Enhanced Magnetic Cooling through Tailoring the Size-Dependent Magnetocaloric Effect of Iron Nanoparticles Embedded in Titanium Nitride Thin Films
Round 1
Reviewer 1 Report
The paper reported Fe nanoparticles and thin films embedded in a TiN matrix grown using the PLD technique, focusing on their structure, magnetism, and magnetocaloric properties. The results of investigation are supported by the number of Figures and Tables. The manuscript is written clearly and the experimental facts are described carefully. However, in my opinion, these are still some questions that should be properly addressed before its acceptance.
1. Q: Why the smaller the nanoparticle size of the sample is, the stronger the magnetocaloric effect is, while the thin film sample shows the lowest effect.
2. Q: The author observed that the magnetocaloric effect was better in the sample with smaller nanoparticle size (D=7 nm). However, it remains unclear whether studying Fe particle sizes (D=6 nm or D=5 nm) would result in a further improvement in the magnetocaloric effect.
3. Q: There are some errors in the reference section, the author should carefully check the reference before submission. For example, ref. 3, 7, 11, 27, 28, 32, 38 in the manuscript.
Minor editing of English language required.
Author Response
The paper reported Fe nanoparticles and thin films embedded in a TiN matrix grown using the PLD technique, focusing on their structure, magnetism, and magnetocaloric properties. The results of investigation are supported by the number of Figures and Tables. The manuscript is written clearly and the experimental facts are described carefully. However, in my opinion, these are still some questions that should be properly addressed before its acceptance.
- Q: Why the smaller the nanoparticle size of the sample is, the stronger the magnetocaloric effect is, while the thin film sample shows the lowest effect.
Response: The superior magnetocaloric effect (MCE) and refrigerant capacity (RC) of the nanoparticles are attributed to their ability to undergo a wider entropy change within the experimental temperature range. The experimental measurements, however, have shown that if the particles are too small, the magnetic moments as well as blocking temperature, are low. If the particles are big, they tend to coalesce, and the samples eventually transform into continuous thin films. The text is marked on page 21.
- Q: The author observed that the magnetocaloric effect was better in the sample with smaller nanoparticle size (D=7 nm). However, it remains unclear whether studying Fe particle sizes (D=6 nm or D=5 nm) would result in a further improvement in the magnetocaloric effect.
Response: It will be interesting to consider smaller variations in the particle size to establish the points suggested by the referee. However, we envision limitations in making particle size too big or too small for the reason described in the above question.
- Q: There are some errors in the reference section, the author should carefully check the reference before submission. For example, ref. 3, 7, 11, 27, 28, 32, 38 in the manuscript.
Response: The errors in those references are fixed; the new references are #4, #12, #24, #42, #43, #50, #54.
Reviewer 2 Report
The current work illustrates the effect of the size of Fe nanoparticles on the MCE of TiNi thin films, an enhancement in the MC properties for the samples that have different sizes of Fe NPs. I found the manuscript very interesting and will make a good contribution to the scientific community. Thus, I recommend accepting the manuscript to be published in Magnetochemistry, after the authors maintain these necessary points.
The introduction.
The introduction is very poor and needs to be enhanced with relevant references which have an improving the MCE in different physical forms of the same composition such as nanostructured thin films, and microwires,…. Also to illustrate the gap of this research point and the important of the current study to fill this gap.
Materials and methods:
1- The authors should add more information and details in the experimental part and how they estimate the layer thickness of the film. In addition, more details about the coating process and its parameters to control it.
2- Figure 1 it is better to move to the materials and method and enhance it with the step of sample fabrications.
Results:
1- The authors should add the uncertainties for all outcome data in the tables and the figures to see the real behaviour of all parameters studied in the current manuscript.
2- What about the AFM measurement for the rest of the samples? Kindly include some of them.
3- It will be great if the authors add more discussion and calculation to describe the present data in Figure 3 and add the scale bar for Figure 3 a, c and d.
4- Kindly add the references for all equations presented in the manuscript.
Author Response
The current work illustrates the effect of the size of Fe nanoparticles on the MCE of TiNi thin films, an enhancement in the MC properties for the samples that have different sizes of Fe NPs. I found the manuscript very interesting and will make a good contribution to the scientific community. Thus, I recommend accepting the manuscript to be published in Magnetochemistry, after the authors maintain these necessary points.
The introduction.
The introduction is very poor and needs to be enhanced with relevant references which have an improving the MCE in different physical forms of the same composition such as nanostructured thin films, and microwires,…. Also to illustrate the gap of this research point and the important of the current study to fill this gap.
Response: The re-written introduction section that includes/expands the description on the MCE in different physical forms and research with new references undoubtedly reads better. These changes are marked in yellow.
Materials and methods:
1- The authors should add more information and details in the experimental part and how they estimate the layer thickness of the film. In addition, more details about the coating process and its parameters to control it.
Response: Thank you for the suggestion. Adequate detail has been provided in the experimental sections. Please see the changes marked.
2- Figure 1 it is better to move to the materials and method and enhance it with the step of sample fabrications.
Response: The suggestion has been implemented.
Results:
1- The authors should add the uncertainties for all outcome data in the tables and the figures to see the real behaviour of all parameters studied in the current manuscript.
Response: Thank you for the suggestions. To avoid errors in data and to check the property reproducibility, a control set of samples is prepared a second time, and the same samples are subjected to a repeat measurement, such as XRD, SEM, AFM, TEM, thickness, SQUID Magnetometer, etc. The primary disparity in our experimental data is brought about by an unintentional variation in the two most deposition parameters (laser energy and substrate temperature) during sample preparations by the PLD method. Therefore, precautions are taken to avoid variation in these parameters that would yield films more than 5 % different in terms of thickness, FWHM, particle size, and four-point electrical resistivity, magnetic moments. The films are redeposited if the variation in these characteristics is more than the aforesaid percentage. The absence of an error bar in a given figure means that the data presented is average data for more than one sample obtained using more than one measurement. The text to this effect is marked on page 8.
Please see the changes made in Table 1 and Fig. 4d, Fig. 8 and Fig. 9a.
2- What about the AFM measurement for the rest of the samples? Kindly include some of them.
Response: The suggestion has been implemented. Fig. 2c and d are AFM images are two more samples.
3- It will be great if the authors add more discussion and calculation to describe the present data in Figure 3 and add the scale bar for Figure 3 a, c and d.
Response: The discussion has been expanded and the missing scale bars for Fig. 3 c and d are more clearly marked.
4- Kindly add the references for all equations presented in the manuscript.
Response: The suggestion has been implemented ( ref #12, #32, #39, #51, #52, #53, #57).
Reviewer 3 Report
The present manuscript entitled “Enhanced Magnetic Cooling through Tailoring the Size-Dependent Magnetocaloric Effect of Iron Nanoparticles Embed- 3 ded in Titanium Nitride Thin Films” by Sarkar et al., explores the magnetic and magnetocaloric properties of nanostructured iron (Fe) with different morphologies (nanoparticles and thin film) incorporated in a TiN thin film matrix. The structural properties of the samples were analyzed using X-ray diffraction, atomic force microscopy (AFM) and to obtain more precise information about the shape and size of Fe nanoparticles, cross-sectional scanning transmission electron microscopy (STEM) was employed. The authors report an interesting work. The objective and justification of the work are clear. Therefore, I recommend it for publication. However, some issues are detailed below which need to be addressed before its final acceptance in Magnetochemistry.
I advise the authors to take the following points into account while revising their manuscript.
Comment 1: There are some typographical and grammatical errors in the manuscript text, also superscript and subscript errors are there in the references (For e.g. Gd 5 (Si 2 Ge 2); La0. 6Ca0. 4MnO3; La 2/3 Ca 1/3 MnO 3; Gd Al 2∕ Al 2 O 3; Gd3Ga5− x Fe x O12). So the authors need to correct them in the revised manuscript.
Comment 2: The whole manuscript must be cross-checked thoroughly for English editing, grammatical, spelling mistakes, and syntax errors. So, I suggest the author's English language should be polished.
Comment 3: The Abstract needs to be revised, let the author focus main points and explain the research question clearly, and also mention the performed characterization techniques such as XRD, AFM and STEM etc., in the abstract section.
Comment 4: In the introduction section most of the references are before the year 2020, so include some more recent year references (2022-2023) to strengthen the section.
Comment 5: The iron nanoparticles procured /preparation details is not mentioned clearly. So it needs to be provided in the revised manuscript text.
Comment 6: Surface topography of sample 1 as captured by atomic force microscopy, is there any specific reason for sample 1 selection for AFM analysis?
Comment 7: XRD analysis Figure 2(a) revise the X-axis from 30-85°. Also, discuss the XRD section with some more references in order to prepare a better discussion.
Comment 8: Regarding the conclusions section, include clear quantitative findings and more emphasis on the findings and its implication may be mentioned in the conclusion section.
Comment 9: The homogeneity of the reference section needs to be maintained. In some references, journal names are written full form and some in abbreviation form (E.g. Reference Nos. 18 and 19, etc.,). So please check and revise accordingly to the journal's instructions.
Moderate editing of English language required
Author Response
Comment 1: There are some typographical and grammatical errors in the manuscript text, also superscript and subscript errors are there in the references (For e.g. Gd 5 (Si 2 Ge 2); La0. 6Ca0. 4MnO3; La 2/3 Ca 1/3 MnO 3; Gd Al 2∕ Al 2 O 3; Gd3Ga5− x Fe x O12). So the authors need to correct them in the revised manuscript.
Response: The suggestion has been implemented.
Comment 2: The whole manuscript must be cross-checked thoroughly for English editing, grammatical, spelling mistakes, and syntax errors. So, I suggest the author's English language should be polished.
Response: The manuscript has been checked by a person more conversant with the English language.
Comment 3: The Abstract needs to be revised, let the author focus main points and explain the research question clearly, and also mention the performed characterization techniques such as XRD, AFM and STEM etc., in the abstract section.
Response: The abstract has been re-rewritten to include these points suggested by the referee.
Comment 4: In the introduction section most of the references are before the year 2020, so include some more recent year references (2022-2023) to strengthen the section.
Response: Several new references (#3, #5, #9, #11, #15, #16, #17, #18) after 2022 have been added.
Comment 5: The iron nanoparticles procured /preparation details is not mentioned clearly. So it needs to be provided in the revised manuscript text.
Response: The suggestion has been implemented; please see the text marked in the experimental section on page 6.
Comment 6: Surface topography of sample 1 as captured by atomic force microscopy, is there any specific reason for sample 1 selection for AFM analysis?
Response: The suggestion has been implemented. Fig. 2c and d are AFM images are two more samples.
Comment 7: XRD analysis Figure 2(a) revise the X-axis from 30-85°. Also, discuss the XRD section with some more references in order to prepare a better discussion.
Response: The x-axis has been modified, and references (#30, #31) have been included to support the discussion.
Comment 8: Regarding the conclusions section, include clear quantitative findings and more emphasis on the findings and its implication may be mentioned in the conclusion section.
Response: The conclusion section has been expanded to address the suggested changes.
Comment 9: The homogeneity of the reference section needs to be maintained. In some references, journal names are written full form and some in abbreviation form (E.g. Reference Nos. 18 and 19, etc.,). So please check and revise accordingly to the journal's instructions.
Response: All the references are complete and have the same format/style.
Round 2
Reviewer 2 Report
The authors almost fixed my comments and I recommend to accept the manuscript in the present form.
