多壁碳纳米管-丙烯酸酯嵌段共聚物共改性环氧树脂三元复合材料性能

采用多壁碳纳米管(MWCNTs)和丙烯酸酯嵌段共聚物(ACRBC)协同改性制备了多壁碳纳米管-丙烯酸酯嵌段共聚物/环氧树脂(MWCNTs-ACRBC/EP)三元复合材料。通过FTIR、 XPS和SEM对强酸处理后的MWCNTs的性能进行表征,利用DSC法对MWCNTs-ACRBC/EP复合材料的固化反应参数进行表征,采用DMA对MWCNTs-ACRBC/EP复合材料的耐热性进行表征,采用电子力学试验机对MWCNTs-ACRBC/EP复合材料的力学性能进行测试。结果表明:强酸处理后在MWCNTs表面成功形成反应官能团。采用150℃×1 h+180℃×3 h作为MWCNTs-ACRBC/EP复合材料的固化工艺, MWCNTs-ACRBC/EP复合材料的玻璃化转变温度可达197.5℃,提高了13.3%, MWCNTs-ACRBC/EP复合材料的力学性能提高,抗弯强度为144 MPa,弯曲模量为3662 MPa,冲击强度为19.5 kJ/m^2。     

多壁碳纳米管功能化及其增韧环氧树脂的研究

采用混酸氧化多壁碳纳米管(MWCNTs),然后将其与过氧化丁二酸反应,接着对其进行酰胺功能化处理,并用功能化后的MWCNTs对环氧树脂(EP)进行增韧改性,研究了不同含量MWCNTs对EP力学性能的影响,探讨了其改性机理.研究结果表明,经过功能化处理,MWCNTs表面成功接上了一定数量的酰胺基团,将其加入到EP中可大幅度提高EP的冲击强度,在其用量为1.5wt%时,冲击强度提高了92%;SEM结果显示,加入MWCNTs后EP由脆性断裂转变为韧性断裂.     

酸氧化处理对多壁碳纳米管表面基团的影响

120℃下用浓硝酸对多壁碳纳米管(MWCNTs)进行不同时间的酸氧化处理,考察处理前后碳纳米管的形貌和元素变化,分析酸氧化处理MWCNTs表面功能基团的种类和含量.结果表明:浓硝酸处理,可在MWCNTs表面产生不同数量的羧基、羟基和羰基含氧基团;在最初2h内,羧基含量增加,羟基和羰基含量先增后减,含氧基团总量迅速增加;处理时间继续增加,羧基含量逐渐减少,羟基和羰基含量发生不规则变化,含氧基团总量趋于稳定;MWC-NTs表面首先形成羟基和羰基,这些基团继续被氧化生成羧基,并且它们被氧化生成羧基的能力不同,生成的羧基可进一步氧化最终以CO2释放出来;可通过控制浓硝酸处理的时间来控制MWCNTs表面含氧基团的种类和数量.     

双亲无规共聚物修饰碳纳米管/环氧树脂复合材料的制备与性能

通过自由基聚合法制备无规共聚物聚甲基丙烯酸缩水甘油酯/N-乙烯基咔唑P(GMA-co-NVC),并将其对多壁碳纳米管(MWCNTs)进行非共价键表面修饰得到P(GMA-co-NVC)/MWCNTs,再与环氧树脂(EP)复合,采用浇注成型法制备聚合物改性碳纳米管/环氧树脂复合材料。通过拉伸实验、电阻率测试和差式扫描量热法研究聚合物改性碳纳米管对环氧树脂力学、电学和热学性能的影响。结果表明:修饰后的碳纳米管比原始碳纳米管对环氧树脂有更明显的增强和增韧作用,当P(GMA-co-NVC)/MWCNTs质量分数为0.25%时,复合材料的体积电阻率为106Ω·m,相比于纯环氧树脂(1014Ω·m)下降了8个数量级,玻璃化转变温度(Tg)也由144℃提高至149℃。     

多壁碳纳米管功能化及其增韧环氧树脂的研究

采用混酸氧化多壁碳纳米管（MWCNTs），然后将其与过氧化丁二酸反应，接着对其进行酰胺功能化处理，并用功能化后的MWCNTs对环氧树脂（EP）进行增韧改性，研究了不同含量MWCNTs对EP力学性能的影响，探讨了其改性机理。研究结果表明，经过功能化处理，MWCNTs表面成功接上了一定数量的酰胺基团，将其加入到EP中可大幅度提高EP的冲击强度，在其用量为1．5wt％时，冲击强度提高了92%,SEM结果显示，加入MWCNTs后印由脆性断裂转变为韧性断裂。     

聚乙烯/马来酸酐接枝聚合物修饰多壁碳纳米管

多壁碳纳米管(MWCNTs)与混酸(浓硫酸∶浓硝酸体积比为3∶1)和无水乙二胺进行酸化、胺化反应使MWCNTs表面产生羧基和氨基基团,进而与聚乙烯/马来酸酐接枝聚合物(PE-g-MA)发生开环反应制备PE-g-MWCNTs,以提高MWCNTs在聚乙烯基体中的分散性。采用红外光谱、X-射线光电子能谱(XPS)和拉曼光谱对MWCNTs的化学修饰进行定性表征。结果表明:当MWCNTs的体积分数为0.67%时,MWCNT/PE复合材料的体积电阻率发生渗流突变。MWCNTs的体积分数在0.1%～1.2%时,MWCNT/PE复合材料体积电阻率由1016Ω.m下降至105Ω.m。     

蒙脱土和碳纳米管共掺改性环氧树脂复合材料的力学性能和热性能

采用有机化蒙脱土(OMMT)和碳纳米管(MWCNTs)2种纳米材料改性双酚A型环氧树脂。通过溶液共混法制备OMMT/EP、MWCNTs/EP、OMMT/MWCNTs/EP环氧树脂纳米复合材料。利用扫描电子显微镜观察了复合材料的冲击断面,测试了复合材料的力学性能和热性能,探讨了OMMT、MWCNTs增韧环氧树脂的机理。结果表明,当试样中OMMT质量分数为4%,MWCNTs质量分数为0.7%时,OMMT/EP、MWCNTs/EP和OMMT/MWCNTs/EP的冲击强度分别达到16.8kJ/m2,23.1kJ/m2,30.4kJ/m2,较未掺杂环氧树脂分别提高了16.7%,60.4%,110%。弯曲强度较未改性环氧树脂分别提高了27.54%,35.74%,54.12%。3种复合材料的热分解温度和马丁耐热温度均较未改性环氧树脂略有提高。     

均匀电子束辐照诱导多壁碳纳米管非晶化

室温下利用已经发展成熟的透射电镜原位观察技术,在均匀电子束辐照下对多壁碳纳米管(MWCNT)的非晶化过程进行研究。实验结果表明,在均匀电子束辐照下MWCNT内、外壁完整的石墨结构开始出现断裂或塌陷,即内层和外层优先开始非晶化,但是内层非晶化的速度明显更快。随着辐照时间的延长,非晶化逐渐由内、外表面向中间推进。同时,内壁断裂或塌陷形成的无定形碳开始向管的内部中空部分填充,而外壁非晶化的碳原子部分被融蒸到真空中。最终,无定形碳填满整个管的内部空间,导致MWCNT完全非晶化。另外,在整个过程中由于非晶化体积膨胀补偿,MWCNT的外径基本保持不变。利用在碳纳米管纳米曲率效应和能量束诱导非热激活效应基础上新发展的碳原子"融蒸"机制,对上述MWCNT的非晶化过程进行了全新、合理的解释。     

碳纳米管/碳纤维环氧树脂复合材料的制备及力学性能

对多壁碳纳米管(MWCNTs)进行改性处理,得到表面接枝1,3,5-苯三甲酸的碳纳米管(B-MWCNTs)。分别将MWCNTs和B-MWCNTs分散在环氧树脂基体及上浆剂中,通过缠绕成型法制备含有MWCNTs的碳纤维增强环氧树脂预浸料,并采用热压成型工艺制备MWCNTs/碳纤维环氧树脂复合材料层合板。结果表明,B-MWCNTs在环氧树脂基体和上浆剂中的分散状态明显优于MWCNTs。添加B-MWCNTs后复合材料的玻璃化转变温度(Tg)和失重5%时对应的温度均有所提高。而且,添加B-MWCNTs可以明显提高碳纤维环氧树脂复合材料的力学性能。当MWCNTs含量为0.5%(质量分数)时,B-MWCNTs/碳纤维环氧树脂复合材料层合板的压缩强度、层间剪切强度和冲击后压缩强度(CAI)分别提高了14.3%,37.1%和23.4%。     

多壁碳纳米管改性氰酸酯/环氧树脂基纳米复合材料的力学性能

用强酸氧化法与等离子体镀膜法分别对原始多壁碳纳米管(MWCNTs)进行表面修饰,制备了MWCNTs改性氰酸酯/环氧树脂基纳米复合材料。对复合材料的断裂面进行SEM分析,研究了表面处理方法对复合材料室温及低温力学性能的影响。结果表明,经等离子体镀膜表面修饰后的MWCNT在基体中分散更为均匀,与基体的界面结合力更强。经等离子体镀膜表面改性后的MWCNTs复合材料,当MWCNTs质量分数为0.3%时,其室温及低温拉伸强度、弹性模量和冲击强度较纯氰酸酯/环氧树脂基体均有不同程度的提高。     

Enhanced interfacial properties of domestic aramid fiber-12 via high energy gamma ray irradiation

The high energy irradiation was used to modify domestic aramid fiber-12 (DAF12) in epoxy chloropropane. The properties of the interphase between DAF12 and epoxy matrix systems were optimized. Scanning electron microscopy was employed to characterize the surface morphology of DAF12 and high energy irradiated fibers (HEI-DAF12) and composites de-bonding section. Atomic force microscopy showed the original smooth surface disappeared. Single fiber pull-out tests revealed that the interfacial shear strength of HEI-DAF12/epoxy composite was substantially improved by 45.17% after irradiation in 400 kGy dose. Dynamic contact angle analysis indicated the increased total surface free energy. The changes of elemental composition investigated via X-ray Photoelectron Spectrometer verified the increase polar groups on fiber surface caused by high energy irradiation.     

Interconnected multi-walled carbon nanotubes reinforced polymer-matrix composites

A modified method for interconnecting multi-walled carbon nanotubes (MWCNTs) was put forward. And interconnected MWCNTs by reaction of acyl chloride and amino groups were obtained. Scanning electron microscopy shows that hetero-junctions of MWCNTs with different morphologies were formed. Then specimens of pristine MWCNTs, chemically functionalized MWCNTs and interconnected MWCNTs reinforced epoxy resin composites were fabricated by cast moulding. Tensile properties and fracture surfaces of the specimens were investigated. The results show that, compared with pristine MWCNTs and chemically functionalized MWCNTs, the chemically interconnected MWCNTs improved the fracture strain and therefore the toughness of the composites significantly.     

表面官能团化多壁碳纳米管/环氧树脂复合材料的制备及性能

本文首先将多壁碳纳米管(MWNT)进行表面化学修饰,接入羧基、胺基等官能团,采用红外光谱进行了表征.以纯化后的MWNT和表面化学修饰的MWNT作为填料,制备了MWNT /环氧树脂复合材料,研究了MWNT的加入对环氧树脂的力学性能、电学性能、热稳定性和玻璃化转变温度等的影响,并利用场发射电镜观察了胺基化MWNT在环氧树脂基体中的分散情况.     

电子束辐照对高密度聚乙烯/炭黑导电复合材料电阻率的影响

研究了电子束辐照固态和熔融态高密度聚乙烯／炭黑（ＨＤＰＥ／ＣＢ）导电复合材料的电性能随辐照温度和辐照剂量的变化。结果表明,对固态或熔融态辐照材料而言,其电阻率均随温度的升而而增大。等剂量下,固态辐照材料的ＰＴＣ强度比熔嘈态辐照的要高,两各状态经高剂量辐后其材料ＮＴＣ效应消失,,ＤＳＣ测试证明电阻率的２与基体的结晶行为以及交联链的形成密切相关。     

电场诱导多壁碳纳米管有序排列对多壁碳纳米管/环氧树脂复合材料性能的影响

采用交流（AC）电场诱导法制备了多壁碳纳米管（MWCNTs）均匀分散且定向有序排列的MWCNTs/环氧树脂复合材料。采用SEM、偏振拉曼光谱等研究了电场强度、MWCNTs含量、加电时间及温度（黏度）等因素对MWCNTs定向排列的影响,讨论了MWCNTs有序排列对MWCNTs/环氧树脂复合材料电学和力学性能的影响。结果表明：MWCNTs沿电场方向有序排列;MWCNTs/环氧树脂复合材料施加AC电场后的拉曼强度明显高于未施加电场的情况;当MWCNTs含量从0wt%增加到0.025wt%时,MWCNTs/环氧树脂复合材料导电率从2.3×10^-12 S/cm增加到1.3×10^-8 S/cm,增加了约4个数量级;MWCNTs含量为2.5wt%时,MWCNTs/环氧树脂复合材料拉伸强度提高了26.3%。     

石墨烯/环氧树脂复合涂层的γ射线辐照损伤及其腐蚀防护性能

用硅烷偶联剂对石墨烯表面进行修饰, 制备石墨烯/环氧树脂复合涂层。通过交流阻抗(EIS)和塔菲尔极化曲线(Tafel slope)等电化学方法分析复合涂层经伽马射线辐照后的腐蚀防护性能。采用电子自旋共振(ESR)和傅里叶红外光谱分析仪(FTIR)等测试复合涂层的γ射线辐照损伤, 探索了石墨烯在环氧树脂中抗辐照损伤的作用机理。Tafel结果显示复合涂层经280 kGy辐照后, 腐蚀电流为6.140×10^-9 A/cm², 而纯环氧树脂涂层的腐蚀电流则为1.340×10^-8 A/cm², 说明石墨烯可以使复合涂层保持较好的腐蚀防护性能。ESR分析表明, 复合涂层中的石墨烯可以降低环氧树脂基体在γ射线辐照过程中产生的过氧自由基, 表明石墨烯可有效吸收辐照过程中的自由基。辐照前后复合涂层的FT-IR图谱没有发生明显变化, 说明石墨烯有效降低了伽马射线对环氧树脂的结构损伤。因此, 可以认为石墨烯能够减缓环氧树脂在高能辐照环境中的老化, 从而延长其使用寿命。     

碳纳米管-玻璃纤维织物增强环氧复合材料的结构与性能

通过物理沉积法和静电吸附法在玻璃纤维织物(GF)表面包覆多壁碳纳米管(MWCNTs),制备GF-d-CNTs和GF-a-CNTs两种多尺度增强体,采用真空灌注工艺制备MWCNTs-GF增强环氧复合材料。采用静态、动态力学法、扫描电镜、红外光谱等分析手段,对复合材料的拉伸、弯曲、层间剪切、黏弹性和微观组成结构表征。结果表明:MWCNTs包覆于GF表面形成"倒刺"结构,并通过啮合作用增强了复合材料界面的强度和树脂韧性,提高了复合材料的玻璃化温度(Tg)等;与纯GF复合材料相比,GF-d-CNTs复合材料的拉伸强度和模量分别提高14.5%和37.9%,弯曲强度和模量分别提高26.2%和36.6%,层间剪切强度提高31.5%;GF-a-CNTs复合材料的Tg提高了8.9℃。     

Influence of ultrasonic dual mixing on thermal and tensile properties of MWCNTs-epoxy composite

Multiwalled carbon nanotubes (MWCNTs) reinforced epoxy based composites were fabricated by using an innovative ultrasonic dual mixing (UDM) process consists of ultrasonic mixing with simultaneous magnetic stirring. The effect of addition of varying amount of MWCNTs on thermal stability and tensile properties of the epoxy based composite has been investigated. It is found that the thermal stability, tensile strength and toughness of the epoxy base improves with the increase of MWCNTs addition up to 1.5 wt.% and UDM processing at certain capacity of the system. Tensile tests and thermal gravimetric analysis (TGA) were performed on each group of composites containing different amount of MWCNTs to determine their mechanical and thermal properties respectively. The dispersion of 1.5 wt.% MWCNTs fillers in epoxy nanocomposites was studied by transmission electron microscopy (TEM) as well as by field emission scanning electron microscopy (FESEM) applied on their tensile fracture surface.     

Mixed resin and carbon fibres surface treatment for preparation of carbon fibres composites with good interfacial bonding strength

The objective of this work is to improve the interlaminar shear strength of composites by mixing epoxy resin and modifying carbon fibres. The effect of mixed resin matrix’s structure on carbon fibres composites was studied. Anodic oxidation treatment was used to modify the surface of carbon fibres. The tensile strength of multifilament and interlaminar shear strength of composites were investigated respectively. The morphologies of untreated and treated carbon fibres were characterized by scanning electron microscope and X-ray photoelectron spectroscopy. Surface analysis indicates that the amount of carbon fibres chemisorbed oxygen-containing groups, active carbon atom, the surface roughness, and wetting ability increases after treatment. The tensile strength of carbon fibres decreased little after treatment by anodic oxidation. The results show that the treated carbon fibres composites could possess excellent interfacial properties with mixed resins, and interlaminar shear strength of the composites is up to 85.41 MPa. The mechanism of mixed resins and treated carbon fibres to improve the interfacial property of composites is obtained.     

A novel approach to the chemical stabilization of gamma-irradiated ultrahigh molecular weight polyethylene using arc-discharge multi-walled carbon nanotubes

A complete study was made of the stabilization of gamma-irradiated ultrahigh molecular weight polyethylene (UHMWPE) using arc-discharge multi-walled carbon nanotubes (MWCNTs) as inhibitors of the oxidative process. MWCNTs were efficiently incorporated into the polymer matrix by ball milling and thermo-compression processes at concentrations up to 5 wt% and subsequently gamma irradiated at 90 kGy. Raman spectroscopy demonstrated the generation of radicals on the walls of the MWCNTs and that the G/D ratio was altered by their generation. The same spectra showed interactions between the polymer chains as a series of shifts are observed in the UHMWPE bands. The effect of the MWCNTs as inhibitors for the oxidative process of the UHMWPE was evaluated by means of Electron Spin Resonance (ESR) and Fourier Transformed Infrared Spectroscopy (FTIR). ESR detection of the radiation-induced radicals proved the radical scavenger behaviour of MWCNTs. FTIR measurements were performed to ascertain the influence of the irradiation and of the accelerated ageing protocol in the oxidation index of the polymer and the composites. The results pointed to the positive contribution of the MWCNTs in increasing the oxidative stability of the composite when compared to pure UHMWPE. A comparison is made between composites obtained using MWCNTs produced by the carbon vapour deposition and arc-discharge methods.