纳米石墨烯片-正十八烷复合相变材料制备及热物性研究

本文分别制备了纳米石墨烯片质量分数为0%, 0.5%, 1%, 1.5%, 2%的纳米石墨烯片-正十八烷复合相变材料,并通过扫描电镜测试、红外光谱分析、差示扫描量热实验及导热分析等实验对其形貌结构及热物性进行表征和研究.实验表明本文制备的纳米石墨烯-正十八烷复合相变材料具有很好的相变稳定性;当纳米石墨烯片的质量分数达到2%时,复合相变材料的导热系数相对于纯十八烷高出了89.4%.     

正二十四烷烃石蜡/膨胀石墨（EG）复合相变材料分子动力学模拟

相变材料(PCMs)在相变时的恒温、高能量密度等特性,经常应用于设备的热管理,但是PCMs导热系数低的缺点影响了其使用范围.本文采用分子动力学方法,模拟了在正二十四烷烃石蜡PCMs中添加不同结构(层状、交叉状)的膨胀石墨(EG)之后构成的复合PCMs的物性.文章通过径向分布函数(RDF)、声子态密度(PDOS)、比热容和导热系数这四个指标,分析了夹角为0°的层状结构,夹角为45°、90°的交叉状EG添加物对于石蜡热物性的影响. EG(0°、45°、90°)添加使得石蜡的原子分布在不同程度上变得更加均匀、紧密,使得石蜡的比热容有所增加.同时,两种类型的添加物提高了石蜡的PDOS,提高了导热系数.其中,EG(90°)添加物对于石蜡导热系数的提升最为明显,石蜡/EG(0°、45°、90°)模型中EG的含量分别为33.63 wt%、30.86 wt%和23.20 wt%,相比于的石蜡的导热系数分别提升了417.1%、345.7%和522.9%. EG的添加能够提高石蜡的导热系数,不同结构的EG对石蜡导热系数的影响有着较大的区别.     

石墨烯气凝胶复合相变材料的热物性研究

相变材料利用其相变潜热能力可吸收储存和释放利用热量,同时在相变过程中其温度浮动小,能够实现温度控制从而用于热管理.但是其低热导率和易泄露问题严重制约了其性能.石墨烯气凝胶因其丰富的多孔结构而具有较大的比表面积,可吸附相变材料解决其泄露问题,同时石墨烯的高导热系数可提高相变材料的热导率.这里选取正十八烷为相变材料,制备了不同质量分数的石墨烯气凝胶复合相变材料.测得石墨烯气凝胶含量为13.99 wt%的样品,其导热系数比纯正十八烷高出306.2%,熔化潜热和凝固潜热分别下降了13.8%和10.8%.分子动力学模拟结果表明,石墨烯气凝胶的引入会在一定程度上增强正十八烷分子的有序性和一致性,即在同一温度下复合相变材料中的正十八烷分子比纯正十八烷分子拥有更集中分布的末端距和扭转角,径向分布函数和自扩散系数都相对较低,说明石墨烯材料的引入可以提升正十八烷的导热系数.     

Melting temperature and enthalpy variations of phase change materials (PCMs): a differential scanning calorimetry (DSC) analysis

Differential scanning calorimetry (DSC) analysis is a standard thermal analysis technique used to determine the phase transition temperature, enthalpy, heat of fusion, specific heat and activation energy of phase change materials (PCMs). To determine the appropriate heating rate and sample mass, various DSC measurements were carried out using two kinds of PCMs, namely N-octadecane paraffin and calcium chloride hexahydrate. The variations in phase transition temperature, enthalpy, heat of fusion, specific heat and activation energy were observed within applicable heating rates and sample masses. It was found that the phase transition temperature range increased with increasing heating rate and sample mass; while the heat of fusion varied without any established pattern. The specific heat decreased with the increase of heating rate and sample mass. For accuracy purpose, it is recommended that for PCMs with high thermal conductivity (e.g. hydrated salt) the focus will be on heating rate rather than sample mass.     

Experimental study on enhanced heat transfer of nanocomposite phase change materials

Nanocomposite phase change materials (NCPCMs) containing different mass fractions (nanomaterial concentration) and different copper nanoparticle (CN)/multi-walled carbon nanotubes (MWCNT) mass ratios were prepared and experimentally studied. Latent heat and thermal conductivity of the NCPCMs were studied and calculated by using the T-history method. The results revealed that addition of CN or MWCNT to the phase change material (PCM) resulted in NCPCMs with enhanced thermal conductivity and charge rates, respectively. However, when both nanoparticle materials were added to the PCM simultaneously, the resulting NCPCMs improved their thermal performance below expectations as a result of agglomeration and sedimentation between the two additives. Thus, the NCPCMs containing only CN or MWCNT showed superior thermophysical properties than the pure PCM, while the NCPCM containing both CN and MWCNT did not improve the thermal characteristic of PCM significantly.     

Experimental study on the phase change and thermal properties of paraffin/carbon materials based thermal energy storage materials

In order to enhance the thermal energy storage efficiency of phase change materials, in this paper, expanded graphite (EG), multi-layer graphene nanoplatelet (MGN), graphite powder (GP) and multi-walled carbon nanotube (MWCNT) as the effective heat transfer promoters in different mass fraction (0.1, 0.5, 1.0, 1.5 and 2.5 wt.%) were added into the paraffin. The chemical properties, latent heat capacities, thermal conductivities and heat storage performances of paraffin and the composites were investigated. The results showed that the addition of EG, MGN, GP and MWCNT could increase the thermal conductivity of paraffin. At 20 °C, the thermal conductivity of the paraffin was increased by 61.04%, 51.2%, 12.18% and 10.22% with 2.5 wt.% EG, MGN, GP and MWCNT, respectively. In addition, with the same mass fraction, the heat storage and release time of the composite were 56.03% and 54.26%, respectively, shorter than that of paraffin when the additive was EG.     

Effects of titanium addition on the microstructure of carbon/copper composite materials

Carbon(C)/copper(Cu)-based materials with high thermal conductivity and good stability at high temperatures were developed by adding a small amount of titanium, which has a low enthalpy of alloy formation with C and Cu. The isotropic fine-grained nuclear grade graphite and felt type C/C composite, which were impregnated by Cu and titanium, provided 1.3 times higher thermal conductivity at 1200 K than the original carbon materials. Microstructural analysis showed that the increase of thermal conductivity is due to the formation of titanium compounds at the C/Cu interface. These carbon-based materials could be a candidate material for the plasma facing components of fusion devices.     

Room-temperature power factor of CuAlO2 composite tablets enhanced by MWCNTs

CuAlO₂ with high theoretical thermoelectric performance has potential applications in thermal energy conversion. Herein, multi-wall carbon nanotubes (MWCNTs)/CuAlO₂ composite tablets are prepared by using different amounts of MWCNTs and solid paraffin binder, where MWCNTs served as a conductive agent and rendered three orders of magnitude increase in electrical conductivity. Seebeck coefficient of the composites was reduced with increasing MWCNTs content. Consequently, an optimal room-temperature thermoelectric power factor (PF) of 1.31 μW m⁻¹K⁻² has been rendered by MWCNTs/CuAlO₂ composite tablet with 1 wt % MWCNTs. Moreover, PF value increased with increasing temperature after a slight decrease at 333 K, which can be ascribed to the modulation of electrical conductivity. Current work provides an effective strategy to improve thermoelectric performance of CuAlO₂ materials.     

A composite theoretical model for the thermal conductivity of nanocrystalline materials

In order to study the thermal conductivity of nanocrystalline (NC) materials, a two-phase composite model consisting of grain interior (GI) regarded as an ordered crystal phase and plastically softer grain boundary-affected zone (GBAZ) phase was presented. The effects of GI and GBAZ on thermal conduction were considered, respectively. In this work, time independent Schrodinger’s wave equation (TISWE) was used to study the carriers’ transmission in a crystal particle, through which we can get the thermal conductivity of the GBAZ. The thermal conductivity of GI was calculated based on a kinetic theory. The whole effective grain thermal conductivity was simulated by a modified formula for composite materials. The results showed that as the grain size decreases to 80 nm, it has a strong size effect, and the thermal conductivity decreases with the decreasing of grain size.     

Investigation on Properties of Polypropylene/Multi-walled Carbon Nanotubes Nanocomposites Prepared by a Novel Eccentric Rotor Extruder Based on Elongational Rheology

The properties of polymer matrix composites are related not only to the chemical composition of the materials but also to the processing equipment used for their preparation which has a direct influence on the microstructure of the composites. In this paper polypropylene (PP)/multi-walled carbon nanotubes (MWCNTs) nanocomposites were prepared by melt blending through a self-developed, eccentric rotor extruder (ERE). The structure and elongational deformation mechanism of an ERE were described in detail. The morphological, rheological, thermal and mechanical properties of the resulting PP/MWCNTs nanocomposites were investigated. Scanning electron microscopy (SEM) and rheological analysis showed that the MWCNTs were well dispersed in the PP matrix. The thermal stability was investigated by thermogravimetric analysis (TGA) and indicated that the addition of MWCNTs could effectively improve the thermal stability of pure PP. The percentage of crystallinity and tensile strength of the composites were improved as a result of the heterogeneous nucleation effect of the MWCNTs in the PP matrix. The research results revealed that the enhancement of the properties of PP/MWCNTs composites could be attributed to a better dispersion of the MWCNTs in the matrix as compared to samples prepared by conventional extrusion.     

Thermal transport enhancement of multi-walled carbon nanotubes/ high-density polyethylene composites

Multi-walled carbon nanotubes (MWCNTs) enhanced high-density polyethylene (HDPE) composites were prepared and their thermophysical properties were measured. The thermal diffusivity of the composites increases with the increase in the amount of MWCNTs. A thermal diffusivity of more than three times that of pure HDPE was obtained for 38 vol. % MWCNTs/HDPE composites. An equation based on an effective medium approach model was used to discuss the thermal diffusivity enhancement of MWCNTs/HDPE composites as a function of the volume fraction of MWCNTs. The results from this analysis can be a predictive guideline for further improvements in the thermal transport properties of MWCNTs/HDPE composites. Moreover, the intrinsic longitudinal thermal conductivity k_z of an individual MWCNT was deduced from the measured results on the MWCNTs/HDPE composites. PACS 67.55.Hc; 61.46.Fg; 66.30.Xj     

Thermal and Mechanical Properties of Epoxy/Carbon Fiber Composites Reinforced with Multi-walled Carbon Nanotubes

Multi-scale hybrid composite laminates of epoxy/carbon fiber (CF) reinforced with multi-walled carbon nanotubes (MWCNTs) were fabricated in an autoclave. For laminate fabrication, 0.5 wt% of pristine MWCNTs or silane-functionalized MWNCTs (f-MWCNTs) were dispersed into a diglycidyl ether of bisphenol-A epoxy system and applied on the woven carbon fabric. The neat epoxy/CF composite and the MWCNTs-reinforced epoxy/CF hybrid composites were characterized by thermogravimetric analysis (TGA), thermomechanical analysis (TMA), tensile testing, and field emission scanning electron microscopy (FE-SEM). A significant improvement in initial decomposition temperature and glass transition temperature of epoxy/CF composite was observed when reinforced with 0.5 wt% of f-MWCNTs. The coefficient of thermal expansion (CTE), measured by TMA, diminished by 22% compared to the epoxy/CF composite, indicating an improvement in dimensional stability of the hybrid composite. No significant improvement in tensile properties of either MWCNTs/epoxy/CF composites was observed compared to those of the neat epoxy/CF composite.     

Effect of dispersion state of carbon nanotube on the thermal conductivity of poly(dimethyl siloxane) composites

Herein, the effect of dispersion uniformity of multi-walled carbon nanotube (MWCNT) on the thermal conductivity of poly(dimethyl siloxane) (PDMS) composites was investigated by comparing experimentally obtained and calculated results based on simple models. Two different MWCNTs, i.e., raw and oxidized/masterbatched MWCNTs, were used and compared. For raw MWCNT, the dispersion in PDMS was poor, resulting in the significant reduction in the aspect ratio of MWCNT. However, for composites using masterbatched MWCNT, the thermal conductivity was always about 10% greater than those prepared with raw MWCNT and the aspect ratio calculated by the model equation was also 1.7 times greater. Above 1.5 phr masterbatched MWCNT concentrations, the aspect ratio of 430 was maintained. Finally, the results suggest that the thermal conductivity can be correlated with the degree of dispersion and aspect ratio obtained from the model equation used.     

Improvement in characteristics of natural rubber nanocomposite by surface modification of multi-walled carbon nanotubes

We aim to develop high-level applications of NR through the innovative use of multi-walled carbon nanotubes (MWCNTs) to improve reinforcing performance and thermal resistance. In this study, we examined the structures and characteristics of composite materials in which NR was the matrix and MWCNTs were the fillers. We studied the properties of composites containing surface-activated MWCNTs with three different diameters. The results show that the reinforcing performance improves as MWCNT diameter decreases, while thermal resistance improves as we decrease the heat-treatment temperature. The latter occurs because adherence between MWCNTs and NR becomes stronger at lower heat-treatment temperatures. We also found that for practical applications, we need to control active sites on MWCNTs to balance adhesion against thermal resistance.     

快速热响应复合材料的储/放热性能分析

以膨胀石墨为无机支撑材料、石蜡为有机相变材料,制备出高导热系数和储热密度的快速热响应复合材料,并构建传热性能测试系统对该复合材料的储/放热性能进行研究分析。研究结果表明,复合材料不仅能在熔融状态下保持形状稳定,而且显著提高了在储/放热过程的传热性能,从而有效地解决了传统相变材料高储热密度和低导热系数之间的矛盾。     

Thermal and electrical conductivity of poly(l-lactide)/multiwalled carbon nanotube nanocomposites

Multiwalled carbon nanotubes (MWCNTs) are considered to be the ideal reinforcing agent for high-strength polymer composites, because of their fantastic mechanical strength, high electrical and thermal conductivity and high aspect ratio. Polymer/MWCNTs composites are easily molded, and the resulting shaped plastic articles have a perfect surface appearance compared with polymer composites made using usual carbon or glass fibers. Good interfacial adhesion between the MWCNTs and the polymer matrix is essential for efficient load transfer in the composite. The ultrahigh strength polymer composites demand the uniform dispersion of the MWCNTs in the polymer matrix without their aggregation and the good miscibility between MWCNT and polymer matrix. This approach can also be applied to biodegradable synthetic aliphatic polyesters such as poly(l-lactide) (PLLA), which has received a great deal of attention due to environmental concerns. In this study, PLLA was melt-compounded with MWCNTs. A high degree of dispersion of the MWCNTs in the composites was obtained by grafting PLLA onto the MWCNTs (PLLA-g-MWCNTs). After oxidizing the MWCNTs by treating them with strong acids, they were reacted with l-lactide to produce the PLLA-g-MWCNTs. The mechanical properties of the PLLA/PLLA-g-MWCNT composite were higher than those of the PLLA/MWCNT composite. The electrical conductivity of the composites was determined by measuring the volume resistivity, which is a value of the resistance expressed in a unit volume by two-probe method. The thermal diffusivity and heat capacity of composites was measured by laser flash method, and the effects of modification of the MWCNT in PLLA matrix are discussed.     

Study on the properties of a novel shape-stable epoxy resin sealed expanded graphite/paraffin composite PCM and its application in buildings

In this study, a novel phase change material (PCM) of epoxy resin sealed expanded graphite/paraffin composite was developed as an independent attachment for building applications. A relatively high thermal energy storage density and a high thermal conductivity (2.141?W/(m·K)) were obtained in the composite PCM. The mass fraction of paraffin in the composite PCM could reach 94% without leakage of liquid paraffin when being heated at 50°C for more than 3 h, and the thermal cycle stability was good. Moreover, the thermal storage and release properties of this composite PCM with different thicknesses were studied by numerical simulation. The results showed that the thermal storage and release time are proportional to the thickness of the composite PCM, and there was almost no temperature gradient during the thermal storage and release process, which indicated that the thermal conductivity of this kind of composite PCM was high enough for building applications.     

Thermoplastic Elastomer Phase Changing Materials for Stiffness Modulation

Abstract

Four natural rubber-based phase changing materials (PCMs) were synthesized and evaluated with the goal of achieving controlled stiffness modulation at elevated temperatures (～100-120?°C). The phase changing was achieved through either the glass transition or melt transition of one of four phase changing fillers: polystyrene, poly(methyl methacrylate), low density polyethylene, and indium tin alloy. The PCM stiffness was analyzed using dynamic mechanical analysis and the results showed that all four PCMs exhibited two thermal transitions: a low temperature transition at ?58?°C due to the glass transition of the natural rubber matrix and a high temperature transition at ～100-120?°C due to the thermal transitions in the four filler materials. The degree of stiffness change of all PCMs at 100-120?°C was found to be strongly influenced by the type of the phase changing filler as well as the type of thermal transition (glass transition versus melt transition). The compatibilities of the phase changing materials were analyzed using the Flory-Huggins interaction parameter and it was shown that natural rubber and low density polyethylene had the best compatibility. All systems exhibited effective stiffness modulation with the change in temperature, enabling them to be used for applications requiring variable stiffness control.     

Characterization of aluminum-carbon composites obtained via mechanical activation of aluminum and carbon nanotubes

The relaxation of structural defects of aluminum-multiwall carbon nanotubes (MWCNT) composite materials obtained via mechanical activation is studied in situ by X-ray diffraction using synchrotron radiation. Mechanically activated Al-MWCNT mixtures are annealed at temperatures of up to 600°C in an inert gas flow and X-ray diffraction patterns are simultaneously registered with a position-sensitive X-ray detector. It is demonstrated that mechanically activated samples of pure Al and composites with large-diameter MWCNTs (～20 nm) begin to experience the relaxation of defects accumulated during mechanical activation at temperatures as low as 100–150°C, while samples with small-diameter MWCNTs (～10 nm) exhibit thermal stability of structural defects up to 500°C.     

Effect of plasma treatment on electrical conductivity and Raman spectra of carbon nanotubes

Multi-walled carbon nanotubes (MWCNTs) were treated with a radio-frequency discharge. We found that MWCNTs showed opposite trends in electrical conductivity when treated with oxygen and hydrogen plasmas. MWCNTs showed enhanced electrical conductivity when placed at cathode with oxygen plasma treatment, whereas MWCNTs treated at positive column did not show such a trend. In contrast, the conductivity of MWCNTs dropped sharply with hydrogen plasma treatment. The measured conductivity trends of MWCNTs are correlated with observed Raman spectral shift. The possible mechanisms of the change in electrical conductivity in plasma-treated MWCNTs are discussed.