液-液相分离工质用于微通道散热的研究进展与展望

doi:10.3976/j.issn.1002-4026.20260004

摘要/Abstract

摘要： 随着电子器件向小型化、高功率发展，其热流密度已远超传统风冷、液冷等散热技术的极限。液-液相分离作为一种新兴的被动热管理技术，利用工质在超过下临界溶液温度时发生相变吸热并产生强烈流体扰动的特性，为微通道极高热流散热提供了革命性解决方案。本文对其热力学基本原理及水-三乙胺、水-乙二醇单丁醚等有限的环境友好型工质体系进行了阐述；梳理了数值模拟（如相场模型、分子动力学）在揭示斯宾那多分解、液滴动力学等微观机理方面的进展，以及实验研究在验证其宏观强化传热、降低流动压降效能方面的成果；创新性地探讨了将化工分离中成熟的“盐析效应”引入本领域，以无机盐的水合作用主动调控工质相变特性、拓展其适用温区的巨大潜力。同时指出现有研究存在的关键空白，包括微观机理与宏观性能之间的关联缺失、流体物性主动调控能力的缺乏，以及系统级可靠性研究的不足。最后对未来发展方向进行了展望，认为未来研究应致力于发展相变特性可智能调控的复合工质，并深化盐析等外场效应下的跨尺度传热机理研究，以推动该技术从实验室走向工程应用。

关键词: 液-液相分离, 微通道散热, 强化传热, 临界溶液温度, 盐析效应

Abstract: With the trend towards miniaturization and higher power in electronic devices, their heat flux has far exceeded the limits of traditional cooling technologies such as air cooling and liquid cooling. Liquid-liquid phase separation (LLPS) has emerged as a novel passive thermal management technique. It leverages the characteristic of a working fluid to absorb heat and generate intense fluid perturbation upon phase separation when exceeding its lower critical solution temperature (LCST), offering a revolutionary solution for cooling extremely high heat fluxes in microchannels. This paper systematically reviews the research progress in this field. First, the thermodynamic principles and the limited selection of environmentally friendly working fluid systems, such as water-triethylamine and water-butoxyethanol, are elucidated. Second, advances in numerical simulations (e.g., phase-field models, molecular dynamics) in revealing microscopic mechanisms like spinodal decomposition and droplet dynamics, as well as experimental studies validating its macroscopic efficacy in enhancing heat transfer and reducing flow pressure drop, are summarized. Furthermore, this paper innovatively explores the significant potential of introducing the well-established "salting-out effect" from chemical separation into this domain. The hydration effect of inorganic salts can actively tune the phase-change characteristics of the working fluid and expand its applicable temperature range. The review identifies existing research gaps, including the missing links between microscopic mechanisms and macroscopic performance, the lack of active control over fluid properties, and the scarcity of system-level reliability studies. Future research should focus on developing intelligent composite working fluids with tunable phase-change properties and deepening the understanding of cross-scale heat transfer mechanisms under external fields like salting-out, to facilitate the transition of this technology from the laboratory to engineering applications.

Key words: liquid-liquid phase separation, microchannel cooling, enhanced heat transfer, critical solution temperature, salting-out effect

中图分类号:

TK124

赵东煜. 液-液相分离工质用于微通道散热的研究进展与展望[J]. 山东科学, 0, (): 1-.

ZhaoDongyu. Advances and liquid-liquid phase separation working fluids for microchannel heat dissipation[J]. Shandong Science, 0, (): 1-.

参考文献

[1] He Wei, Zhang Gan, Zhang Xingxing, et al. Recent development and application of thermoelectric generator and cooler[J]. Applied Energy, 2015, 143: 1-25.

[2] Xie Gongnan, Peng, others. Efficient on-chip hotspot removal combined solution of thermoelectric cooler and mini-channel heat sink[J]. Applied Thermal Engineering, 2016, 100: 174-181. DOI:10.1016/j.applthermaleng.2016.02.035.

[3] Anandan S, Ramalingam V. Thermal management of electronics: A review of literature[J]. Thermal Science, 2008, 12(2): 5-26. DOI:10.2298/tsci0802005a.

[4] Ullmann A, Gat S, Ludmer Z, et al. Phase separation of partially miscible solvent systems: Flow phenomena and heat and mass transfer applications[J]. Reviews in Chemical Engineering, 2008, 24(4/5): 159-262. DOI:10.1515/revce.2008.24.4-5.159.

[5] Francis A W. Liquid-Liquid Equilibriums[M]. New York: Wiley-Interscience, 1963.

[6]. Solubilities of inorganic and organic compounds. Volume 2, ternary and multicomponent systems, part 2 (Stephen, H.; Stephen, T.)[J]. Journal of Chemical Education, 1965, 42(8): 460. DOI:10.1021/ed042p460.2.

[7] Mauri R, Shinnar R, Triantafyllou G. Spinodal decomposition in binary mixtures[J]. Physical Review E, 1996, 53(3): 2613-2623. DOI:10.1103/physreve.53.2613.

[8] Datt C, Thampi S P, Govindarajan R. Morphological evolution of domains in spinodal decomposition[J]. Physical Review E, Statistical, Nonlinear, and Soft Matter Physics, 2015, 91(1): 010101. DOI:10.1103/PhysRevE.91.010101.

[9] Seol D J, Hu S Y, Li Y L, et al.Computer simulation of spinodal decomposition in constrained films[J]. Acta Materialia, 2003, 51(17): 5173-5185. DOI:10.1016/S1359-6454(03)00378-1.

[10] Lamorgese A G, Mauri R. Nucleation and spinodal decomposition of liquid mixtures[J]. Physics of Fluids, 2005, 17(3): 034107. DOI:10.1063/1.1863752.

[11] Bertei A, Tellini B, Mauri R. Dynamic transition of dendrite orientation in the diffusive spinodal decomposition of binary mixtures under a thermal gradient[J]. Chemical Engineering Science, 2019, 203: 450-463. DOI:10.1016/j.ces.2019.04.014.

[12] Bertei A, Chueh C C, Mauri R. Dynamics of phase separation of sheared binary mixtures after a nonisothermal quenching[J]. Physical Review Fluids, 2021, 6(9): 094302. DOI:10.1103/physrevfluids.6.094302.

[13] Sarkar S, Banerjee S, Roy S, et al. Composition dependent non-ideality in aqueous binary mixtures as a signature of avoided spinodal decomposition[J]. Journal of Chemical Sciences, 2015, 127(1): 49-59. DOI:10.1007/s12039-014-0749-y.

[14] Damone A, Poesio P. Transport properties of water–triethylamine fluid mixtures calculated using molecular dynamics[J]. Journal of Chemical & Engineering Data, 2019, 64(9): 3731-3741. DOI:10.1021/acs.jced.9b00150.

[15] Taha M, Lee M J. TES buffer-induced phase separation of aqueous solutions of several water-miscible organic solvents at 298.15 K: Phase diagrams and molecular dynamic simulations[J]. The Journal of Chemical Physics, 2013, 138(24): 244501. DOI:10.1063/1.4809995.

[16] Molin D, Mauri R. Enhanced heat transport during phase separation of liquid binary mixtures[J]. Physics of Fluids, 2007, 19(7): 074102. DOI:10.1063/1.2749810.

[17] Tree D R, Dos Santos L F, Wilson C B, et al. Mass-transfer driven spinodal decomposition in a ternary polymer solution[J]. Soft Matter, 2019, 15(23): 4614-4628. DOI:10.1039/c9sm00355j.

[18] Rutin S B, Skripov P V, Igolnikov A A. Non-stationary heat transfer beyond diffusion spinodal of a solution[C]//AIP Conference Proceedings, 2020, 2314: 030046. DOI:10.1063/5.0032214.

[19] Poesio P, Lezzi A M, Beretta G P. Evidence of convective heat transfer enhancement induced by spinodal decomposition[J]. Physical Review E, Statistical, Nonlinear, and Soft Matter Physics, 2007, 75(6 Pt 2): 066306. DOI:10.1103/PhysRevE.75.066306.

[20] Ullmann A, Maevski K, Brauner N. Enhancement of forced and free convection heat transfer rates by inducing liquid–liquid phase separation of a partially-miscible equal-density binary liquid system[J]. International Journal of Heat and Mass Transfer, 2014, 70: 363-377. DOI:10.1016/j.ijheatmasstransfer.2013.11.006.

[21] Xing Wei, Vutha A K, Yu Xiangfei, et al. Liquid/liquid phase separation heat transfer at the microscale[J]. International Journal of Heat and Mass Transfer, 2017, 107: 53-65. DOI:10.1016/j.ijheatmasstransfer.2016.11.028.

[22] Xing Wei, Plawsky J, Woodcock C, et al.Liquid-liquid phase separation heat transfer in advanced micro structure[J]. International Journal of Heat and Mass Transfer, 2018, 127: 989-1000. DOI:10.1016/j.ijheatmasstransfer.2018.08.090.

[23] Xing Wei, Ullmann A, Brauner N, et al. Advancing micro-scale cooling by utilizing liquid-liquid phase separation[J]. Scientific Reports, 2018, 8: 12093. DOI:10.1038/s41598-018-30584-6.

[24] Kohler F, Rice O K. Coexistence curve of the triethylamine-water system[J]. The Journal of Chemical Physics, 1957, 26(6): 1614-1618. DOI:10.1063/1.1743594.

[25] Hashimoto T, Matsuzaka K, Moses E, et al. String phase in phase-separating fluids under shear flow[J]. Physical Review Letters, 1995, 74(1): 126-129. DOI:10.1103/PhysRevLett.74.126.

[26] Santonicola G, Mauri R, Shinnar R. Phase separation of initially inhomogeneous liquid mixtures[J]. Industrial & Engineering Chemistry Research, 2001, 40(8): 2004-2010. DOI:10.1021/ie000798v.

[27] Poesio P, Cominardi G, Lezzi A M, et al. Effects of quenching rate and viscosity on spinodal decomposition[J]. Physical Review E, Statistical, Nonlinear, and Soft Matter Physics, 2006, 74(1 Pt 1): 011507. DOI:10.1103/PhysRevE.74.011507.

[28] Califano F, Mauri R. Retardation of the phase segregation of liquid mixtures with a critical point of miscibility[J]. AIChE Journal, 2018, 64(11): 4047-4052. DOI:10.1002/aic.16213.

[29] Weiwei E, Pope K, Duan Xili. Droplet coalescence in liquid/liquid separation[J]. Journal of Fluids Engineering, 2020, 142(11): 111402. DOI:10.1115/1.4047796.

[30] Jiang Hua, Dou Nannan, Fan Guoqiang, et al. Effect of temperature gradient on liquid-liquid phase separation in a polyolefin blend[J]. The Journal of Chemical Physics, 2013, 139(12): 124903. DOI:10.1063/1.4821591.

[31]赵东煜.液-液相分离行为的微观可视化研究[D].东营:中国石油大学(华东), 2023.

[32]张远. LCST溶液相分离特性可视化研究[D].东营:中国石油大学(华东), 2021.

[33] Zhang Yuan, Ding Bin, Zhao Dongyu, et al.Effect of natural convection and diffusion on liquid-liquid phase separation behaviors of partially miscible solutions with lower critical solution temperature[J]. International Journal of Heat and Mass Transfer, 2023, 201: 123566. DOI:10.1016/j.ijheatmasstransfer.2022.123566.

[34] Zhao Dongyu, Ding Bin, Zhu Chuanyong, et al. Effects of inorganic salts on the phase separation of partially miscible solutes[J]. Langmuir, 2024, 40(11): 5818-5827. DOI:10.1021/acs.langmuir.3c03693.

[35] Albertsson P A. Partition of cell particles and macromolecules in polymer two-phase systems[J]. Advances in Protein Chemistry, 1970, 24: 309-341. DOI:10.1016/s0065-3233(08)60244-2.

[36] Matkovich C E, Christian G D. Salting-out of acetone from water. Basis of a new solvent extraction system[J]. Analytical Chemistry, 1973, 45(11): 1915-1921. DOI:10.1021/ac60333a023.

[37] Kumamoto M , Nishimoto J , Takamuku T ,et al.Ion-pair extraction of metalloporphyrins into a mixture of acetonitrile with water[J].Pure & Applied Chemistry, 1998, 70(10):1925-1932.DOI:10.1351/pac199870101925.

[38] Gutowski K E, Broker G A, Willauer H D, et al. Controlling the aqueous miscibility of ionic liquids: Aqueous biphasic systems of water-miscible ionic liquids and water-structuring salts for recycle, metathesis, and separations[J]. Journal of the American Chemical Society, 2003, 125(22): 6632-6633. DOI:10.1021/ja0351802.

[39]谭平华,林金清,陈培钦,等.异丙醇-磷酸氢二钾-水三元体系的溶解度和液液相平衡[J].华侨大学学报(自然科学版), 2003, 24(2): 179-183. DOI:10.3969/j.issn.1000-5013.2003.02.013.

[40]吴艳平,许虹,黄婷婷.硫酸铵-溴化四丁基铵水体系液液萃取分离铅[J].河南师范大学学报(自然科学版), 2009, 37(1): 109-112.DOI:10.3969/j.issn.1000-2367.2009.01.031.

[41] Zhang Chao, Huang Kun, Yu Pinhua, et al.Salting-out induced three-liquid-phase separation of Pt(IV), Pd(II) and Rh(III) in system of S201–acetonitrile–NaCl–water[J]. Separation and Purification Technology, 2011, 80(1): 81-89. DOI:10.1016/j.seppur.2011.04.011.

[42] Li Minglun, Zhuang Bilin, Lu Yuyuan, et al. Salt-induced liquid-liquid phase separation: Combined experimental and theoretical investigation of water-acetonitrile-salt mixtures[J]. Journal of the American Chemical Society, 2021, 143(2): 773-784. DOI:10.1021/jacs.0c09420.

[43] Nie Lirong, Zheng Ziwei, Lu Mingxia, et al. Phase behavior of ionic liquid-based aqueous two-phase systems[J]. International Journal of Molecular Sciences, 2022, 23(20): 12706. DOI:10.3390/ijms232012706.