Carbon foams with high compressive strength derived from mixtures of mesocarbon microbeads and mesophase pitch

Carbon foam with relatively high compressive strength and suitable thermal conductivity was prepared from mixtures of mesocarbon microbeads (MCMBs) and mesophase pitch, followed by foaming, carbonization and graphitization. The influence of addition amount of MCMB on the properties of as-prepared carbon foams was investigated in detail. Results showed that addition of MCMBs into mesophase pitch could significantly reduce the amount and length of cracks in carbon foams, which results in increase of compressive strength of carbon foams. Carbon foam with high compressive strength of 23.7 MPa and suitable thermal conductivity of 43.7 W/mK, was obtained by adding 50% MCMBs into mesophase pitch, followed by foaming, carbonization and graphitization.     

Carbon foams prepared by supercritical foaming method

Multifunctional carbon foams with mean pore size smaller than 200 μm were prepared by supercritical foaming, in which toluene and mesophase pitch were used as the supercritical agent and carbonaceous precursor, respectively. The supercritical foaming behaviors and nucleation mechanisms were analyzed. According to the composition of mesophase pitch and micrographs of resultant carbon foams, the interface between light components and quinoline insoluble components is considered as the nucleation site.     

Carbon foam derived from pitches modified with mineral acids by a low pressure foaming process

Carbon foams with an anisotropic texture and high mechanical strength were produced using precursors obtained after thermo-oxidation treatment of commercial coal-tar pitch with H₂SO₄ and HNO₃. The investigations of the relation between the properties of the precursor and the structure of obtained foam indicate, that the composition and softening point of the pitch precursor significantly affect the foaming process, foam structure and foam mechanical strength. The composition and properties of the modified pitches allow foam formation at relatively low pressure and fast heating rate during the foaming process without a stabilization treatment. The foaming process of pitch-based carbon foams, pre-treatment of the precursors, and the properties of resultant foams are discussed in this paper.     

A two-stage preparation of mesophase pitch from the vacuum residue of FCC decant oil

The preparation of mesophase pitch as a precursor for the high-performance carbon fiber from a vacuum residue of FCC-decant oil (FCC-DOVR) was studied, applying a two-stage heat treatment to improve the pitch yield as well as its liquid crystal properties. The present two-stage preparation consisted of the pressurized heat treatment (1–5 MP) of the first stage at 430–480°C and the successive heat treatment under 13–260 Pa at 430°C. Such a two-stage preparation increased the yield of the spinnable mesophase pitch of 100% domain texture with lower softening point to 45% from 22% by the single-stage one from the same feedstock. Spinning properties of the mesophase pitch were excellent to allow smooth spinning for longer than 15 min and random orientation of mesogen molecules in the tranverse section of the fiber perpendicular to the fiber axis. The chemistry of the two-stage preparation for the higher yield and better properties as the fiber precursor is briefly discussed.     

Carbon foam derived from various precursors

A series of carbon foams was developed by using low-cost precursors, such as coal, coal tar pitch and petroleum pitch. The properties of the resultant carbon foams cover a wide range, e.g., bulk density, 0.32-0.67 g/cm³, compressive strength, 2.5-18.7 MPa, isotropic and anisotropic microstructure, etc. The investigation of foaming mechanism and the relationship between properties and structure indicate that the fluidity and dilatation of the foaming precursors significantly affect the foaming performance and foam structure. Raw coal samples were foamed directly without pretreatment in this work. However, for the pitch based foaming precursor, a thermal pretreatment is necessary to adjust its thermoplastic properties to meet the foaming requirement. The mechanical strength of carbon foam is found to be related to not only the foam cell structure, but also the fluidity and anisotropic domain size of the foaming precursors. In addition, the micro and mesopore structure in carbon foam matrix was investigated by gas adsorption and it was found that it also affects the strength of carbon foam and is related to the fluidity of foaming precursor.     

Effects of pitch fluoride on the thermal conductivity of carbon foam derived from mesophase pitch

Carbon foams with high thermal conductivity were obtained from mixtures of mesophase pitch and pitch fluoride. The addition of pitch fluoride in mesophase pitch could significantly increase the specific thermal conductivity of as-prepared carbon foams. After graphitization at 2873 K, the specific thermal conductivity of carbon foams increased from 82 up to 155.4 (W/mK)/(g/cm³) when the content of pitch fluoride was 3% in the raw material.     

Modeling the principle physical parameters of graphite carbon foam

Graphite carbon foam, a mesophase, pitch-based material, portrays highly ordered topology structures which exhibit superior mechanical and thermal properties. Typical graphite carbon foam with dimensions 5 cm³, can have a surface area greater than 11 m², making it an excellent candidate for heat transfer applications. Accurate three dimensional modeling of carbon foams is necessary to study and predict their properties in simulation. This paper describes a computer algorithm for modeling POCO Foam® and similar carbon foams. The algorithm, written in MATLAB, captures the principle physical parameters of the carbon foam including bubble and pore diameter ranges and overall foam void percentage while retaining the random dispersal of spherical bubbles found in manufactured foams.     

Anisotropy of mesophase pitch-derived carbon foams

Carbon foams with uniform pore size were produced from mesophase pitch in a high-pressure chamber. The morphologies, crystal structure and mechanical properties of as-grown carbon foams, carbonized and graphitic foams were investigated. The microwave absorbing properties of carbon foam sandwich composites at 2-18 GHz were also examined. It was found that the extension of pores in the xz-plane direction (parallel to the direction of gravitational force) was larger than that in the xy-plane direction (perpendicular to the direction of gravitational force). The compressive strength and modulus of resultant foams in the xz-plane direction were higher than those in the xy-plane direction. Further, the reflection loss of the sandwich composites composed of xy-plane carbon foam slabs was lower than that of xz-plane composites. The results of this work showed that carbon foam was a kind of anisotropic material.     

Improving graphitization degree of mesophase pitch-derived carbon fiber by solid-phase annealing of spun fiber

The solid-phase annealing of the mesophase pitch spun fiber was examined between the glass transition (T_g) and softening (T_s) temperatures of the pitch to improve the graphitization degree of the graphitized fiber through recovering or further improving the stacking height of the mesogen molecules in the spun fiber, since the rapid spinning reduced markedly stacking height in the as-spun fiber. A naphthalene mesophase pitch as received carried stacking height of 2.9 nm which was markedly reduced to 1.7 nm by spinning at 230 m/min, giving Lc=40 nm for its graphitized fiber. Annealing at 206 °C improved the stacking height of the spun fiber to 2.4 nm and Lc(002) of the graphitized fiber to 54 nm. Annealing of the methylnaphthalene mesophase pitch fiber at 200 °C was much more effective in improving the stacking height from 3.5 to 5.0 nm and its graphitized fiber to Lc=91 from 40 nm. Such an improved graphitization degree led to improved thermal conductivity and tensile modulus of the graphitized fiber. It must be noted that the annealing of the spun fiber reduced its stabilization rate, indicating densification of molecular stacking in the fiber. The transformation scheme of mesophase pitch into graphite fibers is discussed to clarify the roles of molecular stacking in the clusters and their arrangement in the mesophase pitch fiber during the carbon manufacturing process.     

Development of mesophase pitch derived high thermal conductivity graphite foam using a template method

A simple and inexpensive method is described for preparing high thermal conductivity graphite foam by impregnating a coal tar pitch based mesophase pitch into a substrate polyurethane foam template. Mesophase pitch impregnated polyurethane foam was converted into graphite foam by several heat treatments in air as well as in an inert atmosphere. Scanning electron microscope images show the retention of an excellent open pore structure despite volume shrinkage of over 50%. The graphite foam prepared by this sacrificial template method is found to possess a thermal conductivity of 60 W/m K with a compressive strength in the range of 3.0–5.0 MPa. The X-ray diffraction pattern shows an interlayer spacing (d₀₀₂) of 0.3388 nm at a heat treatment temperature of 2400 °C. Different concentrations of slurries of mesophase pitch in water were used in combination with substrate foams of different densities to prepare graphite foams of density in the range 0.23–0.58 g cm⁻³. The specific thermal conductivity of the carbon foam with a low density of 0.58 g cm⁻³ is found to be higher than that of copper metal traditionally used in thermal management applications.     

Preparation of carbon foams with supercritical toluene

Carbon foams with pore sizes of 10–50 μm were prepared with mesophase pitch and toluene as the carbonaceous precursor and supercritical agent, respectively. Results revealed that the light pitch components and dissolved toluene in pitch significantly affected the pore structures of resultant carbon foams. The amount of toluene dissolved in molten pitch is greatly dependent on the foaming conditions, such as the ratio of toluene to pitch, foaming temperature, foaming pressure and saturation time. Carbon foams with hierarchical porous structures are obtained by controlling the amount of light pitch components.     

反应温度对苯甲醛齐聚物及其中间相沥青性能的影响

以中温煤沥青为原料,通过苯甲醛/对甲苯磺酸交联合成出以次甲基相连接的齐聚物,进一步热解制备了中间相沥青,考察了反应温度对齐聚物及其中间相沥青性能的影响。结果表明,随着反应温度的提高,改性煤沥青的收率、软化点、残炭率和密度都呈现上升的趋势;反应温度适当,易于得到光学各向异性发达、软化点较低的优质中间相沥青。     

中间相沥青基泡沫炭的研究及应用

中间相沥青基泡沫炭具有低密度、高强度、高导热、抗冲击、耐高温、抗氧化等诸多特点,因而具有广泛的应用前景.目前,中间相沥青基泡沫炭最常用的制备方法是自发泡法.本文详细综述了中间相沥青基泡沫炭制备过程中的影响因素,也概述了近几年来国内外对泡沫炭的改性研究及应用.     

New insights on the direct activation of isotropic petroleum pitch by alkaline hydroxides

The paper provides interesting evidences that a low softening point isotropic petroleum pitch can be used as a good carbon precursor for the preparation of activated carbons. The activation is carried out by KOH and/or NaOH and the resulting activated carbons present well developed porosity. Such hydroxide activations can be done directly on the pristine petroleum pitch (P) or on the pitch that has been submitted to an air stabilisation followed by a N₂ heat treatment (TAN). In general, KOH activation produces better results than NaOH, both in terms of porosity and yield, the results obtained for the activation of TAN being impressive because of the good porosity developments and high yields reached. The different treatments carried out over the petroleum pitch precursor clearly show that they significantly influence the extent of microporosity development. This is due to different changes occurring in the porous structure of the precursor as a function of the treatment carried out. The efficiency of the activation process increases as the mesophase content of the precursor decreases, as well as the mesophase formation during the activation process is avoided.     

Influence of heat and pressure treatment on the rheological behavior of petroleum pitches

Pitch rheological properties are extremely important during the manufacturing process of carbon materials, in mesophase formation, and with regard to the final properties of the carbon products. In this work, pitch samples have been prepared from three different FCC decant oils by heat-treatment, under 0.9 MPa pressure, in a reactor at 390 °C, 410 °C, and 430 °C. These samples were analyzed in a rotational rheometer using a parallel-plate sensor. The rheometric softening points matched the results obtained using conventional equipment and exponential relationships were found to exist between these softening points and the pitch cosity when the former approached 180 °C. The quinoline-insoluble content (QI) has been shown to be more important in increasing the pitch viscosity than the toluene-insoluble content (TI). Oscillatory rheometry analysis has shown that an elastic response is not always found in creep and recovery tests, even when the elastic modulus G′ is dominant over the viscous modulus G′′. Pitch elasticity was found to be independent of the mesophase, and this pitch property was either only observed when the cross-over point occurred at very high frequencies or did not occur at all within the frequency range studied.     

煤沥青基中间相沥青的制备研究

以纯化的煤焦油沥青为原料,考察了热聚合温度和恒温时间对中间相沥青的收率、光学显微形态、软化点和族组成的影响.结果表明:反应温度在420℃,恒温5 h时得到了软化点为312℃的流线体型中间相沥青,其收率为79.1%;热聚合反应在相对较低的温度400℃,反应时间为10 h时形成了软化点为305℃、收率为81.4%的优质广域型可纺性中间相沥青.对该原料煤沥青而言,通过控制热聚合反应温度和恒温时间可以达到制备优质中间相的目的.     

Electrochemical impedance study of polyaniline electrocoated porous carbon foam

Electropolymerization of aniline on mesophase pitch based carbon foam has been studied in order to evaluate the influence of conductive polymer coating on the properties of carbon foam. The surface morphology of the coating was determined by scanning electron microscopy (SEM). Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were used to investigate the electrochemical properties of resulting modified carbon foam samples. Polyaniline (PANI) electrocoated-mesophase pitch based carbon foam showed good capacitor behavior in 0.5 M H₂SO₄. Better capacitive behavior is obtained for 100 and 150 mV/s compared to other scan rates, under these faster scan rates thinner films of PANI coatings were combined with more porous structure of carbon foam. Conductivity of the carbon foam was increased from 9.23 to 13.73 S/cm by electrocoating of PANI.     

中间相沥青基泡沫炭的研究进展

中间相沥青基泡沫炭是一种具有低密度、高强度、高导热、高导电、耐火、耐高温、抗冲击、抗氧化等性能的新型炭材料,具有广泛的应用前景.不同的原料和方法所制备的沥青基泡沫炭的结构、性能和应用也有所不同,通过对以石油系、萘系和煤沥青或改性煤沥青为原料制备中间相沥青基泡沫炭,讨论了制备工艺对泡沫炭的影响,同时对泡沫炭的改性研究及应用进行了概述.     

纺丝温度对中间相沥青炭纤维结构性能的影响

以萘催化合成中间相沥青(MP-1)和热缩聚法制备中间相沥青(MP-2)两种中间相沥青为原料,对其进行簇组成分析、偏光显微镜观察及红外光谱分析,研究其组成及结构.采用实验室气压式单孔纺丝装置在不同温度下对两种中间相沥青进行熔融纺丝,探讨纺丝温度对炭纤维结构及性能的影响.研究表明:MP-1低温获得无规结构,高温出现中心放射状边缘洋葱皮混合结构;MP-2随纺丝温度升高依次出现无规结构、准洋葱皮结构和洋葱皮结构.中间相沥青原料的性质影响着纤维截面结构随纺丝温度变化的规律.     

Carbon foams prepared from coal tar pitch for building thermal insulation material with low cost

A new approach is provided to resolve the large-scale applications of coal tar pitch. Carbon foams with uniform pore size are prepared at the foaming pressure of normal pressure using coal tar pitch as raw materials. The physical and chemical performance of high softening point pitch(HSPP) can be regulated by vacuumizing owing to the cooperation of vacuumizing and polycondensation. Results indicate that the optimum softening point and weight ratio of quinoline insoluble are about 292℃ and 65.7%, respectively. And the optimum viscosity of HSPP during the foaming process is distributed in the range of 1000-10000 Pa·s. The resultant carbon foam exhibits excellent performance, such as uniform pore structure, high compressive strength(4.7 MPa), low thermal conductivity(0.07 W·m~(-1) ·K~(-1)), specially, it cannot be fired under the high temperature of 1200 ℃.Thus, this kind of carbon foam is a potential candidate for thermal insulation material applied in energy saving building.