Fabrication of high mechanical performance UHMWPE nanocomposites with high-loading multiwalled carbon nanotubes

Using conventional mixing techniques, the mechanical properties of prepared carbon nanotube (CNT)/polymer composites are not impressive enough, because of their aggregation problem at a high loading of CNTs. In this article, high mechanical performance ultrahigh molecular weight polyethylene (UHMWPE) nanocomposites with high loading of multiwalled CNTs were successfully fabricated by a new manufacturing technique. Specifically, the tensile strength and storage modulus at 25 °C of UHMWPE nanocomposites with 32 wt % of nanotubes prepared by the novel technique reaches 107.6 MPa and 6.0 GPa, respectively, about 4.7 times and 5.0 times of that of pure UHMWPE resin, which are also very high experimental results compared with polyethylene nanocomposite prepared by traditional hot-compression techniques. These attractive results suggest that the high-loading CNTs without sacrificing their dispersion and the impregnation quality of polymer-impregnated buckypapers are essential for fabricating CNTs/polymer composites with superior mechanical properties. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 137, 48667.     

Effective reinforcement of carbon nanotubes in polypropylene matrices

This study describes an attempt to mechanically reinforce polypropylene (PP) using multi‐wall carbon nanotubes (MWNTs) through a melt compounding process followed by hot‐pressing and solid state drawing. The effect of a high density polyethylene (HDPE) coating on MWNTs and melt flow index (MFI) of PP on the dispersion of MWNTs and composite properties are studied by means of mechanical tests, transmission electron microscopy (TEM), scanning electron microscope (SEM), differential scanning calorimetry (DSC), and wide angle x‐ray diffraction (WAXD). Highly orientated composite tapes are prepared to fully utilize the properties of MWNTs in uniaxial direction. Highly aligned MWNTs are shown by SEM, while highly oriented polymer chains are characterized by WAXD. Composite theory is used to analysis the results and indicate that effective reinforcement of PP by MWNTs is highest at relatively low filler content and draw ratios. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Influence of dispersion states of carbon nanotubes on physical properties of epoxy nanocomposites

Effects of different dispersion states of carbon nanotubes (CNTs) on rheological, mechanical, electrical, and thermal properties of the epoxy nanocomposites were studied. The dispersion states were altered depending upon whether a solvent was employed or not. To characterize dispersion of the CNTs, field emission scanning electron microscope (FESEM) and transmission electron microscopy (TEM) were used. It was found that the nanocomposites containing poorly dispersed CNTs exhibited higher storage modulus, loss modulus, and complex viscosity than ones with well dispersed CNTs. It means that the poorly dispersed CNTs/epoxy composites have, from a rheological point of view, a more solid-like behavior. Tensile strength and elongation at break of the nanocomposites with different dispersion of CNTs were measured. Both of the well and the poorly dispersed CNTs composites showed a percolation threshold of electrical conductivity at less than 0.5 wt.% CNTs loading and the former had higher electrical and thermal conductivities than the latter. Effects of the CNTs content on the physical properties were also examined experimentally. As loading of the CNTs increased, improved results were obtained. From the morphological observation by FESEM and TEM, it was found that when the solvent was not used in the CNTs dispersion process, aggregates of pristine CNTs remained in the nanocomposites.     

Multi-wall carbon nanotubes by catalytic decomposition of carbon monoxide on Ni/MgO

The redox behavior of the catalyst and the catalytic decomposition of carbon monoxide (CO) were investigated in the synthesis process of multi-wall carbon nanotubes (MWCNT) using Ni/MgO catalyst. The surface morphology of the heated Ni layer was observed by TEM to confirm the formation of NiO particles (50 nm or less) and NiO (222). The chemical reaction behavior of the catalyst in CO the atmosphere was displayed via TG-DSC analysis, and the reduction of NiO was revealed due to the mass decrease of 2.71 wt% and the exothermic peak at around 400°C. The deposition of carbon was identified with an increase in mass and the exothermic peak near 600°C. Ni (111) and carbon (002) facets was taken place in a diffraction pattern of carbon deposited catalyst, indicating the reduction in NiO and the graphitic carbon deposition. The crystallinity of the graphitic carbon was analyzed as the ratios of 0.998 for I_D/I_G and 0.26 for sp³/sp² in Raman and photoelectron spectra. The encapsulated Ni in MWCNT was observed through TEM-EDS, verifying the activation of the catalyst by CO.     

碳纳米管增强天然橡胶复合材料的制备与性能研究

碳纳米管以其特殊的结构与优异的性能成为橡胶的理想填料。本文分别采用四种不同牌号(分别为Flotube7000 9000 9011 9400)的碳纳米管为实验原料,制备了碳纳米管/天然橡胶复合材料,并对其性能进行了研究探讨。结果发现,碳纳米管的加入能显著提高复合材料的力学性能和热导率,具有一维取向排列且长径比较大的Flotube7000(以下简称7000)对力学性能的提高程度最大,Flotube7000以及经过酸处理的表面具有-OH、–COOH官能团的Flotube9011(以下简称9011)对导热性能提高程度最为明显。     

On the use of carbon nanotubes as reinforcing fillers for elastomeric materials

Rubber composites containing multiwall carbon nanotubes are investigated. The results are compared with those obtained with conventional carbon black. In each case, the level of reinforcement is assessed from the mechanical and equilibrium swelling behavior. The state of dispersion is evaluated from transmission electron and atomic force microscopy methods. Copyright © 2006 Society of Chemical Industry     

Effect of strain on the properties of a styrene–butadiene rubber filled with multiwall carbon nanotubes

Multiwall carbon nanotubes were dispersed in a styrene–butadiene copolymer. The effect of nanotube concentration on the tensile characteristics of the composites was examined. Electrical properties carried out under uniaxial extension show an increase in resistivity upon gradual stretching. A second stretch performed after total release of the stress was shown to lead to a flat response in resistivity. Atomic force microscopy was used to examine orientational effects and changes in filler structure occurring upon application of an uniaxial deformation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Effect of phenol functionalization of carbon nanotubes on properties of natural rubber nanocomposites

This paper reports the results of studies on the effect of phenol functionalization of carbon nanotubes (CNTs) on the mechanical and dynamic mechanical properties of natural rubber (NR) composites. Fourier transform infrared spectrometry (FTIR) indicates characteristic peaks for ether and aromatic rings in the case of phenol functionalized CNT. Although differential scanning calorimetric (DSC) studies show no changes in the glass‐rubber transition temperature (T_g) of NR in the nanocomposites due to surface modification of CNT, dynamic mechanical studies show marginal shifting of T_g to higher temperature, the effect being pronounced in the case of functionalized CNT. Stress‐strain plots suggest an optimum loading of 5 phr CNT in NR formulations and the phenolic functionalization of CNT does not affect significantly the stress‐strain properties of the NR nanocomposites. The storage moduli register an increase in the presence of CNT and this increase is greater in the case of functionalized CNT. Loss tangent showed a decrease in the presence of CNT, and the effect is more pronounced in the case of phenol functionalized CNT. Transmission electron microscopy (TEM) reveals that phenol functionalization causes improvement in dispersion of CNT in NR matrix. This is corroborated by the increase in electrical resistivity in the case of phenol functionalized CNT/NR composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Strengthening mechanisms in carbon nanotube reinforced bioglass composites

Carbon nanotube reinforced bioglass composites have been successfully synthesized by two comparative sintering techniques, i.e., spark plasma sintering (SPS) and conventional compaction and sinteirng. The composites show improved mechanical properties, with SPS technique substantially better than conventional compact and sintering approach. Using SPS, compared with the 45S5Bioglass matrix, the maximum flexural strength and fracture toughness increased by 159% and 105%, respectively. Enhanced strength and toughness are attributed to the interfacial bonding and bridging effects between the carbon nanotubes and bioglass powders during crack propagations.     

Tribological investigations of carbon nanotube‐reinforced polymer (UHMWPE) nanocomposites using Taguchi methodology

Taguchi design techniques have been applied to investigate the significant influence of various operating and design parameters, such as contact load, rotational sliding speed, and carbon nanotubes (CNTs) concentration on the tribological properties of ultra‐high molecular weight polyethylene nanocomposites. Analysis of variance was conducted to discuss the significance of each of the parameters. Simple regression models were developed for wear rate as well as for the coefficient of friction (COF) of the nanocomposite. Applied normal force was found to be the dominant factor controlling the wear rate and friction coefficient. The significance of CNTs concentration on both COF and wear rate closely follow that of applied load. Rotational sliding speed has the least influence on the tribological properties of the nanocomposite. The developed model for predicting wear rate and the COF was found to give very good predictions against the experimental data. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44018.     

The effect of processing parameters on the bond strength and electrical conductivity of multi-wall carbon nanotube/low-density polyethylene composite

The objective of this paper is to study the influence of processing parameters, such as melt temperature and mold temperature, on the adhesion of low density polyethylene (LDPE) to 2.5?wt/% multi-wall carbon nanotube-filled polyethylene (LDPE/MWCNT). The adhesion was obtained using two-component injection-molding method and measured using tensile experiments. The electrical conductivity of the two-component injection-molded specimens was also measured through DC voltage and compared to the volume resistivity of the LDPE and LDPE/MWCNT composite. It was found that the bond strength increases with increasing melt and mold temperatures. However, increasing the melt and mold temperatures over a certain limit can decrease the bond strength. The range of the electrical conductivity of the LDPE-LDPE/MWCNT two-component injection-molded samples was in the range of dissipative materials.     

Structure and properties of UHMWPE fiber/carbon fiber hybrid composites

Ultrahigh molecular weight polyethylene (UHMWPE) fiber/carbon fiber hybrid composites were prepared by inner‐laminar and interlaminar hybrid way. The mechanical properties, dynamic mechanical analysis (DMA), and morphologies of the composites were investigated and compared with each other. The results show that the hybrid way was the major factor to affect mechanical and thermal properties of hybrid composites. The resultant properties of inner‐laminar hybrid composite were better than that of interlaminar hybrid composite. The bending strength, compressive strength, and interlaminar shear strength of hybrid composites increased with an increase in carbon fiber content. The impact strength of inner‐laminar hybrid composite was the largest (423.3 kJ/m²) for the UHMWPE fiber content at 43 wt % to carbon fiber. The results show that the storage modulus (E′), dissipation factor (tan δ), and loss modulus (E″) of the inner‐laminar hybrid composite shift toward high temperature remarkably. The results also indicate that the high‐performance composite with high strength and heat resistance may be prepared by fibers' hybrid. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1880–1884, 2006     

乙醇裂解协同制备氢气和碳纳米管

以乙醇为碳源,采用浸渍法制备的担载量为Fe(5%)/C催化剂,利用化学气相沉积法协同制备碳纳米管和氢气,分析了裂解温度(500⁸00℃)对于产生氢气产率和碳纳米管品质的影响。对于Fe(5%)/C催化裂解乙醇,最佳的反应温度为600℃,碳管的品质较好,氢气的产率最高为75%,生成的碳管为多壁碳纳米管。     

羧化多壁碳纳米管/维生素B_(12)修饰电极测定多巴胺

制备了羧化多壁碳纳米管/维生素B12修饰玻碳电极,利用循环伏安法研究了多巴胺(DA)在此修饰电极上的电化学行为。结果表明,在pH为6.48的PBS缓冲溶液中,此修饰电极对DA有很强的电催化作用,明显增强了峰电流,峰电位差ΔEp由196 mV减小至69 mV,提高了电极反应的可逆性。在优化实验条件下,此修饰电极所测DA氧化峰电流与DA浓度在1.0×10-5~5.0×10-5mol/L及1.0×10-3~1.0×10-2mol/L范围内均呈线性,线性方程分别为y=373.78x+71.726(R2=0.995 8)和y=57.2x+365.22(R2=0.986 6),其中低浓度区的相关系数较高,应用于实际样品测定时结果较为满意。检测限可达8.0×10-8mol/L。     

碳纳米管炭黑天然橡胶复合材料的制备与性能研究

碳纳米管以其特殊的结构与优异的性能成为橡胶补强的理想填料。本文中我们采用两种不同牌号的碳纳米管(分别为Flotube 7000、9011)与炭黑N660作为实验原料,制备了碳纳米管/炭黑/天然橡胶复合材料,并对其性能进行了探讨。结果发现：碳纳米管的加入能明显提高复合材料的定伸应力,具有一维取向排列且长径比较大的Flotube 7000(以下简称7000)对力学性能的提高程度最大。且我们将碳纳米管7000、9011分别与炭黑N660并用,对于提高复合材料的导热性能并没有如我们预期的一样存在所谓的“叠加关系”甚至是“协同效应”,而是对于提高复合材料导热有着一定的“负协同效应”。     

Dynamic mechanical and Raman spectroscopy studies on interaction between single‐walled carbon nanotubes and natural rubber

The effects of the incorporation of single‐walled carbon nanotubes (SWNTs) on the physical and mechanical properties of natural rubber (NR) are described. Characterization of these new materials has been performed by dynamic mechanical analysis, differential scanning calorimetry, and Raman spectroscopy to obtain information about of the possible interactions between both materials as well as the dispersion of SWNTs on elastomer matrix. The results are then compared with those obtained for NR–carbon black composites. Dynamic mechanical analysis indicates a stronger filler–matrix interaction in the case of SWNTs incorporation, showing a noticeable decrease of the height of tan δ peak, as well as a marked shift of T_g towards higher temperatures. In particular, the increase of the storage modulus indicates a beneficial effect of SWNTs incorporation with respect to NR filled with carbon black and the pristine polymer matrix. In addition, calorimetric analysis indicates that both fillers accelerate the NR vulcanization reaction, this effect being more evident when SWNTs are added into the matrix. Raman spectroscopy indicates that SWNTs dispersion into the elastomer matrix creates residual strain on the nanotubes bundle. We demonstrate that the Raman microprobe technique provides a means for load transfer effectiveness of SWNTs. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3394–3400, 2004     

UHMWPE/CNTs复合纤维的结晶行为研究

分别用DSC、X衍射、热台偏光显微镜对超高分子质量聚乙烯（UHMWPE）和UHMWPE／CNTs（碳纳米管）复合纤维的结晶行为进行了研究。结果表明：碳纳米管的加入使得复合材料的熔点较UHMWPE有所提高,碳纳米管起到了成核剂的作用。晶片厚度较UHMWPE增加。     

Electrochemical behavior of multi-wall carbon nanotubes and electrocatalysis of toluene-filled nanotube film on gold electrode

The cyclic voltammetric behaviors of empty nanotubes and toluene-filled nanotubes were described. When the nanotube films exposed to air for one night, a pair of redox waves was observed that is probably ascribed to the presence of oxygen-containing groups bound to the surface of the nanotubes. Toluene-filled nanotube film is demonstrated to catalyze the electrochemical response of biomolecules such as dopamine and epinephrine, while empty multi-wall carbon nanotube film shows no or less electrocatalytic behavior to these biomolecules. This suggests that filled nanotubes have some particular properties compared to empty multi-wall carbon nanotubes and the development of filled nanotubes is necessary.     

Copolyester nanocomposites based on carbon nanotubes: reinforcement effect of carbon nanotubes on viscoelastic and dielectric properties of nanocomposites

Nanocomposites based on an amorphous copolyester, poly(ethylene glycol‐co‐cyclohexane‐1,4‐dimethanol terephthalate) and carbon nanotubes were fabricated using a simple melt processing technique. The reinforcement effect of carbon nanotubes in the copolyester was investigated experimentally using different approaches based on dynamic mechanical analysis, rheology and dielectric analysis. The nanocomposites show a mechanical reinforcement effect with significant increase in the stiffness especially in the rubbery regime with increasing nanotube content. An increase in T_g and a decrease in damping are seen, which are derived from the presence of a percolating superstructure of the filler. Rheological experiments show an increase in storage modulus up to four orders of magnitude. Viscolelastic characterization shows that the percolation threshold is at 3 wt% of nanotubes. Dielectric relaxation spectroscopy confirms the presence of this percolating structure. We conclude that the responses of both rheological and electrical properties are different, although both are related to the formation of a percolating network superstructure of the filler. Copyright © 2007 Society of Chemical Industry     

Improved impact strength of epoxy by the addition of functionalized multiwalled carbon nanotubes and reactive diluent

Multiwalled carbon nanotubes (MWCNTs), both oxidized and amine functionalized (triethylenetetramine—TETA), have been used to improve the mechanical properties of nanocomposites based on epoxy resin. The TGA and XPS analysis allowed the evaluation of the degree of chemical modification on MWCNTs. Nanocomposites were manufactured by a three‐roll milling process with 0.1, 0.5, and 1.0 wt % of MWCNT–COOH and MWCNT–COTETA. A series of nanocomposites with 5.0 wt % of reactive diluent was also prepared. Tensile and impact tests were conducted to evaluate the effects of the nanofillers and diluent on the mechanical properties of the nanocomposites. The results showed higher gains (258% increase) in the impact strength for nanocomposites manufactured with aminated MWCNTs. Optical microscopy (OM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) were used to investigate the overall filler distribution, the dispersion of individual nanotubes, and the interface adhesion on the nanocomposites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42587.