New Glasses in the PbCl2–PbO–B2O3 System: Structure and Optical Properties
, Anna Bakaeva 1, Kristina Runina 1, Igor Krol 1, Maria Uslamina 2, Aleksandr Pynenkov 2, Olga Petrova 1 and Igor Avetissov 1,*
Round 1
Reviewer 1 Report
The study reported a novel oxychloride lead-borate glasses in the PbCl2-PbO-B2O3 system. The obtained results can provide a great reference for researchers of photonics and IR optics materials. This study is systematic, comprehensive, and excellent. The content of the manuscript is in line with the research direction of ceramics. However, there are a several problems with the content in the author's manuscript. The existence of these problems leads me to suggest minor revision.
(1) If the XRF results of synthesized glasses do not prove that the lead chloride content reaches 40 mol%, then this statement of “New oxychloride lead-borate glasses xPbCl2-(50-0.5x)PbO-(50-0.5x)B2O3 have been synthesized with the maximum content of lead chloride of 40 mol%.” is not appropriate.
(2) In high-temperature melts, the valence state of Pb may change, affecting its structural form. How does the authors consider this?
(3) This article involves a lot of spectral and structural analysis of glasses. Maybe the following studies are helpful:
-Structural and Viscous Insight into Impact of MoO3 on Molten Slags. Metall. Mater. Trans. B 52, 3730–3743 (2021). https://doi.org/10.1007/s11663-021-02261-z.
-Modification of the Structure of Ti-Bearing Mold Flux by the Simultaneous Addition of B2O3 and Na2O. Metall. Mater. Trans. E. https://doi.org/10.1007/s40553-016-0066-0.
(4) Please check P5, Line 166&169: “While weakly bound Pb2+ cations” and “the mode around 135 cm-1 indicates the”.
Author Response
Thank you for the fruitful comments. We made the necessary corrections.
(1) If the XRF results of synthesized glasses do not prove that the lead chloride content reaches 40 mol%, then this statement of “New oxychloride lead-borate glasses xPbCl2-(50-0.5x)PbO-(50-0.5x)B2O3 have been synthesized with the maximum content of lead chloride of 40 mol%.” is not appropriate.
Replay
XRD patterns (Fig.2) prove the synthesis of glass material from the initial batch 40PbCl2-30PbO-30B2O3. Fig 3 as a result of EDX measurements shows that Cl/Pb ratio stays constant for the initial batch and for the synthesized glass. This means that we really obtained the glass with PbCl2 content of 40 mol%.
(2) In high-temperature melts, the valence state of Pb may change, affecting its structural form. How does the authors consider this?
Replay
We conducted all the experiments under room atmosphere with oxygen partial pressure 140 Torr. In this situation Pb will be in the highest valence state, namely, Pb2+ in the melt. See [Hongli Wen, Peter A. Tanner, Bing-Ming Cheng. Optical properties of 3dN transition metal ion-doped lead borate glasses // Materials Research Bulletin. 2016. V.83, P. 400-407 https://doi.org/10.1016/j.materresbull.2016.06.032]. In Ref/ [Dalba, G.; Fornasini, P.; Grisenti, R.; Rocca, F.; Afify, N.; Affatigato, M. XAFS study on the local order of Pb in PbO borate glasses // Physics and Chemistry of Glasses - European Journal of Glass Science and Technology Part B, V. 47, №4, 2006, P 518-520] the authors determined that in lead-borate glasses there was no form of Pb except Pb2+. No segeregation and reduction was found out.
(3) This article involves a lot of spectral and structural analysis of glasses. Maybe the following studies are helpful:
Replay
We included the ref Modification of the Structure of Ti-Bearing Mold Flux by the Simultaneous Addition of B2O3 and Na2O. Metall. Mater. Trans. E. https://doi.org/10.1007/s40553-016-0066-0. as Ref 39
Ссылка 39 -Modification of the Structure of Ti-Bearing Mold Flux by the Simultaneous Addition of B2O3 and Na2O. Metall. Mater. Trans. E. https://doi.org/10.1007/s40553-016-0066-0.
Reviewer 2 Report
Manuscript ID-Ceramics-2445744
Date: 08/06/2023
Title: New glasses in the PbCl2-PbO-B2O3 system: structure and optical properties
Recommendation: Accept after minor revision
The authors of the current manuscript titled “New glasses in the PbCl2-PbO-B2O3 system: structure and optical properties” have reported the borate-based glasses containing PbCl2 and their structure as well as optical properties are discussed. The manuscript the well organized and well written. In my opinion, the manuscript can be accepted in Ceramics after minor revision.
· Revise the introduction part. Include previous reports consisting of the other glass compositions and their pitfalls.
· Check grammatical errors and improve English.
Moderate editing of English language required
Author Response
The Introduction contains a brief review of previous works on glasses of the PbCl2-PbO-B2O3 system and related ones. The compositions from previous works are presented in Figure 1. In addition, difficulties of investigation of such systems are indicated, such as the toxicity of reagents, the tendency to crystallize and hygroscopicity (lines 37-39).
We checked the English and made our best to improve the article reading.
All changes are marked by yellow or grey.
Reviewer 3 Report
Dear Editor,
I recommend the paper for publication after minor corrections:
1) Abstract; line 15 …,, A decrease in microhardness, density, and glass transition temperatures are a consequence...” Change to …,, A decrease in microhardness, density, and glass transition temperatures is a consequence...”
Line 17 …,, The structure of PbCl2-PbO-B2O3 have been analyzed in detail...” Change to …,, The structure of PbCl2-PbO-B2O3 has been analyzed in detail...”
2) 1. Introduction; line 38 …,, glasses is often limited due to their high tendency to crystallization, toxicity of reagents, and rather high content of OH-groups...” Change to …,, glasses are often limited due to their high tendency to crystallization, the toxicity of reagents, and the rather high content of OH-groups...”
Line 42 …,, The aim of the work was to develop a synthesis technique of new oxychloride...” Change to …,, The work aimed to develop a synthesis technique for new oxychloride...”
3) 2. Materials and Methods; line 55…,, by other glassy carbon mold....” Please change to…,. by another glassy carbon mold....” or …,, by other glassy carbon molds....”
Line 68 …,, We used the X-ray fluorescent spectroscopy (XFS)...” Please remove the definite article and change to …,, We used X-ray fluorescent spectroscopy (XFS)...”
Line 79-80…,, begins to penetrate into the sample volume through the surface of the measuring prism, similarly to...” Please change to …,, begins to penetrate the sample volume through the surface of the measuring prism, similar to...”
Line 83 …,, using a SDT Q-600 thermal analyzer....” Please change to…,, using an SDT Q-600 thermal analyzer....”
4) 3. Results; 3.1. Glass composition and structure characterization; …,, line 112 Figure 2. and S1 please remove from abscissa angle, deg and leave only 2Ɵ.
Dear Colleagues, you forgot to mention the cards you used to identify the phases, the space group, and the number to which the phases belong and please mention them in the paragraph related to XRD.
Line 144 …,, We did not observed significant ...” Please change to …,, We did not observe significant...”
Line 145 …,, the physico-chemical properties...” Please change to …,, the physicochemical properties...”
Line 160 …,, They are resulted from bending vibrations...” Please change to …,, They are the result of bending vibrations...”
Line 167 …,, and weakening glass network...” Change to …,, and weaken the glass network...”
Line 175 …,, results to the generation....” Change to …,, results in the generation...”
Line 177 …,, This leads to destruction of [PbO4]2- units and formation of Pb2+ cations....” Change to …,, This leads to the destruction of [PbO4]2- units and the formation of Pb2+ cations. ....”
Line 191 …,, An increase of...” Change to …,, An increase in....”
Line 208 …,, which indicates a greater stability...” Please remove the indefinite article and change to …,, which indicates greater stability...”
Line 222 …,, interpreted in the Table 2. ...” Please remove the definite article and change to …,, interpreted in Table 2. ...”
line 240 …,,results to generation...” Change to …,, results in the generation...”
3.2. DSC characterisation and physical properties; line 242 …,,DSC characterisation and physical ...” Change to …,, DSC characterization and physical
Line 251 …,, Incorporation of halogen ions Please add the definite article and change to …,, The incorporation of halogen ions. ...”
Line 264 …,, resulted to the...” Change to …,, resulted in the...”
Line 276 …,,was higher 70 °C. ...” Please insert word …,, was higher than 70 °C ...”
Line 297 …,,caused to the density...” Please remove the word and change it to …,, caused the density...”
Line 299 …,,space than smaller O2- ...” Please add the definite article and change to …,, space than the smaller O2- ...”
Line 360 …,,an increase of...” Change to …,, an increase in...”
Line 364 …,,It has resulted to the shift...” Change to …,, It has resulted in the shift...”
Line 365 …,,and expansion of ...” Please add the definite article and change to …,, and the expansion of...”
Line 367 …,, compared for borate ...” Change to …,, compared to borate...”
Pay attention to the language.
Author Response
Thanks a lot for the fruitful help with English. The correct usage of articles is very difficult for non-native speakers.
We made sll correction for English.
We added the information about PBCl2 phase structural parameters
PbCl2 phase as rombic (space group Pnma, a = 7.623 Å, b= 9.048 Å, c = 4.535 Å, Z = 4. Card ID 01-084-1177 (MATCH) or pdf 26-1159 PCPDFWIN.
