Wet Ball Milling Applied to Production of Composites and Coatings Based on Ti, W, and Nb Carbides
Round 1
Reviewer 1 Report
First of all, an important topic on the development of efficient and low-cost techniques for the production of carbide-based composites and coatings. However, I would suggest reconsidering the paper after inviting the authors to respond to the following comments.
1. The type and producers of “X-ray diffractometer” and “high-speed selective laser sintering” had better be noted.
2. Some information, such as the shape, material and precision of the thermocouple, should be given.
3. L112-114: As shown in Figure 2a, the phase composition of MA powder annealed at 600 ℃ are Ti2CH0.6 and Ti(C,H), but the Authors subjectively assume it close to Ti2CH0.6,please give the explanation. In addition, how can the authors get the lattice information of carbide-based composites based on the XRD patterns in this study?
4. It would be nice if the authors could give the possible reason/analysis for the formation of the Nb3(Fe,Cu)Cx and Nb5Al3Сх phase in the Niobium-based systems.
5. Please give the reasons why compacts and coatings prepared from the wet-milled powders exhibit high wear resistance.
6. In the XRD patterns, the corresponding PDF card of the object should be marked in the picture or presented in the text.
Author Response
Dear Reviewer!
We express our appreciation for your comments. We tried to consider all the comments and suggestions and made the appropriate revision of the manuscript. All the changes are highlighted within the manuscript. Below are comments on the changes made.
"First of all, an important topic on the development of efficient and low-cost techniques for the production of carbide-based composites and coatings. However, I would suggest reconsidering the paper after inviting the authors to respond to the following comments.
1. The type and producers of “X-ray diffractometer” and “high-speed selective laser sintering” had better be noted."
Reply: Thank you for your comments. Data on the type of diffractometer added to the section "Materials and methods". The device is based on a serial laser generator (BULAT, LRS AUTOMATIC, Russia).
2. "Some information, such as the shape, material and precision of the thermocouple, should be given.")
Reply: The corresponding information has been added to the text of the manuscript (in the "Materials and methods" section).
3. "L112-114: As shown in Figure 2a, the phase composition of MA powder annealed at 600 ℃ are Ti2CH0.6 and Ti(C,H), but the Authors subjectively assume it close to Ti2CH0.6,please give the explanation. In addition, how can the authors get the lattice information of carbide-based composites based on the XRD patterns in this study?"
Reply: We agree with your comment. This part is revised and the information about lattice parameters has been added trough the text.
4. "It would be nice if the authors could give the possible reason/analysis for the formation of the Nb3(Fe,Cu)Cx and Nb5Al3Сх phase in the Niobium-based systems."
Reply: This is an important and interesting question. We tried to make assumptions about the possible mechanisms for the formation of these phases, however, confirmation of these assumptions requires careful study for each of the systems using an analysis of the local atomic environment. In the case of the Nb-Al-C system, one of the possible mechanisms is the transformation of bcc solid solution (Im m) to metastable phase with B2 structure (Pm m, L12), and then decomposition of the last one, accompanied by the formation of hexagonal phase Nb5Al3Сх. The formation of Nb3(Fe,Cu)Cx phase can be caused by ordering and transformation of metastable fcc phase into L12. The nature of the metastable fcc phase in the Nb-Cu-C system also requires further careful study, especially regarding the presence of copper in its composition.
5. "Please give the reasons why compacts and coatings prepared from the wet-milled powders exhibit high wear resistance."
Reply: The high wear resistance is most likely due to the nanostructural state and the high hardness of the inclusions. The hardness of the counterbody made of the WC-6Co alloy was ~14 GPa, but after wear tests, we observe wear tracks on the surface of the counterbody. This means that abrasive wear of the counterbody surface takes place and the hardness of individual grains in the coatings is noticeably higher than 14 GPa. Nanosized inclusions of carbides are strongly bonded to the substrate due to the formation of solid solutions and intermetallic phases.
6. "In the XRD patterns, the corresponding PDF card of the object should be marked in the picture or presented in the text."
Reply: The corresponding ICSD numbers of phases are noted in the text.
Reviewer 2 Report
The manuscript "Wet ball milling applied to production of carbide-based composites and coatings " is a nice paper and results presented in the manuscript are interesting. The author has used wet ball milling of metals for the synthesis of various carbides and carbohydrides. The author has finally subjected the as-fabricated powders were used to produce bulk compacts as well as to apply coatings on steel (iron) exhibiting high wear resistance. The work was supported by XRD and Scanning electron microscopy, the results of both these techniques confirms the target synthesis.
Overall the quality of paper is well enough for the publication in the journal, however the author must concentrate on the followings:
1. The title of the manuscript is very broad, the title should be more specific and self explanatory, as the work is very interesting the title should be the attractive and of readers interest.
2. There are slight grammatical and syntax errors, the author should check it carefully.
3. In the result and discussion section, the author should cite latest work, the author should replace the old citations with the new ones.
My recommendation: Accept after minor revision mentioned above
Author Response
Dear Reviewer!
We express our appreciation for your comments. We tried to consider all the comments and suggestions and made the appropriate revision of the manuscript. All the changes are highlighted within the manuscript. Below are comments on the changes made.
"The manuscript "Wet ball milling applied to production of carbide-based composites and coatings " is a nice paper and results presented in the manuscript are interesting. The author has used wet ball milling of metals for the synthesis of various carbides and carbohydrides. The author has finally subjected the as-fabricated powders were used to produce bulk compacts as well as to apply coatings on steel (iron) exhibiting high wear resistance. The work was supported by XRD and Scanning electron microscopy, the results of both these techniques confirms the target synthesis.
Overall the quality of paper is well enough for the publication in the journal, however the author must concentrate on the followings:
- The title of the manuscript is very broad, the title should be more specific and self explanatory, as the work is very interesting the title should be the attractive and of readers interest."
Reply: Thank you for your comments. The title was slightly changed, marking the main component of the systems studied in the work.
- "There are slight grammatical and syntax errors, the author should check it carefully."
Reply: Thank you for your comment. The text has been revised.
- "In the result and discussion section, the author should cite latest work, the author should replace the old citations with the new ones."
Reply: Old citations have been removed or replaced with more recent ones, where possible. Unfortunately, it is very difficult to find works on titanium and niobium carbohydrides, as well as on poorly studied bimetallic carbides. We were forced to keep the citation [23 – H. Holleck et al, 1981].
Reviewer 3 Report
This paper focuses on the Wet ball milling applied to production of carbide-based composites and coatings. Though the work in this paper is of fundamental importance, it lacks the novelty and detailing required for publication in Powders. However, there are some major concerns regarding the claims and conclusions drawn from this study:
1. The author did not explain why he choose the experimental parameters for this study.
2.Why 2 different loads and 2 different counterface for the tribological test
3.The author fails to explains why the peaks are broadening ad a function of milling time and fails to coherently specify the peak compositions
4.The author doesn't have the clear justification and its poorly shown and explained the microstructure characterization
5. The author also needs to explain how the annealing is done and why he chose those annealing temperature
6. No EDS/compositional maps to prove the composition or elemental enichment.
7. Table 2 needs to be explained properly and why are the cited in the last row if the tests are done by the authors
8. Comments on grain size and other eveauation from the microstructure is poorly shown and determined
9. The detailing in the microstructure is now well explained and shown in the figures.
10. Phase and composition evaluation by XRD is not enough to confirm from the analyses. Additional experiments or characterization should be done.
11. Conclusions are poorly written.
Author Response
Dear Reviewer!
We express our appreciation for your comments. We tried to consider all the comments and suggestions and made the appropriate revision of the manuscript. All the changes are highlighted within the manuscript. Below are comments on the changes made.
"This paper focuses on the Wet ball milling applied to production of carbide-based composites and coatings. Though the work in this paper is of fundamental importance, it lacks the novelty and detailing required for publication in Powders. However, there are some major concerns regarding the claims and conclusions drawn from this study.
- The author did not explain why he choose the experimental parameters for this study."
Reply: Thank you for your comments. The manuscript is a brief overview of our results on the mechanosynthesis of carbon-containing phases using liquid hydrocarbons. This approach turned out to be quite effective for obtaining bulk samples of multicomponent carbides, metastable and high-temperature intermetallic compounds stabilized by intercalated carbon. To obtain these phases by traditional methods, long-term annealing at high temperatures is required; many of these phases were previously obtained only in the form of highly dispersed inclusions or thin films. Some of the phases were synthesized by us for the first time.
Preparation of carbide phases using steel vials and balls and annealing at relatively low temperatures is more economical than using a tungsten carbide- based vials and balls and high temperature sintering. In addition, it is shown that iron impurities from steel vials and balls can be used for the synthesis of multicomponent iron-containing carbides.
The choice of the compositions of the starting materials was determined by the stoichiometry of the compounds to be obtained. The choice of mechanosynthesis conditions (milling time, material of grinding vials and balls, the medium, etc.) was made based on previously obtained experimental data given in the works to which we gave references. In the text of this paper, conditions are given that are optimal for the synthesis of the systems under study.
The choice of annealing temperature was based on differential thermal analysis data, which we did not present in this paper so as not to overload the text. The section "Materials and Methods" is supplemented.
- "Why 2 different loads and 2 different counterface for the tribological test."
Reply: When testing for wear resistance, one load was selected – 10 N. The use of two different types of counterbodies is due to the possible practical application of the obtained materials.
3. "The author fails to explains why the peaks are broadening ad a function of milling time and fails to coherently specify the peak compositions"
Reply: We partially agree with your comment. The peaks broaden with milling time due to an increase in the contribution of microstrains, the degree of disorder, and the formation of a nanostructural state. This is denoted in the text of the paper. We cannot clearly distinguish the contributions of different phases on the diffraction patterns of milled powders before annealing; we can only qualitatively judge their probable presence.
4. "The author doesn't have the clear justification and its poorly shown and explained the microstructure characterization."
Reply: The paper presents the data of scanning electron microscopy. Unfortunately, the manuscript's word limit does not allow for additional images and detailed consideration of the microstructure for each system. For the case of a coating based on titanium carbide, we have added one more image (Please, see Fig. 2c).
5. "The author also needs to explain how the annealing is done and why he chose those annealing temperature."
Reply: The annealing conditions are specified in the methodological part of the paper. The choice of the annealing temperatures was based on differential thermal analysis data, as well as based on data on the thermal desorption of hydrogen obtained earlier (for example, Titanium carbohydride synthesis by mechanical activation in liquid hydrocarbon, M.A. Eremina, S.F. Lomaeva, et al. DOI: 10.1134/S0036023618100066).
- "No EDS/compositional maps to prove the composition or elemental enichment."
Reply: Unfortunately, the EDS maps were not recorded. The EDX spectra are added to the text of the manuscript, or the ratios of the metal components are indicated in the tables below the SEM images.
- "Table 2 needs to be explained properly and why are the cited in the last row if the tests are done by the authors."
Reply: References removed from Table 2.
- "Comments on grain size and other eveauation from the microstructure is poorly shown and determined."
Reply: The text gives an estimation of the size of inclusions in coatings and compacts, determined from SEM images. The diameter of coherent scattering regions and the level of microstrains in grains (except for titanium monocarbide) are not determined in most cases due to the lack of standards (and cif-files) and the strong overlap of line sets in the XRD patterns.
- "The detailing in the microstructure is now well explained and shown in the figures."
Reply: To our great regret, we did not understand this comment.
- "Phase and composition evaluation by XRD is not enough to confirm from the analyses. Additional experiments or characterization should be done."
Reply: We agree with your comment. Additional research is planned and ongoing. For some iron-containing systems, there are Mössbauer spectroscopy data that do not contradict the conclusions made in the paper.
- "Conclusions are poorly written."
Reply: The conclusion to the manuscript has been revised, additions have been made.
Round 2
Reviewer 3 Report
The author has modified the manuscript and it is in shape of accepting to the journal with slight discussion on the wear properties in a support document/supplementary document
