Thermophysical properties of densified pitch based carbon/carbon materials—II. Bidirectional composites

Bidirectional carbon/carbon composites were developed using high-pressure impregnation/carbonization technique with PAN based carbon fabric as reinforcement and coal tar and synthetic pitches as matrix precursors. Microstructure of these composites has been evaluated using scanning electron microscope and polarized light optical microscope. Thermophysical properties i.e. thermal conductivity and specific heat have been evaluated both at room temperature and between 40 and 300 °C. The temperature dependence of thermal diffusion, specific heat and thermal conductivity has been studied and correlated with microstructure of carbon/carbon composites. It is found that the specific heat of carbon/carbon composites shows increase with temperature with an inverse slope in the temperature range of 150-200 °C. Accordingly, though the thermal conductivity decrease with temperature due to increased phonon interactions, it shows reversible action between 150 and 200 °C.     

Effect of HfC nanowires grown on carbon fibers on the microstructure and thermophysical properties of C/C composites

One-dimensional (1D) hafnium carbide nanowires (HfCnws) were grown in situ on carbon fibers (CFs) via a Ni-assisted pyrolysis method of organometallic polymer precursor. Scanning electron microscopy (SEM), transmission electron microscope (TEM), polarized-light optical microscopy (PLM), and Raman were used to analyze the effect of HfCnws on the microstructure of pyrolytic carbon (PyC). The specific heat capacity (HC), thermal diffusivity (TD), thermal conductivity (TC), and coefficient of thermal expansion (CTE) of HfCnws-C/C composites were also investigated. Results show that HfCnws wrapped by carbon nanosheet were successfully synthesized. The diameter of HfCnws is about 30 nm and the thickness of carbon nanosheet is about 10 nm, which could induce the formation of isotropic (ISO) PyC. After introducing HfCnws, the TD and CTE of HfCnws-C/C composites were increased. Ni2HfCnws-C/C composites show a higher TC and TD, and the CTE increased with the increasing content of HfCnws.     

碳／碳复合材料的性能和应用进展

碳／碳（c／c）复合材料是以碳为基体、碳纤维增强的复合材料,具有高比强度、高比模量、耐高温、耐腐蚀、耐疲劳、抗蠕变、导电、传热和线胀系数小等一系列优异性能,既可作为结构材料承栽负荷,又可作为功能材料发挥作用。同时,碳／碳（c／c）复合材料是一种能在超高温条件下工作的高温结构材料,所以在航空航天领域具有广阔的应用前景。本文综述了碳／碳（c／c）复合材料的力学、热学、化学性能及其在各领域的应用进展。     

Thermophysical properties of carbon/carbon composites and physical mechanism of thermal expansion and thermal conductivity

Five different carbon/carbon composites (C/C) have been prepared and their thermophysical properties studied. These were three needled carbon felts impregnated with pyrocarbons (PyC) of different microstructures, chopped fibers/resin carbon + PyC, and carbon cloth/PyC. The results show that the X-Y direction thermal expansion coefficient (CTE) is negative in the range 0-100 °C with values ranging from −0.29 to −0.85 × 10⁻⁶/K. In the range 0-900 °C, their CTE is also very low, and the CTE vs. T curves have almost the same slope. In the same temperature range composites prepared using chopped fibers show the smallest CTE values and those using the felts show the highest. The microstructure of the PyC has no obvious effect on the CTE for composites with the same preform architecture. Their expansion is mainly caused by atomic vibration, pore shrinkage and volatilization of water. However, the PyC structure has a large effect on thermal conductivity (TC) with rough laminar PyC giving the highest value and isotropic PyC giving the lowest. All five composites have a high TC, and values in the X-Y direction (25.6-174 W/m K) are much larger than in the Z direction (3.5-50 W/m K). Heat transmission in these composites is by phonon interaction and is related to the preform and PyC structures.     

Thermal properties and performance of carbon fiber-based ultra-high temperature ceramic matrix composites (Cf-UHTCMCs)

The thermophysical properties of carbon fiber-based ultra-high temperature ceramic matrix composites have been determined to aid designers who need these properties when considering using the composites in ultra-high temperature aerospace applications. The coefficient of thermal expansion (CTE) and thermal diffusivity of the composites were measured parallel and perpendicular to the ply direction; the thermal conductivity was measured using the laser-flash method and the heat capacity calculated from the relationship between the thermal diffusivity, density, and thermal conductivity. Both the CTE and thermal conductivity showed higher values across the ply and increased with increasing temperature as expected, whilst the thermal diffusivity showed higher values parallel to the ply and increased smoothly with temperature. In addition, two different but related oxyfuel torch tests, based on oxyacetylene and oxypropane, were used to evaluate the thermo-ablation behavior of the composites. The tests showed how good the composites were at withstanding the ultra-high temperatures, high heat fluxes, and gas velocities involved.     

Thermal properties of carbon fibers at very high temperature

Thermal properties such as specific heat C_p, thermal diffusivity a, and thermal conductivity λ of carbon fibers are important parameters in the behaviour of the carbon/carbon composites. In this study, the specific heat and the thermal diffusivity are measured at very high temperatures (up to 2500 K). The experimental thermal conductivity estimated by the indirect relation λ = aρC_p is presented as a function of the temperature. Validations are carried out on isotropic metallic (tungsten) and ceramic (Al₂O₃) fibers. Measurements were obtained on three carbon fibers (rayon-based, PAN-based and pitch-based). Thermal conductivity results allow us to classify fibers from the most insulated to most conductive. The main result is that insulated carbon fibers have an increasing thermal conductivity when the temperature and the heat treatment temperature rise. Relationships between thermal conductivity and the structural properties (L_c and d₀₀₂) of such carbon fibers are studied. We also describe the influence of heat treatment on the thermal conductivity of carbon fibers.     

炭前驱体形态对C/C复合材料导热系数的影响

利用热塑性中间相沥青为黏结剂,短炭纤维.增强体,一步热压成型制备C/C导热复合材料.采用SEM和偏光显微镜观察等分析手段,研究了2∶1,2.5∶1和3∶1三种不同管径比对C/C复合材料的影响.结果表明:通过热压模具空腔结构的改变可以引起炭前驱体挤出形态的变化,使得轴向基体炭有序生长与短炭纤维增强体呈现有序排列,其中间相液晶分子垂直和平行于模压压力方向均排列成纤维状长程有序结构,短切纤维呈现出与压力平行方向排布.当空腔管径比为3:1,轴向导热系数由86.2 W/(m·K)增大至115.5 W/(m· K),各向异性比由1.6减小为1.2.由此所得块体C/C复合材料具有显著的二维取向结构,轴径向导热系数趋于平衡.     

The catalytic effect of boric acid on polyacrylonitrile-based carbon fibers and the thermal conductivity of carbon/carbon composites produced from them

The catalytic effect of boric acid on the graphitization and surface structure of polyacrylonitrile-based carbon fibers was investigated by dipping fibers in boric acid before heating at 2500 °C. The thermal conductivity of carbon/carbon composites produced from the modified carbon performs by chemical vapor infiltration was also studied. The results show that the treatment by boric acid has a catalytic-graphitization effect on the fibers that increases the crystallinity and changes the surface state of carbon fibers during high temperature treatment. The modified carbon fibers induce the deposition of pyrocarbon with high crystallinity and an obvious transition interface between the carbon fiber and pyrocarbon during chemical vapor infiltration. By changing the microscopic structure of the carbon fibers, the interface bonding between fibers and pyrocarbon is improved and the microstructure of pyrocarbon is regulated. The thermal conductivity of the carbon/carbon composites is therefore improved, especially that in the direction perpendicular to fiber axis.     

Improved thermal conductivity and mechanical properties of SiC/SiC composites using pitch-based carbon fibers

Pitch-based carbon fibers were assembled in horizontal and thickness directions of SiC/SiC composites to form three-dimensional heat conduction networks. The effects of heat conduction networks on microstructures, mechanics, and thermal conductivities were investigated. The results revealed the benefit of introducing heat conduction networks in the densification of composites. The maximum bending strength and interlaminar shear strength of the modified composites reached 568.67 MPa and 68.48 MPa, respectively. These values were equivalent to 18.6% and 69.4% increase compared to those of composites without channels. However, channels in thickness direction destroyed the continuity of fibers and matrix, creating numerous defects. As the volume fraction of heat conduction channels rose, the pinning strengthening effect of channels and influence of defects competed with each other to result in first enhanced mechanical properties followed by a decline. The in-plane thermal conductivity was found anisotropic with a maximum value reaching 86.20 W/(m·K) after introducing pitch-based carbon unidirectional tapes. The thermal conductivity in thickness direction increased with volume fraction of pitch-based carbon fibers and reached 19.13 W/(m·K) at 3.87 vol% pitch-based carbon fibers in the thickness direction. This value was 90.75% higher than that of composites without channels.     

Microstructure of carbon/carbon composites reinforced with pitch-based ribbon-shape carbon fibers

Carbon/carbon composites were prepared with ribbon-shape pitch-based carbon fibers serving as reinforcement and thermosetting PFA resin and thermoplastic pitch as matrix precursors. The composites were heat treated to 1000, 1600 and 2700 °C. Microstructural transformations taking place in the reinforcement, carbon matrix, and the interface were studied using polarized optical and scanning electron microscopy. The fiber/matrix bond and ordering of the carbon matrix in heat-treated composites was found to vary depending on the heat treatment temperature of the fibers. Stabilized fiber cleaved during carbonization of resin-derived composites. In contrast, fibers retain their shape during carbonization of pitch matrix composites. Optical activity was observed in composites made with carbonized fibers; the extent decreases with increased heat treatment of the fibers. Studies at various heat treatment temperatures indicate that ribbon-shape fibers developed ordered structure at 1600 °C when co-carbonized with thermosetting resin or thermoplastic pitches.     

A comparison of the interfacial, thermal, and ablative properties between spun and filament yarn type carbon fabric/phenolic composites

In the present paper, the interfacial, thermal, and ablative properties of phenolic composites reinforced with spun yarn type carbon fabrics (spun C/P composite) and filament yarn type carbon fabrics (filament C/P composite) heat-treated at 1100 °C have been extensively compared. The interlaminar shear strength, crack growth rate, and fracture surface were studied to evaluate the interfacial characteristics of the composites using short-beam shear test, double cantilever beam test, and scanning electron microscopy, respectively. The thermal conductivity and the coefficient of thermal expansion were also measured in the longitudinal and transverse directions, respectively. To explore the ablative characteristics of the composites in terms of insulation index, erosion rate, and microscopic pattern of ablation, an arc plasma torch was used. The interfacial properties of the spun C/P composite are significantly greater than those of the filament C/P composite, with qualitative support of fracture surface observations. It has been investigated that the presence of protruded fibers in the phenolic matrix of the spun C/P composite may play an important role in enhancing the properties due to a fiber bridging effect. The longitudinal thermal conductivity of the spun C/P composite is about 7% lower than that of the filament C/P counterpart. It has been found from the ablation test using arc plasma torch flame that the erosion rate is 14% higher than that of the filament C/P counterpart. Consequently, all the experimental results suggest that use of spun yarn type carbon fabrics heat-treated at low carbonization temperature as reinforcement in a phenolic composite may significantly contribute to improving the interfacial, thermal, and ablative properties of C/P composites.     

Dielectric effects on positive temperature coefficient composites of polyethylene and short carbon fibers

By adding the short carbon fibers to the polyethylene matrix, excellent positive temperature coefficient (PTC) effect was achieved. Alternating current (AC) electrical properties of this PTC composite were studied as a function of frequency. The analysis of AC electrical conductivity and dielectric permittivity was done by using a micro-morphology model, which included conductive carbon fiber-aggregates in series with an equivalent circuit of resistor-capacitor parallel that represent the blends at these contact regions. The observed electrical properties of PTC composites were due to the breakage of the conduction networks caused by thermal expansion. The dielectric behaviors of the interfacial polarization between polyethylene matrix and carbon fibers could be described by Maxwell-Wagner-Sillars relaxation when the composite was heated above 116 °C. The analysis of the electric modulus in the frequency range from 100 Hz to 10 MHz revealed that the interfacial relaxation followed the Cole-Davidson distribution of relaxation time.     

Mechanical and thermophysical properties of carbon/carbon composites with hafnium carbide

Carbon/carbon (C/C) composites with addition of hafnium carbide (HfC) were prepared by immersing the carbon felt in a hafnium oxychloride aqueous solution, followed by densification and graphitization. Mechanical properties, coefficients of thermal expansion (CTE), and thermal conductivity of the composites were investigated. Results show that mechanical properties of the composites decrease dramatically when the HfC content is greater than 6.5 wt%. CTE of the composites increases with the increase of HfC contents. The composites with addition of 6.5 wt% HfC show the highest thermal conductivity. The high thermal conductivity results from the thermal motion of CO in the gaps and pores, which can improve phonon–defect interaction of the C/C composites. Thermal conductivities of the composites decrease when the HfC content is greater than 6.5 wt%, which is due to formation of a large number of cracks in the composites. Cracks increase the phonon scattering and hence restrain heat transport, which results in the decrease of thermal conductivity of the composites.     

氧化石墨烯的制备及其掺杂的炭/炭复合材料导热性能研究

设定两种不同配比强酸氧化剂,以鳞片石墨为原料,采用Hummers法,制备了氧化石墨烯,再经过高温炭化得到热处理氧化石墨烯。并分别以中间相沥青为基体炭前驱体,炭纤维为增强相,氧化石墨烯及其热处理物为热疏导功能体,制备出掺杂氧化石墨烯的炭/炭复合材料。TEM、SEM等表征表明,选用强酸氧化剂组合配比用量较少的制备出的氧化石墨烯,其形貌整体上要优于用量较多的,具有独特的褶皱结构;相比于氧化石墨烯,掺杂其热处理物的复合材料界面覆盖均匀平滑且结合更优良,且其导热系数可达到60 W.m-1.K-1,是无掺杂的纯复合材料两倍多,导热系数得到了较大幅度提高。     

炭黑橡胶体系热物性影响因素研究

用激光导热分析仪测试3种炭黑填充橡胶复合材料的热物性,探索其影响规律,包括热扩散系数、导热系数和定压比热容随温度、炭黑用量以及炭黑种类的变化规律。结果表明,温度对于3种胶料的热物性影响不大;炭黑用量对热物性有较明显的影响,热扩散系数和导热系数均随填充量的增加而增大,而定压比热容则随填充用量的增加而减小;炭黑的品种对于复合材料的热物性有一定的影响。乙炔炭黑橡胶体系呈现优良的热物性。     

Preparation by tape casting and hot pressing of copper carbon composites films

During this last decade, the use of metal matrix composites (MMCs) such as AlSiC or CuW for heat dissipation in microelectronic devices has been leading to the improvement of the reliability of electronic power modules. Today, the continuous increasing complexity, miniaturization and density of components in modern devices requires new heat dissipating films with high thermal conductivity, low coefficient of thermal expansion (CTE), and good machinability. This article presents the original use of copper carbon composites, made by tape casting and hot pressing, as heat dissipation materials. The tape casting process and the sintering have been adapted and optimised to obtain near fully dense, flat and homogeneous Cu/C composites.A good electrical contact between carbon fibres and copper matrix and a low porosity at matrix/copper interfaces allow obtaining a low electrical resistivity of 3.8 μΩ cm⁻¹ for 35 vol.% carbon fibre (electrical resistivity of copper = 1.7 μΩ cm⁻¹). The CTE and the thermal conductivity are strongly anisotropic due to the preferential orientation of carbon fibres in the plan of laminated sheets. Values in the parallel plan are, respectively, 9 × 10⁻⁶ °C⁻¹ and 160–210 W m⁻¹ K⁻¹ for 40 vol.% fibres. These CTE and thermal conductivity values are in agreement with the thermo-elastic Kerner's model and with the Hashin and Shtrikman model, respectively.     

Effect of functionalized carbon nanotubes on the thermal conductivity of epoxy composites

Direct functionalized carbon nanotubes (CNTs) were utilized to form the heat flow network for epoxy composites through covalent integration. A method of preparing a fully heat flow network between benzenetricarboxylic acid grafted multi-walled carbon nanotubes (BTC-MWCNTs) and epoxy matrix is described. A Friedel-Crafts modification was used to functionalize MWCNTs effectively and without damaging the MWCNT surface. Raman spectra, X-ray photoelectron spectra and thermogravimetric analysis reveal the characteristics of functionalized MWCNTs. The scanning electron microscope images of the fracture surfaces of the epoxy matrix showed BTC-MWCNTs exhibited higher solubility and compatibility than pristine-MWCNTs. The MWCNTs/epoxy composites were prepared by mixing BTC-MWCNTs and epoxy resin in tetrahydrofuran, followed by a cross-linking reaction with a curing agent. The BTC was grafted onto the MWCNTs, creating a rigid covalent bond between MWCNTs and epoxy resin and forming an effective network for heat flow. The effect of functionalized MWCNTs on the formation of the heat flow network and thermal conductivity was also investigated. The thermal conductivity of composites exhibits a significant improvement from 0.13 to 0.96 W/m K (an increase of 684%) with the addition of a small quantity (1-5 vol%) of BTC-MWCNTs.     

炭/炭复合材料的热物理性能

综述了炭／炭复合材料的热物理性能及其影响因素。炭／炭复合材料热导率的大小由炭纤维的类型、取向、体积分数以及基体的结构类型决定，热处理工艺也对它有很大的影响。炭／炭复合材料的热导率随温度升高一般先升高后降低。炭／炭复合材料在低温时具有负热膨胀系数，影响其这一性能的因素除了坯体结构和基体     

Nano- and microstructural effects on thermal properties of poly (l-lactide)/multi-wall carbon nanotube composites

In this work the thermal properties of poly (l-lactide)/multi-wall carbon nanotube (PLLA/MWCNT) composites have been investigated. Thermal conductivity was determined after measuring specific heat capacity (C_p), thermal diffusivity (D) and bulk density (ρ) of composites. Thermal conductivity rises up to 0.345 W/m K at 5 wt.% after reaching a minimum value of about 0.12 W/m K at 0.75 wt.%. In order to understand the heat-conduction process, experimentally obtained thermal conductivities were fitted to an existing theoretical model. The much lower thermal conductivity of composites compared with the value estimated from the intrinsic thermal conductivity of the nanotubes and their volume fraction could be explained in terms of the obtained large thermal resistance (R_k) of 1.8 ± 0.3 × 10^?8 m² K/W at nanotube–matrix interface. The CNT dispersion in the composites was analyzed by atomic force microscopy (AFM) and transmission electron microscopy (TEM). Although the thermal resistance dramatically reduces the estimated bulk thermal conductivity of composites, the existence of an interconnected conductive nanotube network for thermal diffusion in PLLA/MWCNT composites demonstrates that the addition of carbon nanotubes represents an efficient strategy in order to successfully enhance the thermal conductivity of insulator polymers.     

Pitch-based ribbon-shaped carbon-fiber-reinforced one-dimensional carbon/carbon composites with ultrahigh thermal conductivity

Ribbon-shaped carbon fibers have been prepared from mesophase pitch by melt-spinning, oxidative stabilization and further heat treatment. The internal graphitic layers of ribbon-shaped carbon fibers graphitized at 2800 °C show a highly preferred orientation along the longitudinal direction. Parallel stretched and unidirectional arranged ribbon-shaped carbon fibers treated at about 450 °C were sprayed with a mesophase pitch powder grout, and then hot-pressed at 500 °C and subsequently carbonized and graphitized at various temperatures to produce one-dimensional carbon/carbon (C/C) composite blocks. The shape and microstructural orientation of ribbon fibers have been maintained in the process of hot-pressing and subsequent heat treatments and the main planes of the ribbon fibers are orderly accumulated along the hot-pressing direction. Microstructural analyses indicate that the C/C composite blocks have a typical structural anisotropy derived from the unidirectional arrangement of the highly oriented wide ribbon-shaped fibers in the composite block. The thermal conductivities of the C/C composites along the longitudinal direction of ribbon fibers increase with heat-treatment temperatures. The longitudinal thermal conductivity and thermal diffusivity at room temperature of the C/C composite blocks graphitized at 3100 °C are 896 W/m K and 642 mm²/s, respectively.