Devitrification and Recrystallization of Glass Forming Aqueous Solutions

  • Douglas R. MacFarlane
  • Maria Forsyth
Part of the NATO ASI Series book series (NSSA, volume 147)


The ideal aqueous solution for use in cryobiology would be one which was completely non-toxic and which could be cooled to liquid nitrogen temperatures and returned to room temperature without the formation of ice or any other crystalline phase. Unfortunately requirements of non-toxicity and non-freezing are rarely compatible and the cryobiological techniques which have been developed represent a variety of compromises. On one extreme is the technique known as cryopreservation by vitrification (1,2,3). In this technique large weight fractions of solute are added to the cryopreservation solution and the solution forms a glass on cooling, but the solutes are usually toxic to some extent at the high concentrations involved. Given the toxicity problem, the concentration of solutes is usually kept to the minimum needed for glass formation and as a result the glass usually forms ice briefly during warming. Hence ice is not totally avoided. At the other extreme (4), the solutions are loaded with only relatively minor amounts of solute and the solution inevitably forms a large, approaching equilibrium, quantity of ice during the cooling and heating excursion.


Differential Thermal Analysis Order Phase Transition Diffusion Control Growth Lithium Chloride Solution Interface Control Growth 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.


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  1. 1.
    G.M. Fahy, D.R. MacFarlane, C.A. Angell, and H.T. Meryman, Vitrification as an approach to cryopreservation. Cryobiology 21:407 (1984).PubMedCrossRefGoogle Scholar
  2. 2.
    G. M. Fahy, and A. Hirsh, Prospects for organ preservation by vitrification, in “Organ Preservation, Basic and Applied Aspects” D.E. Pegg, I.A. Jacobson, and N.A. Halasz, eds., pp.399, MTP Press, Lancaster, (1982).Google Scholar
  3. 3.
    G.M. Fahy, D.I. Levy, and S.E. Ali, Some emerging principles underlying the physical properties, biological actions, and utility of vitrification solutions. Cryobiology, in press.Google Scholar
  4. 4.
    P. Mazur, Cryobiology: The freezing of biological systems. Science 168:939 (1970).PubMedCrossRefGoogle Scholar
  5. 5.
    A.O. Trounson, in press 1987.Google Scholar
  6. 6.
    D.R. MacFarlane, Devitrification in glass-forming aqueous solutions. Cryobiology, 23:230 (1986).CrossRefGoogle Scholar
  7. 7.
    D.R. MacFarlane, Physical aspects of Devitrification in aqueous solutions. Cryobiology (in press 1987).Google Scholar
  8. 8.
    D.R. MacFarlane, Comment on the low temperature phase behaviour of amorphous solid water. Cryo-Lett., 7:136 (1986).Google Scholar
  9. 9.
    D.R. MacFarlane, M. Fragoulis, Theory of devitrification in multicomponent glass forming systems under diffusion control. Phys. Chem. Glasses 27:228 (1986).Google Scholar
  10. 10.
    G. Rapatz and B. Luyet, Recrystallization at high subzero temperatures in gelatin gels subjected to various cooling treatment, Biodynamica 8:985, (1959).Google Scholar
  11. 11.
    B. Luyet, and G. Rapatz, Devitrification of aqueous solutions. Bull. Amer. Phys. Soc, 2:342 (1957)Google Scholar
  12. 12.
    P. Boutron, Stability of the amorphous state in system water — 1,2-propanediol. Cryobiology 16:557 (1979).PubMedCrossRefGoogle Scholar
  13. 13.
    P. Boutron, and A. Kaufmann. Stability of the amorphous state in the system water-glycerol-dimethyl sulfoxide. Cryobiology 15:93, (1978).PubMedCrossRefGoogle Scholar
  14. 14.
    P. Boutron, and A. Kaufmann. Stability of the amorphous state in the system water-glycerol-ethylene glycol. Cryobiology 16:83 (1979).PubMedCrossRefGoogle Scholar
  15. 15.
    P. Boutron, A. Kaufmann, and Nguyen Van Dang. Maximum in the stability of the amorphous state in the system water-glycerol-ethanol. Cryobiology 16:372 (1979).PubMedCrossRefGoogle Scholar
  16. 16.
    P. Boutron, Glass-forming tendency, stability of the amorphous state, and cryoprotection of red blood cells. J. Phys. Chem. 87:4273 (1983).CrossRefGoogle Scholar
  17. 17.
    P. Boutron, D. Delage, B. Roustit, and C. Körber, Ternary systems with 1,2-propanediol — A new gain in the stability of the amorphous state in the system water — 1,2-propanediol-l-propanol, Cryobiology, 19:550 (1982).CrossRefGoogle Scholar
  18. 18.
    P. Boutron, P. Mehl, A. Kaufmann, and P. Angibaud, Glass-forming Tendency and stability of the amorphous state in the aqueous solutions of linear polyalcohols with four carbons. Cryobiology, 23:453 (1986).PubMedCrossRefGoogle Scholar
  19. 19.
    P. Boutron, Comparison with the theory of the kinetics and extent of ice crystallization and of the glass forming tendency in aqueous cryoprotective solutions. Cryobiology, 23:88 (1986).PubMedCrossRefGoogle Scholar
  20. 20.
    P. Boutron, and P. Mehl, Non equilibrium ice crystallization in aqueous solutions: comparison with theory, case of solutions of polyalcohols with four carbons, ability to form glasses, compounds favoring cubic ice. submitted to J. de Physique.Google Scholar
  21. 21.
    J. Dupuy, J.F. Jal, C. Ferradou, P. Chieux, A.F. Wright, R. Calemczuk, and C.A. Angell, Controlled nucleation and quasi-ordered growth of ice crystals from low temperature electrolyte solutions. Nature (London) 296:138 (1982).CrossRefGoogle Scholar
  22. 22.
    A. Elarby-Aouizerat, J.F. Jal, C. Ferradou, J. Dupuy, P. Chieux, and A. Wright, Optimal Conditions for the Homogeneous Nucleation of Cubic ice from Concentrated Solutions of LiCl. D20, J. Phys. Chem. 87:4170 (1983).CrossRefGoogle Scholar
  23. 23.
    C.A. Angell, and D.R. MacFarlane, Conductimetric and calorimetric methods for the study of homogeneous nucleation below both Th and Tg. Adv. Ceram. 4:66 (1982).Google Scholar
  24. 24.
    D.R. MacFarlane, R.K. Kadiyala, and C.A. Angell, Emulsion studies of isothermal homogeneous nucleation and growth: Direct determination of TTT curves for ice from aqueous solutions. J. Chem. Phys. 79(8):3921 (1983).CrossRefGoogle Scholar
  25. 25.
    D.R. MacFarlane, M. Fragoulis, B. Uhlherr, and S.D. Jay, Devitrification in aqueous solutions at high heating rates. Cryo-Lett., 7:73 (1986).Google Scholar
  26. 26.
    D.R. MacFarlane, R.K. Kadiyala, and C.A. Angell, Direct observation of TTT curves for crystallization of ice from solutions by a homogeneous mechanism. J. Phys. Chem. 87:1094 (1983).CrossRefGoogle Scholar
  27. 27.
    D.R. MacFarlane, M. Forsyth, J. Johnson, and R. Lawrence, Homogeneous nucleation, glass formation and devitrification in aqueous solutions at high pressures. To be submitted to Cryoletters.Google Scholar
  28. 28.
    N. Alberola, J. Perez, J. Tatlbouet and R. Vassoille, Stability of the vitreous phase in water-ethylene glycol mixtures studied by internal friction. J. Phys. Chem. 87:4264 (1983).CrossRefGoogle Scholar
  29. 29.
    R. Vassoille, A. El Hachadi, G. Vigier, Study by means of internal friction measurements of the vitreous transition in aqueous 1,2-propanediol solutions. Cryo-Letters 7:305 (1986).Google Scholar
  30. 30.
    D.R. MacFarlane, DUNG PhD Thesis, Purdue University, (1982).Google Scholar
  31. 31.
    B. Luyet, Attacks from different fronts on some complex cases of instability in aqueous solutions solidified at low temperatures in ‘International conference on Low Temperature Science.’ Ed. O. Hirobumi, pt 1., 71 (1966).Google Scholar
  32. 32.
    I. Gutzow, D. Kaschiev and I. Anramov, J. Non-Cryst. Sol. 73:477 (1985).CrossRefGoogle Scholar
  33. 33.
    C.T. Moynihan, N. Balitactac, L. Boone and T.A. Litovitz, Comparison of shear and Conductivity Relaxation Times for Concentrated Lithium Chloride Solution. J. Chem Phys., 55:3013.Google Scholar
  34. 34.
    J.W. Christian, “The Theory of Transformations in Metals and Alloys,” 2nd edition, Pergamon Press, Oxford.Google Scholar
  35. 35.
    B. Luyet, Various modes of recrystallization of ice. in ‘International conference on Low Temperature Science.’ Proceedings. Ed. O. Hirobumi, 51 (1966).Google Scholar
  36. 36.
    B.J. Luyet and D.H. Rasmussen, On some inconspicuous changes occurring in aqueous systems subjected to below 0°C temperatures. Biodynamica 11:209 (1973)Google Scholar
  37. 37.
    B. Luyet and D. Sager, On the existence of two temperature ranges of instability in rapidly cooled solutions of PVP, Biodynamica 10:133 (1967).PubMedGoogle Scholar
  38. 38.
    B. Luyet, D. Sager and P.M. Gehenio, The phenomenon of ‘Premelting recrystallization’, Biodynamica 10:123 (1967)PubMedGoogle Scholar
  39. 39.
    A.P. MacKenzie and B.J. Luyet, Electron miscroscope study of recrystallization in rapidly frozen gelatin gels, Biodynamica 10:95 (1967).PubMedGoogle Scholar
  40. 40.
    B. Luyet, D. Rasmussen and C. Kroener, Successive crystallization and recrystallization, during rewarming of rapidly cooled solutions of glycerol and ethylene glycol, Bioynamica 10:53 (1966).Google Scholar
  41. 41.
    B. Luyet, The problem of structural instability and molecular mobility in aqueous solutions ‘solidified’ at low temperatures, Biodynamica 10:1 (1966).PubMedGoogle Scholar
  42. 42.
    M.D. Persidsky and B.J. Luyet, Low temperature recrystallization in gelatin gels and its relationship to concentration, Biodynamica 8:107 (1959).PubMedGoogle Scholar
  43. 43.
    P.M. Gehenio and B.J. Luyet, On the existence of two ranges of recrystallisation temperatures in gelatin gels, Biodynamica 8:81 (1959).PubMedGoogle Scholar
  44. 44.
    B. Luyet and D. Rasmussen, Study by differential thermal analysis of the temperatures of instability in rapidly cooled solutions of PVP, Biodynamica 10:137 (1967).PubMedGoogle Scholar
  45. 45.
    B. Luyet and D. Rasmussen, Study by differential thermal analysis of the temperatures of instability of rapidly cooled solutions of glycerol, ethylene glycol, sucrose of glucose, Biodynamica 10:167 (1968).Google Scholar
  46. 46.
    B. Luyet, Phase transitions encountered in the rapid freezing of aqueous solutions, N.Y. Academy of Science 125:502 (1965).CrossRefGoogle Scholar
  47. 47.
    M. Forsyth and D.R. MacFarlane, Recrystallization Revisited, Cryoletters 7:367 (1986).Google Scholar
  48. 48.
    D. E. Pegg, private communication 1987.Google Scholar
  49. 49.
    C.H. Korber, M.W. Scheiwe, P. Boutron and G. Rau The influence of Hydroxyethyl starch on ice formation in aqueous solutions. Cryobiology 19:478 (1982).CrossRefGoogle Scholar
  50. 50.
    F. Franks Aqueous Solutions at Sub Zero Temperatures in ‘Water — a comprehensive treatise’ vol 7 (1981).Google Scholar
  51. 51.
    C.A. Knight, L.A. DeVries and L.D. Oolman, Fish antifreeze protein and the freezing of recrystallisation of ice, Nature 308:295 (1984).PubMedCrossRefGoogle Scholar
  52. 52.
    F. Franks, J. Darlington, T. Schenz, S.F. Mathias, L. Slade and H. Levine, Antifreeze activity of Antarctic fish glycoprotein and a synthetic polymer, Nature 325:146 (1987).CrossRefGoogle Scholar
  53. 53.
    C.A. Knight and J.G. Duman, Inhibition of recrystallization of ice by insect thermal hysteresis proteins: A possible cryoprotective role, Cryobiology 23:256 (1986).CrossRefGoogle Scholar
  54. 54.
    I.M. Lifshitz and V.V. Slyozov, The kinetics of precipitation from supersaturated solid solutions, J. Phys. Chem. Solids, 19:35 (1961).CrossRefGoogle Scholar
  55. 55.
    I.M. Lifshitz, and V.V. Slyozov, Kinetics of diffusive description of supersaturated solid solutions, J. Exptl. Theoret. Phys. (USSR), 35:479 (1958).Google Scholar
  56. 56.
    C. Wagner, Theorie der Alterung von Niederschlagen durch Umlosen, Z. Elektrochem, 65:581 (1961), (German).Google Scholar
  57. 57.
    S.C. Jain and A.E. Hughes, Ostwald ripening and its application to precipitate and colloids in ionic crystals and glasses, J. Mat. Sci, 13:1611 (1978).CrossRefGoogle Scholar
  58. 58.
    A.J. Ardell, The effect of volume fraction on particle coarsening: theoretical considerations, Acta Metallurgica, 20:61 (1972).CrossRefGoogle Scholar
  59. 59.
    P.W. Voorlees and M.E. Glicksman, Solution to the multiparticle diffusion problem with applications to Ostwald ripening, Parts I, II Acta Metall, 32:2001 (1984).CrossRefGoogle Scholar
  60. 60.
    L.G. Dowell and A.P. Rinfret Low temperature forms of ice as studied by X-ray diffraction, Nature, 188:1144 (1960).CrossRefGoogle Scholar
  61. 1.
    E.C. Trantham, H.E. Rorschach, J.S. Clegg, C.F. Hazlewood, R.M. Nicklow and N. Wakabayashi, Diffusive properties of water in Artemia cysts as determined from quasi-elastic neutron scattering spectra, Biophys. J. 45:927 (1984).PubMedCrossRefGoogle Scholar

Copyright information

© Plenum Press, New York 1987

Authors and Affiliations

  • Douglas R. MacFarlane
    • 1
  • Maria Forsyth
    • 1
  1. 1.Department of ChemistryMonash UniversityClaytonAustralia

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