碳纤维/聚苯并(噁)嗪复合材料的界面与力学性能的关系研究

本文采用含不同上胶剂的碳纤维与苯并(噁)嗪树脂复合,制备碳纤维/聚苯并(噁)嗪单向复合材料,研究了碳纤维表面上胶剂对于复合材料的层间剪切强度(ILSS)、弯曲性能、断口形貌及动态机械性能的影响.结果表明,含有环氧树脂上胶剂的碳纤维/苯并(噁)嗪树脂基复合材料(EPCF/PBZ)的ILSS和弯曲性能优于含非环氧类树脂上胶剂的碳纤维/苯并(噁)嗪树脂基复合材料(VECF/PBZ)和不含上胶剂的碳纤维/苯并(噁)嗪树脂基复合材料(USCF/PBZ).环氧树脂上胶剂改善了纤维与苯并(噁)嗪树脂的粘结性能,使复合材料的内耗峰峰高降低,能量损耗减小.电镜照片同样验证了这一结果.     

硅氧烷改性苯并噁嗪材料的合成及研究进展

苯并噁嗪树脂存在脆性大、成膜性低、开环温度过高以及与复合材料的相容性差等缺点,可用硅氧烷对其进行改性。概括了硅氧烷改性苯并噁嗪的方法及硅氧烷的引入对苯并噁嗪性能的影响;综述了硅氧烷改性苯并噁嗪的研究进展(作为紫外光固化、热致性形状记忆及人体运动检测材料),并展望了未来硅氧烷改性苯并噁嗪的发展方向。     

含烯炔基苯并噁嗪的制备与分析

本文以二氧六环为溶剂、以烯丙基双酚A、间氨基苯乙炔和甲醛为原料,合成了含烯炔结构的苯并噁嗪化合物.采用FTIR、1H NMR方法确定了苯并噁嗪化合物的化学结构.该噁嗪化合物室温下为液态,对噁嗪化合物固化产物进行了动态力学分析(DMA),结果表明,制备的噁嗪化合物固化物具有较高的使用温度,玻璃化转变温度高达367.61℃,有望作为高性能复合材料树脂基体使用.     

热固性树脂苯并噁嗪-氰酸酯固化反应研究

苯并噁嗪是最近发展起来的新型酚醛树脂,有许多优良的特性,并能克服传统酚醛树脂的许多缺点。这使得聚苯并噁嗪在复合材料上得到很大的应用,像RTM树脂,复合层压板和电子封装材料。本论文对利用 DSC和FT-IR对双酚A二氰酸酯与二胺型苯并噁嗪共固化反应历程进行了研究。研究表明:通过热激活的共固化反应有多重的聚合机制,噁嗪环与—OCN不直接发生反应。随着反应温度的升高,苯并噁嗪的噁嗪环发生开环,生成—OH,并与氰酸酯发生共聚反应。当体系中存在少量—OH时,在140 ℃下就能与—OCN反应,生成亚胺基或三聚环结构,说明—OH对—OCN的反应具有催化作用。     

苯并(噁)嗪/环氧树脂共聚固化过程研究

采用FT-IR、DSC研究苯并(噁)嗪与环氧树脂通过熔融搅拌混合均匀后,固化过程中2种树脂发生开环共聚合的可能性.结果表明:苯并(噁)嗪与环氧树脂熔融混合后,在高温区(180 ℃,200 ℃)发生了共聚反应,苯并(噁)嗪开环过程形成的中间体可以作为环氧树脂的固化剂使用.玻璃化转变温度随着共聚体系中环氧树脂含量的增加先升高,环氧树脂含量超堵塞30%降低,当苯并(噁)嗪与环氧树脂的质量比为70/30时,Tg达到最高(218 ℃),熔融共混在一起程度上提高了共聚体的玻璃化转变温度.     

双环苯并噁嗪的制备及其与环氧树脂共混体系性能研究

以腰果酚、苯酚、甲醛和相对分子质量为230、400、2 000的聚醚胺为原料,合成双环苯并噁嗪单体,采用红外光谱和黏度仪对其进行表征。将单体CBOZ-230与环氧树脂EE以不同比例共混,研究CBOZ-230/EE固化物的热性能和共混体系固化行为。研究结果表明:双环苯并噁嗪单体黏度低;共混体系的热分解温度比纯苯并噁嗪提高37.6℃,固化反应活化能降低至77.61 KJ/mol。     

苯并噁嗪树脂基芳砜纶纤维及玻璃纤维复合材料性能的研究

本文对苯并噁嗪、苯并噁嗪/芳砜纶纤维、苯并噁嗪/玻璃纤维树脂基复合材料的结构和性能进行了研究,并考察了该树脂的力学性能及耐热性,测试了苯并噁嗪/芳砜纶纤维、苯并噁嗪/玻璃纤维树脂基复合材料的力学性能及介电性能,并对芳砜纶纤维表面进行了电镜扫描。结果表明,树脂的耐热指数为199℃,其耐热性能和稳定性好,芳砜纶纤维与树脂之间形成了一个互溶体系,导致了芳砜纶纤维/苯并噁嗪复合材料的力学性能比玻璃纤维/苯并噁嗪复合材料的低,与树脂浇铸体的力学性能接近。     

苯并噁嗪/环氧树脂/粉煤灰复合材料制备及性能研究

苯并噁嗪树脂是一种新型的热固性树脂,凭借其出色的力学性能和耐热性能得到广泛的关注,然而其固化物质脆的问题限制了其进一步应用.采用环氧树脂体系对其进行改性,可以在有效地提升其韧性的同时保持其出色的耐热性,然而进一步提升基于苯并噁嗪/环氧树脂体系的韧性和强度是目前亟待解决的一个问题.该研究将硅烷偶联剂改性后的粉煤灰与苯并噁...     

苯并恶嗪/环氧树脂/酸酐三元体系固化反应研究

采用重结晶双酚A-苯胺型苯并恶嗪(BA-a)、双酚A型环氧树脂(BPA-E)与聚苯乙烯马来酸酐(EF40)进行共聚反应。通过示差扫描量热分析和红外光谱测试对苯并恶嗪/酸酐、环氧树脂/酸酐二元体系及苯并恶嗪/环氧树脂/酸酐三元体系的固化行为及各阶段固化物结构进行了研究。结果表明:酸酐与苯并恶嗪、环氧树脂均发生反应,分别生成不同类型的酯键结构。在三元体系中,酸酐与环氧树脂首先反应,形成醇酯键;其次,苯并噁恶嗪自聚,聚苯并恶嗪中的酚羟基与少量酸酐、环氧树脂反应,生成酚酯键、羧酸或醚式结构,同时新生成的羧酸结构可促进苯并恶嗪开环聚合。     

苯并(口恶)嗪及其碳纤维复合材料固化动力学研究

采用非等温DSC技术研究了不同升温速率下苯并噁嗪/碳纤维复合材料的固化过程.以Avrami方程分析计算了2种固化体系的动力学参数和表观反应活化能.结果表明Avrami指数n随固化温度的变化能反映出苯并噁嗪固化过程的2个阶段--凝胶粒子形成和增长阶段及扩散控制阶段.用Avrami速率常数计算得到的表观活化能与文献值基本一致,但能更清楚地反映出碳纤维对苯并噁嗪固化反应动力学的影响,即催化作用和延缓作用.     

Multiwalled carbon nanotube/polybenzoxazine nanocomposites: Preparation, characterization and properties

A novel nanocomposite composed of polybenzoxazine (PBZ) and multiwalled carbon nanotubes (MWNT) was prepared successfully. The surface modification of MWNT, including nitric acid modification followed by toluene-2,4-diisocyanate (TDI) treatment, introduced hydroxyl, carboxyl, and isocyanate groups on the MWNT surface. The surface carboxyl groups catalyzed the ring-opening reaction of benzoxazine and thus decreased the curing temperature of the system. The isocyanate groups reacted with the phenolic hydroxyl groups generated by the ring opening of benzoxazine resulting in the significant improvement of the adhesion between PBZ and MWNT. Dynamic mechanical analyses indicated the increase of storage modulus as well as T_g by the addition of MWNT into PBZ. A well dispersed modified-MWNT on nanoscale level inside PBZ matrix was observed by TEM and SEM.     

Pseudoreinforcement effect of multiwalled carbon nanotubes in epoxy matrix composites

The carbon nanotube possesses outstanding physical properties. Theoretically, adding carbon nanotubes into a polymer matrix can remarkably improve the mechanical properties of the polymer matrix. In the present work, a series of composites was prepared by incorporating multiwalled carbon nanotubes (MWNTs) into an epoxy resin. The influences of MWNT content and curing temperature on the flexural properties of the epoxy resin were investigated. The results showed that a very low MWNT content should be used to ensure homogeneous dispersion of MWNTs in the epoxy matrix. A higher MWNT content may lead to deteriorated mechanical properties of the composites because of the aggregation of MWNTs. A decline in the flexural properties of the neat epoxy resin with increasing curing temperature was found. However, under the same curing conditions, improvement in flexural properties was observed for the composite with the low MWNT content and a mild curing temperature. The improvement was far beyond the predictions of the traditional short‐fiber composite theory. In fact, this improvement should be attributed to the retarding effect of MWNTs on the curing reaction of epoxy matrix. Therefore, the improvement in the flexural properties was only a pseudoreinforcement effect, not a nano‐reinforcement effect of the MWNTs on the epoxy resin. Perhaps, it is better for MWNTs to be used as functional fillers, such as electrical or thermal conductive fillers, than as reinforcements. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3664–3672, 2006     

Fabrication and characterization of the mechanical properties of multi-walled carbon nanotube-reinforced epoxy resins by e-beam irradiation

In this study, the multi-walled carbon nanotubes (MWNT) were reinforced to epoxy resin as fabrication of epoxy/MWNT nanocomposites by electron beam (e-beam) curing. An attempt is made to disperse MWNT into diglycidyl ether of bisphenol A (DGEBA) as epoxy resins, using triarylsulfonium hexafluoroantimonate (TASHFA) as an initiator. E-beam irradiation effect on the curing of the epoxy resin was investigated in oxygen and nitrogen atmospheres at room temperature. The flexural modulus was measured by a universal testing machine (UTM). Here, the flexural modulus factor exhibits an upper limit at 0.3 wt% MWNT. The dynamic mechanical and thermal properties of the irradiated epoxy resins were characterized using DMA, DSC and TGA machines. DMA curves of the storage modulus revealed an increase with an increasing MWNT content and radiation dose. However, the T_g curve decreased as a function of the increasing MWNT content and radiation dose. The thermal properties of the TGA and DSC data were improved by increasing the content of the MWNT and the radiation dose. Likewise, the thermal properties were stabilized by increasing the amount of initiator and irradiating the resins in a nitrogen atmosphere.     

Effect of multiwalled carbon nanotubes and phenethyl-bridged DOPO derivative on flame retardancy of epoxy resin

In this study, a phenethyl-bridged DOPO derivative (DiDOPO) was combined with multi-walled carbon nanotubes (MWNT) in epoxy resin (EP) to improve its flame retardancy. The introduction of only 10 wt% DiDOPO/0.8 wt% MWNT into EP increased the limited oxygen index (LOI) from 21.8% to 38.6%, achieving the UL 94 V-0 rating. The thermogravimetric analyses demonstrated that the presence of MWNT raised the char yield and formed thermally stable carbonaceous char. The decomposition and pyrolysis products in the gas phase were characterized by thermogravimetry-Fourier transform infrared spectroscopy (TG-FTIR), and found large amounts of phosphorus released into the gas phase. The flame-retardant effect evaluation by cone calorimetry testified that the MWNT improved the protective-barrier effect of the fire residue of EP/DiDOPO/MWNT, as shown by digital photo and scanning electron microscopy (SEM). Raman showed that MWNT could enhance the graphitization degree of the resin during combustion. Overall, these findings indicated that combination of DiDOPO with MWNT is an effective way in developing high-performance resins with attractive flame retardancy.     

Design and verification of a single slab RAS through mass production of glass/MWNT added epoxy composite prepreg

In this study, glass fiber composite prepreg is manufactured with multi‐walled carbon nanotube (MWNT) added epoxy using two different methods. Because MWNT agglomeration occurs, the calendering dispersion method is used to resolve this problem. The tensile and shear tests of glass/MWNT 1.8wt % added epoxy composite (CNT18) are conducted and the results are compared with the properties of a commercial glass/epoxy composite (GEP 118). The complex permittivity is measured using a network analyzer and a waveguide in the Ku‐band. A single slab radar absorbing structure (RAS) is also designed and verified. It is found that the tensile and shear properties of CNT18 are sufficient to replace GEP 118 as a structural material. Furthermore, the—10 dB bandwidth and reflection loss of the RAS using CNT18 is 12.87 to 17.78 GHz (4.91 GHz) and—29.2 dB at 14.95 GHz, respectively. The measurement results align well with the simulation results. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42019.     

Effects of high nano‐SiO2 contents on properties of epoxy‐modified polybenzoxazine

High‐performance nanosilica composites based on epoxy‐modified polybenzoxazine matrices are developed. Chemorheological study of benzoxazine–epoxy resin mixtures reveals that processing window of the benzoxazine resin (BA‐a) is substantially broadened with an addition of the liquid epoxy. Glass transition temperature (T _g) of the BA‐a copolymerized with epoxy resin shows a synergistic behavior with a maximum T _g value (174°C) at the benzoxazine–epoxy mass ratio of 80:20. The copolymer at this composition is also used as a matrix for nano‐SiO₂ composites. A very low melt viscosity of the benzoxazine–epoxy mixtures promotes good processability with the maximum attainable nano‐SiO₂ loading up to 35 wt%. From scanning electron microscopy investigation, fracture surface of the 35 wt% nano‐SiO₂‐filled benzoxazine–epoxy composite reveals relatively homogeneous distribution of the nano‐SiO₂ in the copolymer with good particle wet‐out. In addition, very high reinforcing effect was also observed in such high content of the nano‐SiO₂, i.e., about 2.5 times in modulus improvement. This improvement is attributed to the strong bonding between the copolymer matrix and the nano‐SiO₂ through ether linkage as confirmed by Fourier‐transform infrared investigation. POLYM. COMPOS., 38:2261–2271, 2017. © 2015 Society of Plastics Engineers     

New type of phenolic resin: Curing reaction of phenol‐novolac based benzoxazine with bisoxazoline or epoxy resin using latent curing agent and the properties of the cured resin

In this study, we aimed to reduce the cure time, and to lower the cure temperature of the benzoxazine compound. Therefore, curing reaction of benzoxazine with bisoxazoline or epoxy resin using the latent curing agent and the properties of the cured resins were investigated. The cure behavior of benzoxazine with bisoxazoline or epoxy resin using the latent curing agent was monitored by differential scanning calorimetry and measurements for storage modulus (G′). The properties of the cured resin were estimated by mechanical properties, electrical insulation, water resistance, heat resistance, and flame resistance. As a result, it was confirmed that by using the latent curing agent, cure time of benzoxazine and bisoxazoline or epoxy resin was reduced, and cure temperature was lowered. And it was found that the curing reaction using phenol‐novolac based benzoxazine (Na) as the benzoxazine compound could proceed more rapidly than that using bisphenol‐A based benzoxazine (Ba) as the benzoxazine compound. However, the cured resins from Ba and bisoxazoline or epoxy resin using the latent curing agent showed good heat resistance, flame resistance, and mechanical properties compared with those from Na and bisoxazoline or epoxy resin using the latent curing agent. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

苯并噁嗪/含磷环氧/含氮酚醛共混体系结构与性能的研究

针对双酚A型苯并噁嗪无法满足较高阻燃要求的缺陷,在双酚A型苯并噁嗪中引入含磷环氧、含氮酚醛,制备了三元共混浇铸体,通过测定凝胶化时间、差示扫描量热仪(DSC)、动态热机械分析(DMA)、热失重分析(TGA)、垂直燃烧、锥形量热等测试手段研究了共混体系固化反应及结构与性能间的关系。研究表明:在共混体系中,随着环氧树脂含量的增加,固化产物的初始储能模量和玻璃化转变温度均减小,同时还有效地发挥了固相、气相阻燃的作用;含氮酚醛的引入,除有效催化固化反应和降低固化反应温度外,还发挥了气相阻燃的作用。含磷环氧和含氮酚醛均能有效提高热稳定性和阻燃性能;含氮酚醛中的氮源比苯并噁嗪中的氮源对阻燃、提高热稳定性等性能所发挥的作用更明显。     

Flammability and thermal properties of epoxy/glass/MWNT Composites

The aim f this work is to study the effect of nanotubes on flammability properties of epoxy/glass composites. Multiwalled carbon nanotubes (MWNT) and its functionalized derivative (amino functionalized nanotubes) were incorporated into epoxy resin. To disperse MWNTs in the epoxy resin, different ways were employed. Microscopic observations showed that, the best dispersion state was gained by using ultrasonication method and high shear flow simultaneously. Thermal resistance of cured epoxy resins containing various amounts of nanotubes (0.25–0.7 wt %), was investigated by thermo gravimetric analysis (TGA). Introducing MWNTs and amino‐MWNTs to samples increased the initial thermal decomposition temperature for about 32 and 37°C, respectively. LOI measurements of composite samples showed an increase up to 32. Cone calorimetry test was carried out on epoxy/glass and epoxy/glass containing 0.5% MWNT. The results showed that, introducing 0.5% MWNTs decreases maximum average rate of heat emission for about 26%. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39849.     

Effect of crosslink density on thermal conductivity of epoxy/carbon nanotube nanocomposites

The effect of the polymeric crosslink density on the thermal conductivity of an epoxy nanocomposite was investigated by adding two different diamine‐functionalized multiwalled carbon nanotubes (diamine‐MWNTs) to the epoxy resin as co‐curing agents and conducting fillers. Tetramethylenediamine (TMDA)‐MWNTs resulted in an epoxy nanocomposite with a higher crosslink density than octamethylenediamine (OMDA)‐MWNTs. Interestingly, epoxy/TMDA‐MWNT nanocomposites under 1.5 wt % nanotube concentration, showed a higher thermal conductivity than an epoxy/OMDA‐MWNT nanocomposite with the same concentration of nanotubes. In contrast, for higher diamine‐MWNT concentrations (over 2.0 wt %), the thermal conductivity of the epoxy/OMDA‐MWNT nanocomposite was higher than that with TMDA‐MWNTs. We observed that for low MWNT concentrations, where a percolating network was not formed, a high crosslink density enhanced the thermal conductivity via phonon transport. However, for high MWNT concentrations, a high crosslink density hinders the formation of a percolating network and lowers the thermal conductivity. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44253.