Multi-Elemental Coatings on Zirconium Alloy for Corrosion Resistance Improvement

Round 1

Reviewer 1 Report

The paper is well written. However, there are still many items which need to be revised. The suggestions are as follows:

(1) Many abbreviates in the paper. It is necessary to point out their meanings when these abbreviates appear firstly.

(2) Almost all SEM micrographs are not very clear, especially those subscripts.

(3) It is necessary to give some mechanical analyses about the interface between the base material and coatings, such as hardness tests, bonding tests and so on.

(4) For this paper, it lacks the detailed analyses. Mostly the paper seems to be an experimental report. It suggested to give some detailed analyses such as interfacial bonding mechanism, oxidation mechanism and so on. 

(5) There are some English errors in the paper.

Author Response

Manuscript ID: coatings - 1653482

Multielemental Coatings on Zirconium Alloy for Corrosion Resistance Improvement

Bożena Sartowska * , Wojciech Starosta , Lech Waliś , Jerzy Smolik , Ewa Pańczyk

ANSWERS to Reviewer 1

The paper is well written. However, there are still many items which need to be revised. The suggestions are as follows:

(1) Many abbreviates in the paper. It is necessary to point out their meanings when these abbreviates appear firstly.

(2) Almost all SEM micrographs are not very clear, especially those subscripts.

(3) It is necessary to give some mechanical analyses about the interface between the base material and coatings, such as hardness tests, bonding tests and so on.

(4) For this paper, it lacks the detailed analyses. Mostly the paper seems to be an experimental report. It suggested to give some detailed analyses such as interfacial bonding mechanism, oxidation mechanism and so on.

(5) There are some English errors in the paper.

Thank you for all remarks, comments and suggestions. They helped authors to improve the text. Changes are highlighted in red in the revised manuscript.

Authors answer and comments are listed below.

• Many abbreviates in the paper. It is necessary to point out their meanings when these abbreviates appear firstly.

Used abbreviations are explained at the first time occurred in the text, starting from introduction part.

Zry-2: Zircalloy-2// Zry-4: Zircalloy- 4// LOCA: loos of coolant accident // SBO (station blackout accident) //  MAX: MAX phases are layered, hexagonal carbides and nitrides which have the general formula: Mn+1AXn, where n = 1 to 3, and M is an early transition metal, A is an A-group (mostly IIIA and IVA, or groups 13 and 14) element and X is either carbon and/or nitrogen phases // PVD: physical vapor deposition // PWR: pressurized water reactor // pH: quantitative measure of the acidity or basicity of aqueous or other liquid solutions // DO: dissolved oxygen // ICP-MS: Inductively Coupled Plasma Mass Spectrometry //  IAEA: International Atomic Energy Agency

• Almost all SEM micrographs are not very clear, especially those subscripts.

SEM images, EDS results diagrams, subscripts and markers/bars were improved.

• It is necessary to give some mechanical analyses about the interface between the base material and coatings, such as hardness tests, bonding tests and so on.

The main aim of this work was to develop and to form coatings on Zry-2 with improved resistance for oxidation and corrosion. Carried out investigations were concentrated on mentioned useful properties determination. After heat treatment tests and air oxidation and long term corrosion in water, the formed coatings were present. No delamination and spallation was observed. This information was very important for authors according to defined challenge and required material-coating bonding properties described in Introduction part. In our understanding the coatings formed at the base material have finished carried out test with positive results. Obtained material in the form of system: base material and formed coating were investigated (surfaces and cross section) using SEMs, EDS, XRD methods. According to obtained results the border between the base material and formed coating was clearly seen. This results as well as their interpretation are now described in the manuscript.

Authors agree that wider and stronger characterization of system base material (here: Zry-2) and surface layer (here: Zr₄₀Si₂₄Cr₃₆ coatings) are important. The next mechanical investigations and analysis of unmodified and modified materials are planned including: hardness measurements, adhesion investigations, scratch tests and sliding wear resistance determination.

(4) For this paper, it lacks the detailed analyses. Mostly the paper seems to be an experimental report. It suggested to give some detailed analyses such as interfacial bonding mechanism, oxidation mechanism and so on.

More information were put in the text. Reference to cited literature were made. Analysis of obtained results were done according to literature. Comparison of results obtained for initial and modified materials characterization were underlined. Authors decided not to divide text for separate parts: “Results” and “Discussion”. These information are written in one part: “Results and discussion”.

Bonding mechanism between base material and formed coating was connected with PVD method used for coatings formation. This point is described in the part 2.2. Coating method.

Initial and modified materials were experimentally subjected to heat and air. As the result of these processes changes in the elemental depth distribution were observed. Details of observed changes are presented in the: 3.2.1., 3.2.2., 3.2.3. points of the manuscript. Interpretation and discussion connected with observed changes as well as possible oxidation processes in the case of initial and modified materials is present in the text now.

(5) There are some English errors in the paper.

The text was submitted to the editing service of MDPI for extensive English revision. It will be completed in 1-5 business days.

Reviewer 2 Report

This article contains good and valuable information about composite coatings. After correcting the manuscript based on the comments, I will announce my opinion regarding the acceptance or rejection of the article. Consider all the comments below and highlight the changes.

1- The overall language quality of the article is poor in some parts. Improve the language of the article.

2- In the abstract, the authors should briefly state what the parameters under consideration are, what tests have been used, and what the overall results have been. Delete extra sentences.

3- The introduction is very poorly written. The relationship between production parameters, microstructure and coating properties has not been properly analyzed and discussed. Use the following articles to complete this section:

- https://doi.org/10.1016/j.ceramint.2018.10.229

- https://doi.org/10.1016/j.ceramint.2019.07.190

4- Prepare a reference for Table 1.

5- Describe the method and standard used to control the chemical composition.

6- State the standard and metallographic conditions for coatings structure.

7- Improve the quality of Figure 8.

8- The results presented in Figure 6 should be presented in a table.

9- You must provide a standard card number for the phases identified in the XRD patterns.

10- The caption of Figure 13 is incorrect. Check the grammar of the whole text.

Author Response

Manuscript ID: coatings-1653482

Multielemental Coatings on Zirconium Alloy for Corrosion Resistance Improvement

Bożena Sartowska * , Wojciech Starosta , Lech Waliś , Jerzy Smolik , Ewa Pańczyk

ANSWERS to Reviewer 2

This article contains good and valuable information about composite coatings. After correcting the manuscript based on the comments, I will announce my opinion regarding the acceptance or rejection of the article. Consider all the comments below and highlight the changes.

1- The overall language quality of the article is poor in some parts. Improve the language of the article.

2- In the abstract, the authors should briefly state what the parameters under consideration are, what tests have been used, and what the overall results have been. Delete extra sentences.

3- The introduction is very poorly written. The relationship between production parameters, microstructure and coating properties has not been properly analyzed and discussed. Use the following articles to complete this section:

- https://doi.org/10.1016/j.ceramint.2018.10.229

- https://doi.org/10.1016/j.ceramint.2019.07.190

4- Prepare a reference for Table 1.

5- Describe the method and standard used to control the chemical composition.

6- State the standard and metallographic conditions for coatings structure.

7- Improve the quality of Figure 8.

8- The results presented in Figure 6 should be presented in a table.

9- You must provide a standard card number for the phases identified in the XRD patterns.

10- The caption of Figure 13 is incorrect. Check the grammar of the whole text.

Thank you for all remarks, comments and suggestions. They helped authors to improve the text.

Authors comments are listed below.

• The overall language quality of the article is poor in some parts. Improve the language of the article.

The text was submitted to the editing service of MDPI for extensive English revision. It will be  completed in 1-5 business days.

• In the abstract, the authors should briefly state what the parameters under consideration are, what tests have been used, and what the overall results have been. Delete extra sentences.

The abstract was changed. The corrosion resistance was the main parameter taken into consideration in presented investigations. Information about carried out tests were added. The main obtained results were presented.

3- The introduction is very poorly written. The relationship between production parameters, microstructure and coating properties has not been properly analyzed and discussed. Use the following articles to complete this section:

- https://doi.org/10.1016/j.ceramint.2018.10.229

- https://doi.org/10.1016/j.ceramint.2019.07.190

Thank you for your suggestion. Both article are very interesting. The part of methodology work out was not mentioned in the work. After some experimental works the coatings with proper elemental composition (Zr-Si-Cr) and thickness were obtained. Then this system (coatings with the base material) were characterised and corrosion resistance was investigated. 

The general background, rules and mechanism of coatings formation using PVD method was added in the manuscript. The relationship between production parameters, microstructure and coating properties were not discussed here. The main challenge/task/point was to formed coatings not too thick for nuclear reactor geometry point of view and not too thin for stable  corrosion protective character presence.

Authors remark: in the same time Reviewer 3 suggested to shortened the PVD method description.

• Prepare a reference for Table 1.

Data in Table 1 are presented according to:

Tang, C.; Stueber, M.; Seifert, H.J; Steinbrueck, M. Protective coatings on zirconium-based alloys as ac-ci-dent-tolerant fuel (ATF) claddings. Corros. Rev., 2017, 35, 141-165.

• Describe the method and standard used to control the chemical composition.

I can’t clearly understand what do you mean as “chemical composition”. The chemical composition - it means presence of chemical compounds was not determined.

Elemental composition was determined using: EDS method and INAA; described in the part “Samples characterization”

Phase analysis and phase presence was determined using: XRD method in Brag-Brentano geometry; described in the part “Samples characterization”

More literature positions were added in the text.

• State the standard and metallographic conditions for coatings structure.

Information about cross-section preparation was added to the text

7- Improve the quality of Figure 8.

Figures were checked and changed for better visualization of presented and discussed results

8- The results presented in Figure 6 should be presented in a table.

Figure 6 was changed and more comments are added in the text.

9- You must provide a standard card number for the phases identified in the XRD patterns.

The information connected with identified phases are as follow:

Zr - PDF 05-0665 (hex. P63/mmc SPGR=194 a=3.232 A, c=5.147A)

Zr2Si - PDF 73-2164 (tetr. I4/mcm SPGR=140 a=6.612 A, c=5.2943 A)

Information connected with crystallographic data  were found at  www.materialsproject.org

In this case marks are as follow:

Zr - mp-131

Zr2Si - mp-1278

ZrO2 - mp-2858

These information were put in the text

10- The caption of Figure 13 is incorrect. Check the grammar of the whole text.

The figures captions were checked and improved. The text was submitted to the editing service of MDPI for extensive English revision.

Reviewer 3 Report

The manuscript entitled "Multielemental Coatings on Zirconium Alloy for Corrosion Resistance Improvement" presents an interesting experimental study conducted on the obtaining and characterization of zirconium alloys coated PVD method. However, the scientific organization of the paper is questionable as the number of tested specimens wasn’t presented, and other issues must be addressed. The paper needs major revisions before it is processed further, some comments follow:

Introduction section

The introduction section must be improved. Multiple affirmations aren’t supported by the provided references or by the obtained experimental results. Also, the citations have been introduced in bulk form "[2,5,7,8]", "[1-3,5,6]" etc. and not distributed in the text in accordance with the affirmations that must be supported. Please introduce citation at a specific position to assure a clear correspondence between the affirmations from the introduction section and the previous publication. Moreover. To avoid this type of bulk citation, please cite review types of studies.

The first two paragraphs contain information without a background in the literature. Please cite corresponding studies to support your affirmations.

Line 57: "safety margin were proposed [1–3,5,6]." – please remove the bulk citations and cite the study at its suitable position, i.e., distribute the citations in the paragraph depending on the affirmation they support.

Lines 72-82: there are no citations. Please provide relevant references.

A good introduction includes a comprehensive presentation of 30  to 40 relevant previous studies, those studies must be quantitatively evaluated and presented in order to show the current state of the art in the field. Currently, the scientific organization of the introduction is very low as it includes paragraphs without a background in the literature and others that have multiple unnecessary citations.

Materials and Methods

Coating Method

The description of the coating method is too long and unnecessary. This is a well-known technique. Please remove all the unnecessary information. This subsection should provide the information/data necessary to assure the experiment's repeatability (equipment no., obtaining parameters, etc.).

Figure 3 - doesn’t have a scientific value. Please remove or provide a schematic representation of the method which can help the reader to understand the particularities of the methods used in this study if there are any.

Figure 4 - Please introduce figure labels to highlight the area of interest for the readers.

Figure 5 and Figure 8 – The quality of the figure is too low. Please provide higher resolution images.

Figure 6 – please replace the figure with a table (and replace "," with ".").

Figure 11 is unclear. Also,

XRD analysis - There are multiple peaks present in the XRD pattern which haven’t been considered. Why do the authors consider some peaks instead of others? Please improve the description of the XRD spectra.

Mineralogical evaluation. The discussion on XRD patterns is approximative, the identification of some phases is questionable and the evaluation of phase change before and after obtaining the composites wasn’t considered. Please evaluate the samples and provide the experimental results. There are some clear around 33, 48, 57, 63, 68, etc.

Results of mass changes – please provide standard deviation bars.

General remark

The study contains some experimental results, however, the scientific organization of the paper is questionable. The obtained results haven’t been correlated with each other. The study doesn’t have a Discussion Section. Moreover, the number of tested samples wasn’t presented. How many samples have been tested for each batch?

Discussion section

The results have been presented without any discussions. Please compare the obtained results with those available in the literature and clearly highlight the novelty of this study.

Conclusion Section

The conclusion section can be improved since those are far too general.

Conclusions present some of the results discussed above in the paper with very limited discussion.

Please improve the conclusions and present them following the main recommendations by Academia of giving the conclusions of the study by points with highlights.

Please rewrite the conclusions in a more quantitative form.

I recommend an in-depth review of the manuscript, including comments, to make it an article suitable for publication in the Coatings.

Author Response

Manuscript ID: coatings-1653482

Multielemental Coatings on Zirconium Alloy for Corrosion Resistance Improvement

Bożena Sartowska * , Wojciech Starosta , Lech Waliś , Jerzy Smolik , Ewa Pańczyk

ANSWERS to Reviewer 3

The manuscript entitled "Multielemental Coatings on Zirconium Alloy for Corrosion Resistance Improvement" presents an interesting experimental study conducted on the obtaining and characterization of zirconium alloys coated PVD method. However, the scientific organization of the paper is questionable as the number of tested specimens wasn’t presented, and other issues must be addressed. The paper needs major revisions before it is processed further, some comments follow:

Introduction section

The introduction section must be improved.

Multiple affirmations aren’t supported by the provided references or by the obtained experimental results.

Also, the citations have been introduced in bulk form "[2,5,7,8]", "[1-3,5,6]" etc. and not distributed in the text in accordance with the affirmations that must be supported.

Please introduce citation at a specific position to assure a clear correspondence between the affirmations from the introduction section and the previous publication.

Moreover. To avoid this type of bulk citation, please cite review types of studies.

The first two paragraphs contain information without a background in the literature. Please cite corresponding studies to support your affirmations.

Line 57: "safety margin were proposed [1–3,5,6]." – please remove the bulk citations and cite the study at its suitable position, i.e., distribute the citations in the paragraph depending on the affirmation they support.

Lines 72-82: there are no citations. Please provide relevant references.

A good introduction includes a comprehensive presentation of 30  to 40 relevant previous studies, those studies must be quantitatively evaluated and presented in order to show the current state of the art in the field. Currently, the scientific organization of the introduction is very low as it includes paragraphs without a background in the literature and others that have multiple unnecessary citations.

Materials and Methods

 Coating Method

The description of the coating method is too long and unnecessary. This is a well-known technique. Please remove all the unnecessary information. This subsection should provide the information/data necessary to assure the experiment's repeatability (equipment no., obtaining parameters, etc.).

Figure 3 - doesn’t have a scientific value. Please remove or provide a schematic representation of the method which can help the reader to understand the particularities of the methods used in this study if there are any.

Figure 4 - Please introduce figure labels to highlight the area of interest for the readers.

Figure 5 and Figure 8 – The quality of the figure is too low. Please provide higher resolution images.

Figure 6 – please replace the figure with a table (and replace "," with ".").

Figure 11 is unclear. Also,

XRD analysis - There are multiple peaks present in the XRD pattern which haven’t been considered. Why do the authors consider some peaks instead of others? Please improve the description of the XRD spectra.

Mineralogical evaluation. The discussion on XRD patterns is approximative, the identification of some phases is questionable and the evaluation of phase change before and after obtaining the composites wasn’t considered. Please evaluate the samples and provide the experimental results. There are some clear around 33, 48, 57, 63, 68, etc.

Results of mass changes – please provide standard deviation bars.

General remark

The study contains some experimental results, however, the scientific organization of the paper is questionable. The obtained results haven’t been correlated with each other. The study doesn’t have a Discussion Section. Moreover, the number of tested samples wasn’t presented. How many samples have been tested for each batch?

Discussion section

The results have been presented without any discussions. Please compare the obtained results with those available in the literature and clearly highlight the novelty of this study.

Conclusion Section

The conclusion section can be improved since those are far too general.

Conclusions present some of the results discussed above in the paper with very limited discussion.

Please improve the conclusions and present them following the main recommendations by Academia of giving the conclusions of the study by points with highlights.

Please rewrite the conclusions in a more quantitative form.

I recommend an in-depth review of the manuscript, including comments, to make it an article suitable for publication in the Coatings.

Thank you for all remarks, comments and suggestions. They helped authors to improve the text. Authors comments are listed below.

1. Introduction section was improved

• affirmations are supported by the provided references
• citations are no in the bulk form and they are distributed in the text in accordance with the affirmations with support.
• citations are put in the proper position to assure a clear correspondence between the affirmations from the introduction section and the previous publication.
• the wider range of citations connected with background are presented. Publications corresponding to the text are added and cited.
• line 57: the bulk citations is removed and cited literature are in the proper position/place, they are now distributed in the Introduction part
• lines 72-82: relevant references are added and cited.
• Introduction part is completed with more references They are presented in order to problem discussed in Introduction part.

1. Materials and Methods Coating Method section was improved

• The description of the coating method is too long and unnecessary. This is a well-known technique. Please remove all the unnecessary information. This subsection should provide the information/data necessary to assure the experiment's repeatability (equipment no., obtaining parameters, etc.).

Authors agree that PVD technique is well-known and widely applied. Authors decided to leave presented description in a little bit shorter form. Information about parameters value a and experimental conditions are presented.

Author remark: in the same time  Reviewer 1 asked for wider explanation of coating formation. So this information were added in spite of Reviewer 3 asked to remove information about used technique.

• Figure 3 was removed.
• figure labels in Figure 4 were added
• Figure 5 and Figure 8 were improved.
• Information about coating homogeneity is presented in the Table 2. Instead of Figure 6
• Figure 11 is unclear. Also,

XRD analysis - There are multiple peaks present in the XRD pattern which haven’t been considered. Why do the authors consider some peaks instead of others? Please improve the description of the XRD spectra.

• Mineralogical evaluation. The discussion on XRD patterns is approximative, the identification of some phases is questionable and the evaluation of phase change before and after obtaining the composites wasn’t considered. Please evaluate the samples and provide the experimental results. There are some clear around 33, 48, 57, 63, 68, etc.

Results of phase analysis obtained by XRD method were analyzed more detail and interpreted. Peaks present in the spectra were analyzd even they were multiplied/ covered/ coated by other one. Phase identification were made according to the crystallographic data:

The information connected with identified phases are as follow:

Zr - PDF 05-0665 (hex. P63/mmc SPGR=194 a=3.232 A, c=5.147A)

Zr2Si - PDF 73-2164 (tetr. I4/mcm SPGR=140 a=6.612 A, c=5.2943 A)

Information connected with crystallographic data  were found at  www.materialsproject.org

In this case marks are as follow:

Zr - mp-131

Zr2Si - mp-1278

ZrO2 - mp-2858

These information are added to the text. 

• The standard deviation bars are provided in the results of mass changes.

1. General remark

The study contains some experimental results, however, the scientific organization of the paper is questionable. The obtained results haven’t been correlated with each other. The study doesn’t have a Discussion Section. Moreover, the number of tested samples wasn’t presented. How many samples have been tested for each batch?

• Authors decided not to divide text for separate parts: “Results” and Discussion”. These information are written in one part: “Results and discussion”.

Obtained results of carried out experiments are presented and discussed separately. Analyze, comparison and interpretation of results was made at the end of this part of the manuscript.

• Information presented together with obtained results were put in the other place of the text: discussion part connected with obtained result interpretation
• Obtained results were presented with some sentences discussions/opinion/ mentioned facts/

 near the obtained results were presented.

• the novelty of idea, carried out works and obtained results presented in manuscript is underlined in the conclusion part.

1.  Conclusion Section was improved.

• conclusion points are changed to the more detailed, less general form
• the discussion part is now more informative and widened, so discussion of present results were widened. Authors have right to write ….
• The presentation style of conclusions is changed. Conclusions underline main achievements.
• conclusions are rewritten in a more quantitative form.

1. According the 3rd reviewer recommendation,  the deeper and stronger analysis  and review of manuscript was made. Reviewer 3 comments and suggestions were took into consideration. 

Round 2

Reviewer 1 Report

Thanks for the efforts from the authors' careful modification on their paper. I suppose the paper can be accepted for the publication in the current form.

Author Response

to Reviewer 1

Thank you for final decision of manuscript acceptance

Reviewer 2 Report

Although the authors have made changes to the article, the quality of this manuscript is very low. Also, the authors did not respond properly to my comments. I will send my comments to the authors again. After correcting the manuscript based on the comments, I will announce my opinion regarding the acceptance or rejection of the article. Changes must be highlighted:

1- The overall language quality of the article is poor in some parts. Improve the language of the article.

2- In the abstract, the authors should briefly state what the parameters under consideration are, what tests have been used, and what the overall results have been. Delete extra sentences.

3- The introduction is very poorly written. The relationship between production parameters, microstructure and coating properties has not been properly analyzed and discussed. Use the following articles to complete this section:

- https://doi.org/10.1016/j.ceramint.2018.10.229

- https://doi.org/10.1016/j.ceramint.2019.07.190

4- Prepare a reference for Table 1.

5- Describe the method and standard used to control the chemical composition.

6- State the standard and metallographic conditions for coatings structure.

7- Improve the quality of Figure 8.

8- The results presented in Figure 6 should be presented in a table.

9- You must provide a standard card number for the phases identified in the XRD patterns.

10- The caption of Figure 13 is incorrect. Check the grammar of the whole text.

Author Response

To Reviewer 2

Thank you for all remarks, comments and suggestions. They helped authors to improve the text. Authors comments are listed below. Changes in the text are highlighted in green

Ad 1.

The text of the manuscript has been corrected. The British English was used for writing and checking. The language improvements were performed professional translator. Company  approved for professional translations for industry and business.

Ad 2.

The abstract was changed according to Reviewer 2 suggestions in the Round 1. Following information were added to the text: (i) parameters considered in the study, (ii) kinds of tests used, (iii) obtained (general) results. Sentences with detailed problem descriptions were deleted.

Ad. 3.

The text of Introduction part was improved. More information according to the “state of art” was included. One part of the text was added according to Reviewer 2 suggestion and respectively references were added to the reference list.

Ad.4.

Data in Table 1 are presented according to position [4] on the reference list: Tang, C.; Stueber, M.; Seifert, H.J; Steinbrueck, M. Protective coatings on zirconium-based alloys as accident-tolerant fuel (ATF) claddings. Corros. Rev., 2017, 35, 141-165.

Ad.5.

The mass fraction (wt.%) and atomic fraction (at.%) of identified elements was used in our work to define the composition of formed coatings. Elemental composition – presence of identified elements were performed using the EDS method. Identification was done using the Quantax 400 library built for HV of 15 kV. So authors knowing the elemental composition of the formed coatings decided to name it as Zr₄₀Si₂₄Cr₃₆.

Ad.6.

The metallographic process of cross-section preparation was presented in details in the materials characterization part of the manuscript (point 2.3.1.). Further investigations of those cross-sections using SEM observations and EDS analysis allowed us to collect following results: (i) formed coatings, (ii) presence of sublayers, (iii) thickness of above mentioned layers, (iv) elemental composition in the  coatings and sublayers as well as changes of elemental distribution, (v) visible oxidized layer (after respectively oxidation processes).

The XRD phase analysis gave the information about phase identified in the coatings.

All information mentioned above are presented in the text.

Ad.7.

The quality of Figure 8 was improved.

Ad.8.

Figure 6 in the manuscript 2 presents graph with XRD spectra. There is no possibility to transform this graph to the table.

Ad.9.

The XRD spectra presented in the manuscript were obtained experimentally. Then they were analyzed for phases identification. The first source of information was database www.materialsproject.org. Information connected with crystallographic data were found at www.materialsproject.org. In this case marks are as follow:

Zr - mp-131

Zr2Si - mp-1278

ZrO2 - mp-2858

These information are in the text.

The second source of information was database with files in pdf form. Information connected with identified phases are as follow:

Zr - PDF 05-0665 (hex. P63/mmc SPGR=194 a=3.232 A, c=5.147A)

Zr2Si - PDF 73-2164 (tetr. I4/mcm SPGR=140 a=6.612 A, c=5.2943 A)

ZrO2 - PDF 78-1807

These information are in the text

Ad.10.

The caption of Figure 13 was corrected.  Grammar of the whole text was checked by professional translator.

Reviewer 3 Report

The authors made most of the changes required. The paper can be accepted in the present form.

Author Response

to Reviewer 3

Thank you for final decision manuscript acceptance