The Impact of Nanoparticles on Previtreous Behavior: Glass-Forming Nematogenic E7 Mixture-Based Nanocolloids

Round 1

Reviewer 1 Report (Previous Reviewer 1)

Comments and Suggestions for Authors

I have the following comments:

1. The changes made to the revised version of the manuscript were difficult to follow, these were not highlighted.
2. The exo or endo effects should be marked on the DSC (Fig. A1). As it looks now it seems that the endo effect is up. If this is the case, then the transition will be N-Iso.
3. Some minor language corrections are still necessary (could be done during the proofreading stage). See for example: p. 17 " The results are for 10/𝑚𝑖𝑛 scan..."; it should be 10oC or K/min, is it cooling or heating?; "agreement", etc.

Author Response

Reviewer #1

 The given report is the resubmission – with notable correction – of the earlier (in Jan. 2025) submitted report. I guess that Reviewer  #1 was one of the reviewers of this previous paper. The following additional comments have been given:

1. Reviewer #1: ‘ The changes made to the revised version of the manuscript were difficult to follow, these were not highlighted ‘

Response:      I am not sure if highlighting is allowed – at least, it is not explicitly indicated. If I am wrong – I apologize. In any case, I agree that the possibility of the submission 3^rd version with ‘marked changes’ would be very convenient for reviewers. I hope MDPI will work on this.

Note: corrections are explicitly indicated by line numbers in the ‘response-to-reviewers’ letter.

2. Reviewer #1: ‘The exo or endo effects should be marked on the DSC (Fig. A1). As it looks now it seems that the endo effect is up. If this is the case, then the transition will be N-Iso.’

Response:      In the Appendix correlates with DSC results for pure E7 presented in refs. [   ]. Related comments now supplement the Appendix.

3. Reviewer #1: ‘ Some minor language corrections are still necessary (could be done during the proofreading stage). See for example: p. 17 " The results are for 10/???.."; it should be 10oC or K/min, is it cooling or heating?; "agreement", etc.

Response:      The report has been cleaned in-depth, including the points above. The text has been additionally tested by a friend, a researcher at NY Rensselaer Polytech. Inst., the native speaker.

Reviewer 2 Report (New Reviewer)

Comments and Suggestions for Authors

My report is attached as a PDF file.

Comments for author File: Comments.pdf

Comments on the Quality of English Language

The paper is not clearly written and is full of grammatical and syntax errors. Careful editing would be needed in case the paper would be rewritten and resubmitted to this or other journal.

Author Response

First the general statements from the introductory parts are addressed:

• Reviewer #2: ‘They claim that the glass transition is not yet understood and attempt to gain insight. However, they do not clearly state which features of the glass transition are not understood and how they tackle them. ‘.
• Response: This issue is ‘in depth’ and addressed in the Introductory section. Please, note it agrees with the pattern of  classic & standard papers regarding the glass transition challenge. Following the comment, I can guess that a better clarification of the target is needed – for researchers beyond the glass transition field. It has been done. See Lines added at the beginning of the Introduction.

 

• Reviewer #2: ‘ The paper is actually not dealing with the general understanding of glass transition, but with the impact of nanoparticles on the I-N and glass transition behavior (as the title says, but the introduction states many things about the glass transition).
• Response: This comment/suggestion is in  so essential disagreement with the evidence and the merit of the report -   that I cannot comment/explain it. As the researcher working in the glass transition field from 3 decades, I can only state: it is strange.

 

• Reviewer #2: ‘ We see comparison of 4 nanoparticle concentrations with pure E7. The analogies in the last part between I-N transition and glass transition make no sense. ‘
• Response: I have been dealing with the glass transition problem for 3 decades and have a significant position here. My experience and the opinion of 2 friends from the ‘top-10’ glass transition researchers list clearly indicate that the analogy/comparison of the I-N transition and glass transition can be a path to a long-awaited cognitive breakthrough.I have been dealing with the glass transition problem for 3 decades and have a significant position here. My experience and the opinion of 2 friends from the ‘top-10’ glass transition researchers list clearly indicate that the analogy/comparison of the I-N transition and glass transition can be a path to a long-awaited cognitive breakthrough.Therefore, I do not see any possibility of responding to the comments formulated by Reviewer #2 in this way, in light of the current state of knowledge on the glass transition problem.

 

• REVIEWER #2: ‘This manuscript is written on a totally fuzzy way, the fitting curves show large difference from the experimental ones, but surprisingly give very precise values of fit parameters. There is quite some experimental work, but the interpretation is wrong and the conclusions not supported.
• RESPONSE: This statement is in such total disagreement with the evidence presented in the paper that I must appeal to the responsible MDPI Nanomaterials editor to investigate the reasons for making such conclusions – without any supporting evidence, and in total disagreement with the facts.

 

• REVIEWER #2: ‘ The statistics regarding nematics is interesting, however, a boost of research in this field is related to the ferroelectric nematics discovered in 2017 (papers of Mandle and Nishikawa). Also, showing statistics about work in nematics, while dealing with the understanding of glass transition is awkward. This part may be removed.‘

RESPONSE:   The suggestion that Liquid Crystals Physics is nowadays driven only by the discovery of ferroelectric nematics is strange. This topic and the above reference are beyond the given report. The suggestion that studies on the glass transition in LC materials ‘are awkward’ – and then should be ‘removed’ is strange and in my opinion, in contradiction not only with glass transition physics but probably also with the Scientific Method itself.

• REVIEWER #2: ‘It is stated that E7 is supercooled at any rate is based on two books. The authors must provide specific papers here, so the reader can realize which rates they refer to. Supercooling may be rate-dependent.’

RESPONSE:  Additional references have been added.

Responses to specific issues indicated in the Opinion of Rev.#2

1. REVIEWER #2: ‘Line 115 what are the reference parameters? It is not clear ‘

RESPONSE:   It is now stated ‘in agreement with reference values of transitions temperatures [38,62,63].

2. REVIEWER #2: ‘Lines 133-134: the meaning is not clear. ‘

RESPONSE:  It is now stated: However, no commercial equipment enables POM reliable tests under conditions related to the described experiment, namely the extreme range of temperatures (down to ~200K) matched with 12 orders changes in viscosity. One can only consider innovative modifications of available facilities that are beyond the given project.

 

3. REVIEWER #2: ‘Samples: no information is given about the sample How the nanoparticles (purchased in powder) were mixed with E7? Was there some solvent involved? If yes, how was this solvent removed? Please provide the missing details on sample preparation.’

RESPONSE:  Note that now 10 hours drying and no solvent are indicated in Materials & Methods section. Note that the description presented in this Section is well above the standards for samples preparation and even more broadband dielectric spectroscopy  for LC+NPs nanocolloids, which most often is minimalistic

4. REVIEWER #2: ‘ Figure 1: the axis titles ε΄ and ε’’ of the right figures are too close to the left figures, and they confuse readers. They should be placed closer to the right figures. Smaller points could help distinguish the blue and purple curves that are close to each other.’

RESPONSE:  Figure 1 has been slightly corrected by shifting  ε΄ and ε’’ labels of axis. We tested that that smaller points,  advised by the Reviewer#2,  makes the insight less visible for readers  - so we do not follow this suggestion

5. REVIEWER #2: ‘ Figure 2: an inset with focus on a short region around the dashed arrow would make it easy to see the discontinuity. The very large temperature scale and the big symbols do not help to visualize this. This figure needs modification.’

RESPONSE: The purpose of this figure is to show the large-scale changes, together with the (so far unknown) parameterization in the nematic phase. The focus on the I-N transition details is precisely given in Figure 3, moreover applying hardly used distortions – sensitive analysis. The introduction of the suggested smaller point sizes significantly worsens the view, as we have verified in practice. We did not follow this advice because it could have worsened the quality of the work.

Please note the consistency of the measurement points' size, shape, and colors in all Figures.

Following above, the focus on the isotropic phase and I-N transition is not needed because it is given in Figure 3. Adding such an inset to Figure 2 would make it very unreadable

6. REVIEWER #2: ‘Line 236: α = 1/2 is a tricritical value for specific heat. It should be explained (by adding proper references) why the tricritical value is taken here and not some other value. There are references in the literature, starting the 70s and 80s (P. Keyes, M.A. Anisimov papers) discussing about tricritical effective exponents for I-N transition.’
7. REVIEWER #2: ‘ Line 245: a mean-field value is used for v, while tricritical α was used earlier. Even if v = 1/2 is the same for tricritical and mean-field, this is creating confusion. Please clarify this point.’

RESPONSE:  Points (6) and (7) address the same issue. First, the aforementioned works by Keyes and Anisimov cannot be considered decisive. Keyes' evidence regarding the nature of TCP and the experiment was met with considerable criticism immediately after publication, which is justified, in my opinion. Anisimov cites numerous results, but even a cursory look at them does not allow us to recognize their decisiveness. Such a role can only be assigned to the distortions sensitive analysis focused on the order parameter (bets=0.5 for MF and beta=0.25 for TCP) in refs. [80.81].

The above remarks refer to the difference between the description of MF and TCP. This is a kind of primer of Critical Phenomena Physics, and we did not consider it appropriate to comment this issue in-depth. However, from the comment by Reviewer#2 we see that it may be useful for less experienced readers. Such a comprehensive explanation addressing the issues raised in points (6) and (7) is given – now – in Lines 288-307

8. REVIEWER #2: ‘Figure 3: the fitting does not follow well the curves. Especially for 0.5%, it misses the curve. It is also interesting that there are regions around 352 K and 364 K where the data points are showing some sudden drop in all curves. Can this be related with some problem during measurements? ….

RESPONSE:  The scaling portrayal is now shown by ‘thicker’ curves. I must stress that the fitting quality is superior, which must be clear for any researcher familiar with the direct numerical derivative analysis of experimental data. Notwithstanding the following comment has been added:

‘ Note that Figure 3 is for the numerical derivative of experimental data presented in Figure 3, for the isotropic liquid phase. Hence, the slight discrepancies between transformed data and the proposed scaling function Eq. (8) is the consequence of such analysis, not a specific phenomenon behind it.’: REVIEWER #2:  ‘Table 1: no errors are given for the obtained fitting parameters. It is unusual to present results like this. Readers miss information if the fitting parameters are obtained on the basis of minimizing chi square or other way. For so noisy data,

RESPONSE:  The ‘strange’ comment does not consider that In Figure 3  is for the NUMERICAL DERIVATIVE.

Such presentation data are superior, which must be clear for any researcher familiar with this advanced analytic technique. This is possible only because of the superior quality of basic data. Following this, I cannot understand how to formulate such objections is possible. Nevertheless, Table I's caption has added an additional sentence regarding the error.

9. REVIEWER #2: ‘More problems about fitting: the density of points (every 1 K or so) is not enough for critical fits. There should be more points close to the transition. If this is not possible due to weak temperature control of the BDS setup, then at least range shrinking should be performed. The authors must also explain why they do not use correction to scaling terms for such long ranges. Close to the transition the critical exponent dominates, but in so large ranges of 20-30 K correction to scaling terms are often needed. If this is not the case here, it has to be explained. Without performing all the above, the presented fitting results are not valid at all. ‘

RESPONSE:  Again, an accusation against the facts and ‘data analysis art’. The decisive factor is primarily the number of parameters relative to the number of parameters fitted. ‘’The relative rarefication’ occurs only around the glass transition but for  any experienced researcher the combination of this fact with the difficult ones (huge relaxation times and viscosity) is clear. I do not think that such obvious things require explanation in a work for professionals.I also explain in the publication, at the end of the Results sections:

‘  It is worth recalling that for precritical effect, supplementary correction-to-scaling terms often appear when shifting away from the critical point. However, it is not the case of the mean-field type behavior where corrections-to-scaling terms are fundamentally absent, as the consequence of their origins matched the basics of the Ginzburg criterion. The existing evidence for various systems and properties explicitly shows that it can extend by tens of Kelvins from the phase transition without corrections-to-scaling terms.

The behavior on both sides of the I-N transition is related to the mean-field (TCP-type) transition. The means-field nature of the glass transition is also indicated. Mean field type behavior manifests itself through pre-transition effects described by exponents that are small integer number or their ratios.’

I was not, and I am not convinced that such elementary properties, evident to every specialist, need to be explained.

10. REVIEWER #2: ‘Figure 5: to talk about discontinuity, the authors need to present close focus with more data in the region around the arrow with better resolution. With points every 1 K or so, the discontinuity is not clear.

RESPONSE: This issue was explained above. The results presented in Figure 5 are UNIQUE:   (i) made under very difficult conditions regarding the time =-scale, ultra-viscosity, and low temperatures; (ii)  here essential is the view in the broader range,  (iii) it is the first-ever evidence for such behavior, which indicates its milestone meaning.

More data near Tg etc…. Yes – but it can be the target of subsequent research. Measurements with such resolution as in the given reports require weeks for a single passage. The temperature stabilization and its cost are not trivial for such long studies studies.

11. REVIEWER #2 ‘ Figure 6: the fitting is missing the curves to a big extent. It is hard to believe that such fits provide the exponent γ with precision ±0.03. Also, when the error is 0.03, then γ = 1.00 ± 0.03 should be the correct representation and not γ = 1 ± 0.03.  ‘

RESPONSE:  The value of the exponent is/was correct. Previously it was explained in the text, now, it is also explained in the caption of Figure 6.
The expectation that pretransitional effects will describe the entire extreme/measured range is incomprehensible. Every specialist in the physics of phase transitions and critical phenomena knows that at a distance, so-called background effects appear unrelated to pretransitional phenomena. The description of the phenomena requires further work but was also not the aim of this work.

12. REVIEWER #2: Figure 8: please use a much smaller size of points, because it is impossible for the reader to distinguish the curves.

RESPONSE: The results presented in Fig. 8 refer to the size obtained from the analysis of the spectra exemplified in Fig. 1, (ii) and then to the numerical derivative of its temperature changes.

In such a situation, a naturally increasing error is shown, indicated by the size of the ‘points’ in Figure 8. Reducing the size of the points would, therefore be dishonest to the reader.

13. REVIEWER #2: ‘What is the meaning of the sentence of lines 508-510?  ‘ 

RESPONSE: this sentence has been slightly corrected to:

In the relatively broad range, supercritical and subcritical domains are described by the Critical Phenomena Physics, and shaped by collective critical fluctuations.

14. REVIEWER #2: ‘Appendix, Figure A1: what is the meaning of a transition within the supercooled nematic phase? This makes no sense, since a transition happens between two phases. Within the same phase (nematic), a transition is not possible. Please provide a reasonable explanation of the DSC thermogram.   ‘

RESPONSE:  please note the following sentence at the end of the Appendix Note the indication for the discontinuous transition within the nematic phase in the nanocolloid, which is also evidenced by the dielectric constant scans presented above. It can suggest a change in the arrangement of permanent dipole moments coupled to rod-like molecules.

15. REVIEWER #2 ‘’ Use of English: a serious editing of English has to be performed. The text is not clear and full of grammatical and syntax errors / mixing adverbs with adjectives and/or singlular and plural forms.

RESPONSE: The language has been corrected, including the test by the native speaker, as explained above

16. REVIEWER #2  ‘  References: a lot of self-citation is obvious  ‘

RESPONSE : Note, the number of self-citations is below 15% allowed by the publisher.

Reviewer#2 is also not convinced of the meaning of the comparison between the I-N transition and glass transition evidence. My opinion is the opposite – I am the author of 130 reports in the glass transition field. Nevertheless, I tested this comment by sending a given report to my 2 friends from the ‘top-10 glass transition field’.  For them – it can be a milestone. Subsequently, I have been invited (plenary) to present this issue at the International Discussion Meeting on Complex Systems (Barcelona, 2025) – the World's most important congress of glass transition researchers.

Reviewer 3 Report (New Reviewer)

Comments and Suggestions for Authors

The authors discuss the impact of low concentrations doping of E7 liquid crystal with BaTiO3 nanoparticles on properties at glass transition, T_g, and nematic-isoptropic transition temperatures. The existing theoretical approaches are reviewed and interesting experimental data on dielectric properties measurement are presented. The paper summaries conceptual ideas and approaches to interpret the temperature dependence of the physical properties of E7 liquid crystal, which can be interesting to readers.

Please consider the following notes:

1) The applied aspect of the presented material is lacking. I guess the authors should suggest and conclude with certain possible applications.

2) line 132-133: The statement 'no commercial equipment enables POM reliable tests under such conditions'(low temperature range) is doubtful. There are special Linkam tables for microscopes that can go down to -195C and up to over 500C. So it is better to change this statement.

3) line 163: '... anchoring 'parasitic impact' ...' can be significant even for 150 um cell-gap. The disclination lines that stabilizes topological defects can significantly contribute to the spread of the measured values. To be correct I suggest to compare the measured data to the measurements for the cells with planar and vertical alignment layers.

4) What is the BaTiO3 nanoparticle? Is it conductive or dielectric? Does it suffer polarizability under the electric field? Why was this partcle chosen for doping the LC?

5) line 419: Typo, please correct 'Sokolov and Novikov and Sokolov [88]'

6) After reading the full paper I am still not clear what is the use of doping the E7 LC with the BaTiO3 nanopartiles. Could you please give few grounded statements?

Author Response

The opinion is positive, with some indications prior to the publication:

1. REVIEWER #3: ‘ The applied aspect of the presented material is lacking. I guess the authors should suggest and conclude with certain possible applications.

RESPONSE: The target of this report is fundamental, but in-depth knowledge is always the basis for practical use, especially for such important application material as E7. However, at present, this could only be speculation. However, I am deeply convinced that BDS studies, and those correlated with glass forming LC, can be groundbreaking for the mystery of glass transition. This is indicated in the work - and this is probably sufficient motivation.

2. REVIEWER #3: ‘ line 132-133: The statement 'no commercial equipment enables POM reliable tests under such conditions'(low temperature range) is doubtful. There are special Linkam tables for microscopes that can go down to -195C and up to over 500C. So it is better to change this statement.

RESPONSE: Corrections have been made. We were not familiar with the mentioned equipment. Its use for further research in glass forming LC can certainly be an interesting possibility.

3. REVIEWER #3: ‘What is the BaTiO3 nanoparticle? Is it conductive or dielectric? Does it suffer polarizability under the electric field? Why was this partcle chosen for doping the LC?

RESPONSE: This issue is now explained in Lines  152-157 .

4. REVIEWER #3: line 163: '... anchoring 'parasitic impact' ...' can be significant even for 150 um cell-gap. The disclination lines that stabilizes topological defects can significantly contribute to the spread of the measured values. To be correct I suggest to compare the measured data to the measurements for the cells with planar and vertical alignment layers.

RESPONSE: For BDS frequency scans, essential for the given report, studies in oriented samples, using capacitors with plates covered by polymeric layers to orient samples introduces a lot of biasing impacts, making the analysis puzzling. The focus of this report was the ‘free’ orientation of LC molecules. Nevertheless, the comment is interesting for further studies. It is always worth noting that measurements in glass forming systems are for samples which viscosity changes from ~1centyPoise to ~1000 GigaPoise at the glass transition. It shows the challenge.

5. REVIEWER #3: ‘ line 419: Typo, please correct 'Sokolov and Novikov and Sokolov [88]'

RESPONSE:  Done

6. REVIEWER #3: After reading the full paper I am still not clear what is the use of doping the E7 LC with the BaTiO3 nanoparticles. Could you please give few grounded statements?

RESPONSE: This issue is now explained in Methods and Materials

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

Comments and Suggestions for Authors

1. The E7 doped samples with BaTiO3 should also be investigated by DSC and POM observations for homogeneity and correlation with the transition temperatures measured by dielectric spectroscopy.
2. The results of the dielectric spectroscopy measurements should be correlated and discussed in the context of other studies on E7/BaTiO3 system reported. See, for example,  Beigmohammadi et al. Optical Materials, 157, Part 2, 2024, 116332. 
3. The text should be checked for language. See, for example, on p. 3: "A small sedimentation effect appeared for 𝑥→1% appeared after 𝑡 > 1ℎ𝑜𝑢𝑟."

Author Response

Attached please find the revised manuscrtipt ‘ The impact of nanoparticles on the previtreous behavior: glass-forming nematogenic E7 mixture-based nanocolloids’ A. Drozd-Rzoska, J.Łoś, and S. J. Rzoska, containing supplementations advised by Reviewer,

Both Reviewers expressed positive opinions, and also formulated some questions and advice supplementations.

All comments have been taken (positively) into account, explicitly explained, and included in the corrected manuscript.

Please note that responses required additional references, and the Appendix with DSC results,  needed to answer the suggestions of Reviewer 1.

The report has also been thoroughly cleaned regarding language errors / misprints.

Finally, I would like to thank the reviewers for their valuable comments, which improved the quality of the presentation and the reasoning.

 

Reviewer #1

1. Reviewer #1: ‘The E7 doped samples with BaTiO3 should also be investigated by DSC and POM observations for homogeneity and correlation with the transition temperatures measured by dielectric spectroscopy.’

Response:  The current version contains the Appendix with results of DSC studies for E7 and the nanocolloid for which the most complex patterns were  detected in dielectric studies – E7 + 0.5% NPs. Comments in the Appendix stress the agreement with existing similar evidence for pure E7.

Regarding the Optical Polarized Microscopy (POM) picture, we would like to note that it has minimal meaning for the given report related to broadband dielectric spectroscopy (BDS) in BULK, whereas texture-related tests are for micrometric gaps, essentially different from bulk conditions. In our opinion, such POM tests are appropriate for further studies, focusing on different gaps (also to test the impact of surface effect significant for micrometric gaps), and the temperature range particularly focused on the vicinity of the glass temperature. To the best of our knowledge, there are no commercial POM facilities for such low temperatures.

Nevertheless, in the Experimental section, earlier reports by the authors for LC compounds that are a part of E7 mixture are now explicitly recalled. The have been carried out for the gap distance between glass plates and the multi-micro-metric gap, which yields only the surface picture (also in nanocolloids with BaTiO3) but is more appropriate when comparing with other tests for bulk samples. They were carried out under pressure to avoid the temperature problem and stabilize the samples. All these are now recalled in the Experimental (Methods) section.

See the Appendix with DSC results and the (very) extendend Experimental (Methods) section.

1. Reviewer #1: ‘The results of the dielectric spectroscopy measurements should be correlated and discussed in the context of other studies on E7/BaTiO3 system reported. See, for example,  Beigmohammadi et al. Optical Materials, 157, Part 2, 2024, 116332. ‘

Response:  The mentioned reference is included in the list of references and discussed in Experimental (Methods). The discussion indicates some problems of this report in respect to the research (in bulk) presented in the given paper. Please note that the above report is for the ‘thin layer’ micrometric gap between electrodes (glass, ITO covered), which causes the behavior in the nematic phase is ‘a bit unusual/atypical’ – due to electrode-related constraints.  Also the description of dielectric studies in the mentioned report is rather general, without the essential masterplot log dielectric permittivity vs. log frequency, validating the selected frequency as the dielectric constant. The next issue is a limited range of temperatures (well, well above Tg) and the lack of explicit phase characterization of nanoparticles. Note the extended discussion addressing the given point in the Conclusions.

 

Reviewer #1:’ The text should be checked for language. See, for example, on p. 3: "A small sedimentation effect appeared for ?→1% appeared after ? > 1ℎ???."

Response:  The ‘language’ and misprint corrections of the manuscript have been done.

Author Response File: Author Response.pdf

Reviewer 2 Report

Comments and Suggestions for Authors

This manuscript appears to report and discuss the BDS experimental results of the composites of E7 nematogen and BaTiO3 nanoparticles in the context of the glass study. Unfortunately, the writing is not straightforward, impeding understanding of what was really done in the experiments and analyses. This reviewer feels that the experiments seem reliable and the research motivation is healthy. Still, he recommends the rejection (or major revision) of the manuscript.

1. The description of experiments is insufficient. 
   1. The description/characterization of the BaTiO3 nanoparticles is crude. Since liquid crystalline molecules are sensitive to the surface state and the dielectric property depends crucially on the orientation of the liquid crystals, the shape, crystalline habit, and habit distribution of the nanoparticles are essential information. Without this information, the readers cannot imagine the sample situation subject to experiments.
   2. Describe the surface anchoring to the electrodes in the nematic state.
2. Describe more explicitly the ways of analyses and explain the analysis results using Figures.
3. The words “parallel”and “perpendicular” in Fig.2 need explanations.
4. The authors quite “naturally” assume a critical dependence on temperature dependencies. However, there appears to be no evidence of such behaviors beyond respective backgrounds. Furthermore, they should discuss the expected temperature range of validity.
5. Related to point 5 above, the ranges of fit seem to be generally artificial.

Comments on the Quality of English Language

Although each sentence is generally OK, the story is broken some places by a skip.

Author Response

Attached please find the revised manuscrtipt ‘ The impact of nanoparticles on the previtreous behavior: glass-forming nematogenic E7 mixture-based nanocolloids’ A. Drozd-Rzoska, J.Łoś, and S. J. Rzoska, containing supplementations advised by Reviewer,

Both Reviewers expressed positive opinions, and also formulated some questions and advice supplementations.

All comments have been taken (positively) into account, explicitly explained, and included in the corrected manuscript.

Please note that responses required additional references, and the Appendix with DSC results,  needed to answer the suggestions of Reviewer 1.

The report has also been thoroughly cleaned regarding language errors / misprints.

Finally, I would like to thank the reviewers for their valuable comments, which improved the quality of the presentation and the reasoning.

 

Reviewer # 2

1. Reviewer # 2: The description of experiments is insufficient.’  Namely:

• Reviewer # 2 comment ‘The description/characterization of the BaTiO3 nanoparticles is crude. Since liquid crystalline molecules are sensitive to the surface state and the dielectric property depends crucially on the orientation of the liquid crystals, the shape, crystalline habit, and habit distribution of the nanoparticles are essential information. Without this information, the readers cannot imagine the sample situation subject to experiments.’

Response: Please note the Experimental / Methods section, which is now very extended. I think it is much above the standards in research reports on the given topic.  Nanoparticles are precisely characterized, recalling all features mentioned in the comments.

Note that the report is related to measurement in bulk. So the surface-related anchoring / constraints –  essential for microlayers gap – are noted to significant for the results presented. This issue is now explained in depth in the mentioned section.

?

1.2__Reviewer # 2:  ‘Describe the surface anchoring to the electrodes in the nematic state.

Response:   The applied distance between capacitor plates in ‘macro’ category, hence, the report presents BDS studies for ‘bulk’ samples, where electrode effects mentioned by the comment are negligible  (nit important). Such effects are essential for micrometric gaps, leading to a set of supplementary tests that should explain effects or simply puzzling results. For the latter, see, for instance: Beigmohammadi et al. Optical Materials, 157, Part 2, 2024, 116332.

The presented research was planned to avoid such problem and  measurements ‘in bulk’ are ( and were) in the basic manuscript)  explicitly stated in the text. 

1. Reviewer # 2:  ‘Describe more explicitly the ways of analyses and explain the analysis results using Figures.

Response:  The report is related to broadband dielectric spectroscopy (BDS) studies. In the Experimental section, there is a (very) extensive description of such data (spectra) treatment and the way of analysis.  Additionally, Figure 1  presents a masterplot of spectra and indicates its essential features relevant to properties discussed in the report.

To the best of (decades) of experience, this description is well above the standards used in research reports.

In the Results section, well–linked descriptions are related to all Figures and supported by related relevant references.

In my opinion, the report explicitly and well describes experimental issues and the method of analysis.

1. Reviewer # 2:  ‘The words “parallel”and “perpendicular” in Fig.2 need explanations.

Response: The issue has been explicitly explained at the end of Figure 2 caption and below Eq. (10).  I am sorry for using ‘jargon comments’ which are clear for a liquid crystals specialist, but can be not-clear for others.

4 & 5_ Reviewer # 2: (4) ‘The authors quite “naturally” assume a critical dependence on temperature dependencies. However, there appears to be no evidence of such behaviors beyond respective backgrounds. Furthermore, they should discuss the expected temperature range of validity.  (5) Related to point above, the ranges of fit seem to be generally artificial.

Response: This comment's meaning is unclear – I can state as the specialist working in the area of Critical Phenomena Physics for many years. The characteristic change on approaching some (singular) temperature  is the only (‘natural’) justification of the critical-type behavior. If such data are well portrayed by a critical – type dependence (such as Eq. (14)), it can be considered as a satisfactory validation of the ‘critical behavior’. It is a canonic way of analysis for Critical Phenomena Physics.

Nevertheless, in Table 2 the value of chi2  () fitting quality parameter, in my opinion the best one. The caption states that this (relative) value remains constant in the plotted (fitted range) and raises when this range is increased.

 

 

Author Response File: Author Response.pdf