Journal of Materials Science

, Volume 55, Issue 7, pp 2994–3004 | Cite as

Supercooling characteristics of mannitol phase transition system under heterogeneous nucleation

  • Jun Ji
  • Yinghui Wang
  • Xuelai ZhangEmail author
  • Yue Chen
  • Jotham Muthoka Munyalo
  • Sheng Liu
Energy materials


Supercooling of phase change materials (PCMs) during solidification is a major problem in cold thermal energy storage (CTES), which reduces energy efficiency and aggravates energy waste. This study focuses on the supercooling characteristics of PCMs under heterogeneous nucleation, which provides a new idea for researching the influence of different dispersants on the supercooling degree of aqueous solution. The optimal ratios of CNTs water dispersant (TNWDIS) and polymer polyacrylic acid sodium (PAAS) to multi-walled carbon nanotubes (MWCNTs) in mannitol aqueous solution are determined through microstructure and cooling characteristics. How these two surfactants and MWCNTs with different concentrations and particle sizes influence the supercooling degree of nanofluids are investigated. The results indicate that the effect of PAAS is greater than that of TNWDIS. Furthermore, under the action of two dispersants and particle sizes of MWCNTs, the fitting equations of supercooling changing with the concentration of MWCNTs are obtained. In the light of the heterogeneous nucleation theory, with the enlargement of the particle size and the diminution of the contact angle affected by the dispersants, the interfacial free energy of heterogeneous nucleation of PCMs on the surface of nanoparticles is reduced. The supercooling degree therefore decreases. Specifically, the nucleation mechanism is deduced and analyzed through the contact angle and nucleation free energy formula.



Multi-walled carbon nanotube


Phase change material


Polymer polyacrylic acid sodium


Cold thermal energy storage


Sodium acetate trihydrate


Multi-walled carbon nanofluid


Sodium dodecylbenzene sulfonate


Scanning electron microscope


Carbon nanotubes water dispersant



Supercooling degree (°C)


Mass concentration (%)


Radius (m)


Contact angle (°)


Interfacial free energy (mN m−1)


Free surface energy (mN m−1)


Density (kg m−3)


Latent heat of fusion (kJ kg−1)



This work was financially supported by National Key Research and Development Project (2018YFD0401305); National Natural Science Foundation of China (51376115); and Shanghai Science and Technology Commission Project (16040501600).


  1. 1.
    Al-Shannaq R, Young B, Farid M (2019) Cold energy storage in a packed bed of novel graphite/PCM composite spheres. Energy 171:296–305CrossRefGoogle Scholar
  2. 2.
    Jia XJ, Zhai XQ, Cheng XW (2019) Thermal performance analysis and optimization of a spherical PCM capsule with pin-fins for cold storage. Appl Therm Eng 148:929–938CrossRefGoogle Scholar
  3. 3.
    Munyalo JM, Zhang XL, Xu XF (2018) Experimental investigation on supercooling, thermal conductivity and stability of nanofluid based composite phase change material. J Energy Storage 17:47–55. CrossRefGoogle Scholar
  4. 4.
    Al-Shannaq R, Kurdi J, Al-Muhtaseb S et al (2015) Supercooling elimination of phase change materials (PCMs) microcapsules. Energy 87:654–662CrossRefGoogle Scholar
  5. 5.
    Safari A, Saidur R, Sulaiman FA et al (2017) A review on supercooling of Phase Change Materials in thermal energy storage systems. Renew Sustain Energy Rev 70:905–919CrossRefGoogle Scholar
  6. 6.
    Sandnes B, Rekstad J (2006) Supercooling salt hydrates: stored enthalpy as a function of temperature. Sol Energy 80:616–625CrossRefGoogle Scholar
  7. 7.
    Jamil N, Kaur J, Pandey AK et al (2019) A review on nano enhanced phase change materials: an enhancement in thermal properties and specific heat capacity. J Adv Res Fluid Mech Therm Sci 57:110–120Google Scholar
  8. 8.
    Sidik NAC, Kean TH, Chow HK et al (2018) Performance enhancement of cold thermal energy storage system using nanofluid phase change materials: a review. Int Commun Heat Mass Transf 94:85–95CrossRefGoogle Scholar
  9. 9.
    Zhang XL, Li Y, Wang YL (2016) Supercooling degree of ethanol solution under action of porous media. Ciesc J 67:4976–4982Google Scholar
  10. 10.
    Yu J, Chen X, Ma XL et al (2014) Influence of nanoparticles and graphite foam on the supercooling of acetamide. J Nanomater 8:214–224Google Scholar
  11. 11.
    Lin SC, Al-Kayiem HH (2016) Evaluation of copper nanoparticles—paraffin wax compositions for solar thermal energy storage. Sol Energy 132:267–278CrossRefGoogle Scholar
  12. 12.
    MaréT Sow O, Halelfadl S et al (2012) Experimental study of the freezing point of γ-Al2O3/water nanofluid. Adv Mech Eng 8:2692–2699Google Scholar
  13. 13.
    Schick C (2014) Kinetics of nucleation and crystallization of poly (epsilon-caprolactone)—multiwalled carbon nanotube composites. Eur Polym J 52:1–11CrossRefGoogle Scholar
  14. 14.
    Kean TH, Sidik NAC, Asako Y et al (2018) Numerical study on heat transfer performance enhancement of phase change material by nanoparticles: a review. J Adv Res Fluid Mech Therm Sci 45:55–63Google Scholar
  15. 15.
    Mohamad AT, Che Sidik NA, M’hamed B (2019) Thermo physical enhancement of advanced nano-composite phase change material. J Adv Res Appl Mech 54:1–8Google Scholar
  16. 16.
    Liu YD, Wang JQ, Su CJ et al (2017) Nucleation rate and supercooling degree of water-based graphene oxide nanofluids. Appl Therm Eng 115:1226–1236CrossRefGoogle Scholar
  17. 17.
    Liu Y, Li X, Hu P et al (2015) Study on the supercooling degree and nucleation behavior of water-based graphene oxide nanofluids PCM. Int J Refrig 52:80–86CrossRefGoogle Scholar
  18. 18.
    Cui WL, Ping YY, Sun LL et al (2016) Experimental studies on the supercooling and melting/freezing characteristics of nano-copper/sodium acetate trihydrate composite phase change materials. Renew Energy 99:1029–1037CrossRefGoogle Scholar
  19. 19.
    Che Sidik NA, Kean TH, Chow HK et al (2018) Performance enhancement of cold thermal energy storage system using nanofluid phase change materials: a review. J Adv Res Mater Sci 43:1–21Google Scholar
  20. 20.
    Shen SL, Tan SJ, Wu S et al (2018) The effects of modified carbon nanotubes on the thermal properties of erythritol as phase change materials. Energy Convers Manag 157:41–48CrossRefGoogle Scholar
  21. 21.
    Kuwabara C, Terauchi R, Tochigi H et al (2014) Analysis of supercooling activities of surfactants. Cryobiology 69:10–16CrossRefGoogle Scholar
  22. 22.
    Zhang XY, Niu JL, Zhang S et al (2015) PCM in water emulsions: supercooling reduction effects of nano-additives, viscosity effects of surfactants and stability. Adv Eng Mater 17:181–188CrossRefGoogle Scholar
  23. 23.
    Matsumoto K, Ueda J, Ehara K et al (2017) Active control of supercooling degree using two surfactants of different molecular size. Int J Refrig 85:462–471CrossRefGoogle Scholar
  24. 24.
    Jia L, Peng L, Chen Y et al (2014) Improving the supercooling degree of titanium dioxide nanofluids with sodium dodecyl sulfate. Appl Energy 124:248–255CrossRefGoogle Scholar
  25. 25.
    Sun RJ, Wei SS, Zhao ZQ et al (2013) Dispersion of mutiwall carbon nanotubes. Appl Mech Mater 357–360:986–989CrossRefGoogle Scholar
  26. 26.
    Ji J, Chen Y, Zhang XL et al (2018) Preparation and thermophysical properties of mannitol aqueous solution PCMs for thermal energy storage. Chem Ind Eng Prog 37:1111–1117Google Scholar
  27. 27.
    Dalla BS, Paineau E, Brubach JB et al (2016) Water in carbon nanotubes: the peculiar hydrogen bond network revealed by infrared spectroscopy. J Am Chem Soc 138:10437–10443CrossRefGoogle Scholar
  28. 28.
    Xu ZJ, Chu RQ (2010) Nanomaterials and nanotechnology. Chemical Industry Press, BeijingGoogle Scholar
  29. 29.
    Ji J, Chen Y, Wang YH et al (2019) Fabrication and characterization of phase change nanofluid with high thermophysical properties for thermal energy storage. J Mol Liq 284:23–28CrossRefGoogle Scholar
  30. 30.
    Gao ZX (2010) Effects of HA nanoparticles on subcooling of EG solutions. Cryogenics 3:52–55Google Scholar
  31. 31.
    Liu XY (2002) Effect of foreign particles: a comprehensive understanding of 3D heterogeneous nucleation. J Cryst Growth 237:1806–1812CrossRefGoogle Scholar
  32. 32.
    Mezgebe M, Jian LH, Shen Q et al (2012) Studies and comparison of the liquid adsorption behavior and surface properties of single- and multiwall carbon nanotubes by capillary rise method. Colloids Surf A: Physicochem Eng Asp 415:86–90CrossRefGoogle Scholar
  33. 33.
    Hobbs PV (2010) Ice physics. Oxford University Press, OxfordGoogle Scholar
  34. 34.
    Tarasov L, Peltier WR (2004) A geophysically constrained large ensemble analysis of the deglacial history of the North American ice-sheet complex. Quat Sci Rev 23:359–388CrossRefGoogle Scholar
  35. 35.
    Devireddy RV, Swanlund DJ, Alghamdi AS et al (2002) Measured effect of collection and cooling conditions on the motility and the water transport parameters at subzero temperatures of equine spermatozoa. Reproduction 124:643–648CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Institute of Cool Storage TechnologyShanghai Maritime UniversityShanghaiChina
  2. 2.Beijing Vegetable Research Center, Academy of Agriculture and Forestry SciencesBeijingChina

Personalised recommendations