Effect of moisture on elastic and viscoelastic properties of epoxy and epoxy-based carbon fibre reinforced plastic filled with multiwall carbon nanotubes

In this study, we investigated the peculiarities of moisture absorption and moisture-induced effects on the elastic and viscoelastic flexural properties of epoxy resin and carbon fibre reinforced plastic (CFRP) filled with multiwall carbon nanotubes (MWCNTs). Short-term cyclic creep-recovery tests of moistened epoxy and CFRP filled with MWCNTs revealed improvements in creep resistance for both materials. The addition of MWCNTs to the epoxy resin suppressed the moisture absorption by the material, causing a reduction in the diffusion coefficient by 31% and equilibrium moisture content by 15%. The addition of MWCNTs reduced the flexural strength of moistened epoxy and CFRP samples by approximately half, and also lowered the flexural modulus by ∼1.4 and ∼3 times, elastic strain by 1.25 and 1.04 times, viscoelastic strain by 1.39 and 1.03 times, and plastic strain by 2.68 and 1.60 times, respectively.     

Improving the mechanical properties of multiwalled carbon nanotube/epoxy nanocomposites using polymerization in a stirring plasma system

Uniform treatment of multiwalled carbon nanotubes by plasma treatment has been investigated using a custom-built stirring plasma system. A thin plasma polymer with high levels of amine groups has been deposited on MWCNTs using a combination of continuous wave and pulsed plasma polymerization of heptylamine in the stirring plasma system. Scanning electron microscopy showed that the plasma polymerization improved the dispersion and interfacial bonding of the MWCNTs with an epoxy resin at loadings of 0.1, 0.3 and 0.5 wt%. The flexural and thermal mechanical properties of plasma polymerized MWCNT/epoxy nanocomposites were also significantly improved while untreated MWCNT/epoxy nanocomposites showed an opposite trend. The epoxy with 0.5 wt% plasma polymerized MWCNTs had the greatest increase in flexural properties, with the flexural modulus, flexural strength and toughness increasing by about 22%, 17% and 70%, respectively.     

静电植绒法处理多壁碳纳米管改性玻纤织物/环氧树脂复合材料的制备及力学性能

为提高玻纤增强环氧树脂复合材料的力学性能,采用静电植绒法将多壁碳纳米管(MWCNTs)附着在玻纤织物表面,得到改性的玻纤织物。利用一种低黏度的环氧树脂和所制得的改性织物,采用真空辅助成型工艺(VARI)制备了MWCNTs改性格玻纤织物/环氧树脂复合材料层合板,表征了层合板的力学性能。对进行力学实验后的MWCNTs改性玻纤织物/环氧树脂复合材料试样断口进行了SEM和OPM观察。结果显示:与未添加MWCNTs的玻纤织物/环氧树脂复合材料层合板相比,添加了MWCNTs的层合板的拉伸强度降低了10.24%,弯曲强度降低了13.90%,压缩强度降低了17.33%,拉伸模量和弯曲模量分别提高了19.38%和16.04%,压缩模量提高了13%;MWCNTs与玻纤织物之间的结合较弱,在拉伸作用下,存在明显的脱粘和分层;将改性玻纤织物在200℃下热压处理2h后,制备的MWCNTs改性玻纤织物/环氧树脂复合材料层合板的力学性能均有所提高,热压处理后树脂与玻纤织物之间的界面结合得到改善。     

环氧化合物上浆处理的MWCNTs对MWCNTs/环氧树脂复合材料性能的影响

利用氨基化多壁碳纳米管(MWCNTs-NH2)与环氧化合物苄基缩水甘油醚(EP 692)和十二-十四烷基缩水甘油醚(EP AGE)反应,通过球磨工艺制备了两种不同分子结构环氧化合物上浆处理的多壁碳纳米管(MWCNTs)MWCNTs-692和MWCNTs-AGE。将均为1wt%的MWCNTs-NH2,MWCNTs-692和MWCNTs-AGE分别添加到二氨基二苯甲烷(DDM)固化双酚A二缩水甘油醚(DGEBA)环氧树脂体系中,分析了三种MWCNTs对树脂体系黏温关系、固化动力学、热力学性能和弯曲性能的影响。FT-IR,TGA和XPS测试表明,EP 692和EP AGE通过共价键接枝到碳纳米管的表面。与MWCNTs-NH2相比,MWCNTs-692和MWCNTs-AGE可以有效提高碳纳米管在环氧树脂基体中的分散性和相容性,减少纳米粒子对树脂体系黏度和固化动力学的影响。此外,添加上述三种碳纳米管都可以改善纯环氧树脂体系的储能模量和弯曲性能,其中经过含有刚性分子结构上浆剂处理的MWCNTs-692增强效果最为显著。添加1wt%MWCNTs-692后,MWCNTs-692/环氧树脂复合材料的常温储能模量提高了30.6%,弯曲强度和模量分别提高了18.8%和22.5%。     

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%。     

高能量超声波改性MWCNTs/环氧树脂特性分析

采用高能量超声波与低能量超声波对一种多壁碳纳米管(MWCNTs)/环氧树脂体系进行改性处理,结合流变仪、DSC、FTIR、XPS、XRD、TEM等测试手段,分析了不同超声波处理条件下MWCNTs物理化学特性的变化及其对MWCNTs在环氧树脂中的分散性和相容性的影响,并进一步考察了MWCNTs/环氧树脂体系的耐热性和弯曲性能。实验结果表明:超声波能量不同,MWCNTs的改性效果不同,高能量超声波对MWCNTs有更好的分散效果和分散效率,并能使MWCNTs表面活性增强,而低能量超声波则不明显;添加少量高能量超声波改性的MWCNTs,可以提高环氧树脂的弯曲模量和玻璃化转变温度,表明MWCNTs与基体之间形成了较强的结合界面。     

MWCNTs对环氧树脂及多尺度MWCNTs-碳纤维/环氧树脂复合材料力学性能的影响

通过对胺基化多壁碳纳米管（MWCNTs-NH₂）进行改性,得到改性MWCNTs悬浮液（MWCNTs-NH₂（M））。分别将羧基化MWCNTs （MWCNTs-COOH）和MWCNTs-NH₂（M）分散在环氧树脂（EP）中,采用热熔法制备了多尺度MWCNTs-碳纤维（CF）/EP复合材料。研究了MWCNTs对EP模量、韧性及EP与CF之间界面黏结强度的影响,并分析了MWCNTs与CF上浆剂的作用,评价了多尺度MWCNTs-CF/EP复合材料的力学性能。结果表明：官能团化的MWCNTs可对EP的模量和韧性起到更好的增强作用。MWCNTs接枝的-COOH或-NH₂可与CF上浆剂中的环氧基团发生化学反应,提高EP与CF之间的界面剪切强度。MWCNTs-NH₂（M）对多尺度MWCNTs-CF/EP复合材料力学性能的增强效果优于MWCNTs-COOH,当MWCNTs-NH₂（M）的含量为1wt%时,多尺度复合材料的0°压缩强度、90°压缩强度、弯曲强度、弯曲模量、冲击后压缩强度（CAI）分别提高了16.7%、16.3%、40.9%、30.3%、20.6%。     

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。     

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℃。     

Modification of surface functionality of multi-walled carbon nanotubes on fracture toughness of basalt fiber-reinforced composites

In this work, we studied the influence of surface functionality of multi-walled carbon nanotubes (MWCNTs) on the mechanical properties of basalt fiber-reinforced composites. Acid and base values of the MWCNTs were determined by Boehm's titration technique. The surface properties of the MWCNTs were determined FT-IR, and XPS. The mechanical properties of the composites were assessed by measuring the interlaminar shear stress, fracture toughness, fracture energy, and impact strength. The chemical treatments led to a change of the surface characteristics of the MWCNTs and of the mechanical interfacial properties of MWCNTs/basalt fibers/epoxy composites. Especially the acid-treated MWCNTs/basalt fibers/epoxy composites had improved mechanical properties compared to the base-treated and non-treated MWCNTs/basalt fibers/epoxy composites. These results can probably be attributed to the improved interfacial bonding strength resulting from the improved dispersion and interfacial adhesion between the epoxy resin and the MWCNTs.     

Improvements in mechanical and thermo-mechanical properties of e-glass/epoxy composites using amino functionalized MWCNTs

The prime objective of this work is to optimize the mechanical and thermo-mechanical properties of e-glass/epoxy composites by utilizing amino-functionalized multi-walled carbon nanotubes (MWCNTs–NH₂) through a combination of dispersion method. At first, 0.1–0.4 wt.% of MWCNT–NH₂ was integrated into SC-15 epoxy suspension using a combination of ultra-sonication and calendaring techniques. E-glass/epoxy nanocomposites were than fabricated at elevated temperature with the modified resin using hand layup and compression hot press. 3-Point flexural and dynamic mechanical analysis (DMA) results demonstrated a linearly increasing trend in properties from 0 to 0.3 wt.% loading. Micrographs of MWCNTs incorporated epoxy and e-glass/epoxy samples revealed uniform dispersion of MWCNTs in epoxy, good interfacial adhesion between CNTs and polymer, and improved interfacial bonding between fiber/matrix at 0.3 wt.% loading. An improved dispersion and hence an improved crosslink interaction between MWCNT–NH₂ and epoxy lead to the stronger shift of the mechanical and thermo-mechanical properties of the composites.     

Cryogenic mechanical behaviors of carbon nanotube reinforced composites based on modified epoxy by poly(ethersulfone)

Cryogenic mechanical properties are important parameters for epoxy resins used in cryogenic engineering areas. In this study, multi-walled carbon nanotubes (MWCNTs) were employed to reinforce diglycidyl ether of bisphenol F (DGBEF)/diethyl toluene diamine (DETD) epoxy system modified by poly(ethersulfone) (PES) for enhancing the cryogenic mechanical properties. The epoxy system was properly modified by PES in our previous work and the optimized formulation of the epoxy system was reinforced by MWCNTs in the present work. The results show that the tensile strength and Young’s modulus at 77 K were enhanced by 57.9% and 10.1%, respectively. The reported decrease in the previous work of the Young’s modulus of the modified epoxy system due to the introduction of flexible PES is offset by the increase of the modulus due to the introduction of MWCNTs. Meanwhile, the fracture toughness (K_IC) at 77 K was improved by about 13.5% compared to that of the PES modified epoxy matrix when the 0.5 wt.% MWCNT content was introduced. These interesting results imply that the simultaneous usage of PES and MWCNTs in a brittle epoxy resin is a promising approach for efficiently modifying and reinforcing epoxy resins for cryogenic engineering applications.     

Mechanical performance of epoxy matrix hybrid nanocomposites containing carbon nanotubes and nanodiamonds

A novel class of epoxy matrix hybrid nanocomposites has been developed containing multiwalled carbon nanotubes (MWCNTs) and nanodiamonds (NDs) to explore the combined effect of nanoreinforcements on the mechanical performance of nanocomposites. Both the nanofillers were functionalized before incorporating into epoxy matrix to promote interfacial interactions. The concentrations of both MWCNTs and NDs in the nanocomposites were increased systematically, i.e. 0.05 wt.%, 0.1 wt.% and 0.2 wt.% while composites containing individual nanoreinforcements were also manufactured for comparison. The developed nanocomposites were characterized microstructurally by scanning electron microscopy (SEM) and mechanically by tensile, flexural, impact and hardness tests. Homogeneous dispersion of MWCNTs and NDs was observed under SEM, which resulted in the enhancement of mechanical properties of nanocomposites. The composites containing 0.2 wt.% MWCNTs and 0.2 wt.% NDs showed 50% increase in hardness while tensile strength and modulus enhanced to 70% and 84%, respectively. Flexural strength and modulus also showed a rise of 104% and 56%, respectively. Interestingly, fracture strain also increased in both the tensile and flexural testing. The impact resistance increased to 161% showing a significant improvement in the toughness of hybrid nanocomposites.     

MWCNTs对碳纤维非褶皱无纺布/环氧层合板力学性能的影响

将羧基化多壁碳纳米管(MWCNTs)添加到TDE85环氧树脂中,然后与碳纤维非褶皱无纺布(C-NCF)复合,制备成[0°/90°/+45°/-45°]_S层合板。采用三点弯曲、短梁剪切和单边切口弯曲测试方法以及动态力学性能分析方法,研究了不同含量的MWCNTs对层合板弯曲性能、层间剪切强度(ILSS)、Ⅱ型层间断裂韧性(G_ⅡC,以及玻璃态转变温度(T_g)的影响。并采用SEM对Ⅱ型试样的断面进行分析。结果表明,MWCNTs的加入显著提高了NCF层合板的力学性能。与空白试样相比,当MWCNTs在树脂中的质量分数为2.0%时,弯曲强度和模量分别提高了约26%和6%;当MWCNTs的质量分数为0.5%时,ILSS、G_ⅡC、T_g分别提高约14%、27%和14%。     

Mechanical Properties of Thermoplastic and Thermoset Composites Reinforced with 3D Biaxial Warp-knitted Fabrics

In this study, two types of thermoplastic matrices (low melting point polyethylene terephthalate (LPET) fiber and polypropylene (PP) fiber) and glass fiber/epoxy resin/multi-walled carbon nanotubes (MWCNTs) were used to fabricate the thermoplastic and thermoset composite materials with 3D biaxial warp-knitted fabrics. Thermoplastic and thermoset composites were fabricated using hot-press and resin transfer molding (RTM) methods. The fabricated samples were tested with tensile and three-point flexural tests. In thermoplastic composites, samples in the 90° direction and LPET matrix showed the best tensile and flexural properties with an improvement of 39 and 21% tensile modulus and strength, 16 and 8% flexural modulus and strength compared to the PP samples in the same direction. In thermoset composites, samples in the 90° direction and MWCNTs showed the best improvement of the flexural modulus and strength with 97 and 58% compared to the samples without MWCNTs. This improvement can most likely be attributed to an increase in interfacial adhesion due to the presence of the carbon nanotubes.     

Influence of functionalization on properties of MWCNT-epoxy nanocomposites

The effects of various functionalized multi-walled carbon nanotubes (MWCNTs) on morphological, thermal, and mechanical properties of an epoxy based nanocomposite system were investigated. Chemical functionalization of MWCNT by oxidation (MWCNT-COOH) and direct-fluorination (MWCNT-F) were confirmed by FTIR, Raman spectroscopy, and TGA. Utilizing in situ polymerization, 1 wt% loading of MWCNT was used to prepare epoxy-based nanocomposites. Compared to the neat epoxy system, nanocomposites prepared with MWCNT-COOH showed 25.5% increase in ultimate flexural strength and 54.8% increase in flexural modulus. A decrease in strength was observed for the MWCNT-F nanocomposites. The premature degradation was attributed to a presumable catalyzation by hydrofluoric acid, HF, which evolved from the MWCNT-F during the curing process. However, only the MWCNT-F nanocomposites showed 22% increase in thermal properties (T_g). All nanophased systems showed increase in storage modulus.     

多壁巴基纸/环氧复合材料拉伸性能的影响因素

采用抽滤法制备了多壁碳纳米管(MWCNTs)纸(又称巴基纸), 研究了巴基纸增强不同环氧基体复合材料(巴基纸复合材料)的拉伸性能及其断口形貌, 分析了MWCNT含量、 树脂基体拉伸性能以及巴基纸与树脂的界面黏附作用对复合材料拉伸性能的影响。结果表明: 在MWCNT质量分数小于39.1%范围内, 增加碳纳米管含量, 可显著提高巴基纸/环氧复合材料的拉伸性能; 巴基纸/环氧复合材料的拉伸强度和模量与树脂基体的性能密切相关, 其拉伸破坏形式受基体的脆韧性影响显著; 相比较而言, 巴基纸与树脂间的黏附功对巴基纸/环氧复合材料拉伸性能的影响不明显。     

粉煤灰微珠含量与粒径级配比对环氧树脂基复合材料弯曲性能的影响

对粉煤灰空心微珠/环氧树脂复合材料进行了弯曲试验,研究了微珠粒径、含量以及级配比例对复合材料弯曲性能的影响,并通过弯曲断口微观形貌分析了内在机理。结果表明,空心微珠的加入对粉煤灰空心微珠/环氧树脂复合材料的弯曲强度影响很大。随空心微珠含量的增加,复合材料的弯曲强度呈现先升高后下降的趋势,填充量为15wt%时,复合材料的弯曲强度最大;随空心微珠粒径的减小,复合材料的弯曲强度随之提高,小粒径微珠对环氧树脂复合材料弯曲强度的提升效果更好;空心微珠级配填充环氧树脂复合材料的弯曲强度主要受级配微珠中小粒径微珠含量的影响,小粒径微珠的比例越大,弯曲强度越高。     

Multiscale carbon fibre–reinforced polymer (CFRP) composites containing carbon nanotubes with tailored interfaces

Pristine and functionalized multiwalled carbon nanotubes (MWCNTs) with tailored interfaces were efficiently dispersed in an epoxy matrix using a three‐roll mill and further reinforced with carbon fibres. 1.3‐Dipolar cycloaddition of azomethine ylides was used for the chemical modification of MWCNTs by a solvent‐free approach. The influence of different loadings and types of MWCNTs on the final properties of the epoxy matrix was studied. Moreover, the most promising formulations were selected for manufacturing of prepreg sheets. The transversal tensile properties and the interlaminar fracture toughness under mode I loading (G_IC) of multiscale carbon fibre–reinforced polymer (CFRP) composites were characterized. The results point out that it is not straightforward to transfer the remarkable intrinsic properties of MWCNTs to the composite level, although an overall positive trend was found. Double cantilever beam experiments showed that G_IC of CFRP composites was improved 44% at ultralow content of functionalized MWCNTs (0.043 wt%).     

Thermal and mechanical properties of phenolic-based composites reinforced by carbon fibres and multiwall carbon nanotubes

The thermal, mechanical and ablation properties of carbon fibre/phenolic composites filled with multiwall carbon nanotubes (MWCNTs) were investigated. Carbon fibre/phenolic/MWCNTs were prepared using different weight percentage of MWCNTs by compression moulding. The samples were characterized by scanning electron microscopy (SEM), flexural tests, thermal gravimetric analysis and oxyacetylene torch tests. The thermal stability and flexural properties of the nanocomposites increased by increasing MWCNTs content (wt% ⩽1), but they decreased when the content of MWCNTs was 2 wt%. The linear and mass ablation rates of the nanocomposites after modified with 1 wt% MWCNTs decreased by about 80% and 52%, respectively. To investigate the material post-test microstructure, a morphological characterization was carried out using SEM. It was shown that the presence of MWCNTs in the composite led to the formation of a strong network char layer without any cracks or opening.