Fabrication of Micron-Structured Heatable Graphene Hydrophobic Surfaces for Deicing and Anti-Icing by Laser Direct Writing
, Yao Zou 1, Man Xu 3, Xinyi Liu 3, Xiaoqing Xing 1, Huazhong Zhang 1, Yong Jiang 3, Chao Qiu 4, Wenfeng Qin 4, Meng Li 4, Qiang He 5,* and Chao Zhou 1,2
Round 1
Reviewer 1 Report
The objects of research and their characteristics correspond to the journal profile.
At the same time, there are certain problems in the presented data.
1. The formation of microrelief at 4 different scan rates was carried out, and the data are given only for 75 mm/s, justifying it only by the smaller gaps between the tracks. Bat if for 50 mm/s it is justified - the ordered microstructure is not formed, than the layers obtained at 100 and 125 have developed micro-roughness, which should definitely affect the value of the contact angle, as well as the time of freezing of the drop. Accordingly, data for these coatings should also be given.
2. Mechanical/adhesive properties of the formed layers are not provided.
3. The images show that a drop of test liquid wets the surface in the Wenzel state, when freezing the water changes its volume, which may cause damage to the microrelief. Accordingly, data on the properties of the coatings after icing/deicing cycling is needed.
4. What is the basis for the conclusion of that formed layer possesses antiicing properties? The data reflect only some delay in the freezing time of the drop. There are no data on the ice adhesion strength nor on the mass of ice formed. Accordingly, this statement is not yet substantiated by anything.
Author Response
Please check attachment
Author Response File: 
Author Response.pdf
Reviewer 2 Report
The author produced laser induced graphene (LIG) hydrophobic surfaces that can be used for deicing and anti-icing.
Works that propose LIG for that application can already be found in literature. Besides the one reported by the authors we can also find this one: Nanomaterials 2021, 11(11), 3093
In the literature can also be founded other works that evaluate the hydrophobic features of the LIG.
It is not easy for me to understand the novelty of the work. The author need to emphasize the novelty of the work in order to justify the publication.
Other comments:
The red numbers of Figure 2 are not well visible.
Author Response
Response to Reviewer 2 Comments
Dear Editor and Reviewer 2,
Thank you very much for your meticulous review of our manuscript and providing valuable suggestions. We sincerely appreciate the time and effort you have dedicated to this process. In this response, we will address each of your comments in order(the changes are highlighted with a green background). and provide detailed explanations of how we plan to address them. The authors welcome further constructive comments if any.
Ponint 1: Works that propose LIG for that application can already be found in literature. Besides the one reported by the authors we can also find this one: Nanomaterials 2021, 11(11), 3093
Response 1: We sincerely appreciate your valuable comments. We have carefully read the literature you mentioned, and believe that the literature provides a very good reference for the application of LIG technology in superhydrophobic aspects, and has very important guiding significance for the revision and improvement of our manuscript, and provides a good idea for our subsequent research content. Meanwhile, we have added and quoted part of the literature in the introduction of the revised manuscript. In addition, relevant references have been added to the references, as shown in line P2. 40 of the revised draft, and the references are shown in the references part [46].
Ponint 2: In the literature can also be founded other works that evaluate the hydrophobic features of the LIG.
Response 2: Thank you very much for your suggestions for improvement. In the introduction part, we have added some other ways to prepare hydrophobic surface using LIG technology (such as changing the atmosphere environment, introducing fluorine functional groups, changing the structure, etc.). After careful reading of these literatures, we found that these literatures further evaluated the hydrophobic characteristics of LIG by establishing surface frosting and contact Angle stability, etc. Therefore, we added corresponding test contents on the basis of the original manuscript. The added parts are shown in P2, lines 36-40, and the cited documents are shown in references [42]-[45]. See data supplement section Figure 4 (a)-(d), and the relevant analysis has been added to lines P6. 24-P7.10 of the revised draft.
Ponint 3: It is not easy for me to understand the novelty of the work. The author need to emphasize the novelty of the work in order to justify the publication.
Response 3: Thanks for your suggestion. Based on the original text and combined with subsequent certification analysis of related test results, we believe that the main highlights of this study are as follows: (1) The relationship between scanning speed and line width is studied, which can provide a reliable reference for subsequent research of this kind; (2) Surface hydrophobic and super-hydrophobic functions are realized by using laser direct writing technology; (3) The efficient and controllable deicing and anti-icing function of graphene surface prepared by LIG technology is realized. The purpose of this study is to expand the exploration and improve the related performance on the basis of the existing relevant research, so as to provide more reference and ideas for this kind of research.
At the same time, we also added some transitional connectivity statements and other changes to the conclusion, as detailed in lines P3. 3-10, P7. 23-28, P8. 12-14, and P10. 6-23 of the revised draft
Thank you once again for your careful review and guidance. We highly value your constructive feedback and will dedicate our efforts to address your comments and submit the revised manuscript as soon as possible. Should you have any further inquiries or require additional guidance, please do not hesitate to contact us.
Author Response File: Author Response.pdf
Reviewer 3 Report
1. It is possible to include error bars in the figures.
2. The authors' rationale for choosing polyimide film as a substrate for micron-scale graphene should be clarified.
3. To verify that it was graphene, HRTEM images are essential to support the claim.
4. The adhesion of the graphene to the surface should be addressed, including any scotch tape peeling tests or other flexible substrate-based tests conducted by the authors.
5. If the objective was to produce graphene, the authors could explain why they selected this particular material, considering that similar tests could be conducted on other films/substrates.
6. The mechanism of graphene formation needs to be elucidated.
7. Given the abundance of similar research in the literature, the authors must emphasize the significant novelty of their work to meet the publication standards of this journal.
8. The authors should clarify how they distinguished graphene from other forms of conducting carbon to ensure the accuracy of their claims.
9. Deconvoluting the Raman spectra would provide additional insights into the type of carbon formed.
10. For the sake of comprehensiveness, the introduction could be supplemented with relevant literature on the conversion of polymers and other substrates into graphene.
1. https://doi.org/10.1021/acsomega.1c06093
2. https://doi.org/10.1021/acsami.3c00569
3. https://doi.org/10.1021/acsami.3c07687
4. https://doi.org/10.1021/acsaelm.0c00542
11. How did the authors verify that the graphene/ carbon formed is micron-scale graphene?
English can be improved.
Author Response
Response to Reviewer 3 Comments
Dear Editor and Reviewer 3,
On behalf of my co-authors, we are very grateful to you for giving us an opportunity to revise our manuscript. we appreciate you very much for your positive and constructive comments and suggestions on our manuscript. We have studied reviewers’ comments carefully and tried our best to revise our manuscript according to the comments. Below are the replies and changes (the changes are highlighted with a yellow background). We have made in response to the reviewers' questions and suggestions on an item-by-item basis. Thanks again to the hard work of the editor and reviewer!
Ponint 1: It is possible to include error bars in the figures.
Response 1: Thank you very much for your suggestions on improving figures. Error bar is indeed an indispensable part of figures. After careful analysis of data processing results, we have modified relevant contents in Figure 2. (f), which will make the data look more reasonable. Since the data is tested under SEM, the accuracy is very high, and we believe that the insertion of the error rod is not necessary. As well as the data in Figure 4, this part is the subsequent supplementary experimental and test data. Due to the short revision cycle, only a single measurement was carried out during the test process, so the insertion of error bars was not allowed in this situation. See Figure. 2(f) of the revised manuscript for the revised part.
Ponint 2: The authors' rationale for choosing polyimide film as a substrate for micron-scale graphene should be clarified.
Response 2: Thank you very much for your suggestions for improvement. In the introduction part, we have added a description of the mainstream materials for LIG preparation, and explain the factors limiting its development: "However its low and high-temperature resistance, hydrophobic stability, and graphene adhesion have always been the main factors that limit its development." We choose polyimide material as carbon precursor, mainly based on the following two reasons: 1. polyimide film has a good temperature adaptation range (-269℃-280℃) and flexible ductility (tensile strength of 200MPa at 20℃), can be a good response to the thermal strain caused by laser irradiation. 2. Polyimide film is the mainstream LIG raw material at present, and the current research basis and results are relatively complete, which has important reference significance for parameter exploration in this paper. The added parts are shown in P2, lines 40-41 and 43-45.
Ponint 3: To verify that it was graphene, HRTEM images are essential to support the claim.
Response 3: Thanks for your suggestion. We very much agree with your opinion that TEM test is indeed crucial to verify the product as graphene and its structure. However, due to the tight time for revision and limited equipment resources, we do not support the testing and analysis of this project for the time being. However, we have conducted Raman spectroscopy test on the surface product. In addition, various characteristics of the test results have shown that the product has the characteristics of graphene, so we did not further test TEM, and this test item will be added in the subsequent research process to obtain more in-depth research conclusions.
Ponint 4: The adhesion of the graphene to the surface should be addressed, including any scotch tape peeling tests or other flexible substrate-based tests conducted by the authors.
Response 4: We are very grateful to the reviewers for their suggested improvements based on “The adhesion of the graphene to the surface”, which is indeed one of the key tests to validate evaluating the stability of graphene layers. Therefore, we used the motion controller to carry out cyclic bending tests on the three samples, in which the bending radius was 1.5cm and the total number of cycles was 1000. We continuously monitored the contact Angle of the surface at the interval of 200 cycles, and obtained the result that the contact Angle of the surface water droplets generally did not exceed 10°. This result is a good demonstration of the adhesion and stability of the graphene microstructure surface. The contact Angle test data of the mechanically bent surface is added in Figure 4 (a), and the related analysis is added in page P6 lines 33 – P7 lines 5.
Ponint 5: If the objective was to produce graphene, the authors could explain why they selected this particular material, considering that similar tests could be conducted on other films/substrates.
Response 5: We are very grateful for the suggestions made by the reviewers. We believe that the purpose of LIG technology is not only to produce graphene, but also to provide more flexibility and innovation for the construction of graphene, and our research focus is not on the impact of base materials on the quality and effect of graphene generation. Instead, it focuses on the multi-functional coupling and flexible application of the mainstream polyimide film substrate to prepare graphene. Therefore, we do not elaborate on the impact of different substrates on the product, but focus on the content of its innovative development and expansion of applications.
Ponint 6: The mechanism of graphene formation needs to be elucidated.
Response 6: We are very grateful to the reviewers for their suggestions. The formation mechanism of graphene is the key to this technology. We believe that during the laser-induced generation of graphene, photothermal effect will occur on the surface of polyimide film after laser irradiation, and C-H, C-O, C=O and C-N in the film will be broken and atoms will be rearranged. The O, N, and H atoms diffuse into the external environment in the form of a gas, and the C atoms combine to form a graphene structure. However, since the research of LIG based on PI thin films has been relatively mature, the mechanism of graphene generation is very easy to consult and understand, and the literature we cited in the introduction of LIG technology will also be very helpful to its generation mechanism, so we did not add the related content of graphene generation mechanism in the revised draft.
Ponint 7: Given the abundance of similar research in the literature, the authors must emphasize the significant novelty of their work to meet the publication standards of this journal.
Response 7: Thank you for your advice. Based on the original text and the subsequent verification analysis of relevant test results, we believe that the main highlights of this study are :(1) The relationship between laser scanning speed and graphene linewidth is obtained through the study, which can provide a reliable reference for subsequent similar research; (2) The hydrophobic and superhydrophobic functions of the surface have been successfully realized by using laser direct writing technology, which is crucial for the expansion of the surface application; (3) This study has realized and confirmed the efficient and controllable deicing and anti-icing functions of the surface, which provides a new way for deicing and anti-icing problems in the aerospace field. At the same time, the ultimate purpose of this study is to expand the exploration on the basis of existing relevant studies, provide more verification and support, and provide more references and ideas for such research.
Ponint 8: The authors should clarify how they distinguished graphene from other forms of conducting carbon to ensure the accuracy of their claims.
Response 8: Thank you very much for your constructive suggestion, which will be of great help to our subsequent research. In response to your question "how they distinguished graphene from other forms of conducting carbon to ensure the accuracy of their According to what we have learned from statistics, analysis and reading literature, the process of laser-induced graphene generation will lead to heptagonal lattice and pentagon lattice structure, and the oxidation of graphene oxide in the air. These conditions and influencing factors cannot be predicted, but since our purpose is to de-ice the application by Joule heat, any form of conductive carbon zone is effective, so we did not add any reference to the differentiation of carbon zones in the revised draft. However, your suggestion is a good reference for further research on the composition and structure of conductive region.
Ponint 9: Deconvoluting the Raman spectra would provide additional insights into the type of carbon formed.
Response 9: Thank you very much for your new insights and ideas. After carefully consulting some data, we have carried out certain peak segmentation and fitting processing on the 2D peaks obtained by Raman spectrum test. And get" the symmetrical 2D peak can be fitted to a single Lorentz curve with a center at 2687.05 cm-1 and a half-peak width of 95 cm-1, which are typical features of highly ordered 2D graphite composed of randomly stacked graphene layers along the C-axis.” This result well supports the conclusion of the typical characteristics of highly ordered two-dimensional graphite, and the obvious D, 2D and G peak eigen-characteristics of Raman spectra well prove the conclusion of the generation of graphene.
Ponint 10: For the sake of comprehensiveness, the introduction could be supplemented with relevant literature on the conversion of polymers and other substrates into graphene.
Response 10: Thank you very much for providing the links of these articles. After careful reading, we add the literatures corresponding to the first three links to the introduction for better support and verification. Although the article corresponding to the fourth link is about the extended application of graphite-carbon-based supercapacitors, it cannot provide reliable reference and basis for our research direction. It was therefore not added to the introduction. References have been added to P6 line 9-10, line 40-41, and added in reference [29] [30] [47].
Ponint 11: How did the authors verify that the graphene/ carbon formed is micron-scale graphene?
Response 11: Thank you very much for your questions and reminders. This may be a misunderstanding caused by the unclear description of our article. Our research emphasizes that the corresponding graphene is generated by laser on the laser scanning path. Due to the small laser spot, graphene composed of micron structure can be induced. Of course, all the above phenomena are observed through SEM images, in order to avoid further understanding and confusion, We changed the title to "Fabrication Of Micron-Structure Heatable Graphene Hydro-phobic Surfaces For Deicing And Anti-Icing By Laser Direct Writing ". See the title on the first page for changes.
In addition, we have finished polishing the manuscript.
Thank you again for your positive and constructive comments and suggestions on our manuscript. We hope you will find our revised manuscript acceptable for publication.
Author Response File: Author Response.pdf
Round 2
Reviewer 1 Report
In my opinion, the manuscript could be published in its present form
Author Response
Coatings No.2507829
August 24, 2023
Response to Reviewer 1 Comments
Dear Editor and Reviewer 1,
We would like to thank you for the efforts in reviewing our manuscript titled "Fabrication Of Micron-Structure Heatable Graphene Hydrophobic Surfaces For Deicing And Anti-Icing By Laser Direct Writing", and You have provided many constructive comments and suggestions, which are very valuable for the structural modification and content improvement of our paper and for guiding our future research. We were pleased to know that our work was rated as potentially acceptable for publication in Journal. We thank the reviewers for the time and effort that they have put into reviewing the previous version of the manuscript. These suggestions have enabled us to improve our work.
Thank you once again for your careful review and guidance. Should you have any further inquiries or require additional guidance, please do not hesitate to contact us.
Author Response File: Author Response.pdf
Reviewer 2 Report
I believe that the level of novelty is not enough to justify the publication of the work in this journal.
Author Response
Coatings No.2507829
August 24, 2023
Response to Reviewer 2 Comments
Dear Editor and Reviewer 2,
On behalf of all the contributing authors, I would like to express our sincere appreciations of your letter and reviewers’ constructive comments concerning our article entitled “Fabrication Of Micron-Structure Heatable Graphene Hydrophobic Surfaces For Deicing And Anti-Icing By Laser Direct Writing” (Manuscript No.2507829).
Your review "I believe that the level of novelty is not enough to justify the publication of the work in this journal The modification and improvement of the framework and content of our paper will be of great help. After carefully analyzing the lack of novelty you mentioned, we conduct a detailed analysis of the existing results of the current research team according to the content of this study and the existing results of this research direction, so as to highlight the differences and existing value of our work.
As for the novelty, it is well-known that LIG technology offers a number of unprecedented advantages. Although there are some reports focusing on preparation of superhydrophobic surfaces by LIG technology, the focus on research on micro-control of scanning speed of traditional CO2 laser has been rarely explored. Especially for mature CO2 laser technology that features some unparalleled merits like economy, flexibility, universality, only several reports underlined method for adjusting laser power, manufacturing atmosphere and DPI parameters. More unfortunately, little attention was paid to the law finding between the CO2 laser scanning speed of the system and the result, joule thermal performance, surface hydrophobic durability and deicing and antiicing performance. Therefore, we believe that this study is not only a repetition of previous work, but also to fill in the gaps in the research of CO2 laser scanning speed micro-regulation and deicing.
In this report, thanks again to the reviewer on suggesting to further improve this manuscript, we have studied comments carefully and have made corresponding corrections which we hope meet with approval. In order to highlight the novelty of this study, we have partially revised the abstract, introduction and conclusion, as shown in red in lines P1 35-36, P2 26-48, and P10 34-35 of the revised draft.
Author Response File: Author Response.pdf
Reviewer 3 Report
1. While it's evident you've taken steps to address reviewers' comments, the manuscript revisions seem to lack the specific corrections related to these comments. Integrating these suggestions into the manuscript would not only enhance its quality but also improve reader understanding, despite the existence of relevant information in the literature. Incorporating these comments into the revisions is recommended to maximize the impact of your work.
2. Do authors imply that adhesion tests and bending tests serve the same purpose?
Author Response
Coatings No.2507829
August 24, 2023
Response to Reviewer 3 Comments
Dear Editor and Reviewer 3,
Thank you for your letter and for the reviewers' comments concerning our manuscript entitled " Fabrication Of Micron-Structure Heatable Graphene Hydrophobic Surfaces For Deicing And Anti-Icing By Laser Direct Writing "（ID: 2507829）. Those comments are all valuable and very helpful for revising and improving our paper, as well as the important guiding significance to our researches. We have studied comments carefully and have made correction which we hope meet with approval. Revised portion are marked in orange in the paper. The main corrections in the paper and the responds to the reviewer's comments are as flowing：
Ponint 1: While it's evident you've taken steps to address reviewers' comments, the manuscript revisions seem to lack the specific corrections related to these comments. Integrating these suggestions into the manuscript would not only enhance its quality but also improve reader understanding, despite the existence of relevant information in the literature. Incorporating these comments into the revisions is recommended to maximize the impact of your work.
Response 1: Thank you very much for your suggestion. Due to some unavoidable deadline for manuscript revision, we did not incorporate your suggestions into manuscript revision too much in the first revision version. Every suggestion you made in the first review is of great help to our research and the improvement of the quality of the article. Therefore, in the second version of the revised draft, we included durability test instrument information (P3 24-25 lines), LIG generation mechanism (P84-8 lines), in-depth Raman spectrum analysis (FIG. 6a, P825 lines), and the explanation of conductive regions without differentiation (P922-23 lines).
Ponint 2: Do authors imply that adhesion tests and bending tests serve the same purpose?
Response 2: Thank you for your reminder, it may be due to the reasons we did not explain clearly in the first comment reply, leading to your question. We believe that the purpose of cyclic bending and water-contact angle tests we performed is the same as that adhesion tests to verify the stability and durability of graphene surface under the influence of external factors. The only difference between the two lies in the different testing methods used. We believe that cyclic bending and water contact Angle test can better reflect the comprehensive adhesion and stability of graphene surface.
Author Response File: Author Response.pdf
