端羧基丁腈橡胶改性环氧树脂的结构与性能

用液体端羧基丁腈橡胶(CTBN)对固体环氧树脂(EP)进行改性,合成了CTBN-EP预聚物,研究了CTBN-EP/HTP-305体系的微观形貌、力学性能和热性能。研究结果表明,随着CTBN含量的增大,冲击强度及断裂伸长率显著提高,说明通过CTBN化学预聚改性的EP韧性提高,而体系的拉伸强度和热性能略有下降。动态热机械分析(DMA)测试体系的动态力学性能结果表明,体系出现了两相结构(Tg对应温度分别是-60℃和80℃～100℃)。扫描电镜(SEM)分析表明,固化过程中析出了橡胶相并均匀分散在环氧树脂基体中,形成了剪切空洞变形结构。     

环氧树脂复合材料的制备及力学性能

通过配方设计,以硅烷偶联剂改性的空心玻璃微珠(HGB)为填料,端羧基液体丁腈橡胶(CTBN)为增稠剂和增韧剂,环氧树脂(EP)为基体,经变温分段固化技术制备环氧树脂/端羧基丁腈橡胶/空心玻璃微珠(EP/CTBN/HGB)三元泡沫复合材料并研究其力学和流变性能。结果表明,CTBN使得复合材料由脆性断裂变为韧性断裂;CTBN劣化了复合材料模量而HGB弥补了复合材料模量;当CTBN、HGB含量分别为12%(质量分数)和30%(体积分数)时,三元复合材料的冲击、弯曲、拉伸强度及弯曲模量均优于纯EP。另外,纯环氧树脂和EP/CTBN共混物的黏度呈现出牛顿流体的流变行为,而三元共混物的黏度表现出明显的剪切变稀现象。     

环氧树脂复合材料的制备及隔声性能

以硅烷偶联剂改性的空心玻璃微珠(HGB)为功能填料,端羧基液体丁腈橡胶(CTBN)为增稠剂和增韧剂,环氧树脂为基体,甲基六氢苯酐为固化剂,2-乙基-4-甲基咪唑为促进剂,通过自转/公转搅拌机将混合物混匀、脱泡处理,再经过改变温度的分段固化技术制备了环氧树脂/端羧基丁腈橡胶/空心玻璃微珠(EP/CTBN/HGB)复合材料,并研究了复合材料的隔音性能。实验结果表明,CTBN和HGB均能提升EP材料的隔音性能,CTBN填充量为12%的EP/CTBN比纯EP的平均隔音量高115%,而填充30%HGB的EP/CTBN/HGB复合材料的平均隔音量又较EP/CTBN提高了30%。在填料和CTBN的添加量及试样厚度均相同的条件下,添加空心玻璃微珠的环氧基复合材料的隔音性能优于实心玻璃微珠复合材料。     

端羧基液体丁腈橡胶改性双组分室温固化环氧结构胶的制备与性能EI北大核心CSCD

将端羧基液体丁腈橡胶(CTBN)与环氧树脂(EP)预聚,采用红外光谱、黏度计、万能电子材料试验机及扫描电镜(SEM)研究了CTBN含量对EP/聚酰胺/聚醚胺室温固化环氧结构胶的性能影响。结果表明,CTBN用量从0phr增加至20phr时,胶体拉伸强度从45MPa降低至29MPa,降低了35.56%;压缩强度从98MPa降低至60.2MPa,降低了38.6%;当CTBN加到10 phr时,极大地提升了粘接强度,钢-钢剪切强度从4.1MPa上升到16.7MPa,增加了3.07倍;结构胶加热至400℃时,EP质量损失达73.7%,而CTBN改性EP的质量损失为59.4%。SEM结果表明,CTBN在胶体固化过程中析出橡胶相,还有一定的空穴出现,橡胶粒子通过空化以及界面脱粘释放其弹性能,使材料的韧性得以提高。     

端羧基液体丁腈橡胶改性海因环氧树脂性能研究

目的 采用端羧基液体丁腈橡胶(CTBN)对海因环氧树脂进行增韧改性。方法 通过热熔法将不同份数的CTBN添加到海因环氧树脂中，以4,4''–二氨基二苯甲烷为固化剂制备了改性环氧树脂，通过固化动力学研究确定了其固化工艺，考察CTBN用量对改性树脂体系的反应活性、力学性能、热性能以及断面微观形貌的影响。结果 随着CTBN的加入，改性树脂的固化放热峰向高温方向偏移。CTBN可显著提高树脂体系的断裂伸长率和冲击强度，其热性能基本保持不变。改性树脂的断面呈现两相“海岛”结构。结论 CTBN对海因环氧树脂有明显的增韧作用，制备的改性树脂体系可用于金属防腐涂料和胶黏剂等材料。     

CTBN改性双酚A型氰酸酯树脂的性能

为改善氰酸酯树脂的冲击韧性,在双酚A型二氰酸酯(BADCy)树脂中混入了不同含量的端羧基丁腈橡胶(CTBN).用差示扫描量热法(DSC)及红外光谱法(FTIR)对CTNB/BADCy共混体系的反应性研究发现,CTBN能促进BADCy低温下的三嗪环反应,但是使BADCy的后处理温度提高.SEM分析表明,当CTBN的含量(质量分数)大于15%后,有CTBN颗粒从BADCy中析出,形成两相结构,且随着CTBN含量的增大,分散相的粒径增大,在断口处产生的银纹和剪切带使BADCy/CTBN共混体系的韧性提高.当CTBN的含量为25%时体系的冲击强度提高了2.3倍.     

纳米SiO2-端羧基丁腈橡胶改性水性环氧树脂复合材料的制备及性能

以端羧基丁腈橡胶（CTBN）和纳米SiO₂（nano SiO₂）为增韧剂,先利用相反转法将CTBN与环氧树脂（EP）的共聚物制备成乳液,然后加入nano SiO₂进行共混,最后加入固化剂经梯度升温固化制得nano SiO₂-CTBN改性的水性环氧树脂（nano SiO₂-CTBN/WEP）复合材料。通过FTIR、SEM、TEM、万能拉伸试验仪和TG对nano SiO₂-CTBN/WEP复合材料的性能进行表征。结果表明：当CTBN含量为20%（与EP E-51的质量比）时,所制备的CTBN/WEP具有较好的储存稳定性,在此基础上加入nano SiO₂,当其含量为3%时增韧效果最好,nano SiO₂-CTBN/WEP的拉伸强度达14.5 MPa,断裂伸长率达9.1%,冲击强度为11.3 kJ/m²,弯曲强度达22.4 MPa,较未添加nano SiO₂的CTBN/WEP分别提高了40.1%、27.4%、73.9%和72.7%,其初始热分解温度也提高了近25℃。     

超高分子量聚乙烯纤维的液相氧化改性及其环氧树脂基复合材料的力学和摩擦性能

为增强超高分子量聚乙烯(UHMWPE)纤维与环氧树脂(EP)基体之间的界面粘结强度,采用重铬酸钾溶液对UHMWPE纤维进行表面改性并制备UHMWPE纤维/EP复合材料。结果表明,UHMWPE纤维经液相氧化后表面刻蚀痕迹明显,表面粗糙度明显增加,结晶度增加了11.3%,与乙二醇的接触角减小了14.12°。与纯环氧树脂相比,纤维含量为0.4%的未改性UHMWPE纤维/EP复合材料的拉伸强度降低18.04%,纤维含量为0.6%的液相氧化改性UHMWPE纤维/EP复合材料的拉伸强度降低51.55%,未改性UHMWPE(纤维含量0.5%)和液相氧化改性UHMWPE(纤维含量0.4%)纤维/EP复合材料的冲击强度分别提升了3.29%和4.39%。当纤维含量为0.3%时,液相氧化改性UHMWPE纤维/EP复合材料的弯曲强度比纯环氧树脂增加6.55%,比未改性UHMWPE纤维/EP复合材料增加19%。当纤维含量由0增大到0.5%时,改性和未改性UHMWPE纤维/EP复合材料的摩擦系数先增加后减小。     

埃洛石复配2-羧乙基苯基次膦酸对环氧树脂阻燃及力学性能的影响

将埃洛石纳米管(HNTs)与2-羧乙基苯基次磷酸(CEPPA)复配并用于环氧树脂(EP)阻燃改性,制备了CEPPA-HNTs/EP复合材料。研究了HNTs与CEPPA的配比对CEPPA-HNTs/EP复合材料热稳定性、阻燃性及力学性能的影响。TG分析表明,CEPPA与HNTs复配可提高CEPPA-HNTs/EP复合材料的热稳定性,促进成炭并降低分解速率。锥形量热和极限氧指数分析表明,加入HNTs可降低EP热释放速率,而CEPPA对提高EP的极限氧指数作用更显著。残炭的红外分析及SEM结果表明,燃烧过程中CEPPA与HNTs反应生成硅铝磷酸盐促进凝聚相的脱水交联,形成更致密的炭层。力学性能分析表明,当HNTs与EP和CEPPA与EP的质量比分别为6%和4%时,CEPPA-HNTs/EP复合材料的拉伸强度和冲击强度分别提高了19.4%和17.3%,冲击断面的SEM图像显示CEPPA-HNTs/EP复合材料呈韧性断裂。      

羧基化碳纳米管/环氧树脂复合材料的制备及其性能研究

首先用混酸法对碳纳米管(CNTs)进行酸化，制得羧基化碳纳米管(C-CNTs)。以C-CNTs作为填料，采用溶剂混合法制备了羧基化碳纳米管/环氧树脂(C-CNTs/EP)复合材料，通过扫描电子显微镜、傅里叶变换红外光谱仪、电子万能试验机、宽频介电阻抗谱仪等对产物进行了表征和分析测试。结果表明：CNTs经羧基化后，长径比相对变小，搭接和缠绕程度相对降低，当C-CNTs质量分数为2%时，C-CNTs/EP复合材料的拉伸强度、弯曲强度、冲击强度分别比EP提高46.1%、27.1%和33.5%;玻璃化转变温度比EP提高8.6℃;当C-CNTs质量分数超过1%,C-CNTs/EP复合材料的介电常数随C-CNTs质量分数的增加而快速增大。     

Effect of carboxyl-terminated poly(butadiene-co-acrylonitrile) (CTBN) concentration on thermal and mechanical properties of binary blends of diglycidyl ether of bisphenol-A (DGEBA) epoxy resin

Six blend samples were prepared by physical mixing of epoxy resin with varying concentrations of liquid carboxyl-terminated butadiene acrylonitrile (CTBN) copolymer having 27% acrylonitrile content. The blend samples were cured with aromatic amine. A comparative study of Fourier-transform infrared (FTIR) spectra showed the modification as a result of chemical reactions between epoxide group, curing agent and CTBN. The tensile strength of cured blend samples decreased slightly from 11 to 46% where as the elongation-at-break showed an increasing trend with increasing rubber content, i.e., up to 25 phr, in the blend samples. Appreciable improvements in impact strength were also observed in the prepared blend systems. The glass transition temperature (T_g) of the epoxy resin matrix was slightly reduced on the addition of CTBN. The cured resin showed a two-phase morphology where the spherical rubber domains were dispersed in the epoxy matrix.     

Microstructure-related fracture toughness and fatigue crack growth behaviour in toughened, anhydride-cured epoxy resins

Fracture toughness and fatigue crack propagation (FCP) of plain and modified anhydride-cured epoxy resin (EP) were studied at ambient temperature. Liquid carboxyl-terminated acrylonitrile-butadiene (CTBN) and silicon (SI) rubber dispersions were used as tougheners for the EP. The morphology of the modified EP was characterized by dynamic mechanical analysis (DMA) and by scanning electron microscopy (SEM). The fracture toughness, K_c, of the compositions decreased with increasing deformation rate. K_c of the EP was slightly improved by CTBN addition and practically unaffected by incorporation of the SI dispersion when tests were performed at low cross-head speed, v. Both modifiers improved K_c at high v, and also the resistance to FCP, by shifting the curves to higher stress intensity factor ranges, ΔK, by comparison with the plain EP. It was established that both fracture and fatigue performance rely on the compliance, J_R, at the rubbery plateau, and thus on the apparent molecular mass between crosslinks, M_c. The failure mechanisms were less dependent upon the loading mode (fracture, fatigue), but differed basically for the various modifiers. Rubber-induced cavitation and shear yielding of the EP were dominant for CTBN, whereas crack bifurcation and branching controlled the cracking in SI-modified EP. The simultaneous use of both modifiers resulted in a synergistic effect for both the fracture toughness at high deformation rate and the FCP behavior.     

三维编织碳复合材料的制备及其力学性能研究

采用真空辅助RTM工艺制备了三维编织碳纤维增强环氧树脂(C3D/EP)复合材料,通过对树脂的粘度特性和固化特性的分析,确定了最佳的工艺参数.金相显微镜对复合材料微观结构的观察表明树脂对纤维的浸润良好.同时,还研究了该工艺制备的C3D/EP复合材料的力学性能,结果表明随着纤维体积比的增加,复合材料的硬度、弯曲强度和冲击强度均提高,断口的扫描电镜观察表明复合材料的破坏方式是以脆性断裂为主.     

环状磷腈/聚磷酸铵/三聚氰胺膨胀阻燃环氧树脂研究

本文以DOPO衍生物六(4-DOPO羟甲基苯氧基)环三磷腈(DOPOMPC)、聚磷酸铵(APP)以及三聚氰胺(MEL)形成复配膨胀体系(IFR)阻燃环氧树脂.采用极限氧指数(LOI)、水平、垂直燃烧(UL-94)方法研究了IFR体系对环氧树脂体系阻燃性能影响,通过锥形量热(CONE)研究了体系燃烧特性,通过扫描电子显微镜(SEM)对体系成炭情况进行观察.结果表明,IFR膨胀阻燃体系对环氧树脂具有良好的协同阻燃作用,其中8%DOPOMPC/8%APP/4%MEL(EP3)体系LOI值较纯EP(EP0)提高37.8%;各项燃烧参数也得到了改善,热释放速率峰值(pk-HRR)、有效燃烧热平均值(av-EHC)、比消光面积平均值(av-SEA)及一氧化碳释放速率平均值(av-CO)相对于10%DOPOMPC/10%APP/EP(EP1)分别降低了53.8%、84.4%、57.7%和75.8%;拉伸强度、弯曲强度和冲击强度较EP1分别提高了1.3倍、79.4%和2.5倍;宏观拍摄和扫描电镜结果表明EP3膨胀炭层连续、均匀、致密,阻燃效果良好.     

聚氨酯和蒙脱土协同增韧增强环氧树脂

采用聚合物互穿技术与原位插层聚合相结合的方法制备了有机蒙脱土修饰的环氧树脂/聚氨酯互穿网络纳米复合材料.傅立叶红外光谱,X射线衍射及透射电镜分析表明剥离或插层的蒙脱土片层表面羟基能与环氧树脂/聚氨酯基体发生交联反应,并且均匀分散在环氧树脂/聚氨酯基体中.力学性能测试结果表明聚氨酯,蒙脱土的加入同时增加了环氧树脂的拉伸强度和断裂韧性.扫描电镜分析表明聚氨酯和蒙脱土协同增韧增强环氧树脂的主要原因为剪切屈服和微裂纹增韧.     

纳米Al2O3/聚醚砜-环氧树脂复合材料的介电性能及热稳定性能

本实验制备了纳米Al_2O_3/聚醚砜-环氧树脂复合材料,考察了不同纳米氧化铝和聚醚砜的用量对复合体系力学和介电性能的影响,并对其热稳定性能进行了研究。结果表明:当添加1phr纳米氧化铝(Nano-Al_2O_3)和5phr聚醚砜(PES)时,三元复合材料EP/5PES/1Al_2O_3的拉伸强度提高到58 MPa,断裂伸长率达到13%,冲击强度达到16.2kJ/m~2,相比纯环氧树脂分别提高了61.1%、20.3%和8.0%。而且在100Hz的室温测试条件下,EP/5PES/1Al_2O_3材料的介电常数和介电损耗分别达到7.6和0.016,较纯环氧树脂均有一定幅度的增加。热重分析(TG)结果表明,EP/5PES/1Al_2O_3复合材料的初始分解温度为358℃,比纯环氧树脂提高了14℃,说明热稳定性有较大幅度的提高。     

Enhancement of fracture toughness,mechanical and thermal properties of rubber/epoxy composites by incorporation of graphene nanoplatelets

Carboxyl terminated butadiene acrylonitrile (CTBN) was added to epoxy resins to improve the fracture toughness, and then two different lateral dimensions of graphene nanoplatelets (GnPs), nominally <1 μm (GnP-C750) and 5 μm (GnP-5) in diameter, were individually incorporated into the CTBN/epoxy to fabricate multi-phase composites. The study showed that GnP-5 is more favorable for enhancing the properties of CTBN/epoxy. GnPs/CTBN/epoxy ternary composites with significant toughness and thermal conductivity enhancements combined with comparable stiffness to that of the neat resin were successfully achieved by incorporating 3 wt.% GnP-5 into 10 wt.% CTBN modified epoxy resins. According to the SEM investigations, GnP-5 debonding from the matrix is suppressed due to the presence of CTBN. Nevertheless, apart from rubber cavitation and matrix shear banding, additional active toughening mechanisms induced by GnP-5, such as crack deflection, layer breakage and separation/delamination of GnP-5 layers contributed to the enhanced fracture toughness of the hybrid composites.