用激光法合成纳米金刚石

使脉冲激光与石墨粉在空气中相互作用，并对其氧化提纯．对产物进行的显微激光拉曼光谱（Raman）与高分辨电子显微镜（HRTEM）分析表明，产物中含大量纳米金刚石颗粒，其尺寸为5nm左右，且具有较多的晶体缺陷和残余内应力．提出了石墨转变为金刚石纳米晶的机理：在脉冲激光产生的高温高压的条件下，具有石墨结构的原子团发生快速滑移切变，形成立方金刚石晶核，碳等离子体中高化学活性的碳粒子集团使金刚石晶核迅速长大，形成金刚石微晶．     

激光法制备碳质纳米材料

通过介绍在气体和液体介质中激光与固体材料相互作用的过程,评述了激光在不同介质中发生物理化学现象的差异.与气相中相比,激光冲蚀液体中固体材料产生的气态等离子区受到了液体限制,在该区域会产生更高的气态密度、温度和压力,适合于亚稳相纳米晶的合成.同时评述了激光制备碳基纳米材料的进展.激光在气相和液相中均可制得碳纳米管,气相中适于制备结构完整的碳纳米管,而液相中有利于纳米金刚石的合成.激光冲蚀液体中的石墨靶制备的纳米金刚石粒径较大,辐照石墨悬浮液工艺不仅可以获得超细的纳米金刚石还可以获得线型碳.激光法制备的碳基纳米材料具有尺寸小、纯度高和形状多样性,在未来有着广泛的潜在应用价值.     

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.     

液相脉冲激光轰击石墨制备碳纳米材料研究进展

碳纳米材料具有特殊的力学、电学及物化性能,在微电子、航空航天、军用材料等领域具有广阔的应用前景,利用脉冲激光高效、可控制备新型碳纳米材料已成为研究热点。简要介绍了激光与碳材料的相互作用及纳米粒子的成形机理,详细阐述了液相脉冲激光制备纳米金刚石、碳纳米管、石墨烯等碳纳米材料的过程及其影响因素,并展望了激光轰击石墨制备碳纳米材料的主要研究方向。     

用纳米非晶Si／N／C粉原位合成Si3N4晶须

采用激光诱导有机硅烷气合成的纳米非晶Ｓｉ／Ｎ／Ｃ粉为原料，在１６００℃，１０１．３ｋＰａＮ２气下，在石墨感应炉中原位制备出α－Ｓｉ３Ｎ４晶须，其直径为０．１－０．５μｍ，长可达几毫米，纯度较高，无过剩碳及金属杂质。     

脉冲激光诱导固—液界面反应法合成亚稳相纳米晶

评述了利用脉冲激光对液体中固体材料进行表面处理以获得亚稳态新相的方法,并采用脉冲激光诱导固－液界面反应法制备了金刚石纳米晶和氮化碳的纳米晶,简要分析了用此方法合成纳米晶的生长过程。     

纳米石墨的制备方法(英文)

简要概述了现有的纳米石墨制备方法,这些方法从材料来源上可以分为2类,一类由鳞片石墨来制备,另一类由富碳材料合成.由鳞片石墨制备纳米石墨的方法主要有球磨法、超声波粉碎法、爆轰裂解法和电化学插层法;由富碳材料合成纳米石墨的方法主要包括爆轰合成法、化学气相沉积法、激光脉冲沉积法和化学合成法.     

超高温高压下石墨向金刚石直接转变的理论研究

根据固体和分子经验电子理论（EET理论）,分别计算了静压法和爆炸法合成金刚石过程中石墨和金刚石的价电子结构,获得了超高温高压下石墨和金刚石12组不同组合晶面间的价电子密度,结果表明,采用静压法合成金刚石．石墨／金刚石晶面的电子密度差均大于10％,说明其晶面的价电子结构差异太大,不能诱发石墨向金刚石的直接转变。而采用爆炸法合成金刚石,石墨结构理论键距和实验键距差是0．1073nm,明显大于稳定的价电子结构键距差的最大值（0．005nm）,因此,爆炸法条件下,石墨的价电子结构不稳定,主要因为超高温高压下,石墨先分解出亚稳相后再转变成金刚石结构。     

金属对炭黑转化为洋葱状中空结构纳米碳的影响

研究了炭黑分别在 Fe、Co、Ni 三种金属化合物作用下的催化转化行为, 以期使炭黑质点中不连续的无规则小石墨片层重新组装、构筑成洋葱状中空结构纳米碳. 采用透射电子显微镜(TEM)、高分辨透射电子显微镜(HRTEM)、X射线衍射(XRD)和Raman光谱分析表征了炭黑及其催化炭化产物的微观形貌和结构. 结果表明: 尽管三种金属催化剂均可通过溶碳-析出机制形成过渡态碳包覆纳米金属颗粒, 继而构筑成由准球形同心石墨壳层组合的洋葱状中空结构纳米碳, 但三种金属催化剂显示不同的催化效果, 终碳产物的形态和纯度差异较大, 其中以Fe 的催化效果最好.     

金刚石薄膜涂层硬质合金刀具的界面表征

采用SEM对金刚石薄膜涂层硬质合金刀具的金刚石薄膜表面、背面及金刚石薄膜剥落后的硬质合金刀片表面的典型形貌进行了观察,并采用TEM对金刚石薄膜／硬质合金刀片横截面的微观组织进行了研究,还采用FT—Raman光谱法对金刚石薄膜表面及金刚石薄膜剥落后的硬质合金刀片表面的微观结构进行了表征．结果表明：经适当的化学侵蚀脱钻和等离子体刻蚀脱碳预处理后,金刚石薄膜涂层硬质合金刀具的界面通常存在薄的（数十nm）石墨碳层;局部区域见到金刚石粒子直接生长在WC颗粒上,金刚石膜／基横截面的典型组织层次为：金刚石薄膜／薄的石墨碳层／细小的WC层／残留的脱碳层（η相＋W相）／原始的硬质合金基体．     

片状石墨增强树脂基复合材料的耐激光烧蚀性能研究

采用刷涂的方法制备了一种新型的片状石墨增强钡酚醛树脂基复合材料, 并采用重频激光辐照的方法, 对其耐烧蚀性能进行了研究. 研究结果表明: 片状石墨增强钡酚醛树脂基复合材料在平均功率密度为1700 J/cm²的重频激光辐照下的热烧蚀率为32.8 μg/J, 耐激光烧蚀性能明显高于碳纤维增强的钡酚醛树脂基复合材料和钡酚醛树脂; 片状石墨增强钡酚醛树脂基复合材料中的片状石墨呈近平行的层状分布方式, 在激光辐照过程中能对入射激光起到平面反射作用, 从而有效地降低激光辐照的能量沉积; 片状石墨的片型对复合材料的耐烧蚀性能有影响, φ0.5 mm的片状石墨增强的复合材料的耐激光烧蚀性能最好.     

A STUDY ON THE THERMAL STABILITY TO 1000°C OF VARIOUS CARBON ALLOTROPES AND CARBONACEOUS MATTER BOTH UNDER NITROGEN AND IN AIR

The thermal behavior of graphite, C₆₀ fullerene, fullerene black (carbon soot containing fullerenes), extracted fullerene black and diamond has been analyzed to 1000°C by TGA-DTA (thermogravimetric analysis and differential thermal analysis) under a nitrogen flow at a heating rate of 20°C/min. Very small weight losses have been recorded in the case of graphite and diamond. Furthermore no diamond graphitization has been observed. The sublimation of pure C₆₀ and the fullerene fraction of fullerene black (both pristine and extracted) has been observed and discussed.

The combustion reaction in air flow of graphite, C₆₀ and C₇₀ fullerenes, fullerene black (both unextracted and extracted), carbon nanotubes and diamond has been studied by TGA-DTA at a heating rate of 20°C/min. C₇₀ fullerene and fullerene black have been found to be the most reactive carbon materials with O₂. The role played by C₇₀ in the degradation of fullerites has been discussed. Among the carbon materials examined, the best resistance to O₂ attack has been shown by diamond and carbon nanotubes. The behavior of graphite is intermediate between diamond and fullerene blacks. The behavior of C₆₀ fullerene appears closer to that of graphite although it appears to be more reactive with O₂. Samples of graphite and carbon blacks N375 and N234 have been studied by TGA-DTA in air flow before and after a radiation treatment with neutrons or γ radiation. The effect of the radiation damage in the combustion reaction of these carbon materials has been discussed.     

石墨/酚醛树脂复合材料双极板的制备与性能

双极板是质子交换膜燃料电池的重要组成部分,石墨与聚合物的复合材料双极板是目前研究的重要方向。采用模压热固化二步法,以酚醛树脂为粘结剂、天然鳞片石墨为导电骨料、炭黑为添加剂制备了质子交换膜燃料电池用复合材料双极板。系统研究了不同种类石墨对石墨/酚醛树脂复合材料电性能和抗弯强度的影响。结果表明:以天然鳞片石墨为导电原料时,所制备的石墨/酚醛树脂双极板的性能最好;添加导电炭黑能有效提高石墨/酚醛树脂复合材料的电导率;在复合材料制备中加入4wt%的碳纤维,碳纤维-石墨/酚醛树脂复合材料的抗弯强度提高了29%;碳纤维表面液相氧化处理能有效提高纤维与基体间的结合强度,随着处理时间的延长与处理温度的升高,碳纤维-石墨/酚醛树脂复合材料的电导率和抗弯强度都有很大程度的提高;最终固化温度主要影响酚醛树脂的交联程度,随着最终固化温度的升高,酚醛树脂的交联程度增加,电导率增大,但抗弯强度有一定程度减小。     

碳元素的另一种同素异形体——白碳

白碳和金刚石、石墨这两种常见的碳的晶态结构不同,它是sp1杂化的碳元素的另一种晶态同素异形体.白碳具有一维直线碳链的特殊结构.本文对白碳材料的制备方法、结构特点、表征方法进行了综述,并展望了其在纳米器件、分子器件、以及场致电子发射等方面的应用前景.     

A STUDY ON THE THERMAL STABILITY TO 1000°C OF VARIOUS CARBON ALLOTROPES AND CARBONACEOUS MATTER BOTH UNDER NITROGEN AND IN AIR

ABSTRACT

The thermal behavior of graphite, C₆₀ fullerene, fullerene black (carbon soot containing fullerenes), extracted fullerene black and diamond has been analyzed to 1000°C by TGA–DTA (thermogravimetric analysis and differential thermal analysis) under a nitrogen flow at a heating rate of 20°C/min. Very small weight losses have been recorded in the case of graphite and diamond. Furthermore no diamond graphitization has been observed. The sublimation of pure C₆₀ and the fullerene fraction of fullerene black (both pristine and extracted) has been observed and discussed.

The combustion reaction in air flow of graphite, C₆₀ and C₇₀ fullerenes, fullerene black (both unextracted and extracted), carbon nanotubes and diamond has been studied by TGA–DTA at a heating rate of 20°C/min. C₇₀ fullerene and fullerene black have been found to be the most reactive carbon materials with O₂. The role played by C₇₀ in the degradation of fullerites has been discussed. Among the carbon materials examined, the best resistance to O₂ attack has been shown by diamond and carbon nanotubes. The behavior of graphite is intermediate between diamond and fullerene blacks. The behavior of C₆₀ fullerene appears closer to that of graphite although it appears to be more reactive with O₂. Samples of graphite and carbon blacks N375 and N234 have been studied by TGA–DTA in air flow before and after a radiation treatment with neutrons or γ radiation. The effect of the radiation damage in the combustion reaction of these carbon materials has been discussed.     

Mineralogy of microbial fossil-like textures in the Precambrian Marble Bar chert and Gunflint chert

Examining two Precambrian chert samples in which microbial fossil-like structures have been reported, textures of the microbial-fossils or similar components were mineralogically described. The Gunflint chert of 1.9 Ga and the Marble Bar chert of 3.5 Ga were used. Microbial fossil-like textures in the Gunflint chert were composed mineralogically of three different parts: the core, middle and outer rim. Among them, the inner core consists of apatite, having a slightly irregular shape. It cannot consistently be confirmed that this is biogenic but these mineral textures are an important factor, possibly supporting the origin of biogenesis. In the black part of Marble Bar chert, carbon materials can be found, covering rounded quartz grains in TEM observations. HRTEM examinations show that the black part contains not only amorphous organic matter but also low crystalline graphite structures.     

ON THE MECHANISM OF CARBON CLUSTERS FORMATION UNDER LASER IRRADIATION. THE CASE OF DIAMOND GRAINS AND SOLID C60 FULLERENE

It is shown by FT-ICR (Fourier transform ion cyclotron resonance) mass spectrometry that carbon clusters considered to be the superior homologues of C₆₀ fullerene are formed by laser irradiation of both synthetic diamond grains or from pure C₆₀ fullerene crystals. The surfaces of the laser irradiated diamond or C₆₀ have been examined by Raman spectroscopy. In the case of diamond the Raman spectrum suggests the superficial formation of mixed carbon nanostructures consisting of disordered graphite, fullerenic nanostructures, onion-like carbon nanostructures and diamond-like carbon. Based on the Raman spectra of the surface and on data taken from the phase diagram of carbon, it is shown that the graphitization is needed in order to produce fullerenes from diamond under laser ablation conditions. In the case of C₆₀ fullerene, it is shown by Raman spectroscopy that the laser irradiation of the crystals causes initially their photopolymerization and after further irradiation their transformation into disordered graphite. Based on these results and on a literature survey on the formation of fullerenes from more than 15 completely different substrates, it is concluded that fullerenes are formed always when laser ablation leads to a graphitization of the laser-irradiated substrate. Some astrochemical implications of the conclusions have been discussed.     

SOME IMPLICATIONS OF THE RADIATION-TREATMENT OF GRAPHITE AND CARBON BLACK

Graphite and carbon black N234 radiation damaged with γ radiation or with neutron bombardment have been studied with Raman spectroscopy. The radiation damaging results completely evident in the case of graphite with the development of the I_D band, but it is less evident in the case of an already disordered material like carbon black. The radiation damage caused by γ radiation appears comparable to that caused by neutrons, at least for the radiation dose used. Moreover, in both cases there are evidences that the radiation-induced defects appear in carbon material under the form of fullerene-like sites (onion-like carbon and carbon nanotubes) as well as under the form of hexagonal diamond and hence sp³ hybridized carbon.

Neutron damaged carbon black once treated with laser light at 782 nm shows a featureless Raman spectrum with a maximum at 2287 cm^?1 suggesting that neutron bombardment followed by laser light annealing causes the formation of carbyne (polyyne) domains.

The radiation treatment of graphite, carbon black and even amorphous precipitated silica enhances in a spectacular way their natural rubber adsorption power. This has been measured through the “bound rubber phenomenon” which is the irreversible rubber grafting reaction on filler surface. This enhancement has been attributed to the increased concentration of “defective” sites on filler surface induced by radiation treatment which improves the rubberfiller interaction. Another macroscopic consequence of this increased interaction can be manifested in SBR-based or in natural rubber based vulcanizates filled with radiation pre-treated carbon blacks. In both cases a dramatic improvement in the reinforcing effect as measured by stress-strain curve can be observed.     

SOME IMPLICATIONS OF THE RADIATION-TREATMENT OF GRAPHITE AND CARBON BLACK

Graphite and carbon black N234 radiation damaged with γ radiation or with neutron bombardment have been studied with Raman spectroscopy. The radiation damaging results completely evident in the case of graphite with the development of the I_D band, but it is less evident in the case of an already disordered material like carbon black. The radiation damage caused by γ radiation appears comparable to that caused by neutrons, at least for the radiation dose used. Moreover, in both cases there are evidences that the radiation-induced defects appear in carbon material under the form of fullerene-like sites (onion-like carbon and carbon nanotubes) as well as under the form of hexagonal diamond and hence sp³ hybridized carbon.

Neutron damaged carbon black once treated with laser light at 782 nm shows a featureless Raman spectrum with a maximum at 2287 cm^-1 suggesting that neutron bombardment followed by laser light annealing causes the formation of carbyne (polyyne) domains.

The radiation treatment of graphite, carbon black and even amorphous precipitated silica enhances in a spectacular way their natural rubber adsorption power. This has been measured through the “bound rubber phenomenon” which is the irreversible rubber grafting reaction on filler surface. This enhancement has been attributed to the increased concentration of “defective” sites on filler surface induced by radiation treatment which improves the rubberfiller interaction. Another macroscopic consequence of this increased interaction can be manifested in SBR-based or in natural rubber based vulcanizates filled with radiation pre-treated carbon blacks. In both cases a dramatic improvement in the reinforcing effect as measured by stress-strain curve can be observed.