不同路易斯酸对中间相沥青转化的影响

中间相沥青具有高炭化收率、高密度和容易石墨化等特点,使其具有广阔的应用前景。人们投入了大量精力研究AlCl3催化中间相沥青的形成与转化,却很少关注其他金属氯化物的催化研究。本文使用不同浓度的AlCl3和ZrCl4作为催化剂催化蒽的热缩聚反应,结果表明,使用AlCl3作为催化剂的沥青较使用ZrCl4作为催化剂的沥青具有更高的聚合度和更好的光学结构;反应时间的延长和ZrCl4催化剂浓度的增加可以很好地加速热缩聚反应的进行和中间相沥青的形成;在使用ZrCl4作为催化剂时,由于反应进行的速度更慢使更容易对其热缩聚过程加以控制。     

共炭化在中间相沥青调制中的应用

为对沥青进行分子改进，将共炭化反应应用于中间相调制，本文综述了几种不同的共炭化作用机理，并介绍共炭化作用的相容性原理。     

改性煤沥青热转化中间相结构性质与表征

采用实验室自制石英管式炉,以中温煤焦油沥青（CTP01）、改性沥青（CTP02）进行热缩聚反应。通过红外光谱（FT-IR）、拉曼（Raman）、X射线衍射法（XRD）、热重（TG/DTG）以及偏光显微镜对CTP01和CTP02在热转化过程中生成的中间相沥青进行了表征分析。结果表明：在反应温度430℃、恒温时间7 h制得中间相沥青,CTP02内部具有排列规整、取向性更好的芳香片层分子,热聚合后明显相对分子质量变大,芳环上的取代基明显增强,稠环芳烃含量增加;CTP01制得中间相沥青光学各向异性含量较低,很难形成稳定的区域型结构,主要以中小区域镶嵌型为主,而CTP02制得中间相沥青光学各向异性含量较高,易形成广域型结构。     

煤直接液化沥青制备中间相沥青炭纤维的研究北大核心

中间相沥青基炭纤维的性能直接取决于纺丝用中间相沥青,煤直接液化沥青因其饱和烃含量高,氢碳比高,高温融变性好,硫含量低等优点成为制备纺丝用中间相沥青的优良前驱体。本文以煤直接液化沥青为原料,研究不同热缩聚工艺对中间相沥青组成和结构的影响,通过考察其偏光织构、软化点、喹啉不溶物含量、黏温曲线和纺丝时长等指标综合评价可纺性。采用高低温结合多段聚合工艺制得具有大融并体结构、可纺性优良的中间相沥青,并进一步制得具有理想微观形貌的纤维,其拉伸强度为2.03 GPa,拉伸模量达到581 GPa。     

中间相沥青及其炭纤维的显微结构和性能

中间相沥青基炭纤维(CF)的力学性能受中间相沥青的微结构和不熔化、炭化。石墨化过程的影响。本文考察了几种不同原料的中间相沥青的微观结构,乙沥渣油两个馏份的中间相沥青为细镶融并体,是难石墨化物质,而T渣油E馏份中间相沥青是由小球有序堆积形成的一种大的各向异性融并体,是易石墨化物质,中间相的不同结构直接影响CF的力学性能.用电子显微镜观察了CF的结构形态,由T渣油E馏份制成的中间相沥青炭纤维呈现放射状的径向结构,并存在孔隙裂纹.它们主要取决于中间相沥青的原料和不熔化、炭化和石墨化的工艺条件,最终影响CF的力学性能。     

中间相沥青炭纤维研究

本文采用石油重质渣油，通过加压－减压两段热缩聚方法调制中间相沥青，并对其进行了收率测算，元素分析，红外光谱分析、热台偏光显微镜观查等，研究了其组成和结构。将上述纤维经单孔纺丝、预氧化、炭化处理后，利用扫描电镜研究了所得炭纤维的横截面形态结构。实验结果表明：两段式热缩聚可获得中间相含量高、收率、热稳定性及可纺性好的中间相沥青。由该沥青制备的炭纤维横截面呈洋葱皮形态结构，平均直径１０μｍ，拉伸强度１．７８８ＧＰａ，断裂伸长１．１％。     

煤沥青中间相热聚合行为研究

以煤沥青为原料,采用程序升温、多管井式坩埚炉进行热转化反应,研究不同结构反应器中中间相的热聚合行为。试验显示:煤沥青中间相的光学结构与均相成核的中间相沥青相似;另一方面,热转化过程中不同结构反应器内样品的中间相生长存在差异。随着反应时间的延长,样品收率、挥发份产率不断降低,而软化点和甲苯不溶物含量则不断升高。对于不同结构的反应器,等径管内热反应样品的收率、挥发份产率比变径管内样品的偏低,甲苯不溶物含量和软化点则偏高;同时光学结构显示,等径管内中间相球体生成、长大、融并到变形的速率比变径管内样品快。分析认为:由于变径管中段直径的改变,对底端样品中的轻组分产生了中段截流作用,致使热聚合反应程度不同。     

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。     

原料及缩聚条件对中间相沥青性质的影响

本研究用刮膜蒸发器对制备中间相沥青的原料（软化点为６０℃的石油沥青）进行了分离，并分别以未分离的沥青及分离出的重质沥青为原料在不同的条件下调制成中间相沥青。探讨了原料分子量分布及缩聚过程中温度、Ｎ２流量、缩聚时间对中间相沥青族组成分布、软化点和可纺性等性质的影响。     

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.     

精制沥青中间相热转化的研究

以2种精制沥青(LSP和HSP)为原料,通过常压热转化反应,研究了热转化过程中产物的QI和TI随反应时间的变化规律.分析表明,随着反应温度的升高和反应时间的延长,沥青的各向异性组分不断增加.其中LSP沥青生成的中间相小球大于HSP沥青生成的中间相小球.400℃恒温9h,LSP沥青的软化点达到242℃,HSP沥青的软化点达到220℃.     

热聚合温度对煤液化沥青制备中间相沥青的影响

为制备优质的中间相沥青,以煤液化沥青为原料,在不同热聚合温度下制备中间相沥青,采用偏光显微镜、红外光谱仪、XRD、热分析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收率、形貌和结构影响显著。随着温度升高,中间相沥青的收率降至86.2%,H含量降至3.96%,S含量有所下降,残炭率增大;中间相小球体的尺寸增大,逐渐出现融并现象,最终形成广域型中间相;煤液化沥青中的稠环芳烃、芳香烃的含量明显增加,烷烃成分则明显减少;煤液化沥青中的无定型区含量减少,分子的排列与取向性变好。选择低的热缩聚温度(410~420℃),适当延长反应时间有利于反应方向的控制,从而达到制备优质中间相的目的。     

Modified characteristics of mesophase pitch prepared from coal tar pitch by adding waste polystyrene

The toluene soluble of coal tar pitch was carbonized with waste polystyrene. The properties of mesophase pitches were characterized using polarized light optical microscope, apparent viscometer, FT-IR, ¹H NMR and X-ray diffractometer. After adding the waste polystyrene into the toluene soluble of coal tar pitch, the soluble mesophase were was increased from about 9% to 52% and the mesophase pitches were changed from 74% with coarse mosaic texture to 100% with flow domain texture. The mesophase pitches were transformed from thixotropy to unthixotropy. By waste polystyrene added into the toluene soluble of coal tar pitch, the methylene group was increased a lot. The presence of more alkyl groups modified the characteristics of mesophase pitches and improved the assembly of mesophase pitch molecules.     

Rheostructural studies on a synthetic mesophase pitch during transient shear flow

The steady, shear viscosities of a synthetic mesophase pitch (Mitsubishi AR-HP) obtained from rate-sweep experiments at 0.1-10 s⁻¹ exhibited shear-thinning (region I) and plateau responses (region II), but displayed a hysteresis during the decreasing rate sweep. Transient tests revealed that the shear stress (and consequently the shear viscosity) displayed a local maximum and a minimum before approaching a steady state. Following steady flow at 1 s⁻¹, a reversal of flow direction or a very short interruption in flow did not lead to the maxima or minima in the transient shear stress, but the maxima and the minima reappeared in the transient stress after a rest time of ∼1000 s. An experimental protocol was developed to preserve the rheological samples, and their microstructure was characterized in three orthogonal planes for the initial and final states. The initial microstructure was found to have a weak, but preferred, orientation of mesophase layers in the radial direction of the rheometer cone-plate (due to the initial squeezing flow). The initial microstructure changed to a flow-aligned fibrous structure after shearing in the viscometric flow.     

中间相沥青制备方法及应用

由于中间相沥青原料丰富、价格低廉、性能优异以及具有较高端炭产率等优点,因此中间相沥青被广泛应用于制造多种重要的高级炭材料,如超高模量碳纤维、超高比表面积活性炭、超高功率电极用针状焦、中间相沥青基泡沫炭等,而这些高级炭材料已被广泛应用于日常生活、工业和国防等众多领域且都已发挥着巨大作用。因此开展对中间相沥青的制备方法和应用研究具有重要的理论和实际意义。     

Liquid crystal surface anchoring of mesophase pitch

Mesophase pitch, in common with other liquid crystalline substances, exhibits preferred angles of molecular orientation at its boundaries with other phases. These orientations, or surface anchoring states, are important because they influence the ultimate graphene layer arrangement in a variety of carbon materials where the pitch precursor encounters a composite filler, a free surface, a bubble cavity, or the surfaces of processing equipment such as a fiber spinneret. This paper presents experimentally determined anchoring states for two mesophase pitches at free surfaces, and on twenty solid substrates. Edge-on anchoring is found to be the most common state, occurring on the free surface, on some metals, on PTFE, and on all oxides with the exception of the lamellar material mica. The optical texture associated with the edge-on films is observed to be stable during carbonization up to 1200 °C. Face-on anchoring is observed on carbon graphene planes, mica and the metals Pt, Ni, and Ag. Trends in the data are discussed in terms of the strength of pitch/substrate intermolecular forces relative to π-π bonding between large discotic mesogens within the pitch. The implications for the structure and properties of carbon materials are discussed.     

A novel method to obtain a petroleum-derived mesophase pitch suitable as carbon fibre precursor

This paper studies a novel method for the preparation of mesophase pitches suitable as carbon fibre precursors. A series of thermally treated petroleum pitches with mesophase contents ranging from 10.8 to 52.2 vol.% was obtained from pitch A-240. Separation of the phases was initially attempted by hot filtration, a suitable method for separating the phases in thermally treated coal-tar pitches. Although filtration failed for the petroleum samples, the behaviour observed led to the development of a new separation method that consists in the sedimentation of the mesophase. This method, after optimisation, yielded pitches with mesophase contents up to 97 vol.%, which were easily spun into carbon fibres of reasonable mechanical properties.     

Structure of carbon fiber obtained from nanotube-reinforced mesophase pitch

Flow-induced orientation of discotic mesophase precursor typically leads to a center-origin, radial microstructure in the resulting carbon fibers. In the present study, we report the microstructure of carbon fibers that were derived from mesophase pitch that was modified using carbon multi-wall nanotubes (MWNTs). For an MWNT content as low as 0.1 wt.%, the microstructure was found to be fairly random (rather than radial).