Pyrolysis of polystyrene in coal tar and ethylene tar pitches

Pyrolysis of polystyrene in the medium of coal tar pitch and of pitch prepared from ethylene production tar was performed in the temperature range 360–420°C at atmospheric pressure.     

Improved technology for manufacture of carbon electrodes

Current industrial carbon electrodes are typically manufactured by blending petroleum coke particles (the filler) with molten coal tar pitch (the binder) and extruding the resultant mix to form the ‘green electrode’. This is then baked under controlled conditions. In case of usage as anodes in steel electric furnaces (or as other carbon and graphite products), the electrodes could undergo further processing like pitch impregnation or graphitization. During heat treatment, some of the organics are destructively distilled, vaporized or decomposed, resulting in carbon deposition in the electrode. As the vaporized materials exit the body of the electrode they cause porosity in the walls, which results in reduction in density, current carrying capacity and flexural strength. The paper presents investigations to improve some physico-chemical characteristics of these electrodes (such as coefficient of thermal expansion, mechanical strengths, density, pore volume, porosity etc.), obtained in different manufacture steps, by addition of varieties of coal tar pitch. These include attempts to improve the chemical compatibility of the coke-pitch system in the mixture and establish the method and the point of introduction of additive, the concentration required and appropriate analytical control during the entire manufacture. Methods of analysis used include thermogravimetry and porosimetry. The microstructure of the electrodes is investigated through a wide range and the data obtained include pore size and pore volume distribution, surface area, porosity, particle size distribution and type of pores. The overall results clearly indicate better characteristics and performance for electrodes with additives as against electrodes without them, such as lower porosity, lower thermal expansion coefficients and greater mechanical strength. These data are analyzed with respect to the process step and electrode type.     

The determination of cholesteric pitch from the diffusion profile A new experimental approach

The optical microscopic mass transport (OMMT) method was utilized to determine the cholesteric pitch values of the mixtures of mesogenic and non-mesogenic chiral species in nematic materials. The cholesteric pitch was determined by transient analysis of the diffusion profile established by allowing an initial cholestric composition (solute) to diffuse under semi-infinite linear boundary conditions into an oriented thin film of its corresponding nematic solvent. During the steady-state diffusion, where the initial concentration (pitch) remains constant, the transient analysis of the profile with a polarization microscope exhibits a maximum number of pitch discontinuity domains. The evaluation of the unknown pitch was carried out by extrapolation of the diffusion pitch gradient to the original diffusion source by using the exact relation between the pitch and the film thickness. The method is experimentally simple; at constant temperature and pressure, determination of the pitch depends only on the film thickness. There is a good agreement between the pitch values obtained with this method and those from conventional techniques.     

The effect of pre-carbonization of mesophase pitch-based activated carbons on their electrochemical performance for electric double-layer capacitors

The activated carbons (ACs) are prepared from mesophase pitch which is pre-carbonized by using potassium hydroxide as an activating agent. Nitrogen adsorption at 77 K is used to characterize the surface area and the porous structure of the ACs. By changing the pre-carbonization temperature from 560 to 750 °C, the arrangement of the ACs’ microcrystallines might be controllable, and the pore size could be adjusted between 1.5 and 2.4 nm. The electrochemical performance of the ACs in organic solvent (1 M Et₄NBF₄ in propylene carbonate) is investigated by voltage sweep cyclic voltammetry and constant current charge–discharge cycling tests. The results show that the ions can transfer rapidly and freely in the pore larger than or equal to 1.85 nm, even when the current density increases to 25 A g⁻¹.     

煤基重质产物对滨州90#沥青的改性作用

对照优质道路沥青改性剂TLA,考察了六种煤基重质产物对滨州90#沥青的改性作用及作用原理。实验结果表明,六种改性剂对滨州90#沥青均表现出一定的改性作用。依据美国ASTM D5710-95以及英国BSI BS3690对TLA改性沥青的标准,六种改性沥青中,四种符合标准要求,其余两种不符合延度指标要求。FT-IR谱图分析表明,煤液化或煤油共处理重质产物的添加,没有生成新官能团,但使官能团的分布发生了变化,从而改善了基质沥青的路用性能,添加TLA,可增加C=O和S=O极性官能团,可增加沥青与石料的作用;煤焦油沥青过高的芳香结构,妨碍了其与基质沥青的混合作用。结合四组分分析结果,基于沥青胶体化学理论分析,发现不符合要求的改性沥青具有较高的饱和分含量,导致了较小的CI值(胶体指数),不利于沥青胶体结构的稳定。按线性加和法计算得到的改性沥青CI值与实测值的差距表明,改性过程包含有一定程度的化学反应。     

Spin probes in structure studies of petroleum mesophase pitch

The ESR spectra of petroleum pitch labeled with the stable copper-porphyrin complex and changes in the spectra due to pyrolysis are analyzed. It is concluded that the functions of carriers and traps for unpaired electrons in mesophase pitch are performed by anisotropic associates or crystallites sized about 2.0 nm. The intermodular interactions between the parallel layers of anisotropic associates may be significant. They increase when the molecular associates pass to the paramagnetic state and determine the preferable packing of the paramagnetic crystallites one over another. Translated fromZhurnal Strukturnoi Khimii, Vol. 38, No. 5, pp. 902–907, September-October, 1997.     

Production of semicokes with increased content of nitrogen by cocarbonization of various cakes with polyacrilonitrile

Pyrolysis of polyacrylonitrile mixtures with coal-tar pitch, pitch from heavy tar in ethylene production, and poly(vinyl chloride), a precursor of poly(vinyl chloride) pitch, was subjected to a comparative analysis. The content of various forms of nitrogen in the carbon materials obtained was determined.     

用于高性能锂硫电池的二维氮硫共掺杂多孔碳纳米片的快速合成

本工作基于工业炼油产品沥青,开发了一种无金属、氮和硫共掺杂多孔碳纳米片（NSPC）的合成方法。获得的多孔碳纳米片具有高比表面积（339 m²·g^-1）和优异的固硫能力。同时,高含量氮、硫共掺杂可以有效增强碳材料的导电性,同时促进多硫化物的高效催化转化。通过熔融法固硫后,制备得到的NSPC/S电极具有较高的比容量和优异的循环稳定性（在0.6C电流密度下,200次循环后容量为762 mAh·g^-1）,实现了高含量氮和硫共掺杂的二维多孔碳材料的快速批量生产并用于高性能锂硫电池正极材料。     

An experimental investigation of discrete changes in pitch in a thin, planar chiral nematic device

The phenomenon whereby sudden changes in helicoidal pitch occur in thin chiral nematic devices with strong surface anchoring has been studied experimentally. This has been done with the aim of examining the underlying process in the context of existing theory. Thin devices (∼2.5 µm thick) containing two commercially available chiral nematic liquid crystals were employed in the study. The samples were chosen for their dependence of pitch on temperature; one exhibits a very slow increase in pitch with increasing temperature (95.6% of the Merck material BL131 in BL130), while the second shows the more common rapid reduction in pitch with increasing temperature (the Merck mixture TM1001). High resolution reflection spectra were obtained for the devices and a numerical fitting algorithm, based on the Berreman 4×4 matrix technique, provided accurate information on changes in the pitch, refractive indices, device thickness and changes in the surface director across the pitch jump region. We demonstrate that changes in refractive index and device thickness are negligible in analysis of the reflection spectra across the pitch jumps. We further show that the pitch changes discontinuously at the pitch jump, with no variation in its value as the process occurs. We find evidence that the surface directors also change by less than 10° during this process in a manner analogous to coiling or uncoiling a constrained spring. This mechanism differs somewhat from others proposed in the literature.     

The semi-phenomenological model of antiferroelectricity in chiral smectic liquid crystals III. Dielectric spectroscopy

In the framework of the model of short pitch modes (SPM) developed for antiferroelectric liquid crystals, the sets of various relaxation modes related to ferro-, antiferro- and ferrielectric phases are explained. The 'soft-like' modes describe the amplitude perturbations of short pitch modes, while the Goldstone modes describe the azimuthal perturbations of the molecular packings related to short pitch modes. The frequencies of the Goldstone modes are mainly determined by the chirality parameter, depending on the number of short pitch modes. The relaxation modes described correspond to the observed phase diagrams in liquid crystal materials for which the measurements of dielectric spectra are presented.     

Photo-optical properties of photopolymerizable cholesteric compositions

Compositions consisting of nematogenic diacrylate monomer and chiral dopants capable of forming the cholesteric mesophase and of photopolymerizing were obtained and studied. For the first time, the change of optical properties and cholesteric helix pitch during photocrosslinking of diacrylate under UV irradiation (365 nm) was investigated. The kinetics of photopolymerization was studied and several stages of this process were observed. Cholesteric photopolymerizable blends containing chiral photosensitive dopant capable of E–Z isomerizing under UV irradiation (313 nm) were studied. The decrease of the helix twisting power of the dopant during photoisomerization was observed resulting in untwisting of the helix and shift of the selective light reflection peak into the long-wavelength region of the spectrum. The possibility of the photoregulation of optical properties of such blends with following fixation of structure and of these properties by means of photopolymerization under UV irradiation (365 nm) was demonstrated.     

Adsorption and DSC study of mineral–carbon sorbents obtained from coal tar pitch–polymer compositions

The purpose of this study was to determine the possibility of producing hydrophobic mesoporous mineral–carbon sorbents from aluminum hydroxide and compositions of coal tar pitch–polymers on carbonization at 600 °C in a nitrogen atmosphere. Blends of the products of co-precipitation of aluminum hydroxide in the carbonaceous substances medium were subjected to carbonization process. The extent of porous structure development was evaluated using low temperature nitrogen adsorption, adsorption of benzene vapors, and adsorption of iodine from aqueous solution. The highest value of BET surface area of about 370 m²/g was achieved for the carbonization product obtained from co-precipitated raw components with 10 wt% compositions coal tar pitch–polymer. These materials demonstrated high capacity to reduce organic pollutions from sewage. Pitch–polymer composition containing poly(ethylene terephthalate) or phenol–formaldehyde resin was studied by the means of DSC method in order to determine the high-temperature transformations taking place under the conditions of carbonization. DSC method enables to determine i.a. the decomposition temperatures of carbonizates produced from pitch–polymer compositions and the evaluation of their sorption abilities. The additive of poly(ethylene terephthalate) and phenol–formaldehyde resin caused the increase of thermal resistance of the pitch expressed by higher decomposition temperatures.     

Microstructure and performance of carbonization products of component from soft coal pitch

Pitch is constituted of aromatic hydrocarbon, which is one kind of organic liquid with high viscosity. The soft coal pitch was divided into different group components by solvent extraction, and the different fractions of soft coal pitch were carbonized separately. The relationship between the microstructures of carbonization products and the chemical compositions of group components was investigated in this paper. Results show that the structure and morphology of the carbonization products from pitch were significantly influenced by the chemical composition of the group components. The main microstructure of the toluene soluble (TS) fraction-derived carbonization products is streamline and partial regional type. The microstructure of products from toluene insoluble (TI) fraction is mosaic and regional type. The structure of toluene insoluble-quinoline soluble (TI-QS) fraction-derived carbonization product is mainly streamline type. Nevertheless, the carbonization product from quinoline insoluble (QI) fraction is constituted with isotropy micron grade isotropic particles.     

中温煤焦油沥青的超临界溶剂抽提和分离

用超临界溶剂在半连续装置上对中温煤焦油沥青（ＭＣＴＰ）进行了抽提和分离，考察了抽提段的实验条件对灰分和吡啶不溶物（ＰＩ组分）脱除率的影响；在分离段使用升温和／或降压法、精馏法调节ＭＣＴＰ族组成分布，并用分步抽提法调节ＭＣＴＰ的族组成。实验表明：用甲苯为超临界溶剂抽提可脱除全部灰分，ＰＩ组分也可在较低的压力下选择性地脱除；采用升温和／或降压法对抽出物可进行一定程度的分离，但对庚烷可溶物（ＨＳ组分）分离的选择性不高；采用精馏法可选择性地脱除ＨＳ组分，但尚需改进设备进一步提高分离效率；采用分步抽提法用石油醚作一次抽提溶剂可高选择性地脱除ＨＳ组分，其选择性在９５％以上。     

Determination of polyaromatic hydrocarbons in coal tar pitch

Different techniques for extracting polyaromatic hydrocarbons (PAHs) from coal tar pitch for their quantitative determination by gas chromatography-mass spectrometry are compared. It has been found that the ultrasonic treatment of a sample allowed the quantitative extraction of PAHs from coal tar pitch. The results of the quantitative determination of PAHs in samples of coal tar pitch obtained by Soxhlet extraction and liquid-liquid extraction with ultrasonic treatment agree within the experimental error range.     

Interaction forces between talc and pitch probed by atomic force microscopy

Colloidal wood resin components present in pulp are collectively called "pitch". The presence of pitch may cause severe problems due to deposits in and on the paper machine. There is thus a need for controlling pitch aggregation and adsorption. To be able to develop more efficient pitch control systems, one needs to develop the understanding of pitch-pitch interactions and of the interactions between pitch and other materials. With this general goal in mind, we present methods for preparing geometrically well-defined pitch particles attached to atomic force microscopy tips. This has enabled us to investigate the interactions between pitch and talc, an additive commonly used for pitch control. We have used model pitch particles consisting of one component only (abietic acid), a mixture of components (collophonium), and particles prepared from real pitch deposits. We show that the forces acting between pitch and talc are attractive and, once the initial approach is made, exert this attraction out to large distances of separation. We present evidence that the formation of bridging air bubbles or cavities is responsible for this interaction.     

Template–polymer commensurability and directed self‐assembly block copolymer lithography

Block copolymer directed self‐assembly (BCP) with chemical epitaxy is a promising lithographic solution for patterning features with critical dimensions under 20 nm. In this work, we study the extent to which lamellae‐forming poly(styrene‐b‐methyl methacrylate) can be directed with chemical contrast patterns when the pitch of the block copolymer is slightly compressed or stretched compared to the equilibrium pitch observed in unpatterned films. Critical dimension small angle X‐ray scattering complemented with SEM analysis was used to quantify the shape and roughness of the line/space features. It was found that the BCP was more lenient to pitch compression than to pitch stretching, tolerating at least 4.9% pitch compression, but only 2.5% pitch stretching before disrupting into dislocation or disclination defects. The more tolerant range of pitch compression is explained by considering the change in free energy with template mismatch, which suggests a larger penalty for pitch stretching than compressing. Additionally, the effect of width mismatch between chemical contrast pattern and BCP is considered for two different pattern transfer techniques. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 595–603     

脱晶蒽油改质煤焦油沥青的研究——中间相非等温动力学

在热转化装置上,对宝钢Ⅰ期焦油沥青（简称I－CTP）及其添加18％、30％脱晶蒽油（简称DCAO）制成的软沥青进行了中间相转化非等温动力学研究,采用积分法求得了有关动力学参数。结果表明,沥青中间相形成过程可以用一级反应来描述。宝钢Ⅰ期焦油沥青活化能为180.02kJ/mol。添加80％脱晶蒽油则提高了原料沥青的反应性,活化能为147.89kJ/mol,不利于优质中间相的形成。     

煤沥青的电化学加氢：Ⅱ.精制沥青的电化学加氢

在隔离式是电解中，用泡沫铅作用阴极，铂作阳极，饱和甘汞电极做参考电极，对太原钢铁公司焦化厂煤沥青经溶剂萃取后所得的精制沥青进行了电化学加氢的研究，考察了电解体系工艺条件对加氢效果的影响。     

Double UV polymerisation with variable temperature-controllable selective reflection of polymer-stabilised liquid crystal (PSLC) composites

In this study, a method of preparing wide-band reflection cholesteric liquid crystals (CLCs) films by UV-radical polymerisation in combination with UV-cationic polymerisation is proposed. Because the helical twisting power (HTP) of the chiral dopant decreases with increasing temperature and the polymerisation rate of UV-initiated free radical polymerisation is faster than UV-initiated cationic polymerisation, by adjusting the temperature, broadband reflective films with non-uniform pitch distribution are obtained. The fractured surface of the polymer network of the broadband reflective films is observed by scanning electron microscopy (SEM), which reveals the presence of non-uniform pitch distribution. In addition, the influences of monomer concentration, UV light intensity and UV curing time on the consequent non-uniform pitch distribution have been studied.