Molecular dynamics study of solid-liquid phase change and heat conduction of erythritol at microscale

doi:10.11949/j.issn.0438-1157.20171376

Abstract

Abstract:

The solid-liquid phase change and heat conduction phenomena of erythritol at the microscale were studied using molecular dynamics (MD) simulation. The GROMOS force field was first utilized to calculate the density of erythritol in both solid and liquid phases. The applicability of this force field was verified by comparing the predicted density with the measured values. The microscale melting process of erythritol was simulated using interface/NPT method. The temperature corresponding to a sudden volume increase of the simulated system was identified as the melting point (~400 K), which is in agreement with the measured value of (392±1) K. Due to lowering of the nucleation free energy barrier by introducing a solid-liquid interface, this method was exhibited to have a better performance in simulating the microscale melting process than the direct heating method on solid erythritol. Moreover, non-equilibrium MD simulation was performed to study the microscale heat conduction between erythritol molecules. The thermal conductivity of liquid erythritol was predicted in the range of 0.33-0.35 Wm^-1K^-1, which is consistent with the measured value of (0.33±0.02) Wm^-1K^-1 on bulk erythritol. The predicted thermal conductivity was found to have a negligible dependence on the size of the simulated system because of the random distribution of erythritol molecules in liquid phase.

Key words: erythritol, molecular simulation, phase change, interface/NPT method, heat conduction

摘要：

采用分子动力学方法对微尺度下赤藓糖醇的固液相变及热传导现象进行了模拟研究。首先选用GROMOS力场计算了赤藓糖醇固液两相的密度并将预测结果与实测值进行对比，验证了该力场的适用性。采用界面/NPT法模拟了赤藓糖醇的微观熔化过程，通过体系的体积突变得到预测熔点约为400 K，和实测值（392±1） K较为吻合。与直接加热纯固态赤藓糖醇的方法相比，该方法由于引入固液界面降低了成核自由能位垒，使得微观熔化过程的模拟更准确。此外，基于非平衡分子动力学方法研究了赤藓糖醇分子间的微观热传导现象。模拟得到液态赤藓糖醇的热导率为0.33～0.35 Wm^-1K^-1，与宏观实测值（0.33±0.02） Wm^-1K^-1保持一致。因为处于液态时赤藓糖醇的分子分布具有无序性，所以其热导率预测值几乎不随模拟系统的尺寸而变化。

关键词: 赤藓糖醇, 分子模拟, 相变, 界面/NPT法, 热传导

CLC Number:

TK124

FENG Biao, SHAO Xuefeng, ZHU Ziqin, FAN Liwu. Molecular dynamics study of solid-liquid phase change and heat conduction of erythritol at microscale[J]. CIESC Journal, 2018, 69(6): 2388-2395.

冯飙, 邵雪峰, 朱子钦, 范利武. 赤藓糖醇微观固液相变及热传导的分子动力学研究[J]. 化工学报, 2018, 69(6): 2388-2395.

References 30

[1]	KAIZAWA A, MARUOKA N, KAWAI A, et al. Thermophysical and heat transfer properties of phase change material candidate for waste heat transportation system[J]. Heat and Mass Transfer, 2008, 44(7):763-769.
[2]	SOLÉ A, NEUMANN H, NIEDERMAIER S, et al. Stability of sugar alcohols as PCM for thermal energy storage[J]. Solar Energy Materials and Solar Cells, 2014, 126(11):125-134.
[3]	WANG W, HE S, GUO S, et al. A combined experimental and simulation study on charging process of erythritol-HTO direct-blending based energy storage system[J]. Energy Conversion and Management, 2014, 83:306-313.
[4]	AGYENIM F, EAMES P, SMYTH M. Experimental study on the melting and solidification behaviour of a medium temperature phase change storage material (erythritol) system augmented with fins to power a LiBr/H2O absorption cooling system[J]. Renewable Energy, 2011, 36(1):108-117.
[5]	HÖHLEIN S, KÖNIG-HAAGEN A, BRÜGGEMANN D. Thermophysical characterization of MgCl2·6H2O, xylitol and erythritol as phase change materials (PCM) for latent heat thermal energy storage (LHTES)[J]. Materials, 2017, 10(4):444.
[6]	WANG Y, WANG L, XIE N, et al. Experimental study on the melting and solidification behavior of erythritol in a vertical shell-and-tube latent heat thermal storage unit[J]. International Journal of Heat and Mass Transfer, 2016, 99:770-781.
[7]	SHIN H K, RHEE K Y, PARK S J. Effects of exfoliated graphite on the thermal properties of erythritol-based composites used as phase-change materials[J]. Composites Part B:Engineering, 2016, 96:350-353.
[8]	GAO L, ZHAO J, AN Q, et al. Experiments on thermal performance of erythritol/expanded graphite in a direct contact thermal energy storage container[J]. Applied Thermal Engineering, 2017, 113:858-866.
[9]	NOMURA T, OKINAKA N, AKIYAMA T. Impregnation of porous material with phase change material for thermal energy storage[J]. Materials Chemistry and Physics, 2009, 115(2):846-850.
[10]	ZHANG H, DUQUESNE M, GODIN A, et al. Experimental and in silico characterization of xylitol as seasonal heat storage material[J]. Fluid Phase Equilibria, 2016, 436:55-68.
[11]	JORGENSEN W L, AND D S M, TIRADORIVES J. Development and testing of the OPLS all-atom force field on conformational energetics and properties of organic liquids[J]. Journal of the American Chemical Society, 1996, 118(45):11225-11236.
[12]	WANG J, WOLF R M, CALDWELL J W, et al. Development and testing of a general amber force field[J]. Journal of Computational Chemistry, 2004, 25(9):1157-1174.
[13]	BROOKS B R, BROOKS C L, MACKERELL A D, et al. CHARMM:The biomolecular simulation program[J]. Journal of Computational Chemistry, 2009, 30(10):1545-1614.
[14]	INAGAKI T, ISHIDA T. Computational analysis of sugar alcohols as phase-change material:insight into the molecular mechanism of thermal energy storage[J]. Journal of Physical Chemistry C, 2016, 120(15):7903-7915.
[15]	CALDWELL J W, ROSS W R, CHEATHAM Ⅲ T E, et al. AMBER, a computer program for applying molecular mechanics, normal mode analysis, molecular dynamics and free energy calculations to elucidate the structures and energies of molecules[J]. Computer Physics Communications, 1995, 91:1-41.
[16]	SASTRI S R S, RAO K K. A new temperature-thermal conductivity relationship for predicting saturated liquid thermal conductivity[J]. Chemical Engineering Journal, 1999, 74(3):161-169.
[17]	MATSUBARA H, KIKUGAWA G, BESSHO T, et al. Molecular dynamics study on the role of hydroxyl groups in heat conduction in liquid alcohols[J]. International Journal of Heat and Mass Transfer, 2017, 108:749-759.
[18]	朱宇, 陆小华, 丁皓, 等. 分子模拟在化工应用中的若干问题及思考[J]. 化工学报, 2004, 55(8):1213-1223. ZHU Y, LU X H, DING H, et al. Molecular simulation in chemical engineering[J]. Journal of Chemical Industry and Engineering (China), 2004, 55(8):1213-1223.
[19]	陈占秀, 陈冠益, 王艳, 等. 丙三醇与1, 6-己二醇混合物降温凝固过程的分子动力学模拟[J]. 化工学报, 2013, 64(7):2316-2321. CHEN Z X, CHEN G Y, WANG Y, et al. Molecular dynamics simulation of solidification process for mixtures of glycerol and 1, 6-hexanediol[J]. CIESC Journal, 2013, 64(7):2316-2321.
[20]	HORTA B A C, FUCHS P F J, VAN GUNSTEREN W F, et al. New interaction parameters for oxygen compounds in the GROMOS force field:improved pure-liquid and solvation properties for alcohols, ethers, aldehydes, ketones, carboxylic acids, and esters[J]. Journal of Chemical Theory and Computation, 2011, 7(4):1016-1031.
[21]	SCHMID N, EICHENBERGER A P, CHOUTKO A, et al. Definition and testing of the GROMOS force-field versions 54A7 and 54B7[J]. European Biophysics Journal, 2011, 40(7):843-856.
[22]	BATISTA M L S, PE?REZ-SA?NCHEZ G, GOMES J R B, et al. Evaluation of the GROMOS 56ACARBO force field for the calculation of structural, volumetric, and dynamic properties of aqueous glucose systems[J]. Journal of Physical Chemistry B, 2015, 119(49):15310-15319.
[23]	SHIMADA A. Crystal structure and lattice energy of i-erythritol. (Ⅰ):Crystal structure of i-erythritol[J]. Bulletin of the Chemical Society of Japan, 1959, 32(4):325-329.
[24]	PLIMPTON S. Fast parallel algorithms for short-range molecular dynamics[J]. Journal of Computational Physics, 1995, 117(1):1-19.
[25]	ZHANG Y, MAGINN E J. A comparison of methods for melting point calculation using molecular dynamics simulations[J]. Journal of Chemical Physics, 2012, 136(14):144116.
[26]	WATT S W, CHISHOLM J A, JONES W, et al. A molecular dynamics simulation of the melting points and glass transition temperatures of myo-and neo-inositol[J]. Journal of Chemical Physics, 2004, 121(19):9565-9573.
[27]	徐上, 赵伶玲, 蔡庄立, 等. 二维氮化铝材料传热性能的模拟研究[J]. 化工学报, 2017, 68(9):3321-3327. XU S, ZHAO L L, CAI Z L, et al. Modeling study on thermal conductivity of two-dimensional hexagonal aluminum nitride aluminum nitride[J]. CIESC Journal, 2017, 68(9):3321-3327.
[28]	WIRNSBERGER P, FRENKEL D, DELLAGO C. An enhanced version of the heat exchange algorithm with excellent energy conservation properties[J]. Journal of Chemical Physics, 2015, 143(12):124104.
[29]	HAFSKJOLD B, IKESHOJI T, RATKJE S K. On the molecular mechanism of thermal diffusion in liquids[J]. Molecular Physics, 1993, 80(6):1389-1412.
[30]	SCHELLING P K, PHILLPOT S R, KEBLINSKI P. Comparison of atomic-level simulation methods for computing thermal conductivity[J]. Physical Review B, 2002, 65(14):144306.