Preparation and properties of nano diamond/6F‐bisphenol A‐based cyanate ester composites

The aim of this study was to improve thermal conductivity, thermal stability, and mechanical properties of bisphenol A dicyanate ester (BADCy) by adding bisphenol A dicyanate ester containing fluorine (F‐BADCy) and nano diamond. The cyanate esters containing fluorine/nano diamond composites having various ratios of BADCy, F‐BADCy, and nano diamond were prepared. Thermal stability and thermal conductivity of the samples were evaluated by thermogravimetric analysis, differential scanning calorimetry and laser flash method, respectively. The samples were characterized with the following analysis; gel content, water absorption capacity, and stress‐strain test. Hydrophobicity of the samples was determined by the contact angle measurements. Moreover, the surface morphology of the samples was investigated by a scanning electron microscopy (SEM). The obtained results prove that the cyanate ester containing fluorine/nano diamond composites have good thermal and mechanical properties and they can be used in many applications such as electronic devices, materials engineering, and other emergent. POLYM. COMPOS., 34:1977–1985, 2013. © 2013 Society of Plastics Engineers     

Bisphenol S and bisphenol A cyanate ester/barium metaborate composites

The aim of this study was to improve thermal stability and surface properties of bisphenol A dicyanate ester (BADCy) by adding bisphenol S dicyanate ester (BSDCy) and Ba(BO₂)₂. Bisphenol S and bisphenol A cyanate ester/barium metaborate composites having various ratios of BADCy, BSDCy, and Ba(BO₂)₂ were prepared. Thermal stability of the samples was evaluated by thermogravimetric analysis and differential scanning calorimetry. Hydrophobicity of the samples was determined by the contact angle measurements. The samples were characterized with the following analysis; gel content, water absorption capacity. Moreover, the surface morphology of the samples was investigated by a scanning electron microscopy. The obtained results prove that the cyanate ester containing sulfonyl/Ba(BO₂)₂ composites have good thermal and surface properties and they can be used in many applications such as electronic devices, materials engineering, and other emergent. POLYM. COMPOS., 37:1312–1317, 2016. © 2014 Society of Plastics Engineers     

Fabrication of Bioactive Material-Reinforced Caprolactam-Based Cyanate Ester Composite for Coating Applications

The nanocomposite material consisting of bioactive amine-terminated cyclotriphosphazene and functionalized titanium dioxide nanoparticle-reinforced caprolactam-based cyanate ester composites (amine-terminated cyclotriphosphazene/functionalized titanium dioxide/cyanate ester–caprolactam) was developed for coating applications. The structural characterization and coating properties of amine-terminated cyclotriphosphazene/functionalized titanium dioxide/cyanate ester–caprolactam composites coated on MS plates were studied by Fourier transform infrared spectroscopy, scanning electron microscope, contact angle, and electrochemical measurements. The antibacterial studies of amine-terminated cyclotriphosphazene/functionalized titanium dioxide/cyanate ester–caprolactam were also performed by disk diffusion method. Hence, the results conclude that the amine-terminated cyclotriphosphazene/functionalized titanium dioxide/cyanate ester–caprolactam nanocomposites have improved hydrophobic, thermal properties, enhanced antimicrobial, and corrosion resistance properties due to the incorporation of amine-terminated cyclotriphosphazene and functionalized titanium dioxide nanoparticles.     

氮化硼粒子增强氰酸酯树脂基复合材料的研究

在玻璃布增强氰酸酯树脂（CE）基复合材料中加入氮化硼(BN)粒子,制得CE/玻璃布/BN复合材料。研究了BN粒子含量对复合材料性能的影响。结果表明,经偶联剂处理的BN粒子使体系凝胶时间缩短,反应活性略有提高。BN粒子的加入可以明显提高复合材料的弯曲强度和层间剪切强度,在BN加入量为8 %时,复合材料的弯曲强度和层间剪切强度达到最大值,分别提高了5 %和36 %。加入BN粒子后,复合材料的起始热分解温度都较未填充体系有所提高,耐热指数升高,热稳定性相应提高。     

Design,Realization, and Characterization of Advanced Adhesives for Joining Ultra‐Stable C/C Based Components

The aim of this work is to develop high‐performance adhesives to join carbon fiber reinforced composites (C/C) for use in aerospace applications; in order to guarantee sound mechanical strength, a low coefficient of thermal expansion, and ease of application on large components. Several different adhesive formulations, based on phenolic or cyanate‐ester resins (charged with the maximum experimentally feasible amount of carbon‐based fillers), are developed and tested. The measurements of the lap shear strength at room temperature of the C/C joined by means of one phenolic and one cyanate ester‐based resin demonstrates that these formulations are the most suitable for the given application. A complete characterization, by means of viscosimetry, dilatometry, and thermal gravimetric analysis, coupled with gas analysis by means of mass spectroscopy, confirms that the phenolic‐based formulation is the most promising joining material. A nano‐indenter is used to obtain its Young modulus and hardness, both inside the joint and as a bulk cured adhesive.     

环氧树脂增韧改性氰酸酯树脂的研究进展

综述了近年来氰酸酯树脂增韧改性的研究进展,介绍了不同热固性树脂(环氧树脂、双马来酰亚胺)增韧改性氰酸酯树脂的方法以及共聚后具有优异力学、电学、耐水及热稳定性等性能的固化产物,并提出其将在电子产品及航空航天材料等高科技领域得到广泛应用。     

Preparation,structures and properties of interpenetrating network structure-type Phosphate/PEEK composites with enhanced compressive strength and high temperature resistance

Phosphate/polyether ether ketone (PEEK) composites were successfully prepared by molding method and thermal treating at the temperature of 360 °C. The structures and compositions of phosphate/PEEK composites were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, differential scanning calorimetry and scanning electron microscopy. The mechanical properties thermal resistance and dielectric properties were strictly evaluated by the mechanical testing, thermogravimetric analysis and dielectric constant analysis. As the results, the interpenetrating network structure (IPNS) of Al₂O₃-phosphates was completely formed in PEEK matrix. And the phosphate/PEEK composite with 40% Al₂O₃-phosphate showed a 15.9% increasing for tensile strength and 74.5% increasing for compressive strength at room temperature. Besides, the phosphate/PEEK composite with 80 wt% Al₂O₃-phosphate dispalyed a dielectric constant of 4.0, a dielectric loss of 0.0601 and a Shore hardness of 91 HD. As the structural materials, these composites would exhibited the potential applications in aviation, aerospace and other fields.     

航空航天用高性能热固性树脂基体应用及研究进展

综述了航空航天领域中应用较多的环氧树脂、氰酸酯树脂、双马来酞亚胺树脂和反应性聚酞亚胺等热固性基体树脂材料的性能、应用以及研究方向,介绍了国内外的最新研究进展,并提出今后的研究重点,即提高基体树脂和增强纤维之间界面强度,提高复合材料的稳定性,降低材料的加工成型温度,减少成本,提高树脂基体的韧性等。     

A study of the thermal and dynamic mechanical properties of functionalized aryl cyanate esters and their polymers

Differential scanning calorimetry (DSC) was employed to examine the thermally initiated and catalysed polymerizations of a number of cyanate ester monomers. Rigorous purification by preparative HPLC was found to have marked effects on the thermal polymerization characteristics of these compounds as determined by DSC. The effects on the thermal behaviour of varying the heating rate and level of catalysis were also examined. The thermal polymerization of the cyanate ester monomers was found to obey a first order model over wide apparent conversion limits. Functionalized cyanate ester/bis-maleimide copolymers were prepared and the thermal stabilities of these were evaluated by thermogravimetric analysis (TGA) alongside a variety of commercial blends and homopolymers. The dynamic mechanical properties of the cured neat resins were also investigated.     

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     

Catalytic effect of 2,2′‐diallyl bisphenol A on thermal curing of cyanate esters

Cyanate esters are a class of thermal resistant polymers widely used as thermal resistant and electrical insulating materials for electric devices and structural composite applications. In this article, the effect of 2,2′‐diallyl bisphenol A (DBA) on catalyzing the thermal curing of cyanate ester resins was studied. The curing behavior, thermal resistance, and thermal mechanical properties of these DBA catalyzed cyanate ester resins were characterized. The results show that DBA is especially suitable for catalyzing the polymerization of the novolac cyanate ester resin (HF‐5), as it acts as both the curing catalyst through depressing the exothermic peak temperature (T_exo) by nearly 100°C and the toughening agent of the novolac cyanate ester resin by slightly reducing the elastic modulus at the glassy state. The thermogravimetric analysis and dynamic mechanical thermal analysis show that the 5 wt % DBA‐catalyzed novolac cyanate ester resin exhibits good thermal resistance with T_d⁵ of 410°C and the char yield at 900°C of 58% and can retain its mechanical strength up to 250°C. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1775–1786, 2006     

Investigation of a combination of novel polyphosphoramide and boron-containing compounds on the thermal and flame-retardant properties of polystyrene

A novel phosphorus, nitrogen-containing compound, poly(4, 4′-diaminodiphenyl methane phenyl dichlorophosphate) (PDMPD) with high thermal stability was synthesized. The PDMPD was then incorporated into polystyrene (PS) to be used as halogen-free flame retardant. Moreover, small amounts of two boron-containing compounds, Zinc borate (ZnB) and boron phosphate (BP) were combined with PDMPD,to explore effective flame-retardant formulations for PS. The flammability and the thermal properties of the composites were evaluated using limiting oxygen index (LOI) test, microscale combustion calorimeter (MCC) and thermogravimetric analysis (TGA) respectively. A Fourier transform infrared (FTIR) spectroscopy coupled with a thermogravimetric analyzer (TG-IR) was also used to study the gas phase from the degradation of PS composites. Furthermore, the char residues of the samples were investigated by scanning electron microscopy (SEM) and FTIR. The results showed that the incorporation of PDMPD can significantly decrease the flammability of virgin PS, and enhance the thermal stability at high temperature region, in both nitrogen and air atmosphere. A combination of PDMPD with small amounts of boron compounds can further decrease the flammability.     

Modification of cyanate ester resin by poly(ethylene phthalate) and related copolyesters

Aromatic polyesters were prepared and used to improve the brittleness of the cyanate ester resin. The aromatic polyesters include poly(ethylene phthalate) (PEP) and poly(ethylene phthalate‐co‐1,4‐phenylene phthalate). The polyesters were effective modifiers for improving the brittleness of the cyanate ester resin. For example, inclusion of 20 wt % PEP (MW 19,800) led to a 120% increase in the fracture toughness (K_IC) with retention in flexural properties and a slight loss of the glass transition temperature compared to the mechanical and thermal properties of the unmodified cured cyanate ester resin. The microstructures of the modified resins were examined by scanning electron microscopy and dynamic viscoelastic analysis. The thermal stability of the modified resins was lower than that of the unmodified resin as determined by thermogravimetric analysis. The water absorptivity of the modified resin increased significantly, compared to that of the unmodified cured cyanate ester resin. The toughening mechanism was discussed in terms of the morphological and dynamic viscoelastic behaviors of the modified cyanate ester resin system. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 208–219, 2000     

UV cured thiol-ene flame retardant hybrid coatings

In this study, bis-(triethoxysilylpropyl) phenyl phosphamide (BESPPA) was synthesized by the reaction between dichlorophenyl phosphine oxide and 3-aminopropyltriethoxysilane. The chemical structure of the BESPPA was characterized with Fourier transform infrared and NMR techniques. Flame retardant, BESPPA and sol–gel precursor containing hybrid materials were prepared by thiol-ene polymerization with the aim to improve their final thermal and flame retardant properties. The thermal stabilities of the phosphorous/sol–gel containing UV-cured hybrid materials were investigated by thermogravimetric analysis. The results showed that the addition of sol-gel precursor and BESPPA into the organic network also improves the thermal-oxidative stability of the hybrid materials. The flame-retardant properties of the UV-cured hybrid materials were also studied. Furthermore, the phosphorus–silicon synergistic effect on LOI enhancement and increasing flame retardancy of the UV-cured hybrid materials were demonstrated. An LOI enhancement from 20.7 to 26.5 is observed for organic resins containing both phosphorus and silicon. The surface morphology was also characterized by scanning electron microscopy (SEM). SEM studies indicated that inorganic particles were dispersed homogenously throughout the organic matrix.     

Perspectives of Epoxy/Graphene Oxide Composite: Significant Features and Technical Applications

In this article, advancement in epoxy/graphene oxide composites is presented. These materials are comprised of graphene oxide (GO) as filler (carbon-based material, thermodynamically stable, two-dimensional, planar and layered structure). Due to improved properties (mechanical response, low density, electrical resistance, and thermal stability), epoxy resins are used in several applications. Graphene oxide proposes unique properties to epoxy composites as high surface area, thermal and electrical conductivity as well as mechanical and barrier properties, relative to neat matrix. The corresponding significance of epoxy/GO-based materials, related challenges, and potential exploitation regarding technical applications (aerospace, gas sensor, electronic devices, etc.) have been overviewed.     

聚醚醚酮/碳纤维复合粉末的制备及性能

将热处理改性的聚醚醚酮(PEEK)粉末和碳纤维(CF)共混制备了PEEK/CF复合粉末。采用表观密度测试、扫描电子显微镜、电子万能试验机、热重分析、差示扫描量热法等对复合粉末材料的微观形貌、力学性能和热性能进行分析。结果表明,热处理后的PEEK粉末表观密度最高可达0.286 g/cm3。与纯PEEK相比,复合粉末的玻璃化转变温度、熔融温度和分解温度都有较大的提高;随着CF质量分数逐渐增加,复合粉末材料的拉伸强度、弯曲强度、弯曲弹性模量、热变形温度和维卡软化温度逐渐增大,冲击强度逐渐减小。改性PEEK/CF复合粉末材料为选择性激光烧结技术提供了高强度、高耐热性能的粉末材料,从而应用于汽车工业、电器工业、医疗器械和航空航天等领域。     

Hybrid networks derived from isosorbide by means of thiol-ene photoaddition and sol–gel chemistry

New bridged silsesquioxanes derived from isosorbide were synthesized, according to the sol–gel process, by acidic or basic hydrolysis and condensation of a bis-trimethoxysilyl precursor. The latter was prepared by thiol-ene photoaddition of 3-(trimethoxysilyl)-1-propane thiol on diallyl isosorbide ether synthesized by a phase-transfer-catalyzed reaction of allyl bromide with isosorbide. The structure of those hybrid networks prepared according to a sol–gel process was investigated by ²⁹Si solid-state NMR and X-ray diffraction experiments. Acid hydrolysis leads to the formation of randomly branched structures while basic catalysis promotes the creation of clusters. The anisotropic character of the hybrid networks was evidenced by cross polarized optical light observations (birefringence), demonstrating an organization at the micrometric-scale. These hybrid networks derived from isosorbide showed a thermal stability up to 360 °C.     

聚苯胺包覆纳米TiO_2/氰酸酯复合材料的介电性能

通过化学氧化原位聚合法制备了聚苯胺包覆纳米TiO2并将其通过溶液共混的方法添加到氰酸酯树脂中,制备了聚苯胺包覆纳米TiO2/氰酸酯复合材料。利用透射电子显微镜,观察了粒子在氰酸酯基体中的分散情况并采用FT-IR、XRD及TGA等手段对其进行了表征。研究了不同粒子添加量对氰酸酯复合材料介电性能的影响。结果表明,包覆了聚苯胺的纳米TiO2对氰酸酯复合材料的介电常数影响较小,但对介电损耗影响较大,粒子的添加量为3%时其介电损耗最大,且其最大吸收损耗峰从频率较低处转移到较高处。聚苯胺包覆纳米TiO2/氰酸酯复合材料有望成为1种新型吸波材料。     

Simultaneous enhancements in the mechanical,thermal, and electrical performances of glass‐fiber‐reinforced cyanate ester/epoxy composites with plasma‐functionalized carbon nanotubes at different temperatures

Woven glass‐fiber‐reinforced cyanate ester/epoxy composites modified with plasma‐functionalized multiwalled carbon nanotubes (MWCNTs) were prepared. The mechanical, thermal, and electrical properties of the composites were investigated at different temperatures. The results show that the interlaminar shear strength, thermal conductivity, and electrical conductivity of the composites at room temperature and the cryogenic temperatures were enhanced simultaneously by the incorporation of MWCNTs, whereas the nonconductive behavior of the composites as electrical insulating materials was not changed. Meanwhile, the reinforcing mechanism was also examined on the basis of the microstructure of the composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41418.     

Modification of bisphenol A dicyanate ester by carboxyl‐terminated liquid butadiene‐acrylonitrile and its composites

Cyanate esters with excellent high‐temperature properties and easy processing are well known as good resin materials used in aerospace and electrical industries, but the drawback of brittleness limits their usage. In this study, carboxyl‐terminated liquid butadiene‐acrylonitrile (CTBN) was introduced to improve the toughness of bisphenol A dicyanate resin (BADCy), a typical kind of the cyanate esters. Fourier transform infrared spectroscopy and differential scanning calorimetry were employed to investigate the effects of CTBN on the curing behavior of BADCy; the results indicate that the addition of CTBN has a great influence on the curing behavior of BADCy at lower temperatures, but little at higher temperatures. Data from the thermogravimetric analysis and heat deflection temperature analysis showed that the thermal properties of the modified systems were poorer than that of pristine BADCy resin. On the basis of the scanning electron micrographs of the modified systems, toughening mechanism of the systems was discussed. Mechanical and dielectric properties of the cured resins and glass fiber‐reinforced composites were also studied. Modified systems exhibit attractive properties for the future applications in aerospace industries. POLYM. ENG. SCI. 46:581–587, 2006. © 2006 Society of Plastics Engineers.