Glass Ceramic with Improved Structure and Properties Made with Wastes from FeNi Production
Round 1
Reviewer 1 Report
Good work , especially it solve a problem of solid waste materials by calculation of only one batch composition . But I have some comments :
1.CS is the converter slag may considered as a rich source of iron ?
2. There are many repeation in the paper
3. The word "mirror " for the surface of glass melt but it is known for the melting of metal
4. What the source of ICSD cards ? ( are there referce ) . Are there card for P1 proxene and also P2
5. In Fig 3 : crystallized at ?? Also in other Figures mention the temperture ?
6. The difference beween proxene volume beween P1 428 and P2 422 is sensative ?
7. One peak in xrd can identfieed two spinel ?
8. In most Figure of microstructure the authour refer to spinel ( Is it the major phase ?)
9. Are there photos of the samples as glass and glass-ceramic
Minor editing of English language required
Author Response
Thank You for the useful comments.
Good work , especially it solve a problem of solid waste materials by calculation of only one batch composition . But I have some comments :
1.CS is the converter slag may considered as a rich source of iron ?
Yes, formally it might be considered as a source of iron. However, an appropriated manufacturer, near to FeNI plant doesn’t exists to justify the transport cost. In addition, it is the most problematic waste (according to the TCLP results) and its total amount is at about 8%.
- There are many repeation in the paper
The manuscript is revised again and some part are re-written.
- The word "mirror " for the surface of glass melt but it is known for the melting of metal
The term “mirror” is used by some technicians to explain the free of babbles surface of a glass forming melt. However, in order to avoid confusions, it is substituted by “clean and free of babbles surface”.
- What the source of ICSD cards ? ( are there referce ) . Are there card for P1 proxene and also P2
The database (2021.1) https://psds.ac.uk/icsd
In the case of pyroxenes, considered enormous variety of compositions, it is not accurate to “fit” the chemical composition by a fixed card. Nevertheless, the following comment is added: “This difference is at about 1.5 % and clearly highlights variation in the chemical compositions of both pyroxene phases. It can be assumed that some larger ions participate in the formation of P1 phase.”
These assumptions are confirmed by the EDS results.
- In Fig 3 : crystallized at ?? Also in other Figures mention the temperture ?
at 730 oC is added in the figure caption. In the SEM images the thermal treatment is noted by the name of the samples.
- The difference beween proxene volume beween P1 428 and P2 422 is sensative ?
See the comments for note 4.
- One peak in xrd can identfieed two spinel ?
Agree, that the identification of the spinel is complicated. Practically, it is accurate only for the “preliminary spinel” formed in the parent glass, where it is the only phase. After the formation of pyroxene overlapping between pyroxenes and spinel occurs, so that it is problematic to distinguish the negligible difference between both spinel. However, since during the crystallization treatment only secondary spinel (i.e. magnetite) is formed (confirmed by SEM, FESEM and TEM results) the S2 amount becomes higher than one of S1. But I don’t want to complicate the discussion.
- In most Figure of microstructure the authour refer to spinel ( Is it the major phase ?)
No, main phase is the secondary pyroxene. But several SEM and TEM studies are made in order to highlight the sequence of the phase formation, because it leads to the final intriguing nano structure.
In fact, in the manuscript is written “The main structure of sample GC60-60 (i.e. free from “preliminary” spinel), where P2 is the predominate crystal phase is shown in Fig. 9. It highlights the high degree of crystallinity of final glass-ceramic and shows that the size of formed pyroxenes, having the typical prismatic habit, is about 200 nm. The additional analysis shows that the number of these pyroxene crystals is 80±15 per µm2. This value is even slightly higher than one of the iron-rich drops formed in sample GC60-1, which confirm that the “secondary” spinel phase act as nucleation agent for the main crystallization process.”
- Are there photos of the samples as glass and glass-ceramic
The glass samples were cut and used. By the way, it is impossible to distinguish a “black” bar of glass, or glass-ceramic from another by a photo. In addition, huge number of similar samples (basalts, iron-rich glasses, products of vitrification of nuclear wastes, etc.) are reported in the literature (including my own works). In the present review the peculiarity is the nano-structure, elucidated by SEM, FISEM and TEM.
Reviewer 2 Report
The integrated use of raw natural resources, the development of waste treatment technology into a useful product, the development of areas and technologies for its use is one of the most important tasks of our time. The relevance of this direction is confirmed by the fact that the solution of these tasks is directly related to the preservation of flora and fauna, a comfortable human life on earth. Since the second half of the 20th century, high human activity has led to an increase in non-utilized solid waste, which has now become a global problem. The amount of waste is already commensurate with the reserves of natural materials. Landfills and industrial waste occupy huge areas of valuable land. There are cities and countries that have been completely turned into landfills. Whole islands of garbage have been discovered in the world's oceans, which poison the wildlife of water resources. The need for the integrated use of natural resources on the principle of “production and consumption” coincides with the problems of environmental safety that arose in the 60s of the last century, the rapid growth of the Earth's population, increased consumption of natural resources, the creation of new types of synthetic materials (for example, plastics) that are not amenable to natural decomposition. The problem of waste disposal and the creation of waste-free technologies has become as acute as the creation of products, i.e. in the technology of creation, an equally important stage is the stage of destruction and use of waste. The problems of integrated use of resources have now reached the international level. There is no doubt that the conducted research on the creation of glass ceramics with improved structure and properties based on Fe Ni waste will bring the solution to this problem closer and, thereby, create an environment of the necessary quality in relation to a person.
Author Response
Thank you for the comment. Unfortunately, the politicians unofficially have quite different opinion.
Reviewer 3 Report
(1) In the title, the “Fe-Ni wastes” is not clear what it means.
(2) P2 Line 48, please check “that silicate melts, reach of iron oxides”.
(3) P4 Line 148, please check “After 1-1.5 melting”.
(4) How do you determine the glass transition temperature? No obvious steps seem to be observed on the DTA curves in Figure 2.
(5) Previous important study on viscosity and crystallization may have been missed:
-ANN-based structure-viscosity relationship model of multicomponent slags for production design in mineral wool, Constr. Build. Mater. 319 (2022) 126010. https://doi.org/10.1016/j.conbuildmat.2021.126010
-Highly porous ceramics production using slags from smelting of spent automotive catalysts, Resour., Conserv. Recycl. 166 (2021) 105373. https://doi.org/10.1016/j.resconrec.2020.105373
(6) P6 Line 231, please check “the surface oxidation of Fe2+ into Fe3+”.
(7) If possible, XPS test may be more suitable to determine FeO/Fe2O3 ratio.
(8) P6 Line 236, please check “and FeO/F2O3 ratio”.
(9) P6 Line 241, please explain why the surface oxidation Fe2+ into Fe3+ leads the increasing viscosity.
Author Response
(1) In the title, the “Fe-Ni wastes” is not clear what it means.
In order to avoid confusion, the title is charged into:
“Glass ceramic with improved structure and properties by wastes from FeNi production”
(2) P2 Line 48, please check “that silicate melts, reach of iron oxides”.
Thank You! - Rich of iron oxides….
(3) P4 Line 148, please check “After 1-1.5 melting”.
Thank You – after 1.5 h melting
(4) How do you determine the glass transition temperature? No obvious steps seem to be observed on the DTA curves in Figure 2.
”(estimated as the first onset in the heat flow signal in the glass transition range)" is added in the text.
By the way, due to the very high intensity of the crystallization peaks, as well as because of the fast immiscibility trend Tg really is not easy distinguished. However, it is notable at higher” zoom” and in the DDTA plot.
(5) Previous important study on viscosity and crystallization may have been missed:
-ANN-based structure-viscosity relationship model of multicomponent slags for production design in mineral wool, Constr. Build. Mater. 319 (2022) 126010. https://doi.org/10.1016/j.conbuildmat.2021.126010
-Highly porous ceramics production using slags from smelting of spent automotive catalysts, Resour., Conserv. Recycl. 166 (2021) 105373. https://doi.org/10.1016/j.resconrec.2020.105373
I read the proposed interesting publications. However, the composition discussed are very different by one in present manuscript. In addition, due to the extremely high immiscibility and crystallization trend the measurement and the prediction of viscosity (i.e. apparent viscosity) in similar compositions is practically impossible (except Tg and at temperatures higher the liquids).
(6) P6 Line 231, please check “the surface oxidation of Fe2+ into Fe3+”.
OK! Fe2+
(7) If possible, XPS test may be more suitable to determine FeO/Fe2O3 ratio.
Unfortunately, we haven’t XPS (or Mossbauer analysis) results for this glass. However, the applicability of the TG oxidation gain “method” is confirmed in several works.
(8) P6 Line 236, please check “and FeO/F2O3 ratio”.
OK! Fe2O3
(9) P6 Line 241, please explain why the surface oxidation Fe2+ into Fe3+ leads the increasing viscosity.
“The viscosity variation is result of the different structural role of Fe2+ (which is typical “modifier”) and Fe3+ (acting as “intermediates”) in glass and melt structures.” Is added in the text.
Round 2
Reviewer 3 Report
The revised manuscript meets the basic requirements for publication in Applied Sciences.
