基于TDTR技术水合物热导率测量方法

doi:10.11949/0438-1157.20190521

摘要/Abstract

摘要：

四氢呋喃水合物（THF）是典形的笼形水合物，目前有关其热导率的报道较少，且都存在测量样品不是单一相、测量过程水合物发生分解等问题。采用基于飞秒脉冲激光的时域热反射法（TDTR）测量THF热导率。根据样品常温下是流体的特点，设计了可同时适用样品制备及TDTR测量的温控台，实现THF热导率非接触原位测量。获得THF热导率为0.6 W/(m?K)，Al/THF界面热导为90.3 MW/(m²?K)。该实验结果有助于理解并完善固体水合物微观导热机理，明晰水分子笼子和客体分子的耦合关系。

关键词: 水合物, TDTR, 热传导, 界面, 原位测量

Abstract:

Tetrahydrofuran (THF) hydrate is a typical cage structure hydrate, and there are few reports on the thermal conductivity of THF, meanwhile, there are many problems such as the measurement sample is not a single phase and the hydrate is decomposed during the measurement process. In this paper, time domain thermal reflectance (TDTR) technique based on femtosecond pulse laser is employed to measure the thermal conductivity of tetrahydrofuran hydrate. According to the characteristic that the sample is fluid at room temperature, a temperature control platform which can be used for both sample preparation and TDTR measurement is designed to realize the non-contact in-situ measurement of THF thermal conductivity. The result of THF thermal conductivity is 0.6 W/(m?K), and interface thermal conductivity between Al and THF is 90.3 MW/(m²·K). The experimental results obtained in this paper have great significance on understanding the microcosmic heat conduction mechanism of solid hydrates and clarifying the coupling relationship between the water molecules cage and guest molecules.

Key words: hydrate, TDTR, heat conduction, interface, in-situ measurement

中图分类号:

TK 01.9

张中印,袁诚阳,樊轩辉,祝捷,赵佳飞,唐大伟. 基于TDTR技术水合物热导率测量方法[J]. 化工学报, 2019, 70(S2): 54-61.

Zhongyin ZHANG,Chengyang YUAN,Xuanhui FAN,Jie ZHU,Jiafei ZHAO,Dawei TANG. Thermal conductivity measurement of hydrate based on TDTR technology[J]. CIESC Journal, 2019, 70(S2): 54-61.

图/表 12

图1 水合物三种晶体结构[1]

Fig.1 Three crystal structures of hydrate[1]

图2 TDTR实验系统光路图

Fig.2 TDTR experimental system optical path diagram

表1 石英玻璃参数

Table 1 Quartz glass parameters

厚度/ $μ m$	纯度	C/( $M J / (m 3 ? K))$	λ/(W/(m?K))
500 $±$ 50	>99.99%	1.63	1.30

表1 石英玻璃参数

Table 1 Quartz glass parameters

厚度/ $μ m$	纯度	C/( $M J / (m 3 ? K))$	λ/(W/(m?K))
500 $±$ 50	>99.99%	1.63	1.30

图3 样品结构

Fig.3 Sample structure

图4 皮秒声学法测量Al膜厚度

Fig.4 Measurement of Al film thickness by picosecond echo method

图5 水合物样品制备方法示意图

Fig.5 Schematic diagram of preparation method of hydrate sample

图6 半导体控温台

Fig.6 Semiconductor temperature control station

图7 样品内部双向热输运示意图

Fig.7 Schematic diagram of internal bidirectional heat transport in sample

图8 实验数据与理论模型拟合结果

Fig.8 Experimental data and theoretical model fitting results

图9 水合物样品各参数敏感度

Fig.9 Hydrate sample parameters sensitivity

表2 THF热导率测试过程中各参数误差传递过程

Table 2 Error propagation of various parameters during THF thermal conductivity test

α	S_α	S_α /S_x	E_x _, _α /%	E_x /%
α = α _Al	0.455	1.5696	3.1392	10.18
α = $λ S i O 2$	0.51688	1.7831	8.9155
α = $C S i O 2$	0.219134	0.756	3.78
x = $λ$ _THF	0.289874

表2 THF热导率测试过程中各参数误差传递过程

Table 2 Error propagation of various parameters during THF thermal conductivity test

α	S_α	S_α /S_x	E_x _, _α /%	E_x /%
α = α _Al	0.455	1.5696	3.1392	10.18
α = $λ S i O 2$	0.51688	1.7831	8.9155
α = $C S i O 2$	0.219134	0.756	3.78
x = $λ$ _THF	0.289874

表3 Al/THF界面热导测试过程中各参数误差传递过程

Table 3 Error propagation of various parameters during Al/THF interface thermal conductance test

α	S_α	S_α /S_x	E_x _, _α /%	E_x /%
α = δ _Al	0.455	2.718	5.436	16.58
α = $λ S i O 2$	0.51688	3.088	15.44
α = $C S i O 2$	0.219134	1.3092	2.6184
x =G _Al/THF	0.167386

表3 Al/THF界面热导测试过程中各参数误差传递过程

Table 3 Error propagation of various parameters during Al/THF interface thermal conductance test

α	S_α	S_α /S_x	E_x _, _α /%	E_x /%
α = δ _Al	0.455	2.718	5.436	16.58
α = $λ S i O 2$	0.51688	3.088	15.44
α = $C S i O 2$	0.219134	1.3092	2.6184
x =G _Al/THF	0.167386

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