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.     

Preparation of mesophase-pitch-based carbon foams at low pressures

A simple method for preparing the mesophase-pitch-based carbon foams at low pressures through prolonging the soaking time in the preparation process of the mesophase pitch was disclosed. The physical properties, morphologies and the crystal structure of the as-obtained foams were investigated. Bulk density of the resultant carbon foams cover a range 0.514-0.624 g/cm³, under the preparation pressure range 0.5-2 MPa. The SEM micrographs revealed that the thermal shrinkage of the graphitized foams derived from the higher softening point mesophase pitch was less than that of the foam from the lower softening point; Optical micrographs showed that higher softening point mesophase pitch derived carbon foams exhibited better orientation and less microcracks in both junctions and ligaments; The XRD results revealed that higher softening point pitch derived graphitized foams exhibited smaller interlayer spacing and larger crystallite size. The properties of the carbon foam can be severely affected by the properties of the precursor, so it is critical to tailor the properties of the pitch precursor so as to obtain high performance and low cost products.     

煤焦油沥青乳化用作燃料油的研究

用软化点为 38.5℃的软沥青作原料 ,在合适的工艺条件下 ,制成含沥青 6 0 %～ 70 %的沥青乳液 (乳液的沥青含量为沥青量与洗油加入量之和 )。该乳液具有流动性好、储存稳定等优点。本研究结果表明 ,沥青乳液可以用作燃料 ,对解决煤沥青的利用具有重大意义     

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.     

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.     

热聚合-氧化法制备高β树脂改性沥青

以中温沥青为原料,通过溶剂萃取沉降分离获得低喹啉不溶物含量(QI<0.1%)的精制沥青。对精制沥青进行热聚合-空气氧化改性处理,得到高β树脂含量的改性沥青。经特定热聚合条件处理后,研究了空气氧化阶段的反应温度、氧化时间和空气流量对沥青改性的影响。实验结果表明,在空气氧化阶段,当氧化温度为280℃,氧化时间为2h,空气流量为0.04m³/h时,可以获得软化点为220℃、甲苯不溶物为61.59% 、喹啉不溶物为4.35%、结焦值为78.44%,β树脂含量为57.24%的优质改性沥青。     

Rheological characteristics of coal tar and petroleum pitches with and without additives

An extensive study of rheological characteristics of coal tar and petroleum pitches with and without additives, namely, petroleum coke, natural graphite and carbon black has been made. It is found that all pitches, pure or mixed with a carbon additive are not Newtonian as reported in the literature, but behave Theologically as Bingham plastics with certain yield stress and plastic viscosity at all temperatures of measurement between 85–180°C. The yield stress and plastic viscosity both decrease with increase in temperature of the pitch. A pure petroleum pitch having the same softening point as that of a coal tar pitch is found to have a lower viscosity compared to that of the latter at all temperatures of measurement. This suggests that the criterion of softening point as a measure of suitability of a coal tar pitch binder in the manufacture of artificial carbon is not sufficient for petroleum pitches. Addition of ten parts of carbon black by weight of pitch results in a considerable decrease in viscosity change with temperature of the coal tar pitch compared to almost insignificant change in the case of the petroleum pitch of the same softening point. However, the addition of petroleum coke or natural graphite makes the pitch more viscous but does not change the temperature dependence of viscosity of either of the two types of pitches. The implications are discussed.     

两种煤沥青的浸渍性能分析

采用热重／差热分析、核磁共振、热台显微镜在位观察等方法,对太钢改质沥青和北京焦化厂中温煤沥青的软化点、元素组成、结构、组成、粘度进行了分析,以评价其作为浸渍沥青的性能。结果表明：太钢改质沥青比北京焦化厂中温煤沥青的吡啶不溶物含量高,芳香度低,高温流动性略好,产碳率也高。     

聚乳酸形状记忆发泡材料制备与形状记忆性能研究

利用超临界CO₂间歇性降压法,制备一系列不同微观结构的聚乳酸(PLA)发泡材料,并探究环境温度、保压压强对PLA发泡材料微观形貌、孔隙率、泡孔尺寸的影响,并分析PLA发泡材料的形状记忆性能。结果表明：制备的PLA发泡材料具有结构可调控、形状记忆性能良好等特点。当保压压强为17.24 MPa,环境温度为140℃,PLA发泡材料具有较大膨胀率,且泡孔形貌均匀,具有良好形状记忆性能。低于20℃的变形温度下,PLA发泡材料的形状记忆固定率与回复率较好,其形状记忆回复率达到90%以上。     

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.     

改性煤沥青在炭素生产中的应用

概述了沥青的分类和性质以及沥青改性、改性方法,讲述了在改性煤沥青生产应用中的要求,改性沥青的应用过程、效果和缺点。根据实验数据阐述了在改性煤沥青生产应用中的温度选择。结果表明,改性煤沥青特有的高软化点和粘度决定了在熔化、输送和混捏过程对温度的要求较高。数据分析表明软化点不能够准确指导下料温度,而粘度与下料温度呈正比例关系。因此,粘度可以作为下料温度的一个可靠的参考指标。     

煤沥青基功能碳材料的研究现状及前景

我国煤沥青资源丰富,但深加工技术落后,产品附加值低,实现煤沥青高附加值利用是亟待解决的重大课题。本文介绍了以煤沥青为原料合成高性能功能碳材料的主要技术,重点阐述了以煤沥青为原料制备中间相沥青、多孔碳材料、碳纤维、二维纳米碳材料及碳基复合材料的研究进展。分析表明,高芳香性和高缩合度分子结构所引起的强π-π相互作用是阻碍煤沥青基高性能功能碳材料设计合成的瓶颈问题。通过催化聚合、氧化、共热解等技术手段可有效改善煤沥青分子结构及其物理、化学性质。结合模板复制、物理/化学活化、界面诱导以及催化石墨化等技术可实现多种功能性碳材料结构设计与表面化学性质调控。发展煤沥青分子结构调控新技术作为改善煤沥青基碳材料性能的重要策略,需要系统深入研究。     

煤沥青改性后流变性能的变化分析

为了探讨对苯二甲醛(TPA)对煤沥青改性后流变性能的变化,采用旋转黏度计测定了煤沥青及TPA改性的煤沥青的表观黏度,研究了表观黏度与温度的关系;采用示差扫描量热法研究了煤沥青和TPA改性的煤沥青的热行为。结果表明,TPA改性的煤沥青的黏度与温度的关系曲线呈现W型,在200℃～225℃处于低黏流区,表观黏度值200mPa.s～400mPa.s,可以作为浸渍剂煤沥青使用;TPA改性的煤沥青在高于225℃时,表观黏度值迅速上升;TPA改性的煤沥青在低黏度区域具有较低的活化能,这对煤沥青的浸渍工艺有益。     

PMI泡沫材料的制备及性能研究

采用偶氮二异庚腈(ABVN)为引发剂,尿素/甲酰胺为复合发泡剂制备了一种高性能聚甲基丙烯酰亚胺(PMI)泡沫材料。重点考察了不同配比的混合发泡剂用量对PMI泡沫材料性能的影响。结果表明:通过改变两种发泡剂的用量可以获得泡孔均匀且密度为38.39⁷5.99 kg/m3的PMI泡沫材料,而PMI泡沫的力学性能和热性能与泡沫密度呈正相关。当尿素和甲酰胺的用量都为1 phr时,所得PMI泡沫材料具有最佳综合性能,其拉伸强度和压缩强度分别为2.0 MPa和1.42 MPa,玻璃化转变温度(Tg)为217.7℃。     

碳纤维用基体前驱体煤沥青的改性研究

煤沥青经喹啉萃取后,以三氟化硼乙醚和硝基苯作为催化剂,在氮气氛下热缩聚制得改性沥青,并对改性沥青的工艺进行初步研究;利用FT-IR、热分析仪对改性沥青的结构和热稳定性进行了分析。结果表明改性后沥青脂肪族侧链明显减少,芳构化程度增加,热失重率减小,适合用于制备碳纤维。     

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。     

A study of the properties of carbon foam reinforced by clay

A novel carbon foam with high strength and very low thermal conductivity was prepared by thermal treating of coal tar based mesophase pitch mixed with montmorillonite clay. SEM observation showed that less micro-cracking appeared on the cell wall of foam by adding of clay-montmorillonite. Foam mechanical properties were improved and its thermal conductivity was markedly decreased. The compressive strengths were increased by 64%, 96% and 100% when the additive amounts of clay were 2%, 5% and 10% (wt%), respectively. Due to the high thermal insulation and lamellar structure of clay, the thermal conductivity of carbon foam decreases from 2 W/m K to 0.25 W/m K.     

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.     

煤焦油喹啉不溶物压滤脱除和超净沥青制备

以高温煤焦油为原料,在自制小型压滤装置上脱除喹啉不溶物(QI),并对滤后煤焦油进行超临界流体萃取分馏制备超净沥青。结果表明,当滤布孔径1 250目、温度125℃、压力0.5MPa时,煤焦油中的QI质量分数可降低到0.037%。对压滤后的焦油进行超临界萃取,所制沥青的QI和甲苯不溶物质量分数分别达到0.10%和20.31%,可满足制备高性能炭素材料前驱体的要求。     

溶剂沉降法制备浸渍剂沥青

通过溶剂沉降法脱除各种原料煤沥青中的喹啉不溶物（QI）,再用减压蒸馏去除溶剂,得到浸渍剂沥青产品,探讨了脱除喹啉不溶物的操作条件,包括溶剂配比、沉降温度、沉降时间、减压蒸馏温度以及对不同原料制备的浸渍沥青产品性能比较,最后以曲靖中温沥青为原料制得了软化点83 ℃,喹啉不溶物0.084%,结焦值49.32%的浸渍剂沥青产品。