Single-walled carbon nanotube/silicone rubber composites for compliant electrodes

Single-walled carbon nanotube (SWCNT)/silicone rubber composites that can be used in fabricating compliant electrodes are prepared by spraying a mixed solution of ionic-liquid-based SWCNT gel and silicone rubber onto an elastic substrate. Subsequently, the composites are exposed to nitric acid vapor. Scanning electron microscopy and atomic force microscopy images of the composites show that the SWCNTs are finely dispersed in the polymer matrix due to the addition of the ionic liquid. Doping of the SWCNTs by nitric acid can significantly lower the sheet resistance (R_s) of the composites; samples with 4 wt% of SWCNT content exhibit the lowest R_s value (50 Ω sq^?1). This sheet resistance corresponds to a conductivity value of 63 S cm^?1. In addition, the composites retain a high conductivity after several tensile strains are applied. Stretching the composite sample to 300% of the original length increased the R_s value to 320 Ω sq^?1 (19 S cm^?1). Even after 20th stretch/release/stretch cycle, the conductivity remains constant at a value of 18 S cm^?1. These results provide a scalable route for preparing highly stretchable and conductive SWCNT composites with relatively low SWCNT concentrations.     

Kinetics of filler wetting and dispersion in carbon nanotube/rubber composites

The effects of the surface modification of multi-walled carbon nanotubes (MWCNTs) by an ionic liquid, 1-butyl 3-methyl imidazolium bis(trifluoromethyl-sulphonyl)imide (BMI) on the kinetics of filler wetting and dispersion as well as resulting electrical conductivity of polychloroprene (CR) composites were studied. Two different MWCNTs were used, Baytubes and Nanocyl, which differ in their structure, purity and compatibility to CR and BMI. The results showed that BMI can significantly improve the macrodispersion of Baytubes, and increases the electrical conductivity of the uncured BMI–Baytube/CR composites up to five orders of magnitude. In contrast, the use of BMI slows the dispersion process and the development of conductivity of BMI–Nanocyl/CR composites. Our wetting concept was further developed for the quantification of the bound polymer on the CNT surface. We found that the bonded BMI on the CNT surface is replaced by the CR molecules during mixing as a result of the concentration compensation effect. The de- and re-agglomeration processes of CNTs taking place during the subsequent curing process can increase or decrease the electrical conductivity significantly. The extent of the conductivity changes is strongly determined by the composition of the bound polymer and the curing technique used.     

Piezoresistive behavior of graphene nanoplatelets/carbon black/silicone rubber nanocomposite

Silicon rubber (SR) filled with carbon black (CB) and carbon black (CB)/graphene nanoplatelets (GNPs) hybrid fillers are synthesized via a liquid mixing method. The effects of filler type on the electrical properties and piezoresistive properties (near the region of the percolation) of the conductive SR composites are studied. It is suggested that the conductivity of the composite filled with CB/GNPs hybrid fillers in the mass ratio of 2 : 4 is much higher than that in other ratio. Percolation threshold for CB/GNPs/SR is found to be 0.18 volume fractions lower than CB/SR. Moreover, force rang and linearity of GNPs/CB/SR is higher than CB alone filling system. And the repeatability of the GNPs/CB/SR composites is better than CB/SR. Not repetitive index () of them is 0.1 and 0.18, respectively. The results suggest that the GNPs/CB/SR composites provide a new route toward fabrication of flexible piezoresistive sensors with high performance. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39778.     

石墨烯/硅橡胶复合材料的研究进展

阐述了通过石墨烯改性以及优化复合材料制备工艺来提高石墨烯在硅橡胶中分散性的研究进展,重点介绍了石墨烯的共价键改性和非共价键改性,以及溶液共混法和直接共混法两种石墨烯/硅橡胶复合材料制备方法。论述了石墨烯可以有效的提高硅橡胶复合材料的强度、导热率、热分解温度和电导率等。最后对石墨烯/硅橡胶复合材料在航空航天领域的研究前景进行了展望。     

Enhanced field emission properties of a reduced graphene oxide/carbon nanotube hybrid film

A facile vacuum filtration method for the preparation of hybrid films to achieve superior field emission properties from carbon nanotubes (CNTs) using reduced graphene oxide (rGO) as a bi-functional filler has been proposed. In the hybrid films, CNTs serve as electron emitters, while rGO helps to control the density of the CNT-emitters and reduce electrical resistance of the films. Via controlling volumes of CNTs and rGO dispersions, electron field emission properties of the hybrid films can be easily tailored. Higher weight ratio of rGO:CNT results in better electrical properties and the best field emission property is achieved when a rGO:CNT weight ratio of 1:3 is employed. The hybrid film reveals a significant improvement in field emission properties, as compared with the CNT film without adding rGO. Decreases in sheet resistance, turn-on field, and threshold field are attributed to the formation of extended conjugated network between CNTs and rGO in association with the reduction of screening effect through the optimization of density of CNT-emitters. The concept that rGO can be employed to control the density of CNT emitters will be of special interest for field emission enhancement.     

碳纳米管／橡胶复合材料研究进展

介绍了碳纳米管(CNT)/橡胶复合材料的制备方法,综述了CNT对橡胶复合材料硫化行为、物理机械性能及电性能的影响.指出CNT在橡胶中分散不均、与橡胶界面结合不佳是CNT/橡胶复合材料拉伸强度提高不显著的主要原因.今后该领域的研究方向应是通过采用新的制备方法或改进现有方法促使CNT在橡胶基质中均匀分散,以提高橡胶复合材料的拉伸强度.     

Enhanced field emission of an electric field assisted single-walled carbon nanotube assembly in colloid interstices

A novel method for fabrication of vertically aligned single-walled carbon nanotubes (SWCNTs) on indium-tin oxide glass substrates modified with self-assembly monolayer has been developed by using a supporting frame composed of a monolayer of monodispersed silica beads and an alternating current electric field. We have found that SWCNTs can be implanted into the interstices of the colloidal superlattices, which function as supporting scaffold to prevent the SWCNTs from falling down and maintain the SWCNTs at low density. As a result, this vertically aligned SWCNT assembly exhibits enhanced field emission.     

氧化石墨烯增强有机硅橡胶复合泡沫材料的性能

以甲基乙烯基硅橡胶（MVQ）为基质,以氧化石墨烯（GO）为增强剂和阻燃剂,制备了有机硅橡胶复合泡沫材料,考察了GO用量对复合泡沫材料力学性能及阻燃性能的影响。结果表明,随着GO用量的增加,有机硅橡胶复合泡沫材料的密度增大,拉伸性能和压缩性能提高,极限氧指数（LOI）增大,熔滴现象和发烟现象减弱。当GO用量为5份时,与纯MVQ相比,复合泡沫材料的拉伸强度提高了6.6倍,撕裂强度提高了4.7倍,压缩强度（50%形变）提高了12.3倍,LOI由22.3%提高至26.5%,且未发生熔滴和发烟现象,阻燃性能显著提高。     

High-throughput production of pristine graphene in an aqueous dispersion assisted by non-ionic surfactants

The preparation of aqueous graphene dispersions by exfoliation of pristine graphite in the presence of a wide range of surfactants is reported. High graphene concentrations, up to about 1 mg mL⁻¹, were obtained with the use of some non-ionic surfactants. The dispersions consisted of single- and few-layer graphene platelets with their basal planes virtually free of even atomic-sized (point) defects. The potential utility of such highly concentrated dispersions toward the low-cost, large-scale manipulation and processing of graphene was demonstrated by processing them into electrically conductive, free-standing paper-like films.     

碳纤维增强硅橡胶复合材料制备

由于硅橡胶具有较好的耐热性但力学性能比较差,本文用高性能的碳纤维作增强剂,硅橡胶（MVQ）作基相及偶联剂作为相容剂制备了碳纤维/硅橡胶复合材料。通过力学性能和热老化测试,确定碳纤维的用量。用偶联剂作相容剂研究了偶联剂对硅橡胶和碳纤维相容性影响;通过傅里叶变换红外光谱（FTIR)和扫描电镜(SEM)分析了碳纤维和硅橡胶交联结构和相容性。结果显示,制备了碳纤维/硅橡胶复合材料的最佳配方为硅橡胶 100份,碳纤维 12份,KH-550 2.5份。碳纤维增强硅橡胶的最佳硫化条件为：温度 175℃,压力为10MPa,时间为30min。由扫描电镜和红外光谱分析,进一步论证了用KH-550处理的比没有处理及用Si69处理的碳纤维与硅橡胶的混合相容性好。     

Single wall carbon nanotube dispersion and exfoliation in polymers

Dispersion and exfoliation of single wall carbon nanotubes (SWNTs) have been studied in poly(acrylonitrile) (PAN), poly(p‐phenylene benzobisoxazole) (PBO) solutions, and composite fibers using transmission electron microscopy. As a result of polymer assisted dispersion and exfoliation, the average SWNT bundle diameter in SWNT/PAN (5/95) was 11 nm, while the average diameter for the pristine SWNT bundles was about 30 nm. High resolution TEM of SWNT/PBO (10/90) composite fibers did not reveal the presence of SWNT aggregates or bundles, suggesting SWNT exfoliation as individuals. On the other hand, both oriented and unoriented nanotube bundles have been observed in SWNT/PBO samples containing 15 wt % nanotubes. Carbon nanotubes are 10⁵ times more radiation resistant than flexible polymers such as polyethylene, and 10³ times more resistant than highly radiation resistant polymers such as PBO. Therefore in the high resolution TEM study of nanotube/polymer composites, nanotubes can be observed long after the polymer has been damaged by electron radiation. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 985–989, 2005     

All-carbon field emission device by direct synthesis of graphene and carbon nanotube

In this paper, an all carbon-based field emission device (FED) fabricated by graphene and carbon nanotubes (CNTs) is presented. Through the combination of highly conductive graphene and photolithographically patterned CNT, the resistivity of the interface is lowered and the FED performance is enhanced. FE measurements indicated that the fabricated all carbon-based FED demonstrated stable electron emission properties with uniform luminance.     

炭黑在橡胶中分散技术研究进展

对于炭黑补强橡胶复合材料,平衡生热、补强以及磨耗之间的关系是炭黑应用的瓶颈问题。炭黑在橡胶基体中的分散性是影响其补强的关键因素之一,从增强炭黑与橡胶之间的相互作用角度出发,炭黑在橡胶中分散技术的研究进展主要体现在炭黑改性、橡胶改性以及液相复合技术方面。重点阐述炭黑的表面改性、聚合物基体的功能化改性以及炭黑与橡胶湿法混炼制备母胶,旨在促进炭黑在橡胶中均匀纳米分散,提高炭黑对橡胶的补强作用,获得性能优异的炭黑/橡胶复合材料。     

炭黑填充型导电硅橡胶的性能研究

研究炭黑品种及用量对硅橡胶导电性能和物理性能的影响。结果表明，乙炔炭黑填充的硅橡胶导电性能优于炭黑N234或N293填充的硅橡胶；随着炭黑用量的增大，硅橡胶邵尔A型硬度增大，拉伸强度和拉断伸长率先增大后减小，体积电阻率先增大后趋于稳定。     

Microcellular foaming of silicone rubber with supercritical carbon dioxide

In spite of great concern on the industrial application of microcellular silicone rubber foams, such as in electric and medical devices, only a few works can be found about the foaming of silicone rubber. In this study, microcellular silicone rubber foams with a cell size of 12 μm were successfully prepared with curing by heat and foaming by supercritical CO₂ as a green blowing agent. The microcellular silicone rubber foams exhibited a well-defined cell structure and a uniform cell size distribution. The crosslinking and foaming of silicone rubber was carried out separately. After foaming, the silicone rubber foam was cross-linked again to stabilize the foam structure and further improve its mechanical properties. Foaming process of cross-linked silicone rubber should be designed carefully based on the viscoelastic properties because of its elastic volume recovery in the atmosphere. The basic crosslinking condition for small cell size and high cell density was obtained after investigating the rheological behavior during crosslinking.     

Resistive viscoelasticity of silicone rubber/carbon black composite

Electrical conductive polymer composites are shown as prospective flexible pressure and stretch sensors for detecting the dangerous deformations and for sensing the pressure with minimal intrusion. To better understand the piezoresistive mechanism and improve the performance of this type of sensor, a series of experiments were conducted to investigate the resistive viscoelasticity of silicone rubber/carbon black composite film. First, the flexible conductive composite film was composed with liquid silicone rubber as the matrix and conductive carbon black as the filler. The filler loading was fixed at 5 phr in mass ratio. Then, the resistive viscoelasticity of the composite film was studied as a function of frequency in the range from DC to 1 MHz, including resistive creep, resistive relaxation, and resistive recovery, although in a standard experiment, one‐step stress or one‐step strain was loaded in transient time and the resistance responses were measured. Result from the experiment shows that the creep of resistance is composed of two distinct segments. One is coincident with the strain creep of a typical viscoelastic material, while the other is quite different. Both the relaxation and the recovery of resistance exhibit strong frequency dependence. The relaxation speed becomes slower with the increase of exciting frequency except DC, and the relaxation speed is marginal when excited by DC electrical field. The recovery time becomes shorter with the increase of the exciting frequency. POLYM. COMPOS., 32:29–35, 2011. © 2010 Society of Plastics Engineers     

Multidimensional characterization of piezoresistive carbon black silicone rubber composites

Flexible and stretchable electronic skins capable of replicating the human sense of touch are a subject of active research. One of the most popular materials for force sensors in skins is carbon black (CB)/polydimethylsiloxane composite. To aid in skin design, a characterization of this composite is presented here. The sensitivity of composite resistance to uniaxial tension, compression, and shear for each CB concentration is measured and found to be similar for tension and compression, but smaller for shear, with resistance monotonically increasing with strain. In addition, under tension and compression the resistance of the material is measured both in line with and perpendicular to the axis of applied strain, and the response is found to be approximately equal in both cases. The electrical and mechanical relaxation time of the material is also measured and modeled for tension, compression, and shear. The mechanical relaxation time is found to be shorter than the electrical, with both increasing with CB concentration. However, the shortest mechanical relaxation time, 200 s, precludes a sensor with human‐like response times without an active modeling and compensation system. Finally, Young's modulus and Poisson's ratio are measured and reported for each CB concentration. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44773.     

碳纳米管流动电极分散性和悬浮稳定性的优化

流动电极作为一种由碳纳米材料、分散剂和去离子水组成的水性悬浮液体系，其良好的材料分散性和悬浮稳定性是确保流动电极电容法去离子装置（FCDI）脱盐性能的关键。本文以碳纳米管（CNT）为流动电极的活性材料，通过磺化剂实现了CNT材料表面的亲水化改性，重点研究分析了CNT改性前后流动电极的比电容、分散性和悬浮稳定性变化规律；探究了水性分散剂种类[十二烷基硫酸钠（SDS）和十六烷基三甲基溴化铵（CTAB）]和含量对流动电极性能的影响。结果表明，改性后的CNT-S流动电极的分散性和悬浮稳定性明显优于CNT流动电极，其比电容略低但比电容的稳定性较高。与CNT-S具有相同电荷特性的分散剂SDS比CTAB更有助于提高CNT-S流动电极的分散性和悬浮稳定性，当SDS比含量为0.6时，CNT-S流动电极的比电容最大，为40.04F/g。在工作电压为1.2V、SDS比含量为0.6、原料液浓度为1.0g/L（NaCl溶液）时，对FCDI装置的脱盐稳定性测试结果表明：装置的初始盐移除效率为51.9%，经20次循环脱盐后其除盐效率仍可保持在51.6%，证明所制备的流动电极具有很好的循环稳定性，为FCDI技术实用化开发提供了实验依据。     

Magnetically aligning multilayer graphene to enhance thermal conductivity of silicone rubber composites

The increasing demand for packaging materials calls for new technologies to achieve excellent thermal conductivity of polymer composites with low content of thermal conductive filler. This article prepared a kind of magnetically functionalized multilayer graphene (Fe₃O₄@MG) via electrostatic interactions, which efficiently enhanced the thermal conductivity of silicone rubber (SR) composites by the alignment of Fe₃O₄@MG in an external magnetic field. The morphology and structure of the Fe₃O₄@MG together with the thermal conductivity of corresponding Fe₃O₄@MG/SR composites were systematically investigated by SEM, TEM, XRD, elemental mapping, and thermal conductivity tester. The obtained results showed that Fe₃O₄@MG was induced to form chain-like bundles in silicone rubber matrix under the applied magnetic field, which enhanced the MG–MG interaction, and formed effective thermal pathways in the alignment direction. Furthermore, as coating mass ratio of Fe₃O₄@MG increased, the thermal conductivity of randomly oriented Fe₃O₄@MG/silicone rubber composites (R-Fe₃O₄@MG/SR) decreased gradually, whereas the through-plane thermal conductivity of vertically aligned Fe₃O₄@MG/silicone rubber composites (V-Fe₃O₄@MG/SR) increased even filled with same contents of thermal conductive filler. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47951.     

Electrical conductivity of carbon black and carbon fibre filled silicone rubber composites

Electrically conductive silicone rubber composites have been prepared through incorporation of conductive acetylene black and short carbon fibre (SCF). The percolation limit for the attainment of high conductivity is found to be relatively less for silicone rubber based composites compared to EPDM or NBR based composites reported earlier. Percolation limit is found to be lower for SCF-filled systems (7.5 phr) compared to black-filled ones (14 phr). Both black- and SCF-filled systems exhibit an increase in resistivity with the increase in temperature (PCT effect). This PCT effect may be explained in terms of differences in the thermal expansion between the rubber matrix and the conductive filler. However, resistivity-versus-temperature plots are not identical during the heating-cooling cycle, leading to some hysteresis and electrical set. The current-voltage relationship is linear (Ohmic in nature) at room temperature but becomes non-linear (non-Ohmic) at elevated temperatures. The resistivity of these composites is measured under different conditions such as on applying pressure and being subjected to different mechanical stress and strain over the specimens. An effort has been made to correlate the effect of different parameters on electrical resistivity with the change in the conductive network structure under different conditions.