Flexible carbon nanotube/polyaniline paper-like films and their enhanced electrochemical properties

The carbon nanotube/polyaniline (CNT/PANI) composites have important potential applications as the electrodes in energy storage devices for their attractive electrochemical properties. In this work, we report a novel method to prepare the interesting paper-like CNT/PANI composites by using the CNT network as the template. Compared with the conventional brittle CNT/PANI composites, these paper-like composites were much thin and flexible. This work demonstrates a new approach, which may transform a brittle polymer into flexible films. Meanwhile, these film electrodes showed much superior electrochemical performance such as higher specific capacitance, lower internal resistivity, and more stability under different current loads. These paper-like composite electrodes have promising applications in new kinds of energy storage devices.     

Mechanical properties and frictional resistance of Al composites reinforced with Ti_3C_2T_x MXene

Two-dimensional(2D) Ti_3C_2T_x MXene is an attractive additive not only used in base oil due to its low friction coefficient,but also used in composites due to its high aspect ratio and rich surface functional groups.So far there has been intense research into polymer matrix composites reinforced with Ti_3C_2T_x,Here we report on the use of 2D Ti_3C_2T_x to enhance the mechanical and frictional properties of Al matrix composites.Ti_3C_2T_x/Al composites were designed and prepared by pre s sureless sintering followed by hot extrusion technique.The prepared composites exhibit a homogeneous distribution of Ti_3C_2T_x.The Vickers hardness and the tensile strength continuously increase with increasing Ti_3C_2T_x content.A hardness of 0.52 GPa and a tensile strength of 148 MPa were achieved in the 3 wt% Ti_3C_2T_x/Al composite.The frictional properties of pure Al and the Ti_3C_2T_x/Al composite were comparably studied under dry sliding.A low friction coefficient of 0.2,twice lower than that of pure Al,was achieved in the 3 wt%Ti_3C_2T_x/Al composite.Ti_3C_2T_x acting as a solid lubricant reduces the abrasive wear in the composite,improving the frictional properties of Al matrix composites.     

Adhesion promotion of Cu on C by Cr intermediate layers investigated by the SIMS method

Copper-carbon composites are candidate materials for heat sinks for high speed/high-performance electronic components. They combine high thermal conductivity with low density and a tailorable coefficient of thermal expansion (CTE). Because of the low wettability of carbon by copper, a thin layer of chromium can be deposited to promote both the adhesion and the thermal contact of copper with the carbon fibers. Therefore, in a first step layers of Cr and Cu were deposited by magnetron sputtering on plane vitreous carbon substrates (Sigradur G), which serve as a model for carbon fibers. From pull-off-adhesion measurements an interlayer thickness of Cr in the range of 2-10 nm was found to provide the optimal adhesion for 1 micro m thick copper overlayers. To model the later serial fabrication of the composite that involves a hot pressing step following the deposition, the C/Cr/Cu samples were heat treated at 800 degrees C under vacuum for 1 h. Adhesion on the heat-treated samples was superior in comparison to the untreated ones. To obtain information about the adhesion mechanism secondary ion mass spectrometry (SIMS) investigations were done on the depth distribution of the main elements copper, chromium, and carbon. Two samples, one as deposited and one subjected to heat treatment after deposition, were compared in this investigation. We found that heat treatment mainly modifies the distribution of Cr in the C/Cr/Cu system.     

Roles of work of adhesion between carbon blacks and thermoplastic polymers on electrical properties of composites

The effect of the work of adhesion between carbon blacks and different thermoplastic polymers on the positive temperature coefficient (PTC) of composites was investigated. Thermoplastic polymers, such as EVA, LDPE, LLDPE, HDPE, and PP, were used with the addition of 30 wt% of carbon blacks. The work of adhesion based on the surface free energy of a composite was studied in the context of two-liquid contact angle measurements using deionized water and diiodomethane. It was observed that the resistivity on PTC behavior was greatly increased near the crystalline melting temperature, due to the thermal expansion of polymeric matrix. It was shown that the PTC intensity defined as the ratio of the maximum resistivity (rho(max)) to the resistivity at room temperature (rho(RT)) had the largest value on CB/HDPE composites. From the experimental results, the decrease in the work of adhesion induced by interactions between carbon black surfaces and polymer chains is an important factor in the fabrication of a PTC composite.     

纳米Cr2O3系列催化剂上CO2氧化乙烷脱氢制乙烯反应

 采用溶胶－凝胶法和共沸蒸馏法耦合技术制备了纳米Cr2O3催化剂，并采用共沉淀法和共沸蒸馏法耦合技术制备了纳米Cr2O3／Al2O3，Cr2O3／ZrO2和Cr2O3／MgO复合催化剂．应用BET，XRD，XPS，TPR和TEM等物理化学方法对催化剂的结构和物化性质进行了表征，并考察了该系列催化剂上CO2氧化乙烷脱氢制乙烯的反应性能．结果表明，纳米Cr2O3催化剂上乙烷和CO2的转化率均明显高于常规Cr2O3催化剂，但乙烯的选择性低于常规Cr2O3催化剂；纳米复合催化剂中的复合成分显著影响催化剂的催化性能．其中，10％Cr2O3／MgO纳米复合催化剂在温度为973K时，乙烷转化率和乙烯选择性分别可达到61．54％和94．79％．纳米催化剂表面Cr的还原性以及Cr6＋／Cr3＋比值是影响乙烷转化率和乙烯选择性的重要因素．     

具有高灵敏性且稳定可重复的正温度系数效应的PVDF/CF导电复合材料

以碳纤维(CF)为填料,聚偏氟乙烯(PVDF)为基体,通过熔融共混法制备PVDF/CF导电复合材料.所得复合材料具有显著的正温度系数(PTC)效应,温度上升到聚合物熔点附近时,电阻率对温度变化敏感.在转折温度区间(155.5~171.0oC,(35)(28)15.5oC)内,其体积电阻率的增加速率约为1.3×105?cm K-1.在不同CF含量下,复合材料表现出不同的PTC行为.随着CF含量的增加,其峰值电阻略有下降.高导电粒子含量下,无负温度系数(NTC)效应.在冷却循环过程,导电网络的重构性良好.复合材料即使经过多次热循环,依然表现出良好的PTC特性重现性.     

Bi-phasic nanostructures for functional applications

Biphasic solid state composites of the type metal/metal oxide or element/element oxide can be synthesized in one pot chemical reactions using so called molecular "single source precursors". Due to their singular genesis these composites show peculiar hetero-structures based on core-shell hierarchies such as superlattices and composite nanospheres or nanowires. They exhibit superior or new functional properties compared to their individual constituent compounds. In the current work, we review in particular the synthetical and mechanistical approach of bi-phasic (Al/Al(2)O(3)) nanostructures such as nanospheres, nanowires and nanoloops using a single source precursor. Other bi-phasic materials of the general formula M/MO(x) (for example M = Ge, Sn, Pb) are addressed for comparison. The impact of different synthetical conditions as well as of modification of surfaces by laser techniques and their technological relevance are presented briefly. Additionally, functional applications of the prepared surfaces are explained with some outstanding case studies. These case studies are primarily concerned with their use as biomaterials and their application in medicine as well as with their use as thin films for optics and functional surfaces.     

Resin impregnation of cellulose nanofibril films facilitated by water swelling

Flexible composite films were produced by impregnating aqueous phenol formaldehyde (PF) resin into water-swollen cellulose nanofibril (CNF) films. CNF films were prepared using a pressurized filtration method in combination with freeze drying. The freeze-dried films were swollen with water then impregnated with PF resin by soaking in aqueous resin solutions of varying concentrations. Small amounts of PF slightly enhanced the tensile properties of CNF films. The formulation with the best mechanical properties was CNF/PF films with 8 wt % resin exhibiting tensile stress and toughness of 248 MPa and 26 MJ/m³, respectively. Resin concentrations higher than about 8 % resulted in composites with decreased tensile properties as compared to neat CNF films. The wet strength of the composite films was significantly higher than that of the neat CNF films. The resulting composites showed greater resistance to moisture absorption accompanied by reduced thickness swelling when soaked in water as compared to neat CNF films. The composites also showed decreased oxygen permeability at low humidity compared to neat films, but the composites did not show improved barrier properties at high humidity.     

LLDPE/纳米SiO_2复合材料的力学性能和光学性能研究

采用熔融共混方法制备了LLDPE 纳米SiO2 复合材料 ,并对该体系的力学性能和光学性能进行了系统研究 .结果表明 ,随着纳米SiO2 的加入 ,复合材料的弹性模量显著提高 ,冲击强度与拉伸强度呈峰形变化 ,且均在SiO2 含量为 3phr左右达到最大值 .加入少量的纳米SiO2 后 ,复合材料薄膜对长波红外线 (7～ 1 1 μm)的吸收能力较LLDPE膜有了显著提高 ,透光率略有下降但雾度提高 ,透光质量得到改善 .同时表明 ,纳米SiO2 的表面处理方法对膜的光学性能有显著影响     

Effect of 2-D BN on enhanced corona-resistant characteristic of PI/AlN+BN composite investigated by quasi-in-situ technology

Incorporating two-dimensional (2-D) boron nitride (BN) into polyimide/aluminum nitride (PI/AlN) renders a simple strategy in producing new ternary composite films with longer corona aging life and higher breakdown strength compared with PI/AlN. During corona aging process, the effects of 2-D BN on adjusting the microstructure evolution of ternary composites were investigated using quasi-in-situ technology systematically as follow: (SEM), (AFM), (FTIR), (XRD) and (SAXS) at different corona time. Quasi-in-situ characterization results show that the corona aging modes of the two composite films are quite different, the introduction of BN nanosheets could protect the C–N–C and C–O–C bonds from breaking as well as accelerate the fillers expose via autoxidation reaction. In addition, BN nanosheets could induce the distance between PI molecular chains to shorten during the corona process, resulting in more dense structures coordinating with AlN and PI. Different corona aging mechanism compared with that of the PI/AlN composite films was proposed. This work demonstrated the effect of 2-D BN nanosheets in the PI/AlN+BN ternary composites, which can be used to expand their application in insulating polymer based composites.     

Comparison of the influence of titanium and chromium adhesion layers on the properties of sol–gel derived NKN thin films

Lead-free (Na_0.5K_0.5)NbO₃ (NKN) thin films were prepared on Pt/X/SiO₂/Si substrates (with the adhesion promoters X = Ti, Cr) by a sol–gel process with and without post-annealing treatment. The effect of the diffusion of the adhesion layer elements Ti and Cr into the NKN film was analysed by secondary ion mass spectrometry, scanning electron microscopy pictures, X-ray diffraction (XRD), and leakage current measurements. It turned out that Cr diffuses into the films to a higher extent than Ti. The high amount of Cr diffusion led to the formation of a secondary phase, as seen in the XRD pattern, and to pore formation on the surface of the NKN films. In contrast, the films with Ti adhesion layer were single phase NKN without pore formation. Also, the leakage current measurements showed a strong influence of the Cr diffusion. The leakage current of the films with Cr adhesion layer was about four orders of magnitude higher than that of the films with Ti adhesion layer. The study shows the strong influence of the adhesion layer of the substrate on the properties of NKN films.     

Study on selective reflection properties of chiral nematic liquid crystalline composites with a non‐uniform pitch distribution

The preparation is reported of particles of photopolymerisable monomer/chiral dopant composites with a crystalline (Cr)‐chiral nematic (N*) phase transition. By mixing particles with different pitches of the N* phase in the Cr phase and crosslinking the liquid crystal (LC) monomer molecules by photopolymerisation in the planarly oriented N* phase, an N*‐LC composite film with a non‐uniform pitch distribution was obtained. Experimental results show that the bandwidth of the reflection spectrum and the location of reflection band of the composite films can be controlled accurately by controlling the pitch lengths of the N* phase of the particles. Effects of polymerisation temperature and UV intensity on the non‐uniform pitch distribution of N*‐LC composite films were investigated.     

Ethanol-assisted graphene oxide-based thin film formation at pentane-water interface

Graphene oxide (GO) can be viewed as an amphiphilic soft material, which form thin films at organic solvent-water interfaces. However, organic solvent evaporation provides little driving force, which results in slow GO transfer in aqueous phase, thus dawdling GO film formation processes for various potential applications. We present an ethanol-assisted self-assembly method for the quick formation of GO or GO-based composite thin films with tunable composition, transmittance, and surface resistivity at pentane-water interface. The thickness of pure GO and reduced GO (rGO) films ranging from ~1 nm to more than 10 nm can be controlled by the concentration of GO in bulk solution. The transmittance of rGO films can be tuned from 72% to 97% at 550 nm while the surface resistivity changes from 8.3 to 464.6 kΩ sq(-1). Ethanol is essential for achieving quick formation of GO thin films. When ethanol is injected into GO aqueous dispersion, it serves as a nonsolvent, compromising the stability of GO and providing driving force to allow GO sheets aggregate at the water-pentane interface. On the other hand, neither the evaporation of pentane nor the mixing between ethanol and water provides sufficient driving forces to allow noteworthy amount of GO sheets to migrate from the bulk aqueous phase to the interface. This method can also be extended to prepare GO-based composites thin films with tunable composition, such as GO/single walled carbon nanotube (SWCNT) composite thin films investigated in this work. Reduced GO/SWCNT composite films show much lower surface resistivity compared to pure rGO thin films. This ethanol-assisted self-assembly method opens opportunities to design and fabricate new functional GO-based hybrid materials for various potential applications.     

Effects of the reduction of PAni-coated oxidized multiwall carbon nanotubes on the positive temperature coefficient behaviors of their carbon black/high density polyethylene composites

Polyaniline (PAni)-coated reduced multiwall carbon nanotubes (PRMWNTs) and carbon black (CB)-filled high-density polyethylene (HDPE) composites (PRMWNTs/CB/HDPE) were prepared through a melt mixing method. Oxidized MWNTs (OMWNTs) were prepared by treating pristine multiwall carbon nanotubes (MWNTs) with an acid mixture (HNO₃:H₂SO₄), and PAni-coated OMWNTs (POMWNTs) were synthesized via in-situ polymerization of aniline monomer in the presence of OMWNTs. POMWNTs were further reduced using hydrazine monohydrate to obtain the PRMWNTs. Fourier transform infrared (FT-IR) spectra and thermogravimetric analysis (TGA) confirmed the formation of PRMWNTs. PRMWNTs showed significantly improved thermal stability and electrical conductivity comparing to POMWNTs. The positive temperature coefficient (PTC) behavior of PRMWNTs/CB/HDPE composites revealed enhanced PTC intensity and electrical conductivity at room temperature compared to POMWNTs/CB/HDPE composites. The PRMWNTs-10/CB/HDPE composite showed high peak resistivity (301.99 MΩ-cm) and low room temperature resistivity compared to the POMWNTs/CB/HDPE composite, and thus showed the highest PTC intensity value of 6.693 as well as very excellent cyclic stability.     

ZnO:Al thin films used in ZnO: Al/p-Si heterojunctions

Al-doped n-ZnO/p-Si heterojunctions were fabricated using a sol–gel dip coating technique at 700 °C, in a nitrogen ambient. The structural, optical, and electrical properties of ZnO:Al thin films, and the heterojunction properties of ZnO:Al/p-Si were investigated with respect to the effects of Al doping concentration. Hexagonal nano-structured ZnO: Al thin films with a 1.2% and a 1.6 at.% Al concentration exhibited high optical transmittance in visible ranges. Electrical resistivity changed with respect to Al doping concentration, and minimum resistivity was detected at a 1.2 at.% Al concentration. The ZnO:Al/p-Si heterojunction properties were analysed using current–voltage (I–V) measurements at four different Al concentrations, ranging from 0.8 to 1.6 (at.%). The ZnO:Al/p-Si heterojunctions exhibited diode-like rectifying behaviour. Under UV illumination, the photoelectric behaviour observed for the ZnO:Al/p-Si heterojunctions was diode.     

Interfacial Aspects of Electrodeposited Conductive Fibers/Epoxy Composites using Electro-Micromechanical Technique and Nondestructive Evaluation

Interfacial adhesion and nondestructive behavior of the electrodeposited (ED) carbon fiber reinforced composites were evaluated using the electro-micromechanical technique and acoustic emission (AE). Interfacial shear strength (IFSS) of the ED carbon fiber/epoxy composites was higher than that of the untreated case. This might be expected because of the possible chemical and hydrogen bonding based on an electrically adsorbed polymeric interlayer. Logarithmic electrical resistivity of the untreated single-carbon fiber composite increased suddenly to infinity when the fiber fracture occurred, whereas that of the ED composite increased relatively broadly up to infinity. This may be due to the retarded fracture time as a result of the enhanced IFSS. In single- and 10-carbon fiber composites, the number of AE signals coming from the interlayer failure of the ED carbon fiber composite was much larger than that of the untreated composite. As the number of each first fiber fracture increased in the 10-carbon fiber composite, the electrical resistivity increased stepwise, and the slope of logarithmic electrical resistance increased. In the three-graphite filament composite with a narrow 1 time inter-filament distance, the total numbers of the filament fracture and the IFSS were smaller than those of the wider 5 times case. This might be because the interacting fracture energy caused by a filament break could affect the adjacent filaments. Copyright 2001 Academic Press.     

Insight into Al existing form and its role on microstructure and properties of Cr1−xAlxN films

A series of Cr_1?xAl_xN (where x denotes the atom fraction of Al in Cr_1?xAl_xN film) films with different Al contents have been deposited by unbalanced reactive magnetron sputtering technique. The chemical composition, microstructure, surface morphology, cross‐sectional structure, mechanical properties, thermal stability and tribological properties of the deposited films were studied by means of different techniques. It is found that with the increase of Al doping, the Al atoms either substitute the Cr atoms or occupy the interstitial sites in the CrN crystal lattice firstly, and when the Al doping content exceeds the solid solubility, superfluous Al atoms then exist in the form of amorphous or nanocrystal state in the films. Meanwhile, the grain size becomes smaller, and the microstructure gets denser because the Al doping leads to multiple crystal orientations and inhibits the grain growth. The Al doping induced solid solution hardening and grain boundary effects contribute to the high hardness of CrAlN films, and the dense structure as well as interstitial solid solution of Al, which can block the diffusion channel, endows the CrAlN films good oxidation resistance. Besides, a small amount of free Al existing in the films is favorable to improve the thermal stability without obvious loss of hardness. Finally, the relatively high hardness and good thermal stability make the Cr_0.29Al_0.71N film has relatively good tribological properties than CrN film under a wide temperature range, which extends the operating temperature of the CrN films in some fields. Copyright © 2015 John Wiley & Sons, Ltd.     

Designing a phthalonitrile/benzoxazine blend for the advanced GFRP composite materials

High performance resin must be used in the high performance glass fiber-reinforced plastic(GFRP) composites, but it is sometimes difficult to balance the processabilities and the final properties in the design of advanced thermoset GFRP composites. In this study, a phthalonitrile/benzoxazine(PPN/BZ) blend with excellent processability has been designed and applied in the GFRP composite materials. PPN/BZ blend with good solubility, low melt viscosity, appropriate gel condition and low-temperature curing behavior could enable their GFRP composite preparation with the prepreg-laminate method under a relatively mild condition. The resulted PPN/BZ GFRP composites exhibit excellent mechanical properties with flexural strength over 700 MPa and flexural modulus more than 19 GPa. Fracture surface morphologies of the PPN/BZ GFRP composites show that the interfacial adhesion between resin and GF is improved. The temperatures at weight loss 5%(T_(5%)) and char residue at 800 °C of all PPN/BZ GFRP composites are over 435 °C and 65% respectively. PPN/BZ GFRP composites with high performance characteristics may find applications under some critical circumstances with requirements of high mechanical properties and high service temperatures.     

基于多层结构设计的高储能密度氧化石墨烯/聚酰亚胺复合材料

采用逐层涂布、 分层控制固化程度的方法, 利用聚酰胺酸(PAA, 聚酰亚胺前体)溶液和含有氧化石墨烯（GO）的PAA溶液制备了一系列由高绝缘性PI层与GO@PI介电层交替组合而成的界面清晰且紧密衔接的多层复合薄膜. 通过调控介电层中GO含量及分层结构, 使多层复合薄膜兼具高介电常数和高击穿强度特征. 结果表明, 三层复合薄膜PI/1.0GO@PI/PI的击穿强度为261.5 kV/mm, 储能密度达到1.27 J/cm³, 与相同介电层厚度的单层薄膜相比, 击穿强度和储能密度分别提高了97%和144%, 同时, 其介电损耗也保持在较低水平(tanδ=0.0079). 绝缘层和高介电常数层的协同作用提升了氧化石墨烯/聚酰亚胺复合薄膜的储能密度. 这种简单的多层结构设计有利于氧化石墨烯/聚合物复合材料在介质储能领域的应用.     

Solid state studies on substituted CuCr2O4 spinel

Changes in crystallographic, electrical, and thermal properties of CuCr₂O₄ spinel were investigated by replacing Cu with Mg, i.e., Cu_1?xMg_xCr₂O₄, and Cr with Al, i.e., CuCr_2?xAl_xO₄. The tetragonal distortion in CuCr₂O₄ disappeared with 60% replacement of Cu by Mg (x = 0.6) or 50% replacement of Cr by Al (x = 1.0). The temperature variation of electrical resistivity for all the tetragonal samples was similar to that of CuCr₂O₄. The first order, diffusionless phase transition was manifest in the hysteresis loops of log ? vs $\text{1}\text{T}$ plots. The resistivity and activation energy for conduction changed sharply near the phase transition composition. With the replacement of Cr by Al, the conduction in CuCr₂O₄ was found to change from p type to n type. The low thermal stability of the spinel was found to be due to a high concentration of tetrahedral Cu²⁺ ions (>80%) and compressed tetragonal distortion which strains the spinel lattice. This strain is removed by replacing either Cu with Mg or Cr with Al, whereby the spinel becomes stable.