纳米炭粉的制备及结构性能的表征
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摘要
20世纪80年代，人们把尺度小于100nm并且具有特异物理性能和化学性能的粉体材料定义为纳米粉体材料。随着科学技术的迅猛发展，纳米材料在人类的生产生活中起到了举足轻重的作用。纳米炭粉是一种新型轻质纳米级无定型炭素材料，由于它具有小尺寸效应、表面效应、量子尺寸效应和宏观量子隧道效应等特性，使得它在磁、光、电、敏感等方面呈现常规材料不具备的特性，从而使其作为一种新型材料在电子、信息、农业、冶金、宇航、化工和生物医学等领域占有十分重要的地位。现在纳米炭粉在催化剂及催化剂载体、功能陶瓷、粘结剂、色谱柱填料和电极材料、造孔剂等领域展现出较大的优越性和广阔的应用前景，所以对纳米炭粉的研究正逐渐引起人们的关注。
本文以煤焦油沥青为原料，以浓硫酸和浓硝酸为氧化剂，利用溶胶凝胶方法制备水性中间相沥青(Aqua mesophase pitch，以下简称AMP)。将AMP溶解于氨水中得到水相炭基凝胶，经过乙醇与水交换后采用不同干燥技术，对湿凝胶进行干燥和950℃热处理制得纳米炭粉。研究内容包括混酸系AMP的制备和性能分析，探讨了不同氧化条件对AMP产率的影响。详细考察了不同工艺条件，如不同原料、氧化温度、氧化反应时间、搅拌速度、碱溶反应时间等氧化条件对水性中间相收率和性能的影响。结合原料的性质、实验现象和各种表征技术获得的信息对氧化机理进行了初步讨论。利用溶胶凝胶法得到湿凝胶之后，通过常温干燥、冷冻干燥(-20℃，干冰冷冻和液氮冷冻)以及超临界干燥等方式进行干燥。并考察了不同冷冻溶剂介质(乙醇、丁醇)对纳米炭粉产率和性能结构的影响。最后，利用FT-IR红外光谱分析，热重分析(TGA)，X-射线衍射分析(XRD)，电镜粒度分析(TEM)等方法对AMP、纳米炭原粉以及纳米炭粉的结构进行表征分析。
结果表明：在沥青与混酸氧化过程中，主要发生硝化、氧化、磺化反应。纳米炭原粉的热解过程分为脱醇脱水、预解热、强烈热分解阶段和结构重排等四个阶段，其中超临界干燥制得纳米炭粉的热解反应最激烈。不同的干燥方式得到的纳米炭原粉和纳米炭粉其化学结构和炭结构有所不同。液氮冷冻干燥得到的纳米炭原粉其杂原子基团的含量较少，制得的纳米炭粉其炭微晶尺寸较大。采用冷冻干燥的方法制备的纳米炭粉粒度均匀、规则，形状近似于球形，平均粒径为10nm左右，其炭结构为无序的乱层石墨结构。采用常温干燥也能成功制备出纳米炭粉。可见，常温干燥和冷冻干燥方法是一种低成本、简单易行的制备纳米炭粉的方法。
Nanopowders are the powders with the size of no more than 100 nm. Owing to the extremely small dimensions, nano-materials are structurally characterized by a large volume fraction of grain boundaries or interphase boundaries, which exhibit some unique structural characteristics and properties compared to the conventional materials. With the development of science and technology, nano-materials play an important role in the society and are widely applied in many fields, such as information, manufacturing, biotechnology and agriculture etc. Nano-carbon powders are the new turbostratic carbon materials and have broad prospects in catalysis and its supports, functional ceramics, binder, stationary phases for chromatography, electrode materials and producer. Therefore, it is much concerned to prepare nano-carbon powders with interesting and useful properties.
In this paper, The nano-carbon powders were prepared by sol-gel method, in which the coal tar pitch was first oxidized into aqua-mesophase pitch (AMP) by mixtures of concentrated sulfuric acid and nitric acid, and then the AMP was dissolved in aqueous solution of ammonia hydroxide to form the carbonaceous hydrogel, which was directly exchanged with ethanol to remove water and dried by different drying methods temperature. After carbonization at 950 ℃, the nano-carbon powders were obtained. Preparation and performance analysis of AMP was investigated by oxidation with mixtures of concentrated sulfuric acid and nitric acid. The effects of oxidation conditions, such as raw materials, temperature, reaction time and stirring velocity, on the yields and properties of AMP were studied in detail. The effect of drying media and methods of wet gel on the nano-carbon powders yield and properties was also investigated. The AMP, the primary nano-carbon powders and their heat-treated products were characterized by FT-IR, TG, XRD and TEM methods. Mechanisms of oxidation are discussed briefly.
The results show that oxidation conditions greatly affect the yields and properties of AMP. The reactions such as nitration, oxidation and sulfonation mainly happen during the reactions of coal tar pitch with mixing acids. The pyrolysis of the primary nano-carbon powders can be divided into four stages, including removal of drying media and water, pre-thermol decomposition, thermol decomposition and rearrangement of carbon structure. The different drying methods and medias of wet gel are found to affect the chemical and carbon structure of the primary nano-carbon powders and nano-carbon powders. The ball-like nano-carbon powders with the average size about 10nm and turbostratic carbon structure can
本文以煤焦油沥青为原料，以浓硫酸和浓硝酸为氧化剂，利用溶胶凝胶方法制备水性中间相沥青(Aqua mesophase pitch，以下简称AMP)。将AMP溶解于氨水中得到水相炭基凝胶，经过乙醇与水交换后采用不同干燥技术，对湿凝胶进行干燥和950℃热处理制得纳米炭粉。研究内容包括混酸系AMP的制备和性能分析，探讨了不同氧化条件对AMP产率的影响。详细考察了不同工艺条件，如不同原料、氧化温度、氧化反应时间、搅拌速度、碱溶反应时间等氧化条件对水性中间相收率和性能的影响。结合原料的性质、实验现象和各种表征技术获得的信息对氧化机理进行了初步讨论。利用溶胶凝胶法得到湿凝胶之后，通过常温干燥、冷冻干燥(-20℃，干冰冷冻和液氮冷冻)以及超临界干燥等方式进行干燥。并考察了不同冷冻溶剂介质(乙醇、丁醇)对纳米炭粉产率和性能结构的影响。最后，利用FT-IR红外光谱分析，热重分析(TGA)，X-射线衍射分析(XRD)，电镜粒度分析(TEM)等方法对AMP、纳米炭原粉以及纳米炭粉的结构进行表征分析。
结果表明：在沥青与混酸氧化过程中，主要发生硝化、氧化、磺化反应。纳米炭原粉的热解过程分为脱醇脱水、预解热、强烈热分解阶段和结构重排等四个阶段，其中超临界干燥制得纳米炭粉的热解反应最激烈。不同的干燥方式得到的纳米炭原粉和纳米炭粉其化学结构和炭结构有所不同。液氮冷冻干燥得到的纳米炭原粉其杂原子基团的含量较少，制得的纳米炭粉其炭微晶尺寸较大。采用冷冻干燥的方法制备的纳米炭粉粒度均匀、规则，形状近似于球形，平均粒径为10nm左右，其炭结构为无序的乱层石墨结构。采用常温干燥也能成功制备出纳米炭粉。可见，常温干燥和冷冻干燥方法是一种低成本、简单易行的制备纳米炭粉的方法。
Nanopowders are the powders with the size of no more than 100 nm. Owing to the extremely small dimensions, nano-materials are structurally characterized by a large volume fraction of grain boundaries or interphase boundaries, which exhibit some unique structural characteristics and properties compared to the conventional materials. With the development of science and technology, nano-materials play an important role in the society and are widely applied in many fields, such as information, manufacturing, biotechnology and agriculture etc. Nano-carbon powders are the new turbostratic carbon materials and have broad prospects in catalysis and its supports, functional ceramics, binder, stationary phases for chromatography, electrode materials and producer. Therefore, it is much concerned to prepare nano-carbon powders with interesting and useful properties.
In this paper, The nano-carbon powders were prepared by sol-gel method, in which the coal tar pitch was first oxidized into aqua-mesophase pitch (AMP) by mixtures of concentrated sulfuric acid and nitric acid, and then the AMP was dissolved in aqueous solution of ammonia hydroxide to form the carbonaceous hydrogel, which was directly exchanged with ethanol to remove water and dried by different drying methods temperature. After carbonization at 950 ℃, the nano-carbon powders were obtained. Preparation and performance analysis of AMP was investigated by oxidation with mixtures of concentrated sulfuric acid and nitric acid. The effects of oxidation conditions, such as raw materials, temperature, reaction time and stirring velocity, on the yields and properties of AMP were studied in detail. The effect of drying media and methods of wet gel on the nano-carbon powders yield and properties was also investigated. The AMP, the primary nano-carbon powders and their heat-treated products were characterized by FT-IR, TG, XRD and TEM methods. Mechanisms of oxidation are discussed briefly.
The results show that oxidation conditions greatly affect the yields and properties of AMP. The reactions such as nitration, oxidation and sulfonation mainly happen during the reactions of coal tar pitch with mixing acids. The pyrolysis of the primary nano-carbon powders can be divided into four stages, including removal of drying media and water, pre-thermol decomposition, thermol decomposition and rearrangement of carbon structure. The different drying methods and medias of wet gel are found to affect the chemical and carbon structure of the primary nano-carbon powders and nano-carbon powders. The ball-like nano-carbon powders with the average size about 10nm and turbostratic carbon structure can
引文
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