模型孔中化学气相渗透过程的热解碳沉积模拟

doi:10.15541/jim20150365

无机材料学报 ›› 2016, Vol. 31 ›› Issue (3): 298-304.DOI: 10.15541/jim20150365 CSTR: 32189.14.10.15541/jim20150365

模型孔中化学气相渗透过程的热解碳沉积模拟

汤哲鹏¹(), 张中伟², 房金铭², 彭雨晴¹, 李爱军¹, 张丹³()

1.上海大学材料复合及先进分散技术教育部工程中心, 上海 200072
2.航天材料及工艺研究所先进功能复合材料技术国防科技重点实验室, 北京 100076
3.上海大学应用数学和力学研究所, 上海 200072

收稿日期:2015-08-06 修回日期:2015-10-10 出版日期:2016-03-20 网络出版日期:2016-02-24
作者简介:
汤哲鹏(1987-), 男, 博士研究生. E-mail: tangzhepong@shu.edu.cn
基金资助:
国家自然科学基金(11202124);教育部博士点基金(20113108120019);上海人才发展资金(2011028);航空基金(2013ZFS6001);上海市科委基金(13521101202)

Modeling of Chemical Vapor Infiltration for Pyrocarbon within Capillaries

TANG Zhe-Peng¹(), ZHANG Zhong-Wei², FANG Jin-Ming², PENG Yu-Qing¹, LI Ai-Jun¹, ZHANG Dan³

1. Research Center for Composite Materials, Shanghai University, Shanghai 200072, China
2. National Key Laboratory of Advanced Functional Composite Materials, Aerospace Research Institute of Materials and Processing Technology, Beijing 100076, China
3. Shanghai Institute of Applied Mathematics and Mechanics, Shanghai 200072, China

Received:2015-08-06 Revised:2015-10-10 Published:2016-03-20 Online:2016-02-24
Supported by:
National Natural Science Foundation of China(11202124);Doctoral Fund of Ministry of Education(20113108120019);Shanghai Talent Development Fund(2011028);Aviation fund (2013ZFS6001);Shanghai Committee of Science and Technology(13521101202)

摘要/Abstract

摘要：

研究耦合均气相反应机理和总括反应机理, 以模拟甲烷在模型孔中的热解碳沉积过程。在平推流反应器模型中, 利用均气相反应机理对甲烷裂解的气相组分的变化进行模拟, 并将平推流反应器相应位置的气体组分浓度作为模型孔入口初始浓度。运用包含总括反应机理及氢气抑制模型的热解碳沉积模型, 对甲烷在模型孔中的化学气相渗透过程进行模拟。在温度1373和1398 K, 甲烷压强10~20 kPa, 停留时间0.08和0.2 s下, 沿模型孔深度方向的热解碳平均沉积速率的模拟结果与文献报道的实验结果有较好的吻合。模拟结果表明: 热解碳平均沉积速率随甲烷压强和模型孔深度的增加而增大, 且通孔的沉积速率要低于相应实验条件下一端闭孔的模型孔沉积速率。

关键词: 模拟, 热解碳, 甲烷, 化学气相渗透, 模型孔

Abstract:

Coupling homogeneous gas-phase reaction mechanism with lumped reaction mechanism, the pyrocarbon deposition process of the methane pyrolysis was simulated within the capillaries. The initial concentrations for the involved gas-phase species at the mouth of capillary are obtained firstly by computation of the plug flow using homogeneous gas-phase reaction mechanism during methane pyrolysis. Chemical vapor infiltration of pyrocarbon from methane in the capillary is simulated by deposition model, hydrogen inhibition model and lumped reaction mechanism. Predicted results for the mean deposition rate along the capillary depth are well validated by previously published experimental results, in which, at temperatures of 1373 and 1398 K, methane pressures are ranging from 10 to 20 kPa, and residence times are of 0.08 and 0.2 s. Simulated results show that the gradient of the mean deposition rate profile increases with methane pressure and capillary depth, and the deposition rate for transition capillary is lower than the corresponding closed capillary.

Key words: modeling, pyrocarbon, methane, chemical vapor infiltration, capillary

中图分类号:

TQ174

汤哲鹏, 张中伟, 房金铭, 彭雨晴, 李爱军, 张丹. 模型孔中化学气相渗透过程的热解碳沉积模拟[J]. 无机材料学报, 2016, 31(3): 298-304.

TANG Zhe-Peng, ZHANG Zhong-Wei, FANG Jin-Ming, PENG Yu-Qing, LI Ai-Jun, ZHANG Dan. Modeling of Chemical Vapor Infiltration for Pyrocarbon within Capillaries[J]. Journal of Inorganic Materials, 2016, 31(3): 298-304.

图/表 10

图1 含内径为1 mm的模型孔的基底示意图

Fig. 1 Sketch of the substrates of capillaries with a diameter of 1.0 mm(a) Small reactor; (b) Large reactorNo.4 of small reactor and No.5 of large reactor are transition capillaries

图2 甲烷裂解过程中计算得到的主要气相组分的变化曲线

Fig. 2 Computed molar fraction profiles of major gas-phase species during the methane pyrolysis(a,b) 20 kPa, 1398 K and with various residence times in small reactor; (c) 0.08 s, 1398 K and with various pressures in small reactor; (d) 0.08 s, 1373 K and with various pressures in large reactor

图3 由甲烷热解碳沉积的气相与表面反应相互作用原理图

Fig. 3 Scheme of interaction between gas phase and surface for pyrocarbon deposition from methane

表1 相关组分的反应项

Table 1 Reaction terms of related species

Species	Index	R_i
CH₄	c₁	c₁(-k₁-Ic₁k₅*S_v)
C₂H₄	c₂	0.5k₁c₁-k₂c₂- Ic₂k₆S_vc₂
C₂H₂	c₃	k₂c₂-k₃c₃- Ic₃k₇S_v*c₃
C₆H₆	c₄	k₃c₃/3- Ic₄k₈S_vc₄
H₂	c₅	k₁c₁+k₂c₂+0.5k₄c₄+2Ic₁k₅S_vc₁+2Ic₂k₆S_vc₂+ Ic₃k₇S_vc₃ +3 Ic₄k₈S_v*c₄

表2 原子/分子体积增量[12]

Table 2 Atom/molecular volume increment[12]

Species	C	H	H₂
Diffusion volume /(cm³·mol^-1)	16.50	1.98	7.07

图4 小反应器中反应条件为1398 K、0.08 s、10 kPa时, 沿模型孔方向热解碳的平均沉积速率的实验结果与模拟结果的比较, 及相应的沉积速率云图(右)

Fig. 4 Comparison of the computational predictions with the experimental data of the mean deposition rates as a function of the capillary depth in small reactor under the reaction conditions of 1398 K, 0.08 s, 10 kPa, and the cloud chart (right) of the related deposition rate for the substrate No.4 is a transition capillary

图5 小反应器中反应条件为1398 K、0.08 s、20 kPa时, 沿模型孔方向热解碳的平均沉积速率实验结果与模拟结果的比较, 及模型孔中相应的沉积速率云图(右)

Fig. 5 Comparison of the computational predictions with the experimental data of the mean deposition rates as a function of the capillary depth in small reactor under the reaction conditions of 1398 K; 0.08 s; 20 kPa, and the cloud chart (right) of the related deposition rate for the substrate No.4 is a transition capillary

图6 大反应器中反应条件为1373 K和0.08 s、压强分别为10 kPa(a)、15 kPa(b)、20 kPa(c)时, 沿模型孔方向热解碳的平均沉积速率实验结果与模拟结果的比较, 及模型孔中相应的沉积速率云图(右)

Fig. 6 Comparison of the computational predictions with the experimental data of the mean deposition rates as a function of the capillary depth in large reactor under the reaction conditions of 1398 K, 0.08 s and 10 kPa (a), 15 kPa (b) or 20 kPa (c), and the cloud chart (right) of the related deposition rate for the substrateNo.5 is a transition capillary

图 7 小反应器中反应条件为1398 K和0.2 s、20 kPa时, 沿模型孔方向热解碳的平均沉积速率实验结果与模拟结果的比较, 及模型孔中相应的沉积速率云图(右)

Fig. 7 Comparison of the computational predictions with the experimental data of the mean deposition rates as a function of the capillary depth in small reactor under the reaction conditions of 1398 K, 0.2 s and 20 kPa, and the cloud chart (right) of the related deposition rate for the substrate No.4 is a transition capillary

图 8 大反应器中反应条件为1373 K和0.2 s、20 kPa时, 沿模型孔方向热解碳的平均沉积速率实验结果与模拟结果的比较, 及模型孔中相应的沉积速率云图(右)

Fig. 8 Comparison of the computational predictions with the experimental data of the mean deposition rates as a function of the capillary depth in large reactor under the reaction conditions of 1373 K, 0.2 s and 20 kPa, and the cloud chart (right) of the related deposition rate for the substrate No.5 is a transition capillary

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模型孔中化学气相渗透过程的热解碳沉积模拟

Modeling of Chemical Vapor Infiltration for Pyrocarbon within Capillaries

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