铁-硫协同作用对甲苯热解产物的影响

以甲苯为碳源，二茂铁为催化剂前躯体，噻吩为生长促进剂，在不同条件下通过甲苯催化热解反应得到不同的炭产物。借助TEM和XRD考察了催化剂和促进剂对热解产物形貌和结构的影响。研究发现，不使用任何催化剂和促进剂时，甲苯热解产物为纳米级球状炭颗粒，且部分颗粒之间会发生各向异性排列，形成链状物。单独使用二茂铁时，产物为球状炭包裹铁纳米颗粒。而二茂铁和噻吩同时使用时，产物的形貌随噻吩浓度的不同而变化。结果表明，铁和硫的协同作用对甲苯热解的反应过程和产物形貌影响很大。     

用Weibull统计方法评价Ni-P镀层对炭纤维抗拉强度的影响

采用化学镀法获取Ni-P镀层炭纤维.通过SEM和XRD考察了未镀和已镀Nj-P炭纤维表面形貌和微观结构的变化,借助EDS研究了其表面元素的变化,利用Weibull统计分布探讨了Ni-P镀层对炭纤维单丝抗拉强度的影响.结果表明:Ni-P镀层使炭纤维表面缺陷减少,外界应力经过Ni-P镀层向纤维传递,改变了炭纤维的断裂机理.当镀层厚度为0.149um时,抗拉强度达到最大值3.10GPa,比未镀的增加8.77%,说明Ni-P镀层能够提高炭纤维抗拉强度.     

微螺旋炭纤维的制备与表征

采用溶剂热法合成出硫化镍, 并将其作为催化剂, 催化热解乙炔制备出微螺旋炭纤维. 通过SEM、FT-IR和XRD分析了催化剂和微螺旋炭纤维的形貌和微观结构. 结果表明: 硫化镍催化颗粒表面光滑、为规则的六方相结构, 直径为1~2 μm; 微螺旋炭纤维具有双螺旋结构, 截面为矩形, 具有相同的螺径. 微螺旋炭纤维分子结构中既含有不饱和的C=C双键, 又含有饱和的-CH₂-和-CH₃基团, 其微观结构整体有序度较差, 存在一定量的无定型炭和晶体缺陷, 石墨化度低.     

高温处理对螺旋炭纤维微观拓扑结构的影响

对高温处理前后螺旋炭纤维的微观拓扑结构进行了探究与表征,结果表明,制备态螺旋炭纤维具有类似年轮状结构的近圆形横截面,在纵截面上体现为近似鲱鱼骨结构,其石墨微晶尺寸小、取向度差;高温处理后,其三维结构可理想地看作是由石墨微晶以具有锥角的多面柱体形式沿螺旋方向堆叠而成,表观上炭纤维显示为尺寸均匀的多面柱体形貌。X射线衍射和Raman散射结果从宏观量级上证明了样品微观尺度有序度得到提高。为基于结构的性能预测和应用设计提供了可靠的参考。     

掺杂难熔金属碳化物对炭/炭复合材料烧蚀微观结构的影响

详细分析和比较了3D炭／炭复合材料及其添加难熔金属碳化物的试样在三种烧蚀条件下的烧蚀结果、微观结构及形貌。SEM观察结果显示，纤维与基体间的界面优先烧蚀现象对纯炭／炭试样是普遍存在的，相反，对难熔金属碳化物掺杂的炭／炭试样而言，纤维却总是优先被烧蚀；纤维单丝相对基体优先烧蚀越明显，材料宏观烧蚀率越大。对纯炭／炭试样烧蚀表层区的TEM观察结果表明，在烧蚀过程中炭纤维和基体炭均发生明显的微观结构变化，具体表现为炭纤维的微晶尺寸显著长大，而基体炭原有层片区则出现柱状炭。烧蚀测试条件对材料宏观和微观形貌及烧蚀机理都有影响：     

微波等离子体法合成洋葱状富勒烯的研究

在微波等离子体条件下, 以乙炔炭黑/二茂铁为原料, 低温合成纳米洋葱状富勒烯(Nano-structured Onion-like Fullerenes: NSOFs). 采用HRTEM、Raman和XRD等分析方法对产物的形貌、尺寸、微观结构及其物相结构进行了表征. 结果表明, 以乙炔炭黑/二茂铁为原料可大量合成NSOFs, 其外观呈准球状或多面体状、实心、直径分布均匀, 最外碳层由闭合的、呈波浪状的石墨片构成.     

热等离子条件下Fe2O3催化裂解甲烷制备纳米炭纤维

以Fe2O3粉末为催化剂,N2,H2混合气体为等离子工作气,常压条件下裂解甲烷制得不同类型的纳米炭纤维.利用SEM、TEM、热重、XRD和拉曼光谱等表征手段揭示甲烷流量对纳米炭纤维(CNFs)形貌、纯度和结晶度的影响.结果表明:甲烷流量为0.3m3/h时,产物形貌为结晶度良好的空心套杯状纳米炭纤维,甲烷流量加大至0.5...     

C/C复合材料显微结构的微米、纳米尺度研究

利用扫描电子显微镜、高分辨透射电子显微镜以及拉曼光谱对化学气相渗透C/C复合材料的形貌特征、显微结构以及石墨化度进行了系统表征.结果表明,热解炭是由厚度在几十到几百纳米的片层结构组成,这些片层结构围绕炭纤维呈层状排列;热解炭为粗糙层结构,在离子束的轰击下很容易撕裂和扭折.炭纤维/热解炭界面上存在一个宽度大约为15nm的无序区,该区域的形成可能与热解炭的沉积工艺有关.炭纤维和热解炭的石墨化度均很低,热解炭的R(R=ID/IG D')值由内层到外层逐渐降低.     

具有中间相沥青过渡层的炭/炭复合材料的微观结构与力学性能

采用液相浸渍-炭化和CVI复合工艺, 制备出在炭纤维和热解炭之间具有中间相沥青过渡层的炭/炭复合材料, 借助偏光显微镜、扫描电镜、透射电镜以及力学性能测试研究了所制备的炭/炭复合材料的微观结构与力学性能. 结果表明: 在偏光显微镜下中间相沥青炭的光学活性高于热解炭的光学活性, 中间相沥青炭在SEM和TEM下均呈片层条带状结构, 热解炭在SEM下呈“皱褶状”片层结构, 在TEM下为粒状结构; 在HRTEM下, 中间相沥青炭、热解炭和炭纤维的晶化程度依次降低. 在加载过程中, 材料内部多层次的界面通过改变裂纹扩展路径而延缓其扩展速度, 在断口形貌上体现出锯齿状的断裂形式, 纤维拔出长度适中, 材料表现出韧性破坏的断裂特征. 材料具有较高的力学性能, 抗弯强度达到244MPa, 断裂韧性达到9.7MPa·m^1/2.     

石墨化温度对炭纤维微观结构及其力学性能的影响

以通用型PAN基炭纤维为原材料，通过1800℃～3000℃连续高温石墨化处理，制备了不同性能的炭(石墨)纤维；采用SEM、XRD、RAMAN、元素分析仪、万能材料测试机等分析手段研究了石墨化温度对炭(石墨)纤维微观结构、元素含量、表面形态及其力学性能的影响。实验表明：随着热处理温度的提高，炭纤维中非碳元素(氮、氢)的含量逐渐减少而碳元素质量分数却从92．62％增加到99．99％；纤维的微观结构也从二维乱层石墨结构向有序的三维层状结构发展，表现为石墨晶体层间距d。随处理温度的提升逐渐减小、d100和d110与La和Lc不断增大，纤维抗拉强度呈下降趋势、弹性模量呈上升趋势。     

Carbon micro/nano spring structures in the absence of sulphurous promoter by CCVD method

Carbon microcoils are generally prepared by catalytic chemical vapor deposition of acetylene, using Ni as the catalyst and thiophene as the promoter. In this work, a new catalyst has been developed on purpose to avoid the introducing of noxious and unpleasant thiophene during the reaction process. The products obtained at temperature of 740 degrees C were pure, regular and had perfect morphology. Scanning electron microscopy and Raman spectroscopy were employed to characterize the asprepared carbon microcoils.     

Toluene pyrolysis in an electric ARC: Products analysis

Toluene pyrolysis in a submerged carbon arc produced at least 72 different molecular species as detected by gas-chromatography coupled with mass spectrometry (GC-MS). The most abundant products found were bibenzyl (1,2-diphenylethane), naphthalene and biphenylene. Furthermore, also diethynylbenzene isomers, fluorene, diphenymethane, indene and biphenyl were produced in appreciable amounts. The formation mechanisms of these and other minor products are discussed mainly in the light of the benzyl radical and its decay into other products. Among polyynes, only 1,3,5,7-octatetrayne was produced above 1% relative yield. The results are discussed in comparison to the products detected in toluene pyrolysis under other experimental conditions, such as shock tube pyrolysis and toluene flames. Furthermore, a comparison with the products obtained from the benzene pyrolysis is reported.     

Thin film of carbon micro-spring forest

Carbon microcoils are generally prepared by catalytic chemical vapor deposition of acetylene, using Ni as the catalyst and thiophene as the promoter. In this work, Ni-sulphide has been used as a catalyst for the purpose of avoiding the introduction of noxious and unpleasant thiophene during the reaction process and getting the thin film of quasi-aligned carbon microcoils. SEM images show that the products obtained in the temperature range of 740-760 °C were pure, regular and had perfect morphology.     

Preparation of carbon nano-microcoils by Ni3S2-catalyzed pyrolysis of acetylene and its vapor-liquid-solid-solid growth mechanism

Carbon microcoils are generally prepared by catalytic chemical vapor deposition of acetylene, using Ni as the catalyst and thiophene as the promoter. In this work, Ni3S2 was chosen as the catalyst on purpose to avoid the introducing of noxious and unpleasant thiophene during the reaction process. The products obtained in the temperature range of 1013-1033 K were pure, regular and had perfect morphology. Using transmission electron microscope, Raman spectrometer and X-ray diffractometer, the microstructure of the as-prepared carbon microcoils were characterized, furthmore, energy dispersive spectrum and selected area electron diffraction analysis reveal that the growth of carbon microcoils is always accomplished with the transformation of the catalyst from Ni3S2 to Ni3C. We first observed that the fiber constructing the carbon microcoil is composed of three sub-fibers, which strongly supports the proposition of vapor-liquid-solid-solid growth mechanism. In this mechanism, every catalyst particle is in the state of the coexistence of solid and liquid. Carbon atoms firstly permeate into the liquid portion from gas, then disperse into the solid portion, and finally deposit from the catalyst grain to form the carbon microcoil.     

碳源对碳纳米管形态的影响

以苯和甲苯为碳源,二茂铁为催化剂,含硫化合物为助催化剂,采用浮游催化裂解法制备了碳纳米管,并采用TEM对不同条件下所得碳纳米管进行了形态分析。结果发现,碳源中苯和甲苯的配比对碳纳米管的形态有着重要的影响。以纯苯为碳源时,产物主要为直线型碳纳米管,并存在极少量短的弯曲型碳纳米管。随着碳源中甲苯比例的增加,产物中折线型碳纳米管增加。以纯甲苯为碳源,产物中仍有少量直线型碳纳米管,而不完全是折线型碳纳米管;此外,产物中还发现了极少量分支型碳纳米管。根据所得结果讨论分析了甲苯的加入对碳纳米管形态的影响以及各种碳纳米管的形成机理,认为可能是由于甲苯在催化热解过程中产生的碳种不同于苯催化热解所产生的碳种,造成碳在催化剂颗粒各处浓度不同,从而在碳纳米管的不同部位引入五元环和七元环而形成各种形态的碳纳米管。     

Characteristics of carbon microspheres and study on its adsorption isotherms

In this paper a great deal of carbon microspheres with high purity, uniform diameter and good features were synthesized by CVD method, while acetylene and toluene were used as carbon sources. The obtained carbon microspheres were almost amorphous. The products were treated by microwave plasma and temperature vacuum heat treatments respectively, then the samples were analyzed and characterized by FESEM, XRD and HRTEM. The results showed that carbon microspheres were well graphitized while their features were undestroyed. Based on their adsorption isotherms of nitrogen, pore structures of carbon spheres were found to be changed greatly after graphitized treatments.     

Comparison of their electrical,optical, and electrochemical properties of as-grown plasma polymerized organic thin films by PECVD

Plasma polymerized organic thin films have been deposited on Si(100), glass and metal substrates at 25∼100 °C using thiophene and toluene precursors by plasma enhanced CVD method. In order to compare physical and electrochemical properties of the as-grown thin films, the effect of the RF (13.56 MHz) plasma power in the range of 30∼100 W and the deposition temperature on the corrosion protection efficiency and optical property were mainly studied in this work. Corrosion protection efficiency (P_k), which is one of important factors for corrosion protection in the interlayer dielectrics of microelectronic devices application, provided an increasing tendency with increasing RF power. The highest P_k value of plasma polymerized toluene film (85.27% at 70 W) was higher than that of the plasma polymerized thiophene film (65.17% at 100 W). The result of contact angle measurement showed that the plasma polymerized toluene films have more hydrophobicity than that of the plasma polymerized thiophene films.     

Conversion of toluene into carbon nanotubes using arc discharge plasmas in solution

In order to form nanocarbon materials, an arc discharge plasma method in hydrocarbon solvent is developed. In the case that the arc discharge is performed in toluene with nickel electrodes, tube-like nanocarbons were formed from toluene. The catalysis of the metal electrodes is found to be an important factor for the formation of the nanocarbons by the arc discharge in toluene. This method has a possibility of forming carbon nanotubes from liquid state solvents as a new carbon source by using catalyst ingredient as discharge electrodes.     

中温沥青中甲苯可溶组分的热解特性及热转化产物的性质

以中温煤沥青的甲苯可溶组分为原料,进行元素分析和TG/DTG分析,并且利用偏光显微镜、X射线单晶衍射仪、拉曼光谱以及相应的分峰拟合等数学方法对热转化的产物进行研究。以实验获得的数据为基础,采用Flynn-Wall-Ozawa法和Kissinger-Akahira-Sunose法计算得到反应活化能,采用Satava-Sastak法求解热解反应动力学参数。实验结果表明,中温沥青中甲苯可溶组分的热解反应活化能为E=88.48kJ/mol,指前因子lgA=10.22,反应级数为2级,热解反应机理适合随机成核及其随后的增长模型。1 000℃焙烧后的炭化产物的光学显微组分含量为:镶嵌型23.74%,粗纤维型14.80%,细纤维17.88%,大片结构30.45%。由XRD研究结果可知,趋于规整结构的碳微晶含量为41.86%。Raman光谱分析研究结果表明,石墨结构的碳微晶含量为11.59%,缺陷石墨碳含量为79.31%,无定形碳含量为9.10%。热转化产物具有很好的可石墨化性。