Optimization of In Situ Formation of a Titanium Carbide Nanohybrid via Mechanical Alloying Using Stearic Acid and Carbon Nanotubes as Carbon Sources

Round 1

Reviewer 1 Report

Comments and Suggestions for Authors

In this paper, preparation of nanosized titanium carbide through mechanical alloying was investigated. I recommend that this paper is published after minor revisions according to a following comments.

 

Comments:

Line 95

Although the text states that 1.0 ml of process control agent (=FC) was used, Table 1 shows the amount of FC as 0.16 or 1.6 g. There is a discrepancy between the notation in the text and the contents of Table 1.

 

Line 109

“The x-ray”: delete

 

Lines 118 and 183

Fullprof --> FullProf

 

Lines 125-126

scanning range (cm^-1): 200 to 1000 cm^-1 --> scanning range: 200-1000 cm^-1

 

Line 130

Hitachi: delete

 

Line 144

B2 --> B1

 

Table 2

Explanation and discussion regarding Table 2 is required.

 

Figure 8

The authors need to explain the peaks at 200-800 cm^-1 seen in Figure 8 A1 and B1.

Author Response

Reviewers’ Comments and Authors' Response

Paper number: jcs-2712153

Paper title: Optimization of in situ Formation of a TiC Nanohybrid by Mechanical Alloying Using Stearic Acid and CNTs as Carbon Sources. 

Authors: María Luisa Camacho-Ríos, Guillermo Herrera-Pérez, Marco Antonio RuizEsparza-Rodriguez, Raúl Pérez-Bustamante, John Edison García-Herrera, José Antonio Betancourt-Cantera, Daniel Lardizábal-Gutiérrez.

We have taken into consideration all the comments and suggestions posed by the reviewers and have modified the manuscript accordingly. We have also addressed the requirements from the Editorial Office. Thank you for your time and for considering this paper for publication in J. Compos. Sci.

In addition, some grammar and spelling mistakes were corrected throughout the manuscript. In this document are the answers to all the questions and comments.

Reviewer #1

Comments:

Line 95 Although the text states that 1.0 ml of process control agent (=FC) was used, Table 1 shows the amount of FC as 0.16 or 1.6 g. There is a discrepancy between the notation in the text and the contents of Table 1.

Answer

We appreciate the valuable suggestion of the reviewer. In the Materials and Methods section, we label carbon sources as (CS) to distinguish them from the process control agent (PCA) in this case n-heptane. (lines 107-117). Also, this correction was achieved in Table 1.

Line 109 “The x-ray”: delete

Answer

We also appreciate the valuable suggestion of the reviewer. We performed this correction.

Lines 128 and 196 Fullprof --> FullProf

Answer

We appreciate the valuable suggestion of the reviewer. In the Materials and Methods section (new version), we performed this correction. We also include references 24 and 25 to cite the FullProf Suite software and to support our analysis. (lines 128-130).

 

24. Rodriguez-Carbajal, J. Recent advances in magnetic structure determination by neutron powder diffraction, Phys. B Condens. Matter. 1993, 192, 55–69.
25. McCusker, L.B.; Von Dreele, R.B.;  Cox, D.E.;  Louer, D.; Scardi, P. Rietveld refinement guidelines. J. Appl. Crystallogr. 1999, 32, 36–50.

In line 195 we also performed the requested correction.

Lines 125-126 scanning range (cm-1): 200 to 1000 cm-1 --> scanning range: 200-1000 cm-1

Answer

Thank you again for this comment. We performed this correction (line 136).

Line 130 Hitachi: delete

Answer

We want to clarify (in this new version) that the SEM micrographs were collected in a Hitachi equipment model SU3500 (lines 140 -141).

Line 144 B2 --> B1

Answer

Thank you for this comment. We performed this correction. (line 151).

Table 2 Explanation and discussion regarding Table 2 is required.

Answer 

In this new version, we include a short discussion about the little difference in the volume cell. The values of the lattice parameter of TiC are in agreement to the data reported in the crystallographic chart ICSD 03-065-8417 (panel b). However, it can be observed in Table 2, a little difference in the volume value. According to T. Kvashina et al; [31]  this difference could be attributed by partial oxidation of the sample resulting in the decrease in the average crystallite size and the formation of dislocations stabilized by the impurity oxygen atoms in the crystal lattice of TiC.

We also add the following reference to support our discussion.

31. Kvashina, T,; Uvarov, N,; Ukhina, A. Synthesis of Titanium Carbide by Means of Pressureless Sintering. Ceramics 2020, 3, 306-311.

 

Thank you also for this observation, we include a description of the parameters summarized in Table 2. (lines 211-213)

Table 2 summarizes the refined lattice parameters, volume, and the relative fraction of each component obtained by considering the space groups for TiC and Ti. This table also reports the R-factors and the chi-square (χ²) goodness of fit. 

Figure 8 The authors need to explain the peaks at 200-800 cm-1 seen in Figure 8 A1 and B1.

Answer

Thank you for this comment, we improved Figure 8 to visualize the Raman band associated with TiCxOy in the range of 200-800 cm-1 for the samples labeled as A1 and B1. 

 

 

Reviewer 2 Report

Comments and Suggestions for Authors

The manuscript presents a simple synthesis of TiC composites by mechanical alloying. The thorough structural analysis including XRD, SEM, TEM is intriguing. Minor revision is suggested. There are a few suggestions that the author may consider:

 

1. The study used CS 2wt% and 20wt% for TiC mechanical alloying. Could the authors explain more on the composition selection?

 

2. It is interesting to see that A2 (80% Ti powder and 20% SA) is not crystallized. The authors claims the TiC-deficient phase is because of acid decomposition. However, it seems from Figure 5 that most particles in A2 is still Ti. Could the authors explain more on the contradiction?

 

3. Mechanical alloying of TiC composite has been extensively studied. The manuscript will be improved if the authors can elaborate the novelty.

 

 

Minor problems:

Should the composition of B2 in Table 1 be Ti/CS=80:20?

Comments on the Quality of English Language

The writing is overall okay

Author Response

Reviewers’ Comments and Authors' Response

Paper number: jcs-2712153

Paper title: Optimization of in situ Formation of a TiC Nanohybrid by Mechanical Alloying Using Stearic Acid and CNTs as Carbon Sources. 

Authors: María Luisa Camacho-Ríos, Guillermo Herrera-Pérez, Marco Antonio RuizEsparza-Rodriguez, Raúl Pérez-Bustamante, John Edison García-Herrera, José Antonio Betancourt-Cantera, Daniel Lardizábal-Gutiérrez.

We have taken into consideration all the comments and suggestions posed by the reviewers and have modified the manuscript accordingly. We have also addressed the requirements from the Editorial Office. Thank you for your time and for considering this paper for publication in J. Compos. Sci.

In addition, some grammar and spelling mistakes were corrected throughout the manuscript. In this document are the answers to all the questions and comments.

 

Reviewer #2

1. The study used CS 2wt% and 20wt% for TiC mechanical alloying. Could the authors explain more on the composition selection?

Answer

Thanks to the reviewer for this observation. Previous reports suggest the use of CS above 20 wt % to prepare TiC. In the current work, we propose the use of 20 wt% or less to prepare TiC. We include the following statement (see lines 76-96, page 3) with the respective literature.

Various strategies have been developed to improve the preparation of TiC using the ball milling method as Lohse et al; [8] reported previously. These authors suggest that the high-energy ball milling method is one of the most effective method. To date, different kinds of ball milling such as conventional ball milling, planetary ball milling, agate ball milling, vibratory mill, magneto ball milling, and SPEX have been attempted. Liu et al; [17]  report the preparation of Ti_100-xC_x (where x = 35, 43, and 50) with milling times of 186, 179, and 140 minutes using an SPEX mill. Ye and Quan [18] prepared Ti₅₀C₅₀ using a planetary ball mill for 5 h. Shaffer and Forrester [19] prepared the same composition using a steel SPEX mill. These previous reports indicate that TiC can be produced by milling elemental titanium and carbon powder mixtures. In addition, Lohse et al; [8] suggest that the key points for the in situ fabrication of Ti_100-xC_x, are the composition, long milling time, and ball milling type. These parameters play an important role in reducing the particle size in the nanometer range for TiC. Therefore, there are ongoing efforts to explore facile in situ TiC preparation with the reduction of particle size in the nanometer range (around 15 nm or less); considering the combination of these parameters with the use of a high-energy ball mill method.

 

The motivation for this work is to prepare in situ TiC composites using the mechanical alloying technique (within a 4-hour timeframe) to reduce the particle size in the nanometer range  (15 nm or less). Then, compare the structural and microstructural effects by the use of two carbon source concentrations (2 wt% and 20 wt%). 

 

17. Liu, Z.G.; Guo, J.T.; Ye, L.L.; Li, G.S.; Hu, Z.Q. Formation mechanism of TiC by mechanical alloying. Appl. Phys. Lett. 1994, 65, 2666-2668.
18. Ye, L.L.; Quan, M.X. Synthesis of nanocrystalline TiC powders by mechanical alloying. Nanostruct. Mater. 1995, 5, 25-31.
19. Schaffer, G.B.; Forrester, J.S. Influence of collision energy and strain accumulation on the kinetics of mechanical alloying. J. Mater. Sci. 1997, 32, 3157-3162.

 

2. It is interesting to see that A2 (80% Ti powder and 20% SA) is not crystallized. The authors claim the TiC-deficient phase is because of acid decomposition. However, it seems from Figure 5 that most particles in A2 is still Ti. Could the authors explain more on the contradiction?

Answer

Thank you very much for this comment. In the current version, we include an indexation according to Jia et al. We include the following statement based on Jia et al report. (lines 148-163)

For sample A2, two broadened signals are observed at 36.56° and 42.32°. The X-ray profile and our indexation are consistent with the previous report by Jia et al; 2009 [7]. According to these authors [7], Ti is gradually consumed due to the formation of TiC with increasing mechanical alloying time. Therefore, in the XRD pattern of the sample labeled as A2, the presence of a small amount of TiC can be identified.

We also improved Figure 1 and its respective figure caption associated with the comment.

3. Mechanical alloying of TiC composite has been extensively studied. The manuscript will be improved if the authors can elaborate the novelty.

Answer

We appreciate the valuable suggestion of the reviewer. Our appreciation is that this comment is related to the first comment.

Several reports suggest the mechanical alloying to prepare TiC. As Lohse et al suggest the combination of several parameters such as milling time and CS concentration is important to prepare TiC. This suggestion opens the possibility to explore other CS concentrations below 30 wt%. Another important aspect is to reduce the milling time as the current work suggests (4 hours) without post-heat treatment. In consequence, we reduce the particle size to around 11 nm.

 

Minor problems:

Should the composition of B2 in Table 1 be Ti/CS=80:20?

Answer

Thank you for this observation. We clarify this value in Table 1.

 

Reviewer 3 Report

Comments and Suggestions for Authors

Optimization of in-situ Formation of a TiC Nanohybrid by 3 Mechanical Alloying Using Stearic Acid and CNTs as Carbon 4 Sources

 

Review:

1. Abbreviations should be displayed and printed separately, abbreviations are usually not used in the Abstract and in the title - correction needed.

2. I recommend that TiC is one of the key words missing from the manuscript.

3. in Part 2 – please use the two subsections - materials and characterization techniques separately, synthesis description is missing.

4. The reference to chapter 3.2 is incorrect - please correct it.

5. in Figure 3a show the site, which is enlarged in Figure 3b.

6. text under figure 4, the descriptions for points A1 to B2 are missing.

7. text under figure 5, descriptions for points A1 to B2 are missing

8. Please specify chapter 3.4 Raman….??

9. in Figure 8, mark the points indicating which phase/component they belong to (the existing diagrams are unclear, unreadable)

10. Formulate conclusions more precisely, clearly and briefly.

Author Response

Please see the attachment.

Reviewers’ Comments and Authors' Response

Paper number: jcs-2712153

Paper title: Optimization of in situ Formation of a TiC Nanohybrid by Mechanical Alloying Using Stearic Acid and CNTs as Carbon Sources. 

Authors: María Luisa Camacho-Ríos, Guillermo Herrera-Pérez, Marco Antonio RuizEsparza-Rodriguez, Raúl Pérez-Bustamante, John Edison García-Herrera, José Antonio Betancourt-Cantera, Daniel Lardizábal-Gutiérrez.

Again, we have taken into consideration all the comments and suggestions posed by the reviewers and have modified the manuscript accordingly. We have also addressed the requirements from the Editorial Office. Thank you for your time and for considering this paper for publication in J. Compos. Sci.

 

Reviewer #3

Comments:

1. Abbreviations should be displayed and printed separately, abbreviations are usually not used in the Abstract and in the title - correction needed.                 Answer

We appreciate the valuable suggestion of the reviewer. We performed these corrections in the Title  (lines 2-4) and Abstract section  (lines 17-27).

2. I recommend that TiC is one of the keywords missing from the manuscript.

Answer

We included this keyword in the respective section (line 29).

3. in Part 2 – please use the two subsections - materials and characterization techniques separately, the synthesis description is missing.

Answer

In the current version, we use three subsections Materials, Synthesis, and Characterization Techniques (lines 108-131).

4. The reference to chapter 3.2 is incorrect - please correct it.

Answer

We clarify the reference to the SEM micrographs (lines 241-251).

5. in Figure 3a show the site, which is enlarged in Figure 3b.

Answer

Thank you for this comment. We re-write the figure caption to show that panel a is related to Ti particles and panel b is related to carbon nanotubes. Also, we want to clarify that the inset shown in panel a is the analysis of the histogram to determine the average particle size of Ti particles (249-251).

6. text under figure 4, the descriptions for points A1 to B2 are missing.

Answer 

The Figure caption for Figure 4 was rewritten to consider the descriptions requested. Thank you. 

7. text under figure 5, descriptions for points A1 to B2 are missing

Answer 

Also, the Figure caption for Figure 5 was re-written to consider the descriptions requested. Thank you, again.

8. Please specify chapter 3.4 Raman….??

Answer 

We improve the line 356 related to Raman spectroscopy section.

9. in Figure 8, mark the points indicating which phase/component they belong to (the existing diagrams are unclear, unreadable).

Answer

We appreciate this comment. We re-plot Figure 8 and we improve the information in the figure caption.

 

10. Formulate conclusions more precisely, clearly and briefly.

 Answer

Thank you for this suggestion, in this new version we re-formulate the conclusions (line 398- 415).

 

Round 2

Reviewer 1 Report

Comments and Suggestions for Authors

This paper is meaningful for the field of titanium carbide.

The revised paper has been carefully changed according to my comments.

I accept in present form.

Author Response

Thank you for your comments.

Reviewer 2 Report

Comments and Suggestions for Authors

The manuscript is improved after revision. I therefore recommend accept it in its present form.

Author Response

Thank you for your comments.

Reviewer 3 Report

Comments and Suggestions for Authors

No Comments and Suggestions for Authors