Multiple Glass Transitions in Bismuth and Tin beyond Melting Temperatures
Round 1
Reviewer 1 Report (New Reviewer)
References must be corrected!
9. —. Validation of non-classical homogeneous nucleation model for G-glass and L-glass formations in liquid elements with recent 399 molecular dynamics simulations. Scripta Mater. 2021, 199, 113859.
16. —. Lindemann's rule applied to the melting of crystals and ultra-stable glasses. Chem. Phys. Lett. 2016, Vol. 651, pp. 198-202. 412 Erratum in 2017, 675, 174.
22. —. Homogeneous nucleation of phase transformations in supercooled water. Physica B. 2020, 579, 411895. 422
23. —. First-order transitions in glasses and melts induced by solid superclusters nucleated by homogeneous nucleation instead of 423 surface melting. Chem. Phys. 2019, 524, 40-54.
Author Response
Please see the attachment
Author Response File: 
Author Response.pdf
Reviewer 2 Report (New Reviewer)
The paper “Multiple glass transitions in bismuth and tin beyond melting temperatures” is a study about thermodynamics of these liquid metals with rising temperature.
In contrast to simple monatomic liquids there exist monatomic liquids which exbibit anomalous behavior with rising temperature. It was suggested that these anomalies are related to a LLT transition above the melting point and structural peculiarities. Here liquid bismuth and tin is studied through thermodynamic calculations. The relation of predictions to various experimental quantities, like density, specific heat or resistivity is then discussed.
The paper could benefit from more general explanations and descriptions of some formalism to make it more accessible to a wider readership. At some parts the text relies heavenly on previous publications, which makes it hard to appreciate the obtained results and conclusions.
I recommend the publication of this manuscript in Metals after the following points are considered:
1) What supports the assumption that the melt consists of 3 liquid states?
2) What is the evidence for Phase3 in liquid Bi and Tin?
3) The “configurons” assumption is based on a sort of bonding in the liquid metals. Please provide evidence for bonding in liquid tin and Bi and how it evolves with temperature. Exists evidence for a percolating network in these liquid metals?
4) Is the calculated transition at T= 784K for tin a glass transition or a LLT? A glass transition is not a first order transition. The expressions should be separated more precisely.
5) What is meant with “glassy fraction” from a structural point of view in contrast to the liquid structure?
6) What is the relation of these transition temperatures to the overheating limit of the crystal?
7) On page 10 is written: “…a fully glassy and ordered state….” . The glass state is structurally completely disordered in contrast to the crystal. These statements should be reformulated.
Author Response
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Author Response File: Author Response.pdf
Reviewer 3 Report (New Reviewer)
This paper is entitled "Multiple Glass Transitions in Bismuth and Tin beyond Melting Temperatures". The glass transitions above melting points for Bi and Sn were studied. The paper is well organized, the language is well polished. The reviewer recommends that the paper be accepted in the current form.
Author Response
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Author Response File: Author Response.pdf
This manuscript is a resubmission of an earlier submission. The following is a list of the peer review reports and author responses from that submission.
Round 1
Reviewer 1 Report
This manuscript presents a theoretical work on the liquid-liquid transition in Bi and Sn system. This kind of phenomena is of importance and interest to the study of liquids. Nonetheless, the manuscript is in general not well prepared enough, and the significance of the findings of this work is not clear and sound enough for its publication in this journal. The following points are suggested to the authors for consideration:
1) The introduction part is mainly a repetition of the abstract, which does not introduce the background, significance, and feasibility of this work.
2) Conceptually, glass transition and liquid-liquid transition differ from each other. While these terms are said to be the same in this work, a sound justification of this idea is necessary.
3) Eq (4) is not presented while being cited.
4) It is said that Eq 6 is a quardratic equation, while it does not seem so from Eq. 6.
5) A Tg/Tm of 2.168 and 1.832 is reported for Sn upon heating and cooling, respectively. Do these numbers depend on the heating/cooling rates? What is the heating/cooling rate adopted here?
6) Section 7, citation of work by Zu FQ is missing.
Answer
- The Introduction is changed
- Conceptually we consider that the liquid-transitions are reminiscent of percolation thresholds already observed in the glassy state. I have already published predictions of liquid-liquid transitions and several papers in collaboration with M Ojovan. The first order transitions below Tm at Tx involve the formation of glassy fractions with glass transition temperatures being higher than Tm together with a crystallized fraction. Our predictions are in perfect agreement with recent simulations published by other authors (references given in the introduction). Other liquid-liquid transitions are observed above Tm in the absence of first-order transitions below Tm. These transitions are due to the formation of new bonds occurring at the same temperature than those due to the first order transition. The glassy fractions induced by relaxation above Tm are much weaker. I distinguish these two types of liquid-liquid transitions in this new version.
- The numbers of various equations have been changed.
- Eq 6 is a quadratic equation only containing q2 and constants. The solutions are ±qn-.
- (Tg) of these glassy phases are time dependent as shown by Zu van Q. The special values of Tg/Tm equal to 2.168 Tm(K) and 1.832 Tm (K) were obtained using heating and cooling rates equal to 7.5 °/min as shown by Zu V Q.
- Citation is given
Reviewer 2 Report
This work gives a study of multiple glass transitions in Bismuth and Tin beyond melting temperatures. However, the abstract and introduction are almost similar, and there is little experimental data and lack of innovation, so this work is not really suited for publication in my opinion.
Answer: I hope that the problems of presentation are solved.
Reviewer 3 Report
Manuscript Number: metals-1923383
Title: Multiple Glass Transitions in Bismuth and Tin beyond Melting Temperatures
Review
The possibility of a phase transition between two forms of the liquid phase in some pure substances has attracted considerable interest and research activity in recent years. Among the materials investigated are water, silica, silicon, germanium, carbon, and hydrogen—these substances form a very significant component of our natural world, living organisms, and technology. A phenomenon common to these is therefore of wide general interest. Furthermore, liquid-liquid transitions offer an avenue for interesting applications that exploit the different properties of distinct liquid phases.
In the present work, the authors carried out a phenomenological study of the glass transitions of the elements Bi and Sn. Many interesting results were presented, diagram of phase transitions, the effects of transitions on specific heat and resistivity, thermodynamic description, among others. The methodology presented was adequate and well endorsed. The figures are legible, but can be improved. The work obtained several results and as a consequence many conclusions.
I think that the topic of this study is quite interesting and that the results are in principle suitable for publication in Metals. I didn't see any technical problems in the methodology. However, there are deficiencies in the presentation that should be addressed before the publication of this manuscript can be recommended. These points are listed in the following.
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In my opinion, the introduction lacked a paragraph on the importance and motivation of the present investigation, technological applications (if applicable), systems already investigated with the same transition, recent history on L-L transitions, etc. In addition, the abstract is practically copied in the introduction.
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The figures can be improved, they need to be the same size and with a better quality to read the results.
It is always a pleasure to review a work to be published in Metals.
Comments for author File: Comments.pdf
Answer: I hope that this new presentation is improved
Reviewer 4 Report
The present manuscript has several strong drawbacks that prevent any further positive recomendation for publication in a scientific journal.
The paper is unclear and many already published results appear in such a way that the actual novel content is hardly found and understable.
Presentation is poor, abstract and introduction are practically the same, which shows that the achievements in this work are unclear and most of the remarkable content can be found in the introduction.
Other deficiencies can be found such as the use of Eq. (10) from Eq (5) in a wrong way.
Predictions of Cp much higher than Dulong-Petit limit (almost twice) is not commented.
Therefore, the lack of clarity and the not evidence of new information in this work move me to propose a reject decission for this contribution.
Answer:
Eq. (10) has been suppressed.
The predictions of specific heat are no longer higher than Dulong et Petit. I propose for the first time that the liquid state can be transformed in a glass phase up to 2Tm and that a weak glassy fraction could exist above 2 Tm. Nobody has never proposed this new idea after looking at many published experimental results and using the non-classical homogeneous nucleation model. I show for the first time that the specific heat is constant in the absence of glassy fractions The density measurements are time dependent because of the formation of glassy phases by relaxation.
You can observe that the discovery of a weak glassy fraction induced around 780 K in Sn (Xu et al) agrees with my predictions of a first-order transition at T= 284 K which correspond to the melting of grey phase and a glass transition around 780 K.
