Comparative Study of the Modification of Coal Tar Pitch for Higher Carbonization Yield and Better Properties

Parent coal tar pitch（CTP） was modified with boric acid（BA）, cinnamaldehyde（CMA） and the mixture of BA and CMA, respectively. The parent CTP and three modified CTPs were characterized by elemental analysis, thermogravimetric analysis, Fourier transform infrared（FT-IR） spectroscopy and scanning electron microscopy. The four samples were carbonized at different temperatures and resultant carbonized products were characterized by FT-IR spectroscopy, X-ray diffraction and polarized-light microscopy. The results show that the morphologies and carbonization behaviors of the parent CTP and modified CTPs are quite different. The carbonization yield of the CTP modified with the mixture of BA and CMA is higher than that of CTP modified with BA or CMA only. In addition, the modification of CTP with 7 g of BA and 10 ml of CMA results in an increase in carbonization yield by 5.64%. During the pyrolysis of modified CTPs, the dehydration of BA or the distillation of CMA occurs at the temperature lower than 300 °C, and methyl and methylene groups of the modified CTPs disappear gradually as temperature rises. Furthermore, the modification of CTP by the mixture of BA and CMA results in more intensive mesophase spheres than other modified CTPs, and the modified CTP is easier to be carbonized to form graphitic carbon.     

Carbonization of Ni-doped Phenol Resin Under Various Conditions

Ni-doped phenol resin was prepared with 1∶100 mass ratio of Ni( NO_3)_2·6H_2O to thermosetting phenol resin to optimize the structure and properties of pyrolytic carbon derived from phenol resin and increase its carbon yield. The specimens were cured at 200 ℃ and carbonized under different atmospheres( carbon-embedded atmosphere and Ar atmosphere) and at different temperatures( 600,800,1000 and 1200 ℃) for3 h,respectively. The carbon yield was measured. Thermal decomposition characteristics of Ni-doped phenol resin,and the oxidation resistance,phase composition and microstructure of pyrolytic carbon were characterized by differential scanning calorimetry,X-ray diffraction,energy dispersive spectroscopy, scanning electron microscopy and transmission electron microscopy. The results show that the carbon yield of Ni-doped phenol resin carbonized at800 or 1 000 ℃ is increased significantly,compared with that without any dopants. The graphitization degree of pyrolytic carbon structure derived from Ni-doped phenol resin increases with the increase of carbonization temperature. The massive multi-wall carbon nanotubes of 50-100 nm in diameter and of micrometre scale in length are generated at 1000 ℃. Compared with the carbonembedded atmosphere,carbon nanotubes can be more easily generated in Ar atmosphere,resulting in higher carbon yield and degree of crystallinity of the pyrolyticcarbon derived from Ni-doped phenol resin. The oxidation resistance of the pyrolytic carbon derived from Ni-doped phenol resin at 1200 ℃ is improved significantly and its highest oxidation temperature is increased by about 84℃,compared with that from Ni free phenol resin.     

超硬材料磨具用烯丙基化酚醛改性双马来酰亚胺树脂的研究

A novel thermosetting resin system for superabrasives based on novolak and bismaleimide （BMI） was developed. The novolak resin was allylated and then copolymerized with BMI. The structure of allyl novolak and reaction mechanism were analyzed by FFIR. Thermal and mechanical properties were characterized by using com- prehensive thermal analyzer （DSC-TG） and strength tester, respectively. The results showed that high molecular weight of novolak was advantageous for heat-resistance, but was unfavorable for the bending strength. High allyl content improved the heat-resistance but lowered the bending strength. When the molecular weight of novolak was 450 and allyl content was 50%, the best resin system with good heat-resistance and bending strength was obtained. It was suitable for the manufacturing of superabrasive tools.     

A comparison of soft magnetic composites designed from different ferromagnetic powders and phenolic resins☆

Soft magnetic composites (SMCs) were prepared from three different ferromagnetic powder particles:iron powder ASC 100.29, spherical FeSi particles and vitroperm (Fe73Cu1Nb3Si16B7) flakes. Two types of hybrid organic–inorganic phenolic resins modified with either silica nanoparticles or boron were used to design a thin insulating layer perfect-ly covering the ferromagnetic particles. Fourier transform infrared (FTIR) spectrometry confirmed an incorporation of silica or boron into the polymer matrix, which manifested itself through an improved thermal stability of the hybrid resins verified by thermogravimetric-differential scanning calorimetry (TG-DSC) analysis. The core-shell particles prepared from the ferromagnetic powder particles and the modified hybrid resins were further compacted to the cylindrical and toroidal shapes for the mechanical, electrical and magnetic testing. A uniform distribution of the resin between the ferromagnetic particles was evidenced by scanning electron microscope (SEM) analysis, which was also reflected in a rather high value of the electrical resistivity. A low porosity and extraordinary high values of mechanical hardness and flexural strength were found in SMC consisting of the iron powder and phenolic resin modified with boron. The coercive fields of the prepared samples were comparable with the commercial SMCs.     

Influence of Ultra-Fine B4C and Nano-SiO2 on the Properties of Alumina-Graphite Refractories

The role of nano-SiO2 and ultra-fine boron carbide on the properties of alumina-graphite materials was investigated.The study showed that the ultra-fine boron carbide added modified the microstructure of residual carbon and promoted the chemical bond between residual carbon from phenolic resin and flake graphite.The carbon white could strengthen the residual carbon from phenolic resin.These two additives improved the mechanical properties of AG refractories at both room temperature and high temperature,and thermal shock resistance was improved noticeably.When the two additives were doped together,carbon white could retard the evaporation of B2O3.Thermal shock resistance was guaranteed with a smaller amount of ultrafine born carbide.     

Effect of Temperature Schedule on the Morphology of SiC Made From Graphite and Silicon Powder

SiC whiskers were synthesized in a coke bed using a two-step heat treatment process.The temperature was held for 3 h at 1 200 ℃ before heating to 1 430 ℃ and holding for 3 h.The morphologies of SiC synthesized by the two-step heat treatment method were much more different from those produced by direct heating to 1 430 ℃.SiC whiskers formed at 1 200 ℃ firstly and grew at1 430 ℃ to obtain a mean diameter about 326 nm,while the SiC grains with a size range from 0.70 to2.30 μm were obtained by direct heating to the target temperature of 1 430 ℃.This was explained by the different formation mechanisms.The result proposes a promising alternative technical process for whisker-reinforced ceramic/refractory composites in-situ during sintering.     

Effect of KCI on Growth of Carbon Fibers During Carbonization of Phenolic Resin

Effects of the KCl additions( 1%,3%,5% and7% of the phenolic resin mass) on phase composition and microstructure of the resin carbon and the growth mechanism of carbon fibers were investigated by using commercial liquid phenolic resin as carbon source and micron-scaled KCl as catalyzer,mixing,hexamethylenetetramine solidification treating,carbon-embedded firing at 1 000 ℃ for 3h in order to accelerate the graphitization of phenolic resin during carbonization. The results show that the graphitization degree of resin carbon is improved by catalysis of KCl,numerous carbon fibers with30-200 nm in diameter and 10-20 μm in length and sheet-like carbon in situ grow in resin carbon. The optimal addition of KCl is 5% when lots of carbon fibers can be found in resin carbon,and d002 diffraction peak of graphite appears obviously in the XRD pattern. The growth mechanism of carbon fiber is that the molten KCl at high temperatures absorbs carbonaceous gas from the decomposition of phenolic resin,accelerating the diffusion of solid C atoms in liquid KCl; after the dissolution of C saturates,carbon atoms separate continuously in local parts to form carbon fibers or flakes; meanwhile,the concentration gradient formed by local carbon atoms in the melt offers growth drive for the separation of carbon fibers or flakes on KCl surface.     

不同结构硫化钼催化剂上酚类模型化合物的加氢脱氧

Several MoS2 catalysts of different structure, prepared by in situ decomposition of ammonium heptamolybdate （AHM） and molybdenum naphthenate （MoNaph）, and by MoS2 exfoliation （TDM）, were characterized by BET, X-ray diffraction （XRD）, Energy Dispersive X-ray （EDX） and transmission electron microscopy （TEM）. The analysis showed that MoS2 structure was dependant upon the preparation procedure. The activity of the catalysts was determined by measuring the hydrodeoxygenation （HDO） of phenol, 4-methylphenol and 4-methoxyphenol using a batch autoclave reactor operated at 2.8 MPa of hydrogen and temperatures ranging from 320-370℃. By comparing the conversion, the reactivity order of the catalysts was： AHM〉TDM-D〉MoNaph〉thermal〉MoS2 powder〉 TDM-W. Also, the effect of reaction temperature on the HDO conversion was explained in terms of equilibrium of reversible reaction kinetics. The main products of the HDO for phenolic compounds were identified by gas chromatography/mass spectrometry （GC/MS）. The results showed that the product distribution and the HDO selectivity were correlated with the reaction temperature. Two parallel reaction routes, direct hydrogenolysis and combined hydrogenation-hydrogenolysis, were confirmed by the analysis of the product distribution. High temperature favored hydrogenolysis over hydrogenation for HDO of phenol and 4-methoxyphenol, whereas for 4-methylphenol the reverse was true.     

In-situ Formation of SiC Whiskers by Ni-catalyzed Silicon-modified Pitch and Its Mechanism

The pitch was dried and modified with 1 mass%nickel nitrate and 10 mass% Si powder successively,then carbonized in Ar atmosphere at 900,1 000,1 100,1 200,1 300,and 1 400 ℃,respectively. Effects of carbonization temperature on phase composition and microstructure of Ni-catalyzed silicon modified pitch were studied by XRD,FESEM and EDS,and the growth mechanism of Si C whiskers was discussed as well. The results show that Si C whiskers form in the carbonized products of modified pitch processed in Ar atmosphere at 1 000,1 100,1 200,1 300,or 1 400 ℃; its length is about1- 6 μm; its growth mode is apical growth,and its growth mechanism accords with V- L- S mechanism.     

HYDRODYNAMIC MODEL FOR THE IMPELLER REGION IN AN AERATED AND STIRRED TANK

The radial and axial distribution of mean 1iquid velocity were measured by a.hot-filmanemometer at the impeller region in an aerated and stirred tank 0.287m in diameter.The tangentialjet model for impeller discharge flow used for single phase flow was modified to conform with thecharacteristics of gas-liquid flow.The radial and axial velocity profiles at the impeller region in thegas-liquid stirred tank were calculated by the model The results predicted by the model were in goodagreement with those obtained in experiment.     

炭化条件对针状焦结构的影响

以除去喹啉不溶物的中温煤沥青为原料,分别在不同的反应温度和保温时间下制备了中间相炭微球(MCMB);在磁场条件下制备了有序结构针状焦;通过扫描电镜(SEM)考察了不同反应条件下中间相炭微球和针状焦的形貌,讨论了中间相形成影响因素对针状焦结构的影响.结果表明,中间相形成阶段的反应温度、保温时间和体系黏度对针状焦的结构和性能具有重要影响,磁场对针状焦的流线型结构有促进作用.     

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.     

反应温度和压力对制备中间相沥青的影响

以中温煤沥青为原料,于高压反应釜中进行热转化,在不同的反应温度和压力条件下制备中间相沥青。采用偏光显微镜、红外光谱仪、x射线衍射仪等测试仪器对所得中间相沥青进行分析和表征。结果表明,温度对中间相沥青的产率、形貌和结构影响显著,随着温度升高,中间相含量增加;中间相小球体的尺寸增大,逐渐出现融并现象,最终形成流域型体中间相。压力对中间相的含量和结构也有一定影响,实验结果显示施加3MPa压力,有利于中间相的形成和其含量的提高。420℃、3MPa条件下形成的中间相含量高达81．0％,并形成流线域状体中间相。     

煤加氢热解物制备中间相炭微球研究

对煤加氢热解物所得精制沥青的中间相转化行为进行了研究,发现其在440℃、1 MPa下保温6 h即可形成广域流线型中间相组织,说明融并性能良好;在常压、420℃、6 h的热处理条件下,添加1%炭黑,制备出了表面光滑、球形度好、粒径集中的中间相炭微球。该精制沥青可以作为高性能炭材料的优良前躯体。     

The microstructure of nuclear graphite binders

The microstructures of the binder in two grades of nuclear graphite, Gilsocarbon graphite and Pile Grade A graphite, were characterized by light microscopy, transmission electron microscopy and high resolution transmission electron microscopy. A variety of structures of carbon were observed, including a well-graphitized structure, nanosized graphite particles, quinoline insoluble (QI) particles, chaotic structures and non-graphitizing carbon. QI particles were observed on the surface of mesophase spheres as well as inside mesophase spheres. The aggregation of QI particles on the surface of mesophase spheres, or very near the surface in mesophase spheres, appears to have a significant influence on the development of the mesophase structure, resulting in refinement of the mesophase spheres before their coalescence. The chaotic structure, which is turbostratic and isotropic, is suggested to have developed from the isotropic pitch remaining between mesophase spheres. The non-graphitizing carbon consisted of flat and curved single layer graphene fragments with a size typically less than 1 nm. The formation of the various structures in the two graphites is attributed to the introduction of different pitches at stages of the graphite manufacture.     

Influence of organic sulfur compounds and metals on mesophase formation

The influence of organic sulfur compounds and metals on the texture of the mesophase formed in pitch during the carbonization process was investigated by the addition of organic sulfur compounds and organometallic compounds to the cracked oil obtained from Khafji asphalt and polyvinyl chloride (PVC) pitch. These pitches, containing sulfur and metals, have been examined by polarised light microscopy, and quinoline insolubles (QI), sulfur and metal contents were determined. The existence of either organic sulfur compounds or organometallic compounds in the pitch has no effect on mesophase texture. However, the coexistence of sulfur and metals (such as vanadium or nickel) has a great effect on mesophase texture. From these results, sulfur and metals coexisting in the pitch have a catalytic effect which activates the thermal decomposition and the thermal polymerization reactions of the pitch. Furthermore, the precursors of mesophase (β resin) are formed abundantly in the pitch by these reactions. These precursors promote the nucleation of mesophase spherules, and a large number of mesophase spherules are formed in the pitch at the same time. Therefore, these spherules coalesce with each other before growing to large spheres and lead to a fine mosaic texture.     

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.     

AR中间相沥青纺丝性能的研究

以AR中间相沥青为原料,采用元素分析与红外分析手段,研究了沥青原料的结构和组成,通过热台偏光显微镜观察和分析了其流动特性。采用氮压式单孔纺丝机进行熔融纺丝,制备中间相沥青纤维,研究了中间相沥青的可纺性及纺丝工艺对于中间相沥青纤维性能的影响。结果表明,在纺丝温度350℃、纺丝压力0.016MPa与收丝速度220m/min的条件下纺丝得到性能优良的沥青纤维,纺丝连续性好,可连续纺丝约5min。经290℃不熔化处理和1000℃碳化后,得到碳纤维拉伸强度1.45GPa、弹性模量120GPa。     

Influence of bonding carbon on low carbon Al2O3-C refractory composites

The carbonized behavior of binders (carbores pitch, mesophase pitch, high temperature pitch and phenolic resins) was investigated. Meanwhile, the influence of binders, Ni-catalyst and heat treatment on structure and properties of low carbon Al₂O₃-C materials was researched. Mesophase pitch and high molecular weight resin provided higher carbon yield. The synergistic interaction of pitch and phenolic resin provided the higher carbon yield than that of single component. Ni-catalyst changed structure and morphology of bonded carbon promoting the transition of amorphous carbon to crystalline carbon increasing carbon yield and degree of graphitization. High molecular weight phenolic resins, mesophase or carbores pitch and Ni-catalyst worked together providing low carbon Al₂O₃-C samples of excellent strength performance in a wide temperature range and high resistance of thermal shock. Embedding coke in N₂ could promote the generating of carbon fibers which obviously enhanced thermal shock resistance of low carbon (6% flake graphite) Al₂O₃-C materials after heat treatment.     

可溶性中间相沥青的制备研究

以净化沥青为原料 ,采用四氢萘高压氢化处理制取了氢化沥青 ,氢化沥青 H/ C原子比提高 14 %左右 ,最佳氢化温度为 4 2 0℃。以氢化沥青为原料 ,炭化热处理制备了中间相沥青 ,对炭化温度和恒温时间进行了优化选择 ,在 4 0 0℃下对氢化沥青炭化热处理 3h(升温速率为 2℃ / min) ,可制得喹啉可溶物 (QS)高达 85 %以上、TI含量为 71%和 β树脂含量为 5 8%的可溶性中间相沥青。