composites showed the behavior of general two‐component composites. Scanning electron microscopic observations indicated that some components in the EP were adsorbed on the surface of the SiO₂ particles. We concluded that the peculiar behavior of the AP/EP/SiO₂ composites was due to the selective adsorption of the EP component. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40409.     

Different microstructure BaO–B2O3–SiO2 glass/ceramic composites depending on high-temperature wetting affinity

In this work, we propose a simple but effective method to fabricate BaO–B₂O₃–SiO₂ glass/ceramic composites with different microstructures that depend on the high-temperature wetting affinity. The experimental results showed that the wetting affinity between oxide ceramic and the BaO–B₂O₃–SiO₂ glass matrix could strongly affect the driving force of densification and crystallization and finally the microstructure of the glass/ceramic composites. It was found that suitable amounts of alumina powders could obviously increase the driving force for sintering of glass by increasing the capillary pressure. In this case, the contact angle between alumina and glass matrix is about 24° at high temperature and a densified and homogeneous microstructure of glass/alumina composite was obtained. On the contrary, rutile powders additive was found to result in higher phase separation and crystallization during the sintering of glass/rutile composites. In this case, the contact angle between rutile and glass matrix is about 124° at high temperature, and the sintered body has a lower dielectric loss than the sample with alumina additive. Therefore, the microstructure and dielectric property of glass/ceramic composites could be controlled by adjusting the ceramic composition and wetting affinity between ceramic additive and glass matrix in our study.     

Effect of nanosilica on the thermal,mechanical, and dielectric properties of polyarylene ether nitriles terminated with phthalonitrile

Nanosilica/polyarylene ether nitriles terminated with phthalonitrile (SiO₂/PEN‐t‐Ph) composites were prepared by hot‐press approach. To ensure the nano‐SiO₂ can disperse uniformly, the solution casting method combined with ultrasonic dispersion technology had been taken previously. The mass fraction of nano‐SiO₂ particles was varied to investigate their effect on the thermal, mechanical, and dielectric properties of the nanocomposites. From scanning electron microscope images, it was found that the nanoSiO₂ particles were dispersed uniformly in the PEN‐t‐Ph matrix when the addition of nano‐SiO₂ was less than 16.0 wt%. However, when the mass fraction of nano‐SiO₂ increased to 20.0 wt%, the nano‐SiO₂ particles tend to self‐aggregate and form microns sized particles. Thermal studies revealed that nano‐SiO₂ particles did not weaken the thermal stabilities of the PEN‐t‐Ph matrix. Mechanical investigation manifested that the SiO₂/PEN‐t‐Ph nanocomposites with 12.0 wt% nano‐SiO₂ loading showed the best mechanical performance with tensile strength of 108.2 MPa and tensile modulus of 2107.5 Mpa, increasing by 14% and 19%, respectively as compared with the pure PEN‐t‐Ph film. Dielectric measurement showed that the dielectric constant increased from 3.70 to 4.15 when the nano‐SiO₂ particles varied from 0.0 to 20.0 wt% at 1 kHz. Therefore, such composite was a good candidate for high performance materials at elevated temperature environment. POLYM. COMPOS., 35:344–350, 2014. © 2013 Society of Plastics Engineers     

氰酸酯树脂/纳米氧化铜复合材料制备及性能

将无机纳米氧化铜(CuO)粒子加入氰酸酯树脂(CE),以有机锡(DBTDL)实现自由基引发,定量加入环氧树脂(E–54)制得CE/CuO系列复合材料.测试了复合材料的力学性能、导热性能和耐酸碱腐蚀性能,讨论了复合材料性能得以改变的原因.结果表明,无机纳米CuO粒子的引入,有利于CE基体树脂的聚合,无机纳米CuO粒子含量...     

Dielectric properties of polymer/ceramic composites based on thermosetting polymers

Summary A series of thermosetting polymer/ceramic composites were prepared. Three kinds of thermosetting polymers, i.e. cyanate resin, bismaleimide resin, and epoxy resin, were used as matrixes, and BaTiO₃ particles were as fillers. The dielectric properties of these composites were investigated. Experimental data of the dielectric constants were fitted to several theoretical equations in order to obtain the best-fitting equations of the dielectric constants of these composites. The result indicates that the dielectric constants of composites all increase with the increase of BaTiO₃ content. Using bismaleimide resin and epoxy resin as matrixes, the dielectric losses both increase obviously as the amount of BaTiO₃ particles is increased, but the dielectric loss of cyanate/BaTiO₃ composite decreases. With the increase of the frequency, the variation ranges of the dielectric constant and dielectric loss of cyanate/BaTiO₃ composite are both the smallest. The predications of the effective dielectric constants by Lichterecker mixing rule are in good agreement with experiment data.     

Novel high‐performance wave‐transparent aluminum phosphate/cyanate ester composites

Advanced wave‐transparent composites are the key materials for many cutting‐edge industries including aviation and aerospace, which should have outstanding heat resistance, low dielectric constant and loss as well as good mechanical properties. A novel kind of high‐performance wave‐transparent composites based on surface‐modified aluminum phosphate AlPO₄(KH‐550) and cyanate ester (CE) was first developed. The dielectric and dynamic mechanical properties of AlPO₄(KH‐550)/CE composites were investigated intensively. Results show that AlPO₄(KH‐550)/CE composites have decreased dielectric loss and higher storage moduli than pure CE resin; in addition, the composites with suitable AlPO₄(KH‐550) concentration remain the outstanding thermal property and low dielectric constant of pure CE resin. The reasons attributing to these results are discussed from the effects of AlPO₄(KH‐550) on the key aspects such as morphology, curing mechanism, and interfacial adhesion of composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The influence of cooling rate on the fracture properties of a glass reiforced/nylon fiber-metal laminate

The effect of varying cooling rate on the microstructure and resulting mechanical properties of a novel fiber-metal laminate (FML) based on a glass fiber-reinforced nylon composite has been investigated. Polished thin sections removed from plain glass fiber/nylon composites and their corresponding fiber-metal laminates indicated that the prevailing microstructure was strongly dependent on the rate of cooling from the melt. Mode I and Mode II interlaminar fracture tests on the plain glass fiber reinforced nylon laminates indicated that the values of G_Ic and G_IIc averaged approximately 1100 J/m² and 3700 J/m² respectively at all cooling rates. The degree of adhesion between the aluminum alloy and composite substrates was investigated using the single cantilever beam geometry. Here, the measured values of G_c were similar in magnitude to the Mode I interlaminar fracture energy of the composite, tending to increase slightly with increasing cooling rate. The tensile and flexural fracture properties of the plain composites and the fiber metal laminates were found to increase by between 10% and 20% as the cooling rate was increased by two orders of magnitude. This effect was attributed to over-aging of the aluminum alloy plies at elevated temperature during cooling. Finally, fiber metal laminates based on glass fiber/nylon composites were shown to exhibit an excellent resistance to low velocity impact loading. Damage, in the form of delamination, fiber fracture, matrix cracking in the composite plies, and plastic deformation and fracture in the aluminum layer, was observed under localized impact loading. Here, the fast-cooled fiber metal laminates offered superior post-impact mechanical properties at low and intermediate impact energies, yet very similar results under high impact energies.     

Improvements in interfacial and heat-resistant properties of carbon fiber/methylphenylsilicone resins composites by incorporating silica-coated multi-walled carbon nanotubes

The multi-scale reinforcement and interfacial strengthening on carbon fiber (CF)-reinforced methylphenylsilicone resin (MPSR) composites by adding silica-coated multi-walled carbon nanotubes (SiO₂-CNTs) were investigated. SiO₂-CNT has been successfully prepared via the hydrolysis of tetraethoxysilane in the presence of acid-oxidized multi-walled carbon nanotubes. Transmission electron microscopy, X-ray diffraction, and Fourier Transform infrared spectroscopy were carried out to examine the functional groups and structures of CNTs. Then, SiO₂-CNT was incorporated into MPSR matrix to prepare CF/MPSR-based composites by the compression molding method. The effects of the introduced SiO₂-CNT on the interfacial, impact, and heat-resistant properties of CF/MPSR composites were evaluated by short-beam bend method, impact test, and thermal oxygen aging experiments, respectively. Experimental results revealed that the CF/MPSR composites reinforced with 0.5 wt% SiO₂-CNT showed a significant increase 34.53% in the interlaminar shear strength (ILSS) and 20.10% in impact properties. Moreover, the heat-resistant properties of composites were enhanced significantly by adding SiO₂-CNT hybrid nanoparticles. These enhancements are mainly attributed to the improved matrix performance resulted from the molecular-level dispersion of SiO₂-CNT in MPSR matrix and the strong interfacial adhesion between SiO₂-CNT and matrix resin, which are beneficial to improve the mechanical stress transfer from MPSR matrix to CFs reinforcement and alleviate stress concentrations.     

Tribological properties of bismaleimide composites with surface‐modified SiO2 nanoparticles

In this article, the surface of SiO₂ nanoparticles was modified by silane coupling agent N‐(2‐aminoethyl)‐γ‐aminopropylmethyl dimethoxy silane. The bismaleimide nanocomposites with surface‐modified SiO₂ nanoparticles or unmodified SiO₂ nanoparticles were prepared by the same casting method. The tribological performance of the nanocomposites was studied on an M‐200 friction and wear tester. The results indicated that the addition of SiO₂ nanoparticles could decrease the frictional coefficient and the wear rate of the composites. The nanocomposites with surface‐modified SiO₂ nanoparticles showed better wear resistance and lower frictional coefficient than that with the unmodified nanoparticles SiO₂. The specific wear rate and the steady frictional coefficient of the composite with 1.0 wt % surface‐modified SiO₂ nanoparticles are only 1.8 × 10^?6 mm³/N m and 0.21, respectively. The dispersion of surface‐modified SiO₂ nanoparticles in resin matrix was observed with transmission electron microscope, and the worn surfaces of pure resin matrix and the nanocomposites were observed with scanning electron microscope. The different tribological behavior of the resin matrix and the filled composites should be dependent on their different mechanical properties and wear mechanism. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Enhanced dielectric permittivity of BaTiO3/epoxy resin composites by particle alignment

Barium titanate (BaTiO₃)/epoxy resin composites with a novel structure, in which the BaTiO₃ particles were directionally aligned in the epoxy resin matrix, were fabricated using the ice-templating method. The effects of the filler particle alignment and the filler fraction on the dielectric permittivity as well as the dielectric loss of the composites were studied. The results show that the aligning filler particles can significantly improve the dielectric permittivity while maintaining the dielectric loss compared with the traditional composite structure (homogeneously distributed). Due to the feasibility of the enhancement of the dielectric properties of the composites, the particle alignment that is achieved via the ice-templating method can be used in the field of high energy density capacitors.     

Glass-Reinforced Composites Based on a Novel Oligoimide-Epoxy Resin System

A novel matrix resin system, oligoimide-epoxy resin, has been developed to prepare glass fiber reinforced composites. Benzidine bismaleimide-diaminodiphenyl methane (BBM-DDM) and ethyl-ene bismaieimide-diaminodiphenyl methane (EBM-DDM) oligo-mers having more —NH₂ groups were prepared through the Michael addition reaction. These oligoimides were used for curing of commercial epoxy resin (i.e., diglycidyl ether of bisphenol-A) at 120°–140°C to fabricate crosslinked oligoimide-epoxy resin glass fiber reinforced composites without the evolution of byproduct. The fabricated composites (i.e., laminates) were characterized by their chemical resistance and mechanical properties.     

Enhanced dielectric constant of acrylonitrile–butadiene rubber/barium titanate composites with mechanical reinforcement by nanosilica

Acrylonitrile–butadiene rubber (NBR), a synthetic rubber having C≡N dipoles, was chosen as a polymer matrix with a higher dielectric constant than other non-polar rubber like silicone rubber or ethylene–propylene–diene monomer. Barium titanate (BaTiO₃), as a ferroelectric material, with a high dielectric constant and low dielectric loss was selected as a main filler to further enhance the dielectric constant of NBR. An effective silane coupling agent (KH845-4), selected from five types of silane coupling agents with different characteristic functional groups, was used to modify the surface of BaTiO₃ particles to enhance its interfacial adhesion to the matrix. Fourier transform infrared spectroscopy (FTIR) was used to verify the successful modification. The addition of BaTiO₃ obviously enhanced the dielectric constants. In particular, an uncommon pattern of dielectric loss has been displayed and analyzed in this paper. Nevertheless, the reinforcing effect of mechanical strength of the NBR/treated BaTiO₃ composites is limited. On this basis, the addition of nanosilica (SiO₂), replacing part of NBR, improved the mechanical strength. Confirmed by scanning electron microscopy (SEM), the SiO₂ and treated BaTiO₃ particles were dispersed well in the NBR matrix. The tensile strength was increased from 4.33 to 6.12 MPa when SiO₂ accounted for 4%. Moreover, the curing characterizations, crosslinking density, resistivity, and oil resistance were evaluated. This composite material can be used in manufacturing electronic devices, which are subjected to oily environments for a long time.     

Processability,morphology, thermal,and mechanical properties of rigid PVC composites with liquid macromolecular modifier‐coated CaCO3

Rigid poly(vinyl chloride) (PVC)/CaCO₃ and PVC/liquid macromolecular modifier (LMM) coated CaCO₃ (PVC/LCC) composites were both fabricated by melt mixing. The processability, micro‐structure, dynamic mechanical behavior and mechanical properties of PVC/CaCO₃ and PVC/LCC composites were studied by using torque rheometer, scanning electron microscope (SEM), dynamic mechanical analysis (DMA), and universal mechanical testing machine. The results showed that the synergistic effect of LMM and CaCO₃ particles accelerated the plasticization of PVC resins. The processability of PVC/LCC composites was improved. The dispersion of LCC in PVC matrix was improved by the modification of CaCO₃ particles with LMM. The T_gs of PVC/LCC composites were enhanced by filling with LCC. Because of the synergistic toughening of LMM and CaCO₃ particles, the PVC/LCC composites exhibited excellent notched impact properties at the optimum value of LCC particles content. POLYM. COMPOS., 36:1286–1292, 2015. © 2014 Society of Plastics Engineers     

Preparation and properties of nano‐Al2O3 particles/polyester/epoxy resin ternary composites

This article presents the results of an experimental study on the preparation and properties of new ternary composites composed of nano‐Al₂O₃ particles, polyester, and epoxy resin. The ternary composites were prepared by the addition of the nano‐Al₂O₃ particles in a binary matrix, with elevated viscosity, of the epoxy resin modified by the polyester. The nano‐Al₂O₃ particles were previously located and dispersed in the polyester phase. The study showed that the ternary system was a type of nanoscale dispersed composite with high strength and toughness as well as modulus, combined with excellent dielectric and heat‐resistance properties. All related properties of the composites were remarkably superior to those of both the binary matrix and the unmodified epoxy resin. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 70–77, 2002     

The Effects of Filler Content and Size on the Properties of PTFE/SiO2 Composites

A study on PTFE reinforced with SiO₂ was described. It included the manufacturing process of SiO₂-reinforced PTFE and the effects of the SiO₂ content and size on the properties of the composite material, such as thermal, dielectric, tensile strength and morphology, etc. PTFE/SiO₂ composites loaded with two sizes (5 μm or 25 μm SiO₂) of filler contents varied from 0–60 wt% were mixed by a high-speed dispersion mixer and made via a two-roll milling machine. Our results showed that the composite filled with 25 μm SiO₂ at 60 wt% filler content had the highest modulus, lowest CTE _z and acceptable dielectric properties. Composites with different sizes of filler showed a similar trend of decreasing tensile strength and coefficient of thermal expansion (CTE _z ), and increasing tensile modulus, water absorption and dielectric properties as the filler content increased. Furthermore, the composites filled with small-size filler showed higher water absorption and dielectric loss properties due to the presence of higher SiO₂ surface area. Poor adhesion between filler and matrix is a primary cause of low tensile properties and lack of increase in thermal stability. Such phenomenon was also confirmed by fracture surface analysis of scanning electron microscope (SEM). Experimental data were compared with theoretical models from the literatures, which are used to predict the properties of two component mixtures. The results revealed that experimental values of dielectric constant and CTE _z agreed with the theoretical calculated values. It was also found that the modified Nicolais-Narkis equation provided a good estimation for the tensile strength of composite. This revised version was published online in July 2006 with corrections to the Cover Date.     

Preparation and characterization of POSS‐SiO2/cyanate ester composites with high performance

In this article, a hybrid filler based on polyhedral oligomeric silsesquioxane and silica, coded as POSS‐SiO₂, has been successfully synthesized. The structure of POSS‐SiO₂ was studied by Fourier‐transform infrared spectra, X‐ray diffraction, and scanning electron microscopy. Then the POSS‐SiO₂ was compounded with dicyclopentadiene bisphenol dicyanate ester (DCPDCE) resin to prepare composites. The effects of POSS‐SiO₂ on the curing reaction, mechanical, thermal, dielectric and tribological properties of DCPDCE resin were investigated systematically. Results of differential scanning calorimetry show that the addition of POSS‐SiO₂ can facilitate the curing reaction of DCPDCE and decrease the curing temperature of DCPDCE. Compared with pure DCPDCE resin, the impact and flexural strengths of the composites materials are improved markedly with up to 72 and 52% increasing magnitude, respectively. Meanwhile, the POSS‐SiO₂/DCPDCE systems exhibit lower dielectric constant and loss than pure DCPDCE resin over the testing frequency from 10 to 60 MHz. In addition, the thermal stability and tribological properties of POSS‐SiO₂/DCPDCE composites are also superior to that of pure DCPDCE resin. POLYM. COMPOS., 36:1840–1848, 2015. © 2014 Society of Plastics Engineers