Research on Interface Modification and Thermal Insulation/Anticorrosive Properties of Vacuum Ceramic Bead Coating

Round 1

Reviewer 1 Report

Dear Editor,

This is an interesting and useful manuscript. So, it deserves publication after considering following issues.

 

Title: “ Research on Interface Modification and Performance of Thermal Insulation Anticorrosive Coating”.

 

1. Abstract: I suggest to add thermal conductivity data of the coatings. There are typo errors in anticorrosive data.

 

2. Introduction: In introduction the authors should reviewed exactly the related researches and highlight their novelty of the present research work.
3. In Experimental Details this part all details in interface modification of vacuum ceramic beads and coating formulation should be described. The commercial grade and company name and origin of all materials should be addressed, for example microbeads, GPTMS, absolute ethanol, epoxy silicone resin, hardener and other additives, … and also details of reaction i.e. temperature, time, ratios, pH, water and acetic acid content, stirring time. I could not find Vacuum Ceramic Microbead specification, what is the supplier name and its commercial grade? What is the specifications of silicon resin, EEW, Viscosity, solid content, …? What’s about the spec. of hardener(cardanol curing?)etc.
4. what was the final dried thickness of the vacuum ceramic microbead coating? 500μm is wet or dried?
5. 3, Line 114: what is range is 2 in 10−2–105 Hz?
6. 4, Fig. 3: Figure 3. There is no significant difference in SEM image of vacuum ceramic microbead coating before and after surface modification.
7. 5, Fig.4: how did authors approve the chemical reaction between modifier and microbead surface?
8. 5, Line 175: it is possible to calculate the critical microbead volume concentration in order to determine the pacing of particles. I suggest calculate it.
9. 7, Line 226: I suggest to compare the simulation with experimental data.
10. I suggest to check the adhesion of the coatings before and after aging tests.
11. The quality of Figure 10,11, 12 and 13 is not enough.
12. Following REFERENCES may be useful:

Model-based analysis of thermal insulation coatings Søren Kiil, J. Coat. Technol. Res. ,DOI 10.1007/s11998-013-9562-7

Preparation and Characterization of a Thermal Barrier Heat-Resistant Silicone Coating, Prog. Color Colorants Coat. 15 (2022), 65-73, 10.30509/PCCC.2022.81667

Author Response

Reviewer#1:

Major comments.

1. Abstract: I suggest to add thermal conductivity data of the coatings. There are typo errors in anticorrosive data.

You suggest to add thermal conductivity data of the coatings is necessary. It is an important data to explain the thermal insulation performance of the coating, so we have added the thermal conductivity data of the coatings on line 21. There may be a problem with the superscript when importing the magnitude of impedance modulus, which has been corrected on line 25, line 27 and line 28.

2. Introduction: In introduction the authors should reviewed exactly the related researches and highlight their novelty of the present research work.

We have made a lot of modifications in the introduction, added the relevant research of micro bead thermal insulation coating, discussed the existing problems, and emphasized the importance and novelty of my work from line 43 to line 71.

3. In Experimental Details this part all details in interface modification of vacuum ceramic beads and coating formulation should be described. The commercial grade and company name and origin of all materials should be addressed, for example microbeads, GPTMS, absolute ethanol, epoxy silicone resin, hardener and other additives, … and also details of reaction i.e. temperature, time, ratios, pH, water and acetic acid content, stirring time. I could not find Vacuum Ceramic Microbead specification, what is the supplier name and its commercial grade? What is the specifications of silicon resin, EEW, Viscosity, solid content, …? What’s about the spec. of hardener (cardanol curing?) etc.

Your suggestion about the test details and materials information is very important for the integrity of the paper, we have added the Materials section to introduce the sources and commercial grade of reagents and raw materials used in the test on line 81. What’s more, the preparation of organic-inorganic hybrid agent, the modification of vacuum ceramic beads and the preparation of coating which include the proportion of each component, mixing speed, mixing temperature, mixing time, etc. All of these have been described in detail in this paper from line 94 to line 117.

4. what was the final dried thickness of the vacuum ceramic microbead coating? 500μm is wet or dried?

Thank you for your careful review of this article, there is indeed a great difference between the wet thickness and the dried thickness of the coating. The final dried thickness of the vacuum ceramic microbead coating is 500μm, corresponding modifications have been made in the paper on line 116.

5. Line 114: what is range is 2 in 10⁻²–10⁵ Hz?

This frequency range of 10^-2-10⁵ Hz is a common range for EIS testing, within this range, enough electrochemical information of the coating can be obtained to explain the anti-corrosion performance of the coating.

6. 3: Figure 3. There is no significant difference in SEM image of vacuum ceramic microbead coating before and after surface modification.

Fig. 3. shows the difference in SEM image of vacuum ceramic microbead coating before and after surface modification. It can be seen that the dispersion of vacuum ceramic beads in the coating before surface modification is poor in Figure 3(a), after surface modification, the dispersion of vacuum ceramic beads in the coating is improved, the beads have no obvious damage and are evenly arranged in Figure 3(b). What’s more, the double graded bead ratio makes the structure more compact. The cross-sectional morphology can be seen that the beads are accumulated in the coating, and there is no extrusion between the beads.

7. 4: how did authors approve the chemical reaction between modifier and microbead surface?

Your suggestion is very meaningful to prove the chemical reaction between modifier and microbeads, so FT-IR analysis of vacuum ceramic microbeads before and after modification was supplemented on line 199, the result shows that there is chemical combination between them, and —CH₃, —CH₂ and —CHO groups appear on the surface of beads, which proves that the surface of beads changed significantly. Especially the appearance of ester group indicates that the —OH on the surface of vacuum ceramic beads reacts with the —OH produced by the hydrolysis of organic-inorganic hybrid agent, which changes the surface structure of vacuum ceramic beads. On the other hand, FT-IR result shows that the —OH group on the surface of microbead increase significantly, it could react with —OH groups in epoxy silicone resin segments.

8. Line 175: it is possible to calculate the critical microbead volume concentration in order to determine the pacing of particles. I suggest calculate it.

You suggest to calculate the critical microbead volume concentration, we know the CPVC which is similar to the mass ratio of pigment and filler to resin is a parameter we often discuss is closely related to coating properties. Therefore, we study the effects of adding different contents of micro beads on the hardness, flexibility, impact resistance and adhesion of the coating during the test, the actual performance data are more helpful to help us determine the content of micro beads. We found that when the content of micro beads was 30%, the adhesion of the coating was less than 20%. Combined with the thermal insulation performance of the coating with different content of micro beads on line 216, we finally confirmed that the content of micro beads was 20%. Considering that adding these results to the article may cause confusion in the structure of the paper, the determination of bead content is not described in detail. Thank you for your suggestion, your suggestion provides new ideas for my research and is of great help to my future work!

9. Line 226: I suggest to compare the simulation with experimental date.

Figure 7 shows the geometric model of oil pipeline is established by using ANSYS finite element software, and the thermal insulation effect of uncoating and coating vacuum ceramic microbead coating is analyzed. We have tried to use experiments to verify the simulation effect of the model, but it is very difficult to implement. Firstly，it is difficult to find the substrate of the oil pipeline coated with insulation layer. Secondly, it is also a challenge to coat the interior of the pipeline. As a result, we made a simple device to explore the thermal insulation effect of the coating, as shown in the figure below. The device only applies the coating on the Q235 substrate and tests the temperature on the other side of the substrate. We found that the temperature on the other side of the substrate remained almost unchanged after reached 40℃, which also reflected the good thermal insulation effect of the coating, but it could not be verified with the simulation result in this paper, so we didn't add this part to the paper.

10. I suggest to check the adhesion of the coatings before and after aging tests.

Your suggestion reminds us, adhesion reflected the interface between the coating and substrate, which was related to the protective effect and protective time of the coating. The coating adhesion has been tested after per cycle of tests, we forgot to discuss it in this paper. We have added the description of adhesion after aging test on line 342.

11. The quality of Figure 10,11, 12 and 13 is not enough.

The pictures you mentioned in the text have poor qualities, we have adjusted the resolution of the pictures to make them clearer on line 304, line 320, line 340 and line 383.

12. Following REFERENCES may be useful.

The two literatures you provided are about the research of thermal insulation coating, including the preparation of thermal insulation coating and the establishment and verification of mathematical model of thermal insulation coating, which are very helpful to our work and the introduction.

Author Response File: Author Response.docx

Reviewer 2 Report

This work report the thermal insulation effect of the coating and organic-inorganic hybrid polymer was used to modify the surface of ceramic. However, there are some issues which should be resolved before acceptance such as.

-More details about coating insulation and what the advantages of this coating.

-The abstract contains organic-inorganic hybrid materials to modify the surface. Thus, the introduction should have information in this regard.

-Recent paper about hybrid materials should be added such as doi.org/10.1016/j.apmt.2021.101142, doi.org/10.1016/j.porgcoat.2021.106652, doi.org/10.1016/j.pmatsci.2020.100663, doi.org/10.1016/j.electacta.2021.139798 doi.org/10.1016/j.compscitech.2020.108383, and doi.org/10.1016/j.cej.2019.123654 .

-What is the novelty form this work?

-Should add more information about the compounds used in this paper in the experimental section.

-Figure 2 needs more details and scale bare not clear.   

-Figures of EIS should be more clear and add the equivalent circle potential.

-If possible, please provide SEM mapping or point of SEM in the Figure 3 and cross-section.

-Should rewrite the conclusion and insert the important results.

Author Response

Reviewer#2:

Major comments.

1. More details about coating insulation and what the advantages of this coating.

After reading your suggestion, we found that the preparation process of the coating in the article is not clearly described. We have described the preparation process of the coating in more detail to make it clearer from line 94 to line 117.

The advantages of vacuum ceramic bead coating are briefly discussed in the abstract on line 16. The coating prepared by modified ceramic beads not only has good heat insulation performance, good heat resistance at 200 ℃, but also has excellent anti-corrosion performance which the low-frequency impedance modulus of the coating was 10¹⁰ Ω·cm² after the 130d immersion test.

2. The abstract contains organic-inorganic hybrid materials to modify the surface. Thus, the introduction should have information in this regard.

Your suggestion to add relevant organic-inorganic hybrid materials to modify the surface research to the introduction is necessary. We have made a lot of modifications in the introduction, added the relevant research of micro bead thermal insulation coating and surface modification of ceramic beads, discussed the existing problems, and emphasized the importance and novelty of our work from line 43 to line 71.

3. Recent paper about hybrid materials should be added such as doi.org/10.1016/j.apmt.2021.101142, doi.org/10.1016/j.porgcoat.2021.106652, doi.org/10.1016/j.pmatsci.2020.100663, doi.org/10.1016/j.electacta.2021.139798 doi.org/10.1016/j.compscitech.2020.108383, and doi.org/10.1016/j.cej.2019.123654 .

First, thank you for providing recent paper about hybrid materials, it has helped us a lot and has great inspiration for our future research direction. What’s more, after reading these documents, some articles which are helpful to the paper have been cited.

4. What is the novelty form this work?

The novelty of vacuum ceramic beads has been discussed in the abstract and introduction. Firstly, in order to solve the problem of interfacial compatibility between vacuum ceramic beads and silicone resin, the surface of vacuum ceramic beads was modified with organic-inorganic hybrid agent which effectively improved the dispersion and compatibility of vacuum ceramic beads in the resin. There are two reasons, one is vacuum ceramic beads are chemically combined with organic-inorganic hybrid agents, the other is that —OH group on the surface of microbead increase significantly, which could react with —OH groups in epoxy silicone resin segments, which reduced the porosity in the resin so that the microbeads could be well dispersed in the coating and the coating has a dense structure. Secondly，the coating with this structure has very excellent comprehensive performance，not only good heat insulation performance, good heat resistance at 200 ℃, but also excellent anti-corrosion performance which the low-frequency impedance modulus of the coating was 10¹⁰ Ω·cm² after the 130d immersion test. The prepared coating with such performance is of great significance for petrochemical, thermal pipeline and other fields.

5. Should add more information about the compounds used in this paper in the experimental section.

Your suggestion about the materials information is very important for the integrity of the paper, we have added the Materials section to introduce the sources and commercial grade of reagents and raw materials used in the test on line 81.

6. Figure 2 needs more details and scale bare not clear.

Your suggestion is very detailed, the lack of ruler in the picture is our mistake. We have corrected the picture on line 165.

7. Figures of EIS should be clearer and add the equivalent circle potential.

We have adjusted the resolution of the pictures to make them clearer and added an equivalent circuit to the Nyquist diagram on line 304, line 340 and line 383.

8. If possible, please provide SEM mapping or point of SEM in the Figure 3 and cross-section.

You suggested to add EDS analysis, it could prove the composition of the vacuum ceramic microbeads, we have added the point scan results of SEM morphology on line 165.

9. Should rewrite the conclusion and insert the important results.

Your suggestion about the conclusion of the text is very important, we have reorganized the article and rewrote the conclusion to illustrate the results of our work on line 415.

Reviewer 3 Report

The manuscript entitled "Research on Interface Modification and Performance of Thermal Insulation Anticorrosive Coating" was reviewed. This work and as-obtained results are interesting. In this manuscript, organic-inorganic hybrid polymer was used to modify the surface of vacuum ceramic microbeads, and epoxy-silicone resin was used as the film-forming material to prepare a heat-insulating and anticorrosive coating that can with- stand 200℃. I have the following comments;

1. The title is informative and relevant, it could be more specific.
2. The authors should clarify in the Introduction section, what is the novelty of their work? What the main significance of paper in comparison is of relates published works?
3. In the “Introduction” section, general description on the importance of manuscript topic is poor. Therefore, the importance of this work cannot be well recognized from general readers. In order to fix this problem, addition of description on recent development in the field of research topic with citing recent comprehensive papers would be important. For improve “Introduction” part, related references should be cited: - ACS Applied Energy Materials, 4 (2021) 680-695.Composites Part B: Engineering 45 (2013), 550-555; Journal of Alloys and Compounds 507 (2010), 77-83; Journal of alloys and compounds 494 (2010), 199-204; Journal of Magnetism and Magnetic Materials 410 (2016) 27-33; Ceramics International 46 (2020), 6095-6107; Journal of Alloys and Compounds 488:1 (2009), 442-447; Polyhedron 27:17 (2008), 3467-3471; Journal of Molecular Catalysis A: Chemical 209 (2004), 209-214
4. The structure of the manuscript might need a minor adjustment for a better understanding.
5. The figures in whole manuscript have poor qualities, leading to difficulty in reading and understanding the manuscript. Please refine.
6. The equivalent circuit model should be added for Nyquist plots.
7. In “Result and Discussions” section, the authors explained irrelevant and unnecessary subjects. There is no scientific clarification and they failed to provide scientific explanation.

Manuscript has however some grammatical mistakes which need to be improved. As a whole, the topic and presented results are interesting. I recommend publication of this article after minor revisions and would like to see the revised version of paper before publication.

Author Response

Reviewer#3:

Major comments.

1. The title is informative and relevant, it could be more specific.

After receiving your suggestion, we give serious thought to the title of the manuscript and the content of the work. In order to make the research content and results of the manuscript more directly reflected in the title, we have changed the title to “Research on interface modification and thermal insulation/anti-corrosion properties of vacuum ceramic bead coating”. The revised title more intuitively reflects our work and is more specific.

2. The authors should clarify in the Introduction section, what is the novelty of their work? What the main significance of paper in comparison is of relates published works?

The novelty and main significance of vacuum ceramic beads have been discussed in the abstract and introduction. Firstly, in order to solve the problem of interfacial compatibility between vacuum ceramic beads and silicone resin, the surface of vacuum ceramic beads was modified with organic-inorganic hybrid agent which effectively improved the dispersion and compatibility of vacuum ceramic beads in the resin. There are two reasons, one is vacuum ceramic beads are chemically combined with organic-inorganic hybrid agents, the other is that —OH group on the surface of microbead increase significantly, which could react with —OH groups in epoxy silicone resin segments, which reduced the porosity in the resin so that the microbeads could be well dispersed in the coating and the coating has a dense structure. Secondly，the coating prepared by modified ceramic beads has very excellent comprehensive performance with this structure，not only good heat insulation performance, good heat resistance at 200 ℃, but also excellent anti-corrosion performance which the low-frequency impedance modulus of the coating was 10¹⁰ Ω·cm² after the 130d immersion test. The prepared coating with such performance is of great significance for petrochemical, thermal pipeline and other fields.

3. In the “Introduction” section, general description on the importance of manuscript topic is poor. Therefore, the importance of this work cannot be well recognized from general readers. In order to fix this problem, addition of description on recent development in the field of research topic with citing recent comprehensive papers would be important. For improve “Introduction” part, related references should be cited: - ACS Applied Energy Materials, 4 (2021) 680-695.Composites Part B: Engineering 45 (2013), 550-555; Journal of Alloys and Compounds 507 (2010), 77-83; Journal of alloys and compounds 494 (2010), 199-204; Journal of Magnetism and Magnetic Materials 410 (2016) 27-33; Ceramics International 46 (2020), 6095-6107; Journal of Alloys and Compounds 488:1 (2009), 442-447; Polyhedron 27:17 (2008), 3467-3471; Journal of Molecular Catalysis A: Chemical 209 (2004), 209-214

Firstly, thank you for your recent paper about the topic, it has helped us a lot and has great inspiration for our future research direction, some articles which are helpful to the paper have been cited. Secondly, we have made a lot of modifications in the introduction, added the relevant research of micro bead thermal insulation coating, discussed the existing problems, and emphasized the importance and novelty of my work from line 43 to line 71.

4. The structure of the manuscript might need a minor adjustment for a better understanding.

After reading your suggestion, we thought carefully about the structure of the manuscript and made some adjustments. Firstly, in order to make the coating preparation process clearer, we added the “Materials” part on lines 80, and described the preparation process and ratio in more detail in “Sample preparation” part. Secondly, in the “Results and discussion” part, our idea is to first explain the changes in the structure of the coating prepared by using the vacuum ceramic microbeads modified with organic-inorganic hybrid agents, and then confirm the excellent thermal insulation, heat resistance and anti-corrosion properties of the coating with this structure through experimental data, we feel this structure can clearly show the results and advantages of our work.

5. The figures in whole manuscript have poor qualities, leading to difficulty in reading and understanding the manuscript. Please refine.

Some pictures in the text have poor qualities, we have adjusted the resolution of the pictures to make them clearer on line 285, line 304, line 321, line 340 and line 383.

6. The equivalent circuit model should be added for Nyquist plots.

After the three environmental tests, the EIS shows that the second time constant does not appear, so the equivalent circuits are all R (Cc R), as shown in Figure 15, which may be unclear, so we have added the corresponding equivalent circuits to the Nyquist diagram on line 304 and line 340.

7. In “Result and Discussions” section, the authors explained irrelevant and unnecessary subjects. There is no scientific clarification and they failed to provide scientific explanation.

Your suggestion is very meaningful to our manuscript, we have made many amendments to the “Results and discussion”. Firstly, in order to confirm that the organic-inorganic hybrid agent changes the surface structure of vacuum ceramic beads, FT-IR analysis of vacuum ceramic microbeads before and after modification was supplemented on line 199, the result shows that there is chemical combination between them, and —CH₃, —CH₂ and —CHO groups appear on the surface of beads, which make the result more reliable. Secondly, the adhesion of the coating after the 200℃ thermal aging test and the 200℃ alternating cold and hot test is added on line 342. Adhesion reflects the interface between the coating and substrate, which was related to the protective effect and protective time of the coating, so the changes of adhesion can further explain the heat resistance and corrosion resistance of the coating. Finally, we adjust the expression of some sentences to make it more consistent with the experimental results, and added some literature support in the analysis part on line 343, line 382, line 386, line 396 and so on.

Round 2

Reviewer 1 Report

I could not find Hubei Xinsihai Chemical 106 Co., Ltd., China, as a supplier for epoxy silicon resin and Shanghai Huijingya Co., Ltd., China  for Vacuum ceramic microbeads.

Reviewer 2 Report

Present form can be accepted in Coating. 

Reviewer 3 Report

ACCEPT