Relaxation Effect on Crystal Nucleation in a Glass Unveiled by Experimental, Numerical, and Analytical Approaches

Rodrigues, L. R.; Abyzov, Alexander S.; Fokin, Vladimir M.; Schmelzer, Jürn W. P.; Zanotto, Edgar Dutra

doi:10.2139/ssrn.3919728

Cited by 3 publications

(10 citation statements)

References 14 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In particular, a detailed analysis of the experimental data on crystal nucleation given in Refs. 31–34 shows in agreement with a study performed in Ref. 158 that for a quantitative correct description, at least, two structural order parameters are required.…”

Section: Resultssupporting

confidence: 91%

“…In line with the analysis performed in Refs. 29–34, we demonstrate here that (ii) at temperatures near to the glass transition range and below it, crystal nucleation is considerably affected by the glass transition. It may result in significant deviations of both thermodynamic driving force and surface tension as compared with the situation when the liquid has approached already the metastable equilibrium state prior to nucleation.…”

Section: Resultsmentioning

confidence: 58%

“…Some of such approaches are described in Refs. 31–34. In the present paper, we employ Equations () and () treating the parameters

\Omega _{\Delta g}

and

\Omega _\sigma

as fit parameters.…”

Section: Glass Transition Relaxation and Crystal Nucleation: Theoreti...mentioning

confidence: 99%

“…In recent years, we addressed several new developments in the description of the phase transformation kinetics partly specific for crystallization of glass‐forming liquids. In particular, we analyzed the relation between the time of formation of the first supercritical nucleus, time lag in nucleation, and steady‐state nucleation rate; 14 formulated simple relations for the dependence of the surface tension on temperature and pressure generalizing the Stefan–Skapski–Turnbull rule; 15,16 performed an analysis of the conditions for applicability of the Tolman equation to the description of the curvature dependence of the surface tension in crystal nucleation; formulated expressions for the Tolman parameter for crystallization caused by variations of temperature; derived simple relations for the specification of the Tolman parameter for crystallization caused both by variation of temperature and pressure; 17–19 performed an analysis of the Kauzmann paradox and Kauzmann's suggestion of the existence of a kinetic spinodal to prevent it 20 and its correlation with crystallization processes; 21–23 advanced estimates of the maxima of nucleation, growth, and overall crystallization rates in dependence on pressure and their correlation with different measures of fragility and the glass transition pressure, 24 formulated the concept of a Kauzmann pressure and performed an analysis of its importance with respect to pressure‐induced crystallization; 16 derived some general results concerning possible applications of the nucleation theorem to crystallization; 25 demonstrated the necessity of incorporation of self‐consistency corrections in the specification of the work of critical cluster formation in nucleation; 26 advanced a description of anisotropic nucleation, growth, and ripening under stirring; 27 analyzed statistical methods in the description of crystal nucleation; 28 and performed an analysis of possible effects of the glass transition and the accompanying its structural relaxation of the supercooled liquid on the crystallization kinetics in the vicinity and below the glass transition temperature 29–34 . In the present paper, we would like to advance two of these developments giving, in particular, also an answer to one of the open problems as described in Ref.…”

Section: Introductionmentioning

confidence: 99%

“…These ideas are applied to the interpretation of experimental data in Refs. 32–34. They lead to a comprehensive solution of the problem of “breakdown” of CNT at temperatures in the glass transition interval and below it.…”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

Theory of crystal nucleation of glass‐forming liquids: Some new developments

Schmelzer

Тропин

2021

Int J of Appl Glass Sci

Self Cite

View full text Add to dashboard Cite

Experiments on crystal nucleation are predominantly interpreted theoretically in terms of classical nucleation theory (CNT). This theory relies on thermodynamic concepts developed by Gibbs. Their application implies that the bulk properties of critical clusters governing nucleation are widely identical to those of the newly evolving macroscopic phases. Size effects are incorporated into CNT exclusively by a curvature dependence of the surface tension. This method works well but only down to temperatures near to the maximum of the steady-state nucleation rate. This maximum (at 𝑇 ≅ 𝑇 max ) is correlated with the glass transition temperature, 𝑇 𝑔 , that is, 𝑇 max ≅ 𝑇 𝑔 . For lower temperatures, significant deviations between theoretical predictions and experimental data are observed. We describe here different methods how a curvature dependence of the surface tension can be introduced to describe crystal nucleation correctly in the range 𝑇 ⪆ 𝑇 max ≅ 𝑇 𝑔 . Problems occurring at 𝑇 ⪅ 𝑇 max ≅ 𝑇 𝑔 , denoted sometimes as "breakdown of CNT," are shown to be caused by the glass transition of the liquid. Modifications of CNT are advanced resolving them and giving also the possibility of interpretation of a variety of further experimental data in crystal nucleation (including hysteresis effects in cooling and heating, nucleation flashes in heating) in terms of CNT.

show abstract

Section: Resultssupporting

confidence: 91%

Section: Resultsmentioning

confidence: 58%

“…Some of such approaches are described in Refs. 31–34. In the present paper, we employ Equations () and () treating the parameters

\Omega _{\Delta g}

and

\Omega _\sigma

as fit parameters.…”

Section: Glass Transition Relaxation and Crystal Nucleation: Theoreti...mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Theory of crystal nucleation of glass‐forming liquids: Some new developments

Schmelzer

Тропин

2021

Int J of Appl Glass Sci

Self Cite

View full text Add to dashboard Cite

show abstract

Effects of Structural Relaxation of Glass-forming Melts on the Overall Crystallization Kinetics in Cooling and Heating

Schmelzer,

Tropin,

Schick

2023

Preprint

View full text Add to dashboard Cite

In the theoretical treatment of crystallization it is commonly assumed that relaxation processes of the liquid proceed fast as compared to crystal nucleation and growth processes. Actually, it is supposed that the liquid is located always in the metastable state corresponding to the current values of pressure and temperature. However, near and below the glass transition temperature, Tg, this condition is commonly not fulfilled. In such cases, in the treatment of crystallization, deviations of the state of the liquid from the respective metastable equilibrium state have to be accounted for in determining the kinetic coefficients governing the crystallization kinetics, the thermodynamic driving force of crystallization, and the surface tension of the aggregates of the newly evolving crystal phase including the surface tension of critical clusters affecting considerably the crystal nucleation rate. These factors may considerably influence the course of the overall crystallization process. A theoretical analysis of the resulting effects is given in the present paper by numerical solutions of the J(ohnson)–M(ehl)–A(vrami)–K(olmogorov)–equation employed as the tool to model the overall crystallization kinetics and by analytical estimates of the crystallization peak temperatures in dependence on cooling and heating rates. The results are shown to be in good agreement with experimental data. Possible extensions of the theory to be explored in future analysis are anticipated.

show abstract

Effects of Structural Relaxation of Glass-Forming Melts on the Overall Crystallization Kinetics in Cooling and Heating

Schmelzer,

Tropin,

Schick

2023

Entropy

View full text Add to dashboard Cite

In the theoretical treatment of crystallization, it is commonly assumed that the relaxation processes of a liquid proceed quickly as compared to crystal nucleation and growth processes. Actually, it is supposed that a liquid is always located in the metastable state corresponding to the current values of pressure and temperature. However, near and below the glass transition temperature, Tg, this condition is commonly not fulfilled. In such cases, in the treatment of crystallization, deviations in the state of the liquid from the respective metastable equilibrium state have to be accounted for when determining the kinetic coefficients governing the crystallization kinetics, the thermodynamic driving force of crystallization, and the surface tension of the aggregates of the newly evolving crystal phase including the surface tension of critical clusters considerably affecting the crystal nucleation rate. These factors may greatly influence the course of the overall crystallization process. A theoretical analysis of the resulting effects is given in the present paper by numerical solutions of the J(ohnson)–M(ehl)–A(vrami)–K(olmogorov) equation employed as the tool to model the overall crystallization kinetics and by analytical estimates of the crystallization peak temperatures in terms of the dependence on cooling and heating rates. The results are shown to be in good agreement with the experimental data. Possible extensions of the theory are anticipated and will be explored in future analysis.

show abstract

Relaxation Effect on Crystal Nucleation in a Glass Unveiled by Experimental, Numerical, and Analytical Approaches

Cited by 3 publications

References 14 publications

Theory of crystal nucleation of glass‐forming liquids: Some new developments

Theory of crystal nucleation of glass‐forming liquids: Some new developments

Effects of Structural Relaxation of Glass-forming Melts on the Overall Crystallization Kinetics in Cooling and Heating

Effects of Structural Relaxation of Glass-Forming Melts on the Overall Crystallization Kinetics in Cooling and Heating

Contact Info

Product

Resources

About