Synthesis of Ti-Cu Multiphase Alloy by Spark Plasma Sintering: Mechanical and Corrosion Properties
, Vladimir N. Sakhnevich 1, Igor Yu. Buravlev 1, Aleksey O. Lembikov 1, Anastasia A. Buravleva 1, Semen A. Azon 1, Sofia B. Yarusova 2,3, Sakhayana N. Danilova 4, Alexander N. Fedorets 1, Anton A. Belov 1 and Evgeniy K. Papynov 1
Round 1
Reviewer 1 Report
This paper cannot be accepted for publication in Metals. The paper was not well written. The authors can refer to a related paper: R. Dong et al., Microstructure, Mechanical Properties, and Sliding Wear Behavior of Spark Plasma Sintered Ti-Cu Alloys, METALLURGICAL AND MATERIALS TRANSACTIONS A-PHYSICAL METALLURGY AND MATERIALS SCIENCE, 49A(12) 6147-6160(2008).
1. Fig. 1 and Fig. 3 were not discussed in the manuscript. What is the phase composition of sample prepared by SPS? The authors did not mention it at all. They claimed that there is CuTi3 phase, in Abstract and Conclusion, but there was not any supporting material. From XRD patterns of Fig. 3, CuTi3 phase and CuTi2 phase has similar XRD patterns, how to judge the phase is CuTi3?
2. The authors claimed the sample has high hardness, but there is not any data about the hardness of Ti-Cu alloys prepared by other methods.
3. There is not scale in the images of Fig. 4. Is the image of 800oC sample correct? In the image of 900oC sample, the light phase is Cu and the dark phase is Ti. The image of 800oC is different obviously.
Author Response
zRe: « Synthesis of Ti-Cu multiphase alloy by spark plasma sintering: mechanical and corrosion properties » by Shichalin O.O. and et al. (Manuscript Number: Metals-1764047)
Dear Editors, dear Reviewers,
We deeply appreciate the time you spent reviewing our paper and the valuable recommendations you made. All the comments are taken into account and corresponding changes are made to the manuscript’s body text. Detailed point-by-point answers are presented below.
On behalf of co-authors,
Oleg Shichalin, Researcher, Ph.D.
Response to Reviewers
Reviewer #1:
General comment:
This paper cannot be accepted for publication in Metals. The paper was not well written. The authors can refer to a related paper: R. Dong et al., Microstructure, Mechanical Properties, and Sliding Wear Behavior of Spark Plasma Sintered Ti-Cu Alloys, METALLURGICAL AND MATERIALS TRANSACTIONS A-PHYSICAL METALLURGY AND MATERIALS SCIENCE, 49A(12) 6147-6160(2008).
Comment #1.
1) Fig. 1 and Fig. 3 were not discussed in the manuscript. What is the phase composition of sample prepared by SPS? The authors did not mention it at all. They claimed that there is CuTi3 phase, in Abstract and Conclusion, but there was not any supporting material. From XRD patterns of Fig. 3, CuTi3 phase and CuTi2 phase has similar XRD patterns, how to judge the phase is CuTi3?
Response to the Comment #1:
The structures are taken from the "Crystallography Open Database" and the diffraction patterns are calculated using the "Vesta" software. According to XRD data, CuTi2, CuTi, TiCu3, Cu, Ti phases are formed on the diffraction pattern of a sample sintered at a temperature of 800°C. During sintering at a temperature of 900°C, CuTi3, Cu and Ti phases are formed. The formation of the CuTi3 phase opposite to CuTi2 can be proved by the missing reflection (-1 -1 1) at 16.5 (2theta), which is characteristic of the CuTi2 phase. Figure 4 has been refined.
Figure 1 and figure 2 now have a more detailed description.
Comment # 2.
2) The authors claimed the sample has high hardness, but there is not any data about the hardness of Ti-Cu alloys prepared by other methods?
Response to the Comment #2:
Samples have high hardness values in comparison with non-ferrous metals, which usually reach no more than 320 HV, other samples with a somewhat quantitative composition of the Ti-Cu system have a higher hardness value, which is now noted in the text.
Comment #3.
3) There is not scale in the images of Fig. 4. Is the image of 800oC sample correct? In the image of 900oC sample, the light phase is Cu and the dark phase is Ti. The image of 800oC is different obviously.
Response to the Comment #3:
The picture for the sample sintered at 800oC was mixed up. Changes have been made to the figure.
Supplemented manuscript after reviewers' comments in the subreddits
Reviewer 2 Report
Dear authors and editors, thank you for sharing your experimental work. There is a lot of interesting data in the article, but the text needs to be finalized. First, correct the content of the text: too many extra words in the introduction, some extra brackets.
1. If you did mention other methods for received ti-cu material, you must compare those examples.
2. Too much information about spark plasma sintering, this process is widely known. Add more information about the ti-cu compositions.
3. Add some description of figure 1. You must let readers understand the choice of experimental design.
Author Response
zRe: « Synthesis of Ti-Cu multiphase alloy by spark plasma sintering: mechanical and corrosion properties » by Shichalin O.O. and et al. (Manuscript Number: Metals-1764047)
Dear Editors, dear Reviewers,
We deeply appreciate the time you spent reviewing our paper and the valuable recommendations you made. All the comments are taken into account and corresponding changes are made to the manuscript’s body text. Detailed point-by-point answers are presented below.
On behalf of co-authors,
Oleg Shichalin, Researcher, Ph.D.
Response to Reviewers
Reviewer #2:
General comment:
Dear authors and editors, thank you for sharing your experimental work. There is a lot of interesting data in the article, but the text needs to be finalized. First, correct the content of the text: too many extra words in the introduction, some extra brackets.
Comment #1.
1) If you did mention other methods for received ti-cu material, you must compare those examples.
Response to the Comment #1:
The text now includes more descriptions of the results and some comparisons with other Ti-Cu systems (synthesis methods and hardness).
Comment # 2.
2) Too much information about spark plasma sintering, this process is widely known. Add more information about the ti-cu compositions.
Response to the Comment #2:
Electrospark plasma sintering is a very important part of any experiment to obtain unusual alloys (intermetallic compounds, etc.). The structure of this method is necessary to understand the results. However, the current version of the article includes a more detailed description of the Ti-Cu system.
Comment #3.
3) Add some description of figure 1. You must let readers understand the choice of experimental design.
Response to the Comment #3:
Description have been added to the figure 1.
Author Response File: 
Author Response.pdf
Reviewer 3 Report
Dear Authors,
Thank you for submitting your article about Ti-Cu alloys. However, the article needs to be significantly improved.
Introduction: The introduction must be improved. There is too much general and unnecessary information and too little information about the Ti-Cu system.
Experimental part: For titanium and copper powders, the particle size of the individual powders is not specified. The data in Table 1 are unnecessary. Rather, in the experiment, state the weight ratio between the grinding balls and the amount of powder (ball to powder ratio).
I am sending comments below that need to be corrected:
a) Please correct the units of density in the abstract.
b) Correct the subscripts for chemical compounds throughout the article.
c) Please check the location of the parentheses throughout the article
d) Why were titanium and copper powders ground in a ball mill in the air? If there is no inert atmosphere in the mill, the powders will oxidize.
e) Figure 2 is very blurred. Please replace the image with a more quality image.
f) Figure 3: The location of the peaks for each phase (first 7 lines) is unnecessary. Show in the picture only 2 lower curves for two of your samples with a description of each phase. What do the numbers on the s axis mean?
g) Move Table 3 from the end to the results section and describe what Sample 1 and 2 mean
h) The article lacks a discussion of the results and a comparison of the results with similar alloys or with the same alloys prepared by another method.
Author Response
zRe: « Synthesis of Ti-Cu multiphase alloy by spark plasma sintering: mechanical and corrosion properties » by Shichalin O.O. and et al. (Manuscript Number: Metals-1764047)
Dear Editors, dear Reviewers,
We deeply appreciate the time you spent reviewing our paper and the valuable recommendations you made. All the comments are taken into account and corresponding changes are made to the manuscript’s body text. Detailed point-by-point answers are presented below.
On behalf of co-authors,
Oleg Shichalin, Researcher, Ph.D.
Response to Reviewers
Reviewer #1:
General comment:
Introduction: The introduction must be improved. There is too much general and unnecessary information and too little information about the Ti-Cu system.
Experimental part: For titanium and copper powders, the particle size of the individual powders is not specified. The data in Table 1 are unnecessary. Rather, in the experiment, state the weight ratio between the grinding balls and the amount of powder (ball to powder ratio).
Comment #1.
- a) Please correct the units of density in the abstract.
Response to the Comment #1:
Changes have been made to the text.
Comment #2.
- b) Correct the subscripts for chemical compounds throughout the article.
Response to the Comment #2:
Changes have been made to the text.
Comment #3.
- c) Please check the location of the parentheses throughout the article.
Response to the Comment #3:
Changes have been made to the text
Comment #4.
- d) Why were titanium and copper powders ground in a ball mill in the air? If there is no inert atmosphere in the mill, the powders will oxidize.
Response to the Comment #4:
It was one of the mistakes from work, the powders milled in argon environment. Changes have been added.
Comment #5.
- e) Figure 2 is very blurred. Please replace the image with a more quality image.
Response to the Comment #5:
Now the text contains the image in a better resolution.
Comment #6.
- f) Figure 3: The location of the peaks for each phase (first 7 lines) is unnecessary. Show in the picture only 2 lower curves for two of your samples with a description of each phase. What do the numbers on the s axis mean?
Response to the Comment #7:
The figure 3 has been corrected. The numbers on the lower axis represent 2-theta degrees.
Comment #7.
- g) Move Table 3 from the end to the results section and describe what Sample 1 and 2 mean
Response to the Comment #7:
The changes have been made to the table.
Comment #8.
- h) The article lacks a discussion of the results and a comparison of the results with similar alloys or with the same alloys prepared by another method.
Response to the Comment #8:
The text now includes more descriptions of the results and some comparisons with other Ti-Cu systems (synthesis methods and hardness).
Supplemented manuscript after reviewers' comments in the subreddits
Round 2
Reviewer 1 Report
The XRD patterns (Fig. 3) is not clear. It cannot prove that CuTi3 phase formed, as the authors claimed. The reflection of CuTi2 at 2theta=16.5 is weak. If CuTi2 content is lower, the peak may disappear. ICDD file 55-296 of CuTi3 has a weak peak at 2theta=16.5. The sintering tempearture id higher than that reported in Dong et al, why the diffraction peaks are so weak? Please provide clearer XRD patterns.
The literarature isurvey is not compelete, at least Dong's paper (now ref. 33) should be cited in Introduction.
Author Response
Thank you for bringing the XRD study to your attention. We have answered your questions, the answers are in the appendix
Author Response File: Author Response.pdf
Reviewer 3 Report
The article can be accepted.
Author Response
Thank you for appreciating the work. Making a common cause in the field of scientific discovery
Round 3
Reviewer 1 Report
The manuscript has been greatly improved, but the phase composition remains questionable.
The new XRD patterns are obviously different, and the attribution of phase composition has also changed. In the first response, the authors claimed that this was not CuTi2 phase in 900°C sintered sample due to the disapperence of peak at 2theta=16.45. In this response, the authors attributed the peak at 16.45° to CuTi3 phase. They believed that CuTi2 phase was not observed on the sample sintered at 900°C, since there are no peaks at 21.4° and 24.8°. Which ICDD file was used for CuTi2 phase? In ICDD files 14-641, 15-717, 04-001-2220, 04-001-3025, 04-002-0043, 04-003-1382, 2231, 5583 and 6095, no peaks at 21.4° and 24.8° were recorded. In all the above files, peak at 16.45° existed. The phase compositions in Cu-Ti alloys is very complicated. The phase compositions are different in sample sintered at 900°C and 800°C. However, phase composition attribution in the manuscript is not acceptable.
In "conclusion", "After sintering at 900°C, the CuTi3 phase clearly appears". In this revised manuscript, CuTi3 phase appears also in 800°C sintered sample.
Since the author claims that for the first time, a material containing the CuTi3 phase (sintered at 900°C) was subjected to acorrosion test and studied. They should provide solid evidence of CuTi3 phase.
On the other hand, the particle size in Table 1 is not consistent with data in Fig 2.
Author Response
Re: « Synthesis of Ti-Cu multiphase alloy by spark plasma sintering: mechanical and corrosion properties » by Shichalin O.O. and et al. (Manuscript ID: 1764047)
Dear Editors, dear Reviewers,
We deeply appreciate the time you spent reviewing our paper and the valuable recommendations you made. All the comments are taken into account and corresponding changes are made to the manuscript’s body text. Detailed point-by-point answers are presented below.
On behalf of co-authors,
Oleg Shichalin, Researcher, Ph.D.
Response to Reviewers
Reviewer #1:
Comment #1.
1) The new XRD patterns are obviously different, and the attribution of phase composition has also changed, accumulation time has been doubled. In the first response, the authors claimed that this was not CuTi2 phase in 900°C sintered sample due to the disapperence of peak at 2theta=16.45. In this response, the authors attributed the peak at 16.45° to CuTi3 phase. They believed that CuTi2 phase was not observed on the sample sintered at 900°C, since there are no peaks at 21.4° and 24.8°. Which ICDD file was used for CuTi2 phase? In ICDD files 14-641, 15-717, 04-001-2220, 04-001-3025, 04-002-0043, 04-003-1382, 2231, 5583 and 6095, no peaks at 21.4° and 24.8° were recorded. In all the above files, peak at 16.45° existed. The phase compositions in Cu-Ti alloys is very complicated. The phase compositions are different in sample sintered at 900°C and 800°C. However, phase composition attribution in the manuscript is not acceptable.
Response to the Comment #1:
Thank you for your careful criticism of our work. We have reviewed the phase analysis of these materials several times and agree with you on the most probable finding of the CuTi2 phase. A more detailed analysis, including molar conversion, is given in the work, and highlighted accordingly. The following phases were used for the analysis: Cu4Ti3 PDF2-03-065-5833, CuTi2 PDF2 - 01-072-0441, Cu PDF2 01-070-3038.
Comment # 2.
In "conclusion", "After sintering at 900°C, the CuTi3 phase clearly appears". In this revised manuscript, CuTi3 phase appears also in 800°C sintered sample.
Response to the Comment #2:
The changes have been added.
Comment # 3.
Since the author claims that for the first time, a material containing the CuTi3 phase (sintered at 900°C) was subjected to acorrosion test and studied. They should provide solid evidence of CuTi3 phase.
Response to the Comment #3:
The changes have been added.
Comment # 4.
In "conclusion", "After sintering at 900°C, the CuTi3 phase clearly appears". In this revised manuscript, CuTi3 phase appears also in 800°C sintered sample.
Response to the Comment #4:
Conclusion has been revised
Round 4
Reviewer 1 Report
In Abstract, "Also, for the first time, a material containing the CuTi3 phase (sintered at 900 0C) was subjected to a corrosion test and studied." has not been revised.
In Table 1, titanium powder and copper powder has particle size 60-70nm, 40-60 nm, respectively. The section 3.1 and Fig.2 is very confused. In section 3.1, "after processing, Ti and Cu powders were obtained with an average particle size of 20–30 μm. " ." as a result of grinding, the average value of the particle size became equal to 40 microns". The initial powders in Fig. 2 are the powders before grinding? The three results are not consistent.
Author Response
Re: « Synthesis of Ti-Cu multiphase alloy by spark plasma sintering: mechanical and corrosion properties » by Shichalin O.O. and et al. (Manuscript ID: 1764047)
Dear Editors, dear Reviewers,
We deeply appreciate the time you spent reviewing our paper and the valuable recommendations you made. All the comments are taken into account and corresponding changes are made to the manuscript’s body text. Detailed point-by-point answers are presented below.
On behalf of co-authors,
Oleg Shichalin, Researcher, Ph.D.
Response to Reviewers
Reviewer #1:
Comment #1.
1) In Abstract, "Also, for the first time, a material containing the CuTi3 phase (sintered at 900 0C) was subjected to a corrosion test and studied." has not been revised.
Response to the Comment #1:
The changes have been added.
Comment # 2.
In Table 1, titanium powder and copper powder has particle size 60-70nm, 40-60 nm, respectively. The section 3.1 and Fig.2 is very confused. In section 3.1, "after processing, Ti and Cu powders were obtained with an average particle size of 20–30 μm. " ." as a result of grinding, the average value of the particle size became equal to 40 microns". The initial powders in Fig. 2 are the powders before grinding? The three results are not consistent.
Response to the Comment #2:
Thank you for your attention to detail, there were indeed errors in the particle sizes. On the image 2 powders of chemical elements are shown before grinding, their average size is 40-70 μm. After joint grinding, the average size became 20-30 μm.
