聚合物热解法制备碳纳米管/铝复合粉末及其反应动力学研究

doi:10.3724/SP.J.1077.2014.13494

无机材料学报 ›› 2014, Vol. 29 ›› Issue (7): 687-694.DOI: 10.3724/SP.J.1077.2014.13494 CSTR: 32189.14.SP.J.1077.2014.13494

聚合物热解法制备碳纳米管/铝复合粉末及其反应动力学研究

徐润¹, 李忻达¹, 李志强¹, 赵仁宇¹, 范根莲¹, 熊定邦¹, 唐婕¹, 许勇², 张荻¹

(上海交通大学1. 金属基复合材料国家重点实验室; 2. 机械与动力工程学院, 上海 200240)

收稿日期:2013-09-29 修回日期:2013-12-25 出版日期:2014-07-20 网络出版日期:2014-06-20
作者简介:徐润(1991-), 男, 博士研究生. E-mail: x.r.my.mail@gmail.com
基金资助:
国家重点基础研究发展计划(973计划)(2012CB619600);国家自然科学基金(51071100, 51131004, 51110222);国家高技术研究发展计划(863计划)(2012AA030311);上海科学与技术委员会资助项目(11JC1405500)

Preparation and Reaction Kinetics of Carbon Nanotubes/Aluminum Composite Powders Using Polymer Pyrolysis Method

XU Run¹, LI Xin-Da¹, LI Zhi-Qiang¹, ZHAO Ren-Yu¹, FAN Gen-Lian¹, XIONG Ding-Bang¹, TANG Jie¹, XU Yong², ZHANG Di¹

(1. State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai 200240, China; 2. School of Mechanical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China)

Received:2013-09-29 Revised:2013-12-25 Published:2014-07-20 Online:2014-06-20
About author:XU Run. E-mail: x.r.my.mail@gmail.com
Supported by:
National Basic Research Program(973 Program) (2012CB619600);National Natural Science Fonndation of China(51071100, 51131004, 51110222);National High-Tech R & D Program(863program)(2012AA030311);Shanghai Science & Technology Committee(11JC1405500)

摘要/Abstract

摘要：

采用聚合物热解化学气相沉积(PP-CVD)法, 通过聚乙二醇(PEG)的原位热解提供碳源、柠檬酸(CA)和硝酸钴反应产生催化剂纳米粒子, 在微纳米级的片状铝粉基底上原位生长碳纳米管(CNTs)。通过实验和反应动力学建模研究了PP-CVD反应机理, 揭示了PEG热解气相成分和催化剂纳米粒子表面气-固反应对CNTs生长速率的影响规律。CO初始分压和反应温度提高, CNTs生长速率提高; H₂初始分压和催化剂密度提高, CNTs生长速率降低。模型预测的CNTs平均长度随反应温度和反应时间的变化趋势符合实验结果。因此, 本研究为进一步优化CNTs/铝复合粉末制备工艺提供了新的理论依据。

关键词: 碳纳米管, 铝, 复合材料, 原位, 聚合物热解化学气相沉积, 反应动力学

Abstract:

The method of polymer pyrolysis chemical vapor deposition (PP-CVD) was used to in situ grow carbon nanotubes (CNTs) on the micro and nano sized flake like aluminum powder substrates. The vapor species were in situ produced by pyrolysis of polyethylene glycol (PEG) including the carbon sources, which was the main difference between the PP-CVD and conventional CVD methods, while the catalyst nanoparticles were produced by the reaction between citric acid (CA) and cobalt nitrate (Co(NO₃)₂) on aluminum powder surfaces. The reaction mechanism of PP-CVD was studied with the analysis of experiments and reaction kinetics modeling, revealing the influence of the vapor species produced by pyrolysis of PEG and CA and surface vapor-solid reactions on catalyst nanoparticles on CNT growth rates. The CNTs growth rates increases with the increase of reaction temperature and initial partial pressure of CO, which is influenced by the content of PEG and CA, and decreases with the increase of catalyst density and initial partial pressure of H₂. The variation trends of the simulated CNTs average length with reaction temperature and time are consistent with the experimental results. Thus, this work provides new theoretical basis to the further optimization of fabricating CNTs/aluminum composite powders.

Key words: carbon nanotubes, aluminum, composites, in situ, polymer pyrolysis chemical vapor deposition, reaction kinetics

中图分类号:

TB331

徐润, 李忻达, 李志强, 赵仁宇, 范根莲, 熊定邦, 唐婕, 许勇, 张荻. 聚合物热解法制备碳纳米管/铝复合粉末及其反应动力学研究[J]. 无机材料学报, 2014, 29(7): 687-694.

XU Run, LI Xin-Da, LI Zhi-Qiang, ZHAO Ren-Yu, FAN Gen-Lian, XIONG Ding-Bang, TANG Jie, XU Yong, ZHANG Di. Preparation and Reaction Kinetics of Carbon Nanotubes/Aluminum Composite Powders Using Polymer Pyrolysis Method[J]. Journal of Inorganic Materials, 2014, 29(7): 687-694.

图/表 10

图1 PP-CVD生长CNTs示意图

Fig. 1 Schematic drawing of CNTs grown by PP-CVD (a) The temperature and pressure monitoring system; (b) The closed batch reactor; (c) Al nanoflakes with Co nanoparticles and CNTs as grown; (d) The gas-solid reaction pathway and tip growth mode of CNTs. The dashed arrows represent collision of gaseous species and the solid arrows represent surface diffusion of carbon atoms around the Co nanoparticle

表1 模型中使用的符号定义

Table 1 Nomenclature of the symbols used in the modeling

Symbols	Definition
Cp	Encapsulating carbon
(S)	Surface species
C(S)	Active carbon atom
	The forward (f ) reaction rate constant of the i th reaction
	The reverse (r) reaction rate constant of the i th reaction
A	The Arrhenius pre-exponential factor
	The Arrhenius temperature coefficient
E_i	The activation energy of the i th reaction
R	The universal gas constant
	The change in the Gibbs free energy of formation as a result of the reaction
	The net stoichiometric coefficient for species j in i th reaction
q_i	The rate of progress of the i th reaction
R_j	The net rate of production of species j
C_j	The volumetric concentration of species j
V_deposited	The volume of deposited carbon atoms
	The volume of encapsulating carbon
V_C	The volume of a carbon atom
	The density of Co nanoparticles
	CNTs growth rate
d	The diameter of Co nanoparticles
N_A	Avogadro constant
Do	The surface diffusion coefficient of carbon atoms

图2 模拟过程流程图

Fig. 2 Flow diagram of modeling process

表2 密闭反应器中PEG-CA-Co(II)热解气体组成

Table 2 Composition of the PEG-CA-Co(II) pyrolysis gases in the batch reactor

The initial pressure /(1.013×10⁵, Pa)	The initial partial pressure /(1.013×10⁵, Pa)
The initial pressure /(1.013×10⁵, Pa)	CH₄	CO	CO₂	H₂O	H₂
22	1.61	6.24	6.18	5.65	1.53

Table 3 The ratio of Co nanoparticle surface area to the projected area of carbon source gas molecules

Species	CH₄	CO	CO₂
Projected area^a	2.43×10^-2	2.01×10^-2	3.45×10^-2
Ratio^b	3656	4388	2531
Active site density ^c	1.72×10^-9	2.06×10^-9	1.19×10^-9

图3 不同尺度下的CNTs形貌

Fig. 3 Morphologies of CNTs at different scales (a) SEM image of the Al flake substrates; (b) SEM image of the CNTs; (c) TEM image of the CNTs; (d) HRTEM image of the CNTs and SEAD pattern of catalyst particle

图4 模型中各项变量对于CNTs生长速率的影响(60 min内)

Fig.4 Effects of different vatiables in the modeling on the CNT growth rates in 60 min (a) Partial pressure of CO; (b) Partial pressure of H2; (c) Co nanoparticles density; (c) Reaction temperature

图5 873 K时反应器中气相成分的摩尔分数与反应时间的关系

Fig. 5 Mole fraction of gaseous species in the batch reactor versus the growth time at 873 K

图6 在873 K反应(a)0 min、(b)30 min、(c)60 min后CNTs的SEM形貌和长度分布以及(d)不同反应时间CNTs/Al复合粉末的拉曼光谱

Fig.6 SEM images with length and normalized frequency statistic (inset) of the CNTs after grown at 873 K for (a) 0 min, (b) 30 min and (c) 60 min. (d) Raman spectra of the CNT/Al composite powders The lengths of CNTs were measured on the corresponding SEM images randomly, and 120 CNTs were counted at each reaction time

图7 873 K, 不同反应时间得到的碳纳米管的长度的实验值与模拟值的比较

Fig. 7 Mean length of CNTs grown at 873 K vs growth time

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聚合物热解法制备碳纳米管/铝复合粉末及其反应动力学研究

Preparation and Reaction Kinetics of Carbon Nanotubes/Aluminum Composite Powders Using Polymer Pyrolysis Method

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