PONE-D-20-31208

Consistent modelling of material weight loss and gas release due to pyrolysis and conducting benchmark tests of the model　-　A case for glovebox panel materials such as polymethyl methacrylate

PLOS ONE

Dear Dr. Ohno

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Reviewers' comments:

Reviewer's Responses to Questions

Comments to the Author

1. Is the manuscript technically sound, and do the data support the conclusions?

The manuscript must describe a technically sound piece of scientific research with data that supports the conclusions. Experiments must have been conducted rigorously, with appropriate controls, replication, and sample sizes. The conclusions must be drawn appropriately based on the data presented.

Reviewer #1: Partly

Reviewer #2: Yes

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2. Has the statistical analysis been performed appropriately and rigorously?

Reviewer #1: Yes

Reviewer #2: Yes

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3. Have the authors made all data underlying the findings in their manuscript fully available?

The PLOS Data policy requires authors to make all data underlying the findings described in their manuscript fully available without restriction, with rare exception (please refer to the Data Availability Statement in the manuscript PDF file). The data should be provided as part of the manuscript or its supporting information, or deposited to a public repository. For example, in addition to summary statistics, the data points behind means, medians and variance measures should be available. If there are restrictions on publicly sharing data—e.g. participant privacy or use of data from a third party—those must be specified.

Reviewer #1: Yes

Reviewer #2: Yes

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4. Is the manuscript presented in an intelligible fashion and written in standard English?

PLOS ONE does not copyedit accepted manuscripts, so the language in submitted articles must be clear, correct, and unambiguous. Any typographical or grammatical errors should be corrected at revision, so please note any specific errors here.

Reviewer #1: Yes

Reviewer #2: Yes

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5. Review Comments to the Author

Please use the space provided to explain your answers to the questions above. You may also include additional comments for the author, including concerns about dual publication, research ethics, or publication ethics. (Please upload your review as an attachment if it exceeds 20,000 characters)

Reviewer #1: This paper is interesting, and the experiment is well designed, but it lacks a more detailed analysis，Major revision is suggested.

1.Abstract: I think the author should summarize the key important information and results rather than expound the content of the experiment. The abstract should be concise and to the point. And line 43-44, the author did not point out the results of the comparison for the tests on bisphenol-A-polycarbonate.

2.In the introduction, it is necessary to add more literature to discuss the previous research of this work in order to further motivate the novelty of this research. Especially for thermogravimetry, the author can refer to the following literature: Journal of Hazardous Materials 402 (2021) 123472; Journal of Cleaner Production 239 (2019) 118113.

3.Line 25, What is the practical significance of this model when evaluating the amount of radioactive material leaking from a nuclear facility during a fire?

4.Line 43-44, “thermogravimetric (TG)-differential thermal analysis (DTA) (TG-DTA) tests and differential scanning calorimetry tests” should be corrected to “thermogravimetric-differential thermal analysis (TG-DTA) tests and differential scanning calorimetry (DSC) tests”. Similar mistakes were found in Line 115. Please check and revise them.

5.Line 137, The " ~2.5-mg" should be corrected to " ~2.5 mg", Similar mistakes were found through this paper. Please check and revise one by one.

6.Line 192, Could you explain why there are three stages in the pyrolysis of PMMA, and what substances are reacting in there three stages?

7.Line 189-197, 203-207, In this section, the pyrolysis behavior of PMMA / PC is lack of in-depth analysis.

8.Line 188, The analysis of kinetic is detailed, but there is a lack of relevant literature support, which can be referred to: Journal of Cleaner Production 253 (2020) 119950.

9.Conclusion: This part was too long. And the specific results discussion should appear in the "Results and Discussion" section and should not appear in the conclusion.

Reviewer #2: Revision of “Consistent modelling of material weight loss and gas release due to pyrolysis and conducting benchmark tests of the model - A case for glovebox panel materials such as polymethyl methacrylate”

Manuscript Number: PONE-D-20-31208

Review comments to the Authors: In this work glove box’s confinement function was studied in order to deeply investigate the issue related to the amount of radioactive material leaking from a nuclear facility during a fire. The authors built a model that consistently explained the weight loss of glove box materials (PMMA and PC based) because of heat input from a flame and accompanying generation of the pyrolysis gas, hence validating their calculation model through experimental data. I would like to congratulate authors for their exceptional research plan. They tried to study the aforementioned system by doing an array of examinations. The work is scientifically worthy of consideration, but technically can be further improved after a minor revision. I suggest authors consider the following points into account and revise their work:

• Lines: 78-80 - If the glove box seal is weakened and air in the process room flows into the glove box, the accumulated pyrolysis gas could explode and burn.

Reviewer: Could you specify which type of material as normally used as seal?

• Lines: 104-107 - The material used in this study was polymethyl methacrylate (PMMA). PMMA is a flammable material used for glovebox panels. This material was set as the principal target in this study because it occupies most of the mass of combustibles present in the glove box.

Reviewer: Is there any other reference in the literature reporting the study of the containment function of the glovebox based on PMMA polymer with a different configuration for the system?

• Lines: 112-116 - This weight loss can be regarded as the total amount of pyrolysis gas released. Next, the breakdown of the total released amount for each gas component was investigated by conducting pyrolysis gas quantitative tests. The tests include analysis by pyrolysis (Py)-gas chromatography (GC)-MS (Py-GC-MS) and experiments using a tubular furnace.

Reviewer: Similar measurements and experiments were recently published in some references (Primpke, Sebastian, et al. "Comparison of pyrolysis gas chromatography/mass spectrometry and hyperspectral FTIR imaging spectroscopy for the analysis of microplastics." Analytical and Bioanalytical Chemistry (2020): 1-16; Steinmetz, Zacharias, et al. "A simple method for the selective quantification of polyethylene, polypropylene, and polystyrene plastic debris in soil by pyrolysis-gas chromatography/mass spectrometry." Journal of Analytical and Applied Pyrolysis (2020): 104803; Yamane, Shogo, et al. "A data mining method from pyrolyzed products: Pyrolysis-gas chromatography-photoionization-high resolution time-of-flight mass spectrometry and kendrick mass defect analysis for polymer semiconductor poly (3-hexylthiophene)." Journal of Analytical and Applied Pyrolysis 151 (2020): 104923; Bifulco, Aurelio, et al. "Fire and mechanical properties of DGEBA-based epoxy resin cured with a cycloaliphatic hardener: Combined action of silica, melamine and DOPO-derivative." Materials & Design (2020): 108862; Bifulco, Aurelio, et al. "Improving flame retardancy of in-situ silica-epoxy nanocomposites cured with aliphatic hardener: Combined effect of DOPO-based flame-retardant and melamine." Composites Part C: Open Access 2 (2020): 100022). The authors should consider reading and citing them during their evaluations along the paper and this introduction section.

• Lines: 139-141 - The heating rate during heating was controlled as an experimental parameter at 5 °C, 10 °C, 15 °C, or 20 °C/min to kinetically analyze the behavior of sample weight loss because of pyrolysis, i.e., TG data, as described below.

Reviewer: Could you specify the ramp temperature at which the TGA measurement was performed?

• Lines: 193-196 - The reduction amount of TG was 2 wt% in Stage 1, 15 wt% in Stage 2, and 80 wt% in Stage 3, and the residue of pyrolysis was 3 wt%. These weight percentages represent the ratio of the initial weight of the sample. The pyrolysis process began at 150 °C and ended at 440 °C.

Reviewer: How do the authors explain these values for the weight losses along the pyrolysis process? Can you describe how the system appears at each stage from a chemical point of view?

• Lines: 245-247 - Fig 5. An example of an Arrhenius plot for the results of TG-DTA-MS analysis—from the slopes and intercepts of the approximate straight lines, and in Table 1 were determined.

Reviewer: Final dot for sentence 247 is missing.

• Lines: 281-283 - Bisphenol-A is a substance equivalent to the monomer material for PC. The species of detectives were like those reported in the literature [17–19].

Reviewer: Some references could be cited and inserted on sentence 283 for better supporting the importance of Py-GC/MS in the Bisphenol A measurement and detection (Becerra, Valentina, and Jürgen Odermatt. "Detection and quantification of traces of bisphenol A and bisphenol S in paper samples using analytical pyrolysis-GC/MS." Analyst 137.9 (2012): 2250-2259; Navarro-González, Rafael, Patrice Coll, and Roustam Aliev. "Pyrolysis of γ-irradiated bisphenol-A polycarbonate." Polymer Bulletin 48.1 (2002): 43-51; Bifulco, Aurelio, et al. "Fire and mechanical properties of DGEBA-based epoxy resin cured with a cycloaliphatic hardener: Combined action of silica, melamine and DOPO-derivative." Materials & Design (2020): 108862).

• Lines: 318-319 - For example, the pyrolysis of bisphenol-A occurs at 265 °C or higher [21].

Reviewer: I would suggest adding more references on sentence 319.

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Reviewer #1: No

Reviewer #2: No

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Consistent modelling of material weight loss and gas release due to pyrolysis and conducting benchmark tests of the model　-　A case for glovebox panel materials such as polymethyl methacrylate

PONE-D-20-31208R1

Dear Dr. Ohno

We’re pleased to inform you that your manuscript has been judged scientifically suitable for publication and will be formally accepted for publication once it meets all outstanding technical requirements.

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PLOS ONE

Reviewers' comments:

Reviewer's Responses to Questions

Comments to the Author

1. If the authors have adequately addressed your comments raised in a previous round of review and you feel that this manuscript is now acceptable for publication, you may indicate that here to bypass the “Comments to the Author” section, enter your conflict of interest statement in the “Confidential to Editor” section, and submit your "Accept" recommendation.

Reviewer #1: All comments have been addressed

Reviewer #2: All comments have been addressed

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2. Is the manuscript technically sound, and do the data support the conclusions?

The manuscript must describe a technically sound piece of scientific research with data that supports the conclusions. Experiments must have been conducted rigorously, with appropriate controls, replication, and sample sizes. The conclusions must be drawn appropriately based on the data presented.

Reviewer #1: Yes

Reviewer #2: Yes

**********

3. Has the statistical analysis been performed appropriately and rigorously?

Reviewer #1: Yes

Reviewer #2: Yes

**********

4. Have the authors made all data underlying the findings in their manuscript fully available?

The PLOS Data policy requires authors to make all data underlying the findings described in their manuscript fully available without restriction, with rare exception (please refer to the Data Availability Statement in the manuscript PDF file). The data should be provided as part of the manuscript or its supporting information, or deposited to a public repository. For example, in addition to summary statistics, the data points behind means, medians and variance measures should be available. If there are restrictions on publicly sharing data—e.g. participant privacy or use of data from a third party—those must be specified.

Reviewer #1: Yes

Reviewer #2: Yes

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5. Is the manuscript presented in an intelligible fashion and written in standard English?

PLOS ONE does not copyedit accepted manuscripts, so the language in submitted articles must be clear, correct, and unambiguous. Any typographical or grammatical errors should be corrected at revision, so please note any specific errors here.

Reviewer #1: Yes

Reviewer #2: Yes

**********

6. Review Comments to the Author

Please use the space provided to explain your answers to the questions above. You may also include additional comments for the author, including concerns about dual publication, research ethics, or publication ethics. (Please upload your review as an attachment if it exceeds 20,000 characters)

Reviewer #1: The authors have adequately addressed the comments raised in a previous round of review and this manuscript can be acceptable for publication.

Reviewer #2: The vast majority of comments received to date have been addressed, and the fixes have been incorporated into later releases of data. Taking into accoiunt the revised version of the manuscript, it can be accepted for publication in PLOS ONE.

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7. PLOS authors have the option to publish the peer review history of their article (what does this mean?). If published, this will include your full peer review and any attached files.

If you choose “no”, your identity will remain anonymous but your review may still be made public.

Do you want your identity to be public for this peer review? For information about this choice, including consent withdrawal, please see our Privacy Policy.

Reviewer #1: No

Reviewer #2: No