化学镀镍碳纳米管的制备及其电磁学和吸波性能研究

首先对碳纳米管(CNTs)进行纯化、敏化、活化预处理,然后利用化学镀方法在其表面沉积金属镍而制备出镀镍碳纳米管(M-CNTs)。SEM、TEM、EDS、XRD和DSC等综合表征结果表明,通过化学镀工艺,在CNTs表面均匀连续的镀覆了一层厚度约为20nm的非晶态镍镀层,且碳纳米管的分散性得到了改善,更有利于用于复合材料领域。原料碳纳米管和镀镍碳纳米管的电磁学性能的对比研究结果表明,M-CNTs的电导率较CNTs有所降低,这也间接反映了镍镀层在CNTs表面的形成;在4～18GHz内,M-CNTs的ε′、ε″、μ和μ″4个电磁参数均较CNTs均有所增加。在此基础上,进一步以M-CNTs为吸波剂,聚氨酯(PU)为粘结剂,制备了PU/M-CNTs吸波涂料,对其吸波性能的研究结果表明,PU/M-CNTs吸波涂料的吸波效果明显受涂层厚度影响,在1.0～2.0mm的范围内,随着涂层厚度的逐渐增大,其吸收峰逐渐向低频移动,且低频段的吸波效果得以加强,高频段的吸波效果有所减弱。     

Electroactive Shape Memory Effect of Polyurethane Composites Filled with Carbon Nanotubes and Conducting Polymer

We report the electroactive shape memory composites obtained by shape memory polyurethane block copolymer (PU) and multi-walled carbon nanotubes (MWNTs), and polypyrrole (PPy). An addition of combined MWNTs and PPy contributed to an enhancement in conductivity of PU-MWNTs composites. PU containing 2.5% MWNTs showed better mechanical and thermal properties than other composites, but conductivity was not sufficient for showing the shape memory effect by applying electrical voltages. However, when the composite was lightly coated by PPy (2.5%), its conductivity was the highest than other composites. Such the conductivity of this composite was enough to show electroactive shape recovery by heating above transition temperature of 40-48°C due to melting of polycaprolactone soft segment domain. The good shape recovery of 90-96% could be obtained in the shape recovery test when an electric field of 25 V was applied.     

Enhanced dispersion of carbon nanotubes in hyperbranched polyurethane and properties of nanocomposites

Hyperbranched polyurethane (HBPU) nanocomposites with multi-walled carbon nanotubes (MWNTs) were prepared by in?situ polymerization on the basis of poly(ε-caprolactone)diol as the soft segment, 4,4'-methylene bis(phenylisocyanate) as the hard segment, and castor oil as the multifunctional group for the hyperbranched structure. A dominant improvement in the dispersion of MWNTs in the HBPU matrix was found, and good solubility of HBPU-MWNT nanocomposites in organic solvents was shown. Due to the well-dispersed MWNTs, the nanocomposites resulted in achieving excellent shape memory properties as well as enhanced mechanical properties compared to pure HBPU.     

Microstructure changes of polyurethane by inclusion of chemically modified carbon nanotubes at low filler contents

The surface of multi-walled carbon nanotubes (MWCNTs) was modified to introduce acidic groups in either covalent or van der Waals interaction bonding environments to establish cross-linking sites with a host polymer. Nanocomposites based on a polyurethane matrix (PU) containing chemically functionalised multi-walled carbon nanotubes (MWCNTs) have been shown to alter its mechanical performance depending on the nature of the surface functional groups on MWCNTs, which correlates to the type of bonding interaction of the surface group and also the dispersibility of MWCNTs and their influence on the domain structure of polyurethane. The stress at break for nanocomposites containing 0.25 wt% of acid-oxidised MWCNTs (MWCNT-ox), bearing covalently attached carboxylic, lactone and phenolic groups, was twice that of the native PU and Young’s Modulus for the nanocomposites increased by four times. Whereas when hemin, which contains carboxylic functionality, was immobilised to the surface of pure MWCNTs, the improvement in Young’s Modulus was only around twice that of pure PU. Differences in the disaggregation of MWCNTs into PU were observed between the samples as well as variation of the native domain structure of PU. The results also infer that the purification of MWCNTs from acid-oxidative lattice fragments (fulvic acids) is vital prior to conducting surface chemistry and polymerisation in order to ensure maximum mechanical performance enhancement in their reinforcement of the host polymer.     

Piezoresistive and compression resistance relaxation behavior of water blown carbon nanotube/polyurethane composite foam

The in-situ bulk polycondensation process in combination with a ball milling dispersion process was used to prepare the water blown multiwall carbon nanotubes (CNT)/polyurethane (PU) composite foam. The mechanical properties, piezoresistive properties, strain sensitivity, stress and resistance relaxation behaviors of the composite foams were investigated. The results show that the CNT/PU composite foam has a better compression strength than the unfilled polyurethane foams and a negative pressure coefficient behavior under uniaxial compression. The resistance response of CNT/PU nanocomposites foam under cyclic compressive loading was quite stable. The nanocomposite foam containing a weight fraction of carbon nanotubes close to the percolation threshold presents the largest strain sensitivity for the resistance. The characteristic of resistance relaxation of CNT/PU composite foam is different from the stress relaxation due to the different relaxation mechanism. During compressive stress relaxation, the CNT/PU foam composites have excellent resistance recoverability while poor stress recoverability.     

Creep behavior of polyurethane nanocomposites with carbon nanotubes

The polyurethane (PU) nanocomposites containing carbon nanotubes (CNTs) were prepared through in situ polymerization for the creep study. The results show that the presence of CNTs leads to a significant improvement of creep resistance of PU. However, this creep resistance does not increase monotonously with increase of CNT contents because it is highly dependent on the dispersion of CNTs. Several theoretical models were then used to establish the relations between CNT dispersion and final creep and creep–recovery behaviors of nanocomposites. The as-obtained viscoelastic and viscoplastic parameters of PU matrix and structural parameters of CNTs further confirmed the retardation effect by CNTs during creep of the nanocomposite systems. Besides, the time–temperature superposition (TTS) principle was also employed in this work to make a further evaluation on the creep of PU/CNT nanocomposites with long-term time scale.     

The physical properties of polyurethane/graphite nanosheets/carbon black foaming conducting nanocomposites

Using polyester polyol and diphenylmethane diisocyanate (MDI) as basic component, and using graphite nanosheets (GN) and carbon black (CB) as conductive filler, polyurethane/graphite nanosheets/carbon black foaming conducting nanocomposites have been prepared by filling mold curing reaction. The morphology, electrical properties and mechanical properties of the prepared PU/GN foams have been investigated. It showed that the percolation threshold effect of PU/GN composite occurred at the content around 12 wt.% of the GN, which was lower than that of carbon black (CB) composite. Besides, PU/GN foams showed much better conductive properties and mechanical properties than that of CB system.     

Acoustic properties of polyurethane compositions enhanced with multi‐walled carbon nanotubes and silica nanoparticles

In this study, in order to enhance acoustic properties of polyurethane (PU) foams multi‐walled carbon nanotubes (MWCNT) and/or silica nanoparticles were added to polyol‐isocyanate composition up to 2 wt%, and acoustic properties of polyurethane foam samples with small amount of carbon nanotubes and silica nanoparticles (spherical and/or amorphous types) were determined in the frequency range from 50 Hz up to 6400 Hz. Acoustic properties, especially absorption coefficient of the produced samples were measured for all the prepared samples and results were investigated to come up with the best polyurethane samples that can be applied for sound absorption application at the desired frequency range. It was found that double combination of carbon nanotubes and silica nanoparticles, especially 0.7 wt% carbon nanotubes and 0.2 wt% spherical silica nanoparticle added polyurethane composition has better sound absorption ratio overall all frequencies levels compared to the other samples. Thus, it is possible to obtain polyurethane nanocomposite with a higher amount of carbon nanotube by weight at the same time enhancing sound absorption properties. Moreover, there is a synergic effect between carbon nanotubes and silica nanoparticles when mixed and added into polyurethane matrix at predetermined levels to get enhanced acoustic response with a higher level of carbon nanotube in polyurethane foam.     

Preparation,characterization and properties of polycaprolactone diol-functionalized multi-walled carbon nanotube/thermoplastic polyurethane composite

Multi-walled carbon nanotubes (MWCNTs) were chemically functionalized to prepare thermoplastic polyurethane (PU) composites with enhanced properties. In order to achieve a high compatibility of functionalized MWCNTs with the PU matrix, polycaprolactone diol (PCL), as one of PU’s monomers, was selectively grafted on the surface of MWCNTs (MWCNT–PCL), while carboxylic acid groups functionalized MWCNTs (MWCNT–COOH) and raw MWCNTs served as control. Both MWCNT–COOH and MWCNT–PCL improved the dispersion of MWCNTs in the PU matrix and interfacial bonding between them at 1 wt% loading fraction. The MWCNT–PCL/PU composite showed the greatest extent of improvement, where the tensile strength and modulus were 51.2% and 33.5% higher than those of pure PU respectively, without sacrificing the elongation at break. The considerable improvement in both mechanical properties and thermal stability of MWCNT–PCL/PU composite should result from the homogeneous dispersion of MWCNT–PCL in the PU matrix and strong interfacial bonding between them.     

From cellulosic waste to nanocomposites. Part 2: synthesis and characterization of polyurethane/cellulose nanocomposites

New polyurethane (PU)-based nanocomposites were synthesized through two-step in situ polymerization by incorporating low loading levels of spherical cellulose nanoparticles (CNs). Structural, mechanical, thermal, and morphological characterization of the nanocomposites was done with infrared spectroscopy, X-ray diffraction, tensile test, dynamic mechanical thermal analysis, thermogravimetry, differential scanning calorimetry, and field emission scanning electron microscopy. The results showed with incorporation of CNs there was no significant change in the structure of PU. However, the addition of 1 % CNs into PU increased the modulus nearly 42 % and tensile strength by 112 %. On the contrary, elongation at break decreased with increasing nanoparticles contents, but the nanocomposites maintained an elongation of greater than 800 %, which was still a large elongation. The thermal stability of PU enhanced with increasing the small amounts of nanoparticles. Also, incorporating of the CNs improved the phase separation between the soft and hard domains which led to an upward shift in melting temperatures and enthalpy of crystalline phase melting. These results were very encouraging in terms of using CNs as an inexpensive nanofiller and improving the mechanical and thermal properties of PU without using solvents in nanocomposite preparation.     

一步法制备聚氨酯/碳纳米管复合泡沫材料及其性能

采用球磨法将碳纳米管分散到聚醚三元醇中,以水为发泡剂,采用一步法原位聚合制备了聚氨酯(PU)/碳纳米管(CNTs)复合泡沫材料,研究了发泡剂水的添加量和碳纳米管的含量对复合材料密度和性能的影响.结果表明,随水添加量的增加,泡沫材料的密度、压缩模量、拉伸模量以及断裂伸长率呈下降的趋势;碳纳米管的加入大幅度提高了材料的压缩...     

Properties and mechanism of two-way shape memory polyurethane composites

Recently, smart materials have drawn wide attention from many researchers. In this paper, laminated shape memory polymer composite (SMPC) exhibiting two-way shape memory effect (SME) has been prepared by combining the pre-elongated shape memory polyurethane (SMPU) with the un-elongated elastic polyurethane (PU). Then the shape memory behaviors, laminated structure and two-way SME mechanism are investigated systematically. The results show that two-way shape memory behaviors, i.e., bending upon heating and reverse bending upon cooling, are achieved in the resulted SMPU-based-SMPCs. In addition, the SMPCs show the compositive thermal properties and dynamic mechanical properties due to their physical combination of layer-by-layer. Furthermore, the shape memory mechanism can be ascribed to the reversible change of two forces, i.e., recovery force in the SMPU layer and bending force in the elastic PU layer.     

聚氨酯/碳纳米管复合材料的制备及其对血小板黏附的抑制作用

通过原位聚合的方法将官能化碳纳米管引入聚氨酯中制备了聚氨酯/碳纳米管复合材料(PU/MWNTs),并对其物理学性能和生物学功能进行了研究.通过差示扫描量热法和拉伸性能测试对材料的基本性能进行了研究;通过血小板黏附实验评价了复合材料的生物学性能.结果表明,PU/MWNTs材料的玻璃化温度升高、力学性能得到了提高,碳纳米管(CNTs)的加入使复合材料显示出与聚氨酯基体材料不同的血小板吸附行为,尽管MWNTs的增加明显促进了纤维蛋白原的吸附,但PU/MWNTs表现出对血小板黏附和活化有抑制作用.     

Effects of organic chain length of layered zirconium phosphonate on the structure and properties of castor oil-based polyurethane nanocomposites

Three novel organic–inorganic hybrid molecules, layered zirconium phosphates or phosphonates, were synthesized. To study the effects of organic chain length of them on the structure and properties of polymer nanocomposites, the polyurethane/α-zirconium phosphate (PU/ZrP), polyurethane/zirconium 2-aminoethylphosphonate (PU/ZrAEP) and polyurethane/zirconium 2-(2-(2-(2-aminoethylamino)ethylamino)ethylamino) ethylphosphonate (PU/Zr(AE)₄P) nanocomposites were prepared, and characterized by Fourier Transform Infrared (FT-IR) spectroscopy, wide-angle X-ray diffraction (XRD), transmission electron microscopy (TEM), thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC) and tensile testing. It was revealed that morphological, mechanical, and thermal properties of these nanocomposites were strongly dependent on the organic chain length of the layered zirconium phosphonates. The results showed that the fillers with longer chain length exhibited better dispersion in the PU matrix. As expected, the mechanical properties and water resistance were improved with the increasing of organic chain length of fillers, which attributed to better interfacial adhesion between fillers and PU matrix.     

Click coupled stitched graphene sheets and their polymer nanocomposites with enhanced photothermal and mechanical properties

The chemically stitched graphene oxide (GO) sheets were obtained using a click chemistry reaction between azide-functionalized GO and alkyne-functionalized GO. The click coupled GO (GO-click-GO) sheets showed the largely increased electrical conductivity and near infrared laser-induced photothermal properties compared to the GO sheets, which result from formation of triazole ring as a bridging linker between the GO sheets. The polyurethane (PU) nanocomposites incorporating the GO-click-GO sheets exhibited enhanced mechanical properties of breaking stress and modulus than the GO/PU nanocomposites. The modulus of GO-click-GO/PU nanocomposites was higher than that of the GO/PU nanocomposites at the same filler loading of 0.1 and 0.5 wt%. The GO-click-GO/PU nanocomposites also showed a significantly improved photothermal properties compared to the GO/PU nanocomposites at the same filler loading. The click coupled stitched GO sheets in this study can be used as the superior reinforcing fillers for mechanically and photothermally high performance polymer nanocomposites.     

混杂功能化碳纳米管/聚氨酯复合材料的制备及性能

以多壁碳纳米管（MWNTs）为原料,采用不同改性方法制得了羧化碳纳米管（MWNTs-COOH）、共价功能化碳纳米管（MWNTs-NH₂）、非共价功能化碳纳米管（MWNTs-PPA）和混杂功能化碳纳米管（MWNTs-COOH-PPA）,将这4种改性碳纳米管按不同质量分数分别加入聚氨酯（PU）中制备了复合材料。使用万能材料试验机和热失重分析仪测试了复合材料的力学和热学性能,研究了碳纳米管对复合材料性能的影响。结果表明:通过在碳纳米管表面接枝少量的共价官能团防止非共价包覆的剥离,混杂功能化方法既能够改善碳纳米管在基体中的分散性,又能够保持其与基体界面间结合力,复合材料增强效果最明显。耐热性良好的碳纳米管的添加提高了PU基体的热分解温度,提高程度由于其功能化方式的不同而稍有差别。MWNTs-COOH-PPA/PU复合材料的力学性能最优,当碳纳米管含量（质量分数,下同）为0.3%时,其拉伸强度与纯PU相比提高104%,其热分解温度与MWNTs-COOH/PU相当,优于纯PU,但低于MWNT8-NH₂/PU和MWNTs-PPA/PU。     

Quantitative image analysis of polyurethane/carbon nanotube composite micostructures

Polyurethane/carbon nanotube (PUR/CNTs) composites are much more functional than pure polyurethanes. High intensity ultrasonic agitation was applied while preparing a mixture of multiwall carbon nanotubes and a monomer. The monomer/MWNT complexes were used to prepare PUR/CNTs nanocomposites. This paper describes the application of quantitative image analysis to characterise the microstructure of the monomer and segmented polyurethane with carbon nanotubes (CNTs). Stereological parameters chosen for analysis were used to evaluate the CNTs' dispersion in the monomer complex and the degree of matrix phase separation in the nanocomposites examined. The nanoparticles induced changes in the structure of the hard and soft domains in the polyurethane matrix and influenced thermal and mechanical properties of the material. Due to the introduction of the nanotubes in the polyurethane matrix, the physical size and glass transition temperature of hard domains increased while the tensile strength and storage modulus decreased.     

Toughening and reinforcement of poly(vinylidene fluoride) nanocomposites with “bud-branched” nanotubes

Bud-branched nanotubes, fabricated by growing metal particles on the surface of multi-wall carbon nanotubes (MWCNTs), were used to prepare poly(vinylidene fluoride) (PVDF) based nanocomposites. The results of differential scanning calorimetry (DSC) showed that the introduction of the MWCNTs and bud-branched nanotubes both increased the crystallization temperature, while no significant variation of T_m (melting temperature), ΔH_c (melting enthalpy) and ΔH_m (crystallization enthalpy) occurred. The results of wide angle X-ray diffraction (WAXD) tests showed that α-phase was the dominated phase for both pure PVDF and its nanocomposites, indicating the addition of the MWCNTs and bud-branched nanotubes did not alter the crystal structures. Dynamic mechanical analysis (DMA) tests showed that bud-branched nanotubes were much more efficient in increasing storage modulus than the smooth MWCNTs. In addition, no significant variation of the T_g (glass transition temperature) was observed with the addition of MWCNTs and bud-branched nanotubes. Tensile tests showed that the introduction of MWCNTs and bud-branched nanotubes increased the modulus. However, a dramatic decrease in the fracture toughness was observed for PVDF/MWCNTs nanocomposites. For PVDF/bud-branched nanotubes nanocomposites, a significant improvement in the fracture toughness was observed compared with PVDF/MWCNTs nanocomposites.     

表面接枝TDI碳纳米管/聚氨酯复合材料的研制

为改善碳纳米管的分散性,用2,4-甲苯二异氰酸酯(TDI)对碳纳米管进行表面修饰,采用溶液复合方法与聚氨酯共混制备了碳纳米管/聚氨酯复合材料.通过FTIR证明了TDI确实接枝到碳纳米管表面,采用SEM、DMA、TGA等手段分析了碳纳米管修饰后的分散性及复合材料的力学性能和热性能.结果表明,经TDI修饰后的碳纳米管可以更好的分散在聚氨酯基体中,提高了聚氨酯的力学性能和热性能.     

The creep behaviour of poly(vinylidene fluoride)/“bud-branched” nanotubes nanocomposites

The creep behaviour of poly(vinylidene fluoride) (PVDF)/multiwall carbon nanotubes nanocomposites has been studied at different stress levels and temperatures. To fine-tune the ability to transfer stress from matrix to carbon nanotubes, bud-branched nanotubes, were fabricated. The PVDF showed improved creep resistance with the addition of carbon nanotubes. However, bud-branched nanotubes showed a modified stress–temperature-dependent creep resistance compared with carbon nanotubes. At low stress levels and low temperatures, bud-branched nanotubes showed better improvement of the creep resistance than that of virgin carbon nanotubes, while at high stress levels and high temperatures, the virgin carbon nanotubes presented better creep resistance than that of bud-branched nanotubes. DSC, WAXD, and FTIR were employed to characterise the crystalline structures and dynamic mechanical properties were characterised by DMA testing. The Burgers’ model and the Findley power law were employed to model the creep behaviour, and both were found well describe the creep behaviour of PVDF and its nanocomposites. The relationship between the structures and properties was analysed based on the parameters of the modelling. The improved creep resistance for PVDF by the addition of nanotubes would benefit its application in thermoset composite welding technology.