预氧化对中间相沥青泡沫炭结构和性能的影响机制研究

研究了预氧化对萘系中间相沥青的表面化学性质、族组成分布以及对泡沫炭的发泡条件、泡孔形成、孔结构及微结构的影响机制.当中间相沥青经210℃预氧化2h后,其喹啉不溶物含量增加32.3%,族组成分布变窄.在600℃/3MPa发泡条件下,所制石墨化泡沫炭的平均孔径、压缩强度分别为200μm、2.8MPa.     

由中间相沥青制备泡沫炭:Fe(NO3)3的影响

以中间相沥青为前驱体制备高性能泡沫炭，在考察中间相沥青、Fe（NO3）3及其混合物热分解行为的基础上，着重研究了Fe（NO3）3对制备中间相沥青基泡沫炭的影响，揭示了Fe（NO3）3对泡沫炭孔泡结构的影响规律及其作用机制，初步研究了在泡沫炭炭化过程中形成的Fe／C之物相结构及其石墨化行为。结果表明，在不同的炭化温度下，Fe在泡沫炭中的存在形态各异；Fe物种的存在有利于提高泡沫炭的石墨化程度。     

超临界发泡制备泡沫炭及其泡孔形成机理

分别以中间相沥青和甲苯作碳质前驱体和发泡剂,采用超临界发泡技术制备出孔径为10~25μm的泡沫炭,并着重研究了超临界发泡条件对泡沫炭的孔形及韧带结构的影响。超临界发泡包括成核、扩散、聚集及膨胀过程,同时泡孔的形成也是热力学、动力学及力学行为综合作用的结果。由于中间相沥青中存在轻组分,超临界发泡过程伴随着自发泡过程,由此可获得层次孔结构的泡沫炭。     

超临界流体制备中间相沥青泡沫炭及其导热性能研究

以奈系中间相沥青为原料,在初始压力2.0～4.0MPa的范围内,利用甲苯作为超临界溶剂制备中间相沥青基泡沫,并经氧化炭化和石墨化获得了三维网状结构的泡沫炭,利用扫描电镜、x射线衍射、激光导热测定仪分析了泡沫碳的结构和导热性能,研究了泡沫炭结构与其导热性能的关系.结果表明,不同条件下所制备得到的泡沫炭泡孔结构和孔分布的不同对导热系数影响较大,在2350℃下石墨化后导热系数达到42(W/mK).     

前驱体对炭泡沫孔结构的影响

分别以煤沥青、石油中间相沥青和AR沥青为前驱体制备炭泡沫材料。采用GPC测定前驱体分子量,SEM观察所制炭泡沫的孔结构,光学显微镜测量所制炭泡沫的孔径及其分布。结果发现,由于煤焦油沥青不含中间相,且QI含量较高,导致在实验条件下不能直接制备出合格的炭泡沫。以石油中间相沥青和AR沥青为原料均能制备出具有分布均匀开孔结构,且微观各向异性的炭泡沫。由AR沥青制备的炭泡沫呈现平均孔径较小(212μm)、孔壁较薄、孔径分布较窄(180μm~300μm)、开孔率较高、以及韧带排列较规整等特点,表明低QI含量、低分子量且分布较窄的前驱体有利于发泡。     

发泡温度对炭泡沫结构及性能的影响

以AR中间相沥青为原料,采用中间相沥青自发泡法在初始发泡压力为3MPa、发泡温度在390～450℃范围内制备了4种炭泡沫。利用SEM观察了炭泡沫的孔隙结构,并测定了其体积密度、抗压强度和导热系数,考察了发泡温度对炭泡沫结构及性能的影响。结果表明,采用较低的发泡温度(430℃)可以消除大的孔隙缺陷;当发泡温度为410℃时,炭泡沫导热系数最高,为0.256W/(m·K)。     

中间相沥青基活性泡沫炭的制备及其电化学性能研究

以中间相沥青为前驱体,经自挥发发泡法、KOH活化法制备的中间相沥青基活性泡沫炭作为超级电容器电极材料。采用扫描电镜、X射线衍射和低温(77K)N2吸附法对中间相沥青基活性泡沫炭的表面形貌和微观结构进行表征。中间相沥青基活性泡沫炭的比表面积为2700m2/g,总孔孔容为1.487cm3/g。通过恒流充放电、循环伏安和交流阻抗测试,考察了中间相沥青基活性泡沫炭作为超级电容器电极材料的电化学性能。在电流密度为0.02A/g时,中间相沥青基活性泡沫炭的比容量为240.48F/g,能量密度为33.4Wh/kg;在电流密度为5A/g时,比容量为166.68F/g,具有良好的电化学特性。     

碳纳米管对中间相沥青基泡沫炭热导率和力学性能的影响

利用超声分散的方法,使改性后的碳纳米管(m-CNTs)在中间相沥青中均匀分散,通过自挥发发泡法制备出不同m-CNTs含量的中间相沥青基泡沫炭。用TEM、SEM等分析方法研究了不同m-CNTs的添加量对泡沫炭结构和性能的影响。实验结果表明,与CNTs相比,m-CNTs的分散性有所提高;添加一定量的m-CNTs后,泡沫炭的平均泡孔尺寸有所减小,并且微裂纹数减少;当m-CNTs的添加量达到5%(质量分数)时,泡沫炭的热导率和压缩强度均达到最大,分别为137W/(m.K)和12.1MPa。     

CVD PyC对炭泡沫结构及性能的影响

以AR中间相沥青为原料,采用中间相沥青自发泡法在发泡压力为0.1、3.0MPa,发泡温度为450℃的条件下制备了两种不同体积密度的炭泡沫CF-1和CF-2.将CF-1经过10h和70h化学气相沉积热解炭(CVDPyC)处理后得到炭泡沫CF-1-PC1和CF-1-PC2.测定了炭泡沫的抗压强度和导热系数,利用SEM和光学显微镜观察了炭泡沫的孔结构,考察了CVD PyC对炭泡沫结构及性能的影响.研究结果表明,CVD PyC处理可以增加炭泡沫韧带宽度,封填孔壁微裂纹;沥青炭和热解炭之间无明显界面,结合良好;经过CVD PyC处理后得到的CF-1-PC1和CF-1-PC2的体积密度、抗压强度、导热系数分别为, 0.196g·cm-3、1.89MPa、0.314W·m-1·K-1和0.461g·cm-3、11.93MPa、1.581W·m-1·K-1.     

炭泡沫的制备、性能及应用

炭泡沫是具有广阔应用前景的新型炭材料,自出现起就成为炭材料研究中的热点.以中间相沥青基炭泡沫为重点,介绍了炭泡沫的发展历史和研究进展,总结了现有炭泡沫制备技术,包括发泡剂发泡法、模板法、中间相沥青自发泡法和限空间法等,概述了炭泡沫的性能和应用前景,并展望了其发展方向.     

基于气体捕捉法的泡沫Ti-6Al-4V等温发泡规律研究

为了确定气体捕捉法制备泡沫Ti-6Al-4V等温发泡过程中孔隙率和微观孔洞的变化规律,在不同发泡温度及发泡时间下制备了泡沫Ti-6Al-4V.运用阿基米德原理对泡沫Ti-6Al-4V的孔隙率进行测量,通过OM和SEM对其微观特征进行观察.研究表明:泡沫Ti-6Al-4V的孔隙率及孔径均随等温发泡温度升高而增加;但当发泡温度大于950℃时,孔隙率和孔径均减小,且孔洞形态由球形变成多边形,这是由于基体内生成大尺寸β相造成的.增加发泡时间能以促进孔洞长大的方式提高泡沫Ti-6Al-4V的孔隙率,球形孔洞数量随着发泡时间的增加逐渐增多.经950℃/10 h发泡得到了孔隙率34.2%、孔径平均值156μm、孔洞为球形且分布弥散的泡沫Ti-6Al-4V.     

一种简单的溶剂热法合成炭微球

利用一种简单的溶剂法合成炭微球.采用无水乙醇作为碳源和溶剂,以无水乙醇还原Ni(Ac)_2得到的Ni作为催化剂,最佳反应条件:温度500℃、时间48h.采用X-射线衍射仪(XRD)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)以及Raman光谱对样品的成分、晶体结构和形貌进行了分析.结果表明:产品为圆球形和纺锤形两种形貌的炭微球,圆球形炭微球直径为1μm～2μm,纺锤形炭微球直径为1μm～2μm,长度为3μm～6μm.此法简便易行,炭微球的产率高达95%以上,且具有较规则的形貌和窄的尺寸分布.     

Mesophase AR pitch derived carbon foam: Effect of temperature, pressure and pressure release time

For the carbon foam production, mesophase pitch pellets are heated up in a reactor in an aluminum mold to specified pressures and finally pressure released to obtain green carbon foam samples. The green foams were then stabilized and carbonized. The effects of various temperatures, pressures and pressure release times on production of carbons foams are investigated. The samples are subjected to SEM, mechanical testing, mercury porosimetry analysis and bulk density determination for characterization. For the processing temperatures of 553, 556, 566 and 573 K, the densities of the foams produced were 380, 390, 410 and 560 kg/m³ respectively. The compressive strengths of the respective samples were increased from 1.47, to 3.31 MPa for the lowest and highest temperatures. The processing pressures were 3.8, 5.8, 6.8 and 7.8 MPa. The bulk density and the compressive strength of the carbon foams produced were changed from 500 to 580 kg/m³, and 1.87 to 3.52 MPa for the lowest and highest pressures respectively. Pressure release times of 5 s, 80 s, 160 s and 600 s are used to produce different carbon foam samples. The densities and the comprehensive strengths measured for the highest and lowest pressure release times changed from 560 to 240 kg/m³ and 3.31 to 2.16 MPa respectively. The pore size distribution of all of the products changed between 0.052×10^-6m and 120×10^-6m. Increase in temperature and pressure increased the bulk density and compressive strength of the carbon foams. The mercury porosimetry results show % porosity increase with increasing temperature and pressure. On the other hand, increase in pressure release time decreased the bulk density, compressive strength of the carbon foam.     

Enhancement in insulation and mechanical properties of PMMA nanocomposite foams infused with multi-walled carbon nanotubes

In this study, PMMA/CNTs composite materials with carboxyl-multi walled carbon nanotubes (c-MWNTs) or untreated MWNTs were prepared via in-situ bulk polymerization. The as-prepared PMMA/CNTs composite materials were then characterized by Fourier-Transformation infrared (FTIR) spectroscopy, and transmission electron microscopy (TEM). The molecular weights of PMMA extracted from PMMA/CNTs composite materials and bulk PMMA were determined by gel permeation chromatography (GPC) with THF used as the eluant. The PMMA/CNTs composite materials were used to produce foams by a batch process in an autoclave using nitrogen as foaming agent. The cellular microstructure, insulation and compressive mechanical properties of PMMA/CNTs composite foams were also investigated in detail. Compared to neat PMMA foam, the presence of CNTs increases in cell density and reduces cell size. The insulation and compressive mechanical properties of PMMA/CNTs composite foams were found to improve substantially those of neat PMMA foam. In particular, 22.6% decrease in thermal conductivity, 19.7% decrease in dielectric constant and 160% increase in compressive modulus were observed with the addition of 0.3 wt% carboxyl-multi walled carbon nanotubes (c-MWNTs).     

加热条件对炭泡沫材料孔结构和性能的影响

以AR沥青为原料,利用高压釜在不同恒温条件下制备了炭泡沫,并测定了其孔结构、体积密度、显气孔率、压缩强度、常温热导率以及微晶参数.结果表明:相对于短恒温时间,长恒温时间制得的炭泡沫孔径大(412nm)、显气孔率高(83.82%)、体积密度小(0.34g/cm~3)、压缩强度高(4.92MPa),多孔连通结构更丰富.经过石墨化处理后,石墨泡沫呈现出较高的常温热导率(71.34W/(m·K))和较小的层片间距d_(002)(0.33556nm).石墨泡沫的常温比导热率能达到210(W·(m·K)~(-1)) /(g·cm~(-3)),是铜的5倍,铝的4倍.     

石油油浆常压研制泡沫炭

以重油催化裂化(FCC)油浆富芳油为原料,经过热解制备中间相沥青,在常压下制备出孔径为150um～400um的沥青基泡沫,然后在马弗炉中炭化制得泡沫炭.定性考察了沥青分子量分布对沥青泡沫形成的影响,以及其沥青泡沫在空气中,在800℃～1400℃炭化温度范围炭化得到泡沫炭产品的光学微观形态、微晶及密度等的变化情况.发现:热解过程中,沥青分子量分布越宽,最终制得的中间相沥青发泡越不利;沥青泡沫在空气中炭化过程中,随炭化温度升高泡沫形态逐渐变形变大,原来的闭孔结构逐渐被打开,同时产生一些新的小孔.在炭化温度800℃以前,先经历一个微品、闭孔被破坏的过程,其微晶尺寸由2.3 nm减小到1.5 nm,微晶品格层间距由0.3459 nm增加到0.3477nm;800℃后,经历一个微晶生长过程,微晶尺寸由1.5 nm增加到4.2nm,微晶品格层间距由0.3477 nm减小到0.3454nm;在整个炭化过程中,泡沫产品的密度一直呈减小趋势,从原有的0.52g/cm3减小到0.16g/cm3.     

Preparation of SiC foams by CVI-R technique with SiCl4/H2/CH4 system

Silicon carbide foams were prepared by the chemical vapor infiltration-reaction (CVI-R) of SiCl₄/H₂/CH₄ with carbon foam derived from mesophase pitch (MP), which had not only high bending strength but also low bulk density. The influence of the CH₄/SiCl₄ ratio in reaction atmosphere on the properties of as-prepared silicon carbide foams was investigated in detail. As the CH₄/SiCl₄ ratio was 0.25, resultant foam possessed the highest bending strength of 17.13 MPa. At the same time, correlations between properties and microstructure are also discussed.     

Controlling bubble density in MWNT/polymer nanocomposite foams by MWNT surface modification

Polymer nanocomposite foams are promising substitutes for polymeric foams. Carbon nanotube/polymer nanocomposite foams possess high strength, low density, and can be made conductive. Creating polymer foams with controlled foam morphology is of great importance for controlling foam properties. The foam morphology is influenced by the foaming conditions and filler properties. For carbon nanotube/polymer composite foams, dispersion state and aspect ratio of the carbon nanotubes have been shown to influence the bubble density and bubble size. In the current study, the influence of carbon nanotube surface chemistry on the bubble density of multi-walled carbon nanotube/poly(methyl methacrylate), MWNT/PMMA, nanocomposite foams was investigated. The surface of the MWNTs with controlled aspect ratio was covalently modified with glycidyl phenyl ether (GPE). Surface modified MWNT/PMMA nanocomposite foams were produced using a supercritical carbon dioxide foaming process. At constant MWNT concentration, the bubble density of polymer nanocomposite foams filled with GPE surface modified MWNT was found to be several times higher than that of polymer nanocomposite foams filled with nitric acid treated MWNT. After the MWNTs were modified with GPE, the surface chemistry of the MWNT became the dominant factor in determining the bubble density while the MWNT aspect ratio became less influential.     

炭化压力对沥青成焦形貌及航空刹车用C/C复合材料浸渍增密效果的影响

将武钢中温沥青和太钢高温沥青在不同压力下炭化，进一步对所得沥青焦进行了高温热处理，利用扫描电子显微镜（SEM）和光学显微镜观察所得沥青焦形貌。结果表明；低压炭化时，沥青焦体积密度小，疏松、多大孔，主要为流线区域型各向异性结构；高压炭化时，沥青焦体积密度明显变大，孔变小且均匀分布，主要为小区域和细镶嵌型各向异笥显微结构。考察了不同炭化压力对浸渍增密航空刹车用C／C复合材料的增密效率的影响，结果显示，对整个沥青而言的宏观残炭率明显高于只针对样品而言的实际残炭率，因此有必要进行高压浸渍／炭化实现快速增密。利用XRD和显微硬度测试仪检测了不同炭化压力所得沥青焦热处理后的石墨化度和显微硬度，发现高压下形成的沥青炭更难于石墨化，但石墨化度与显微硬度的热处理后的粗糙层（RL）CVD炭有较好的可比性。