Determination of the kinetic parameters of fatty acid phase-change materials based on the T-history method

doi:10.19799/j.cnki.2095-4239.2024.0172

Abstract

Abstract:

Existing phase transition models artificially set the phase fraction to be linearly related to the temperature interval, failing to consider the influence of the temperature change rate on the phase transition process and resulting in a low prediction accuracy. In this study, to investigate the two-phase transformation law under the joint effect of temperature and the temperature change rate, a theoretical analysis of the phase change process is conducted and a solidification-melting kinetic model is established through the reversible reaction between the PCM components in the solid and liquid phases using the phase fraction as the key parameter. The Avrami equation was set as the reaction function in the model, and the Arrhenius equation was used as the rate function. Fatty acid phase change materials commonly used in the construction field (i.e., n-decanoic acid, lauric acid, and octanoic acid) were selected as experimental materials, and the Avrami equation was fitted and verified via isothermal crystallization experiments using the T-history method. After verifying that the Avrami equation shows a high degree of consistency and reliability with the data obtained from isothermal crystallization experiments, the thermodynamic characteristics of the phase-change materials at different temperatures and rates of temperature change were evaluated using non-isothermal experiments. The key kinetic parameters in the model were investigated and obtained in conjunction with the kinetic thermal analysis method. The results show that the activation energy and constant factor change via the same trend and exhibit a complementary relationship. Moreover, the activation energy and constant factor differ between different phase-change materials, and these changes vary depending on the phase transition process. The number of reaction levels decreases with increasing temperature change rate, and the number of reaction levels during the solidification process is generally larger than that during the melting process.

Key words: Avrami model, phase transition kinetic model, T-history method, kinetic parameters

CLC Number:

TK 02

Silin LIU, Xiaoling CAO, Peilu ZHANG, Ziyu LENG. Determination of the kinetic parameters of fatty acid phase-change materials based on the T-history method[J]. Energy Storage Science and Technology, 2024, 13(8): 2634-2648.

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References 16

1	JOHNSON W A, MEHL R F. Reaction kinetics in process of nucleation and growth[J]. Transaction of Aime, 1939, 135: 416-442.
2	KOLMOGOROV A N. Local structure of turbulence in an incompressible liquid for very large Reynolds numbers[J]. Comptes Rendus de l'Académie des Sciences, 1941, 30(4): 299-303.
3	TOBIN M C. Theory of phase transition kinetics with growth site impingement. I. Homogeneous nucleation[J]. Journal of Polymer Science: Polymer Physics Edition, 1974, 12(2): 399-406. DOI: 10.1002/pol.1974.180120212.
4	MALKIN A Y, BEGHISHEV V P, KEAPIN I A, et al. General treatment of polymer crystallization kinetics: Part 1. A new macrokinetic equation and its experimental verification[J]. Polymer Engineering & Science, 1984, 24(18): 1396-1401. DOI: 10.1002/pen.760241805.
5	AVRAMI M. Kinetics of phase change. I: General theory[J]. Journal of Chemical Physics, 1939, 7: 1103-1112. DOI: 10.1063/1.1750380.
6	BUTTITTA G, SERALE G, CASCONE Y. Enthalpy-temperature evaluation of slurry phase change materials with T-history method[J]. Energy Procedia, 2015, 78: 1877-1882. DOI: 10.1016/j.egypro.2015.11.352.
7	RATHGEBER C, MIRÓ L, CABEZA L F, et al. Measurement of enthalpy curves of phase change materials via DSC and T-history: When are both methods needed to estimate the behaviour of the bulk material in applications?[J]. Thermochimica Acta, 2014, 596: 79-88. DOI: 10.1016/j.tca.2014.09.022.
8	FANTUCCI S, GOIA F, PERINO M, et al. Sinusoidal response measurement procedure for the thermal performance assessment of PCM by means of dynamic heat flow meter apparatus[J]. Energy and Buildings, 2019, 183: 297-310. DOI: 10.1016/j.enbuild.2018.11.011.
9	KISSINGER H E. Reaction kinetics in differential thermal analysis[J]. Analytical Chemistry, 1957, 29(11): 1702-1706. DOI: 10.1021/ac60131a045.
10	AKAHIRA M, SUNOSE T. Thermogravimetric analysis of the thermal decomposition of solid compounds[J]. Bulletin of the Chemical Society of Japan,1968, 41(9): 2172-2180.
11	OZAWA T. Kinetic analysis of derivative curves in thermal analysis[J]. Journal of Thermal Analysis, 1970, 2(3): 301-324. DOI: 10.1007/BF01911411.
12	GARCIA-MARAVER A, PEREZ-JIMENEZ J A, SERRANO-BERNARDO F, et al. Determination and comparison of combustion kinetics parameters of agricultural biomass from olive trees[J]. Renewable Energy, 2015, 83: 897-904. DOI: 10.1016/j.renene.2015.05.049.
13	ZHANG Y P, JIANG Y, JIANG Y. A simple method, the-history method, of determining the heat of fusion, specific heat and thermal conductivity of phase-change materials[J]. Measurement Science and Technology, 1999, 10(3): 201-205. DOI: 10.1088/0957-0233/10/3/015.
14	HONG H, KIM S K, KIM Y S. Accuracy improvement of T-history method for measuring heat of fusion of various materials[J]. International Journal of Refrigeration, 2004, 27(4): 360-366. DOI: 10.1016/j.ijrefrig.2003.12.006.
15	HARNISCH K, LANZENBERGER R. Determination of the Avrami exponent by non-isothermal analyses[J]. Journal of Non-Crystalline Solids, 1982, 53(3): 235-245. DOI: 10.1016/0022-3093(82)90083-7.
16	CONNER W. A general explanation for the compensation effect: The relationship between ∆S and activation energy[J]. Journal of Catalysis, 1982, 78(1): 238-246. DOI: 10.1016/0021-9517(82)90303-7.

材料	温度变化速率/(℃/min)	熔化温度区间/℃	凝固温度区间/℃
正癸酸	熔化0.4/凝固1.5	27.505~31.679	30.365~24.038
	熔化0.6/凝固1.7	27.709~32.031	30.358~23.502
	熔化0.8/凝固1.9	27.934~32.513	30.292~22.898
	熔化1.0/凝固2.1	28.132~33.032	30.139~22.369
	熔化1.2/凝固2.3	28.328~33.705	29.946~21.764

月桂酸	熔化0.4/凝固1.5	40.944~46.548	42.585~33.917
	熔化0.6/凝固1.7	41.063~47.244	42.320~32.742
	熔化0.8/凝固1.9	41.127~48.013	42.102~31.485
	熔化1.0/凝固2.1	41.226~48.561	41.972~30.316
	熔化1.2/凝固2.3	41.260~49.386	41.711~29.231

辛酸	熔化0.4/凝固1.5	11.602~16.114	13.536~6.932
	熔化0.6/凝固1.7	11.972~16.613	13.351~6.293
	熔化0.8/凝固1.9	12.051~17.124	13.183~5.410
	熔化1.0/凝固2.1	12.231~17.647	13.092~4.842
	熔化1.2/凝固2.3	12.313~18.151	12.931~4.273

材料	熔化相变焓/(J/g)	凝固相变焓/(J/g)
正癸酸	158.123	206.923
月桂酸	202.849	221.585
辛酸	140.688	172.492