Role of Iron on Properties of Calcium Aluminate Glasses and Melts
DOI:
https://doi.org/10.52825/glass-europe.v4i.1139Keywords:
Invert Glasses, Aluminate, Melt, Structure, Viscosity, ClinkerAbstract
CaO-Al2O3 based glasses are studied due to their presence in hydraulic binders/refractory cements. With the addition of Fe, an increased complexity in the phase diagrams and the liquid structure is observed as this element can exist in two different oxidation states which plays different roles in a liquid/glass matrix.
The aim of this study is to understand the influence iron addition in a CaO-Al2O3-B2O3 glass. B2O3 was added to simulate a liquid phase present in some Belite-Ye'elimite-Ferrite clinkers in which a glassy phase is observed. Iron is mainly present in the Fe3+ form in four-fold coordination. Viscosity and glass transition temperatures decrease with the addition of Fe2O3 which has an important impact for the clinkering process. This decrease with iron correlates with the appearance of a new band at 650 cm-1 in the Raman spectrum which can be assigned to the vibration of Al—O—[4]Fe3+—O—Al links.
Downloads
References
[1] IEA (2021), Global Energy Review 2021, IEA, Paris https://www.iea.org/reports/global-energy-review-2021
[2] S. Kucharczyk, M. Zajac, C. Stabler, R.M. Thomsen, M. Ben Haha, J. Skibsted, J. Deja Structure and reactivity of synthetic CaO-Al2O3-SiO2 glasses, Cem. Concr. Res. 120 (2019) 77–91. DOI:10.1016/j.cemconres.2019.03.004
[3] E. Gartner, Industrially interesting approches to “low-CO2” cements, Cem. Concr. Res. 34 (2004) 1489-1498. DOI:10.1016/j.cemconres.2004.01.021
[4] M. Ben Haha, F. Winnefeld & A. Pisch. Advances in understanding ye'elimite-rich ce-ments. Cement and Concrete Research, 123 (2019) 105778. DOI:10.1016/j.cemconres.2019.105778
[5] F. Bullerjahn, M. Zajac, M. Ben Haha, & K.L. Scrivener. Factors influencing the hydration kinetics of ye'elimite; effect of mayenite. Cement and Concrete Research, 116 (2019) 113-119. DOI:10.1016/j.cemconres.2018.10.026
[6] Y. Huang, Y. Pei, J. Qian, X. Gao, J. Liang, G. Duan, P. Zhao, L. Lu, X. Cheng (2020). Bauxite free iron rich calcium sulfoaluminate cement: Preparation, hydration and proper-ties. Construction and Building Materials, 249 (2020) 118774. DOI:10.1016/j.conbuildmat.2020.118774
[7] F. Bullerjahn, T. Scholten, K.L. Scrivener, M.B. Haha, A. Wolter, A. (2020). Formation, composition and stability of ye'elimite and iron-bearing solid solutions. Cement and Con-crete Research, 131, 106009. DOI:10.1016/j.cemconres.2020.106009
[8] H. Liu, W. Chen, R. Pan, Z. Shan, A. Qiao, J.W. Drewitt, L. Hennet, S. Jahn, D.P. Lang-staff, G.A. Chass, H. Tao, Y.Z. Yue, G.N. Greaves. From Molten calcium aluminates through phase transitions to cement phases. Adv. Sci., 7 (2020) 1902209. DOI: 10.1002/advs.201902209
[9] F.M. Lea, T.W. Parker, I—Investigations on a portion of the quaternary system CaO-Al2O3-SiO2-Fe2O3: The quaternary system CaO—2CaO.SiO2—5CaO.3Al2O3-4 CaO.Al2O3.Fe2O3 Philosophical Transactions of the Royal Society of London. Series A, Mathematical and Physical Sciences, 234 (731) (1934) 1-41.
[10] H.F.W. Taylor, Cement chemistry, second edition, Thomas Telford, 1997, 460 pp.
[11] T.I. Barry, F.P. Glasser. Calculations of Portland cement clinkering reactions. Advances in cement research, 12(1) (2000)19-28.doi :10.1680/adcr.2000.12.1.19
[12] V.V. Timashev, 7th ICCC conference, Vol. 1 (1980) I-3-1
[13] Yu.M. Butt, V.V. Timashev, A.P. Osokin, 6th ICCC conference, Vol.1 (1976) 132
[14] B.O. Mysen, D. Virgo, F.A. Seifert. Redox equilibria of iron in alkaline earth silicate melts: relationships between melt structure, oxygen fugacity, temperature and properties of iron-bearing silicate liquids. Amer. Mineral., 69 (1984) 834-848.
[15] B.O. Mysen, D. Virgo, E.R. Neumann, F.A. Seifert. Redox equilibria and the structural states of ferric and ferrous iron in melts in the system CaO-MgO-Al2O3-FeO: relation-ships between redox equilibria, melt structure and liquidus phase equilibria. Am. Mineral., 70 (1985) 317-331.
[16] B.O. Mysen, D. Virgo, C.M. Scarfe, D.J. Cronin. Viscosity and structure of iron and alu-minum bearing calcium melts at 1atm. Am. Mineral., 70 (1985) 487-498.
[17] D.B. Dingwell, D. Virgo. Viscosities of melts in the Na2O-FeO-Fe2O3-SiO2 system and factors controlling relative viscosities of fully polymerized silicate melts. Geochim. Cos-mochim. Acta, 52 (1988) 395-403. DOI: 10.1016/0016-7037(88)90095-6
[18] V.C. Kress, I.S.E Carmichael. Stoichiometry of the iron oxidation reaction in silicate melts. Am. Mineral., 73 (1988) 1267–1274.
[19] V.C. Kress, I.S.E. Carmichael. The compressibility of silicate liquids containing Fe2O3 and the effect of composition, temperature, oxygen fugacity and pressure on their redox states. Contrib. Min. Petrol., 108 (1991) 82–92.
[20] G. Ottonello, R. Moretti, L. Marini, M.V. Zuccholini. Oxidation state of iron in silicate glasses and melts: A thermochemical model. Chem. Geol., 174 (2001) 157-179.
[21] Moretti R. and Neuville D.R. (2021) Redox equilibria: from basic concepts to the mag-matic realm. AGU Geophysical Monography Series eds Moretti and Neuville – DOI : 10.1002/9781119473206.ch1
[22] G.B. Cook, R.F. Cooper, T. Wu. Chemical diffusion and crystalline nucleation during oxi-dation of ferrous iron-bearing magnesium aluminosilicate glass. J. Non-cryst. Sol., 120 (1990) 207-222.
[23] V. Magnien, D.R. Neuville, L. Cormier, J. Roux, J.-L. Hazemann, D. De Ligny, S. Pas-carelli, O. Pinet, P. Richet P. Kinetics or iron redox reactions in silicate melts: the effect of temperature and alkali cations. Geochim. Cosmochim. Acta., 72 (2008) 2157-2168. DOI: 10.1016/j.gca.2008.02.007
[24] D.S. Goldman, P.K. Gupta. Diffusion-controlled redox kinetics in a glassmelt. J. Amer. Ceram. Soc., 66 (1983) 188-190.
[25] H.D. Schreiber, S.J. Kozak, R.C. Merkel, G.B. Balazs, P.W. Jones, Jr. Redox equilibria and kinetics of iron in a borosilicate glass-forming melt J. Non-Cryst. Sol., 84 (1986) 186-195. DOI: 10.1016/0022-3093(86)90777-5
[26] R.F. Wendlandt. Oxygen diffusion in basalt and andesite melts: experimental results and discussion of chemical versus tracer diffusion. Contrib. Mineral. Petrol., 108 (1991) 463-471.
[27] J.L. Barton, D. Banner, D. Caurant, F. Pincemin. The oxidation of ferrous iron in glass at high temperatures II. Fundamentals of Glass Science and Technology, Bul. Soc. Esp. Ceram., 31(6) (1992) 215-220.
[28] R.F. Cooper, J.B. Fanselow, D.B. Poker. The mechanism of oxidation of a basaltic glass: chemical diffusion of network-modifying cations. Geochim. Cosmochim. Acta, 60 (17) (1996) 3253-3265. DOI: 10.1016/0016-7037(96)00160-3
[29] D.R. Smith, R.F. Cooper. Dynamic oxidation of a Fe2+ bearing calcium-magnesium-aluminosilicate glass: the effect of molecular structure on chemical diffusion and reaction morphology. J. Non-Cryst. Solids, 278 (2000) 145-163. DOI: 10.1016/S0022-3093(00)00323-9
[30] V. Magnien, D.R. Neuville, L. Cormier, B.O. Mysen, P. Richet. Kinetics of iron oxidation in silicate melts: a preliminary XANES study., Chem. Geol., 213 (2004) 253-265. doi:10.1016/j.chemgeo.2004.08.047
[31] V. Magnien, D.R. Neuville, L. Cormier, J. Roux, J.-L. Hazemann, O. Pinet, P. Richet Ki-netics or iron redox reactions in silicate liquids: a high-temperature X-ray absorption and Raman spectroscopy study. J. of Nucl. Mater., 352 (2006) 190-195. DOI: 10.1016/j.jnucmat.2006.02.053
[32] B. Cochain, D.R. Neuville, G.S. Henderson, C.A. McCammon, O. Pinet, P. Richet. Ef-fects of the iron content and redox state on the structure of sodium borosilicate glasses: A Raman, Mössbauer and boron k-edge XANES spectroscopy study. J. Am. Ceram. Soc., 95 (2012) 962–971. DOI: 10.1111/j.1551-2916.2011.05020.x
[33] D.R. Neuville, L. Cormier, A.M. Flank, D. de Ligny, J. Roux, P. Lagarde. Environment around Al, Si and Ca in aluminate and aluminosilicate melts by X-ray absorption spec-troscopy at high temperature, Am. Mineral. 93 (2008) 228-237. DOI: 10.2138/am.2008.2646
[34] D.R. Neuville, G.S. Henderson, L. Cormier, D. Massiot. The structure of crystals, glass-es, and melts along the CaO-Al2O3 join: Results from Raman, Al L- and K-edge X-ray absorption, and 27Al NMR spectroscopy. Am. Mineral. 95(10) (2010) 1580–1589. DOI: 10.2138/am.2010.3465
[35] M. Licheron, V. Montouilout, F. Millot, D.R. Neuville. Raman and 27Al NMR structure investigations of aluminate glasses: (1-x)Al2O3-xMO, with M=Ca,Sr, Ba and 0.5
[36] L. Hennet, J.W.E. Drewitt, D.R. Neuville, V. Cristiglio, J. Kozaily, S. Brassamin, D. Zanghi, H.E. Fischer. Neutron diffraction of calcium aluminosilicate glasses and melts. J. of Non-Cryst. Solids. 451 (2016) 89-93. DOI: 10.1016/j.jnoncrysol.2016.05.018
[37] R. El-Hayek, F. Ferey, P. Florian, A. Pisch, D.R. Neuville. Structure and properties of lime aluminoborate glasses and melts. Chem. Geol., 461 (2017) 75-81. DOI: 10.1016/j.chemgeo.2016.11.025
[38] D.R. Neuville, L. Cormier, A.-M. Flank, V. Brios, D. Massiot. Al speciation and Ca envi-ronment in calcium aluminosilicate glasses and crystals by Al and Ca K-edge X-ray ab-sorption spectroscopy. Chem. Geol. 213 (2004) 153-163. DOI: 10.1016/j.chemgeo.2004.08.039
[39] D.R. Neuville, L. Cormier, D. Massiot, Al coordination and speciation in calcium alumino-silicate glasses: Effects of composition determined by 27Al MQ-MAS NMR and Raman spectroscopy. Chem. Geol. 229(1-3) (2006) 173–185. : DOI : 10.1016/j.chemgeo.2006.01.019
[40] J.W.E. Drewitt, L. Hennet, A. Zeidler, S. Jahn, P.S. Salmon, D.R. Neuville, H.E. Fischer. Structural transformations on vitrification in the fragile glass forming system CaAl2O4. Physical Review Letters. 109 (23) (2012) 235501-235506. DOI: 10.1103/PhysRevLett.109.235501
[41] M.R. Cicconi, D. de Ligny, T.M. Gallo, D.R. Neuville. Ca Neighbors from XANES spec-troscopy: a tool to investigate structure, redox and nucleation processes in silicate glass-es, melts and crystals. Am. Mineral., 101 (2016)1232-1235. DOI: 10.2138/am-2016-5663
[42] J.W.E. Drewitt, A.C. Barnes, S. Jahn, S.C. Kohn, M.J. Walter, A. Novikov, D.R. Neuville, H.E. Fischer, L. Hennet. Structure of liquid tri-calcium aluminate. Physical Review B. 95 (2017) 064203-064214. DOI: 10.1103/PhysRevB.95.064203
[43] D.R. Neuville, G.S Henderson, D.B. Dingwell (2022) "Geological melts" Review in Miner-alogy and Geochemistry. DOI: 10.2138/rmg.2022.87.03
[44] J. Drewitt, L. Hennet, D.R. Neuville, (2022) The structure of glasses from short distance order to long distance. In Neuville D.R., Henderson G.S, Dingwell D. B. (2022) "Geologi-cal melts" Review in Mineralogy and Geochemistry. DOI: 10.2138/rmg.2022.87.02
[45] P.L. Higby, R.J. Ginther, I.D. Aggarwal, E.J. Friebele. Glass-formation and thermal-properties of low-silica calcium aluminosilicate glasses. J. Non-Cryst. Solids 126(3), (1990) 209–215. DOI: 10.1016/0022-3093(90)90821-3
[46] M. García-Maté, I. Santacruz, A. Cuesta, L. León-Reina, M.A. Aranda, I. Baco, V. Morin, G. Walenta, E. Gartner, A.G. de la Torre. Amorphous determination in calcium sulfoalu-minate materials by external and internal methods. Advances in Cement Research, 27(7) (2015) 417-423.
[47] A.J. Cuberos, A.G. De la Torre, G. Alvarez-Pinazo, M.C. Martín-Sedeño, K. Schollbach, H. Pöllmann, M.A. Aranda. Active iron-rich belite sulfoaluminate cements: clinkering and hydration. Environmental science & technology, 44(17) (2010) 6855-6862. DOI: 10.1021/es101785n
[48] G. Alvarez-Pinazo, A. Cuesta, M. Garcia-Maté, I. Santacruz, E.R. Losilla, A.G. De la Torre, L. Leon-Reina, M.A. Aranda. Rietveld quantitative phase analysis of Yeelimite-containing cemenets, Cement and Concrete Research, 42 (2012) 960-971 doi:10.1016/j.cemconres.2012.03.018
[49] D. Vantelon, N. Trcera, D. Roy, T. Moreno, D. Mailly, S. Guilet, F. Delmotte, E. Meltcha-kov, B. Lassalle, P. Lagarde, A.-M. Flank. The LUCIA beamline at SOLEIL. Journal of Synchrotron radiation, 23(2) (2016) 635-640. DOI: 10.1107/S1600577516000746
[50] Henderson, G. S., De Groot, F. M., & Moulton, B. J. (2014). X-ray absorption near-edge structure (XANES) spectroscopy. Reviews in Mineralogy and Geochemistry, 78(1) (2014) 75-138. DOI: 10.2138/rmg.2014.78.3
[51] G. Calas, J. Petiau (1983) Coordinance of iron in oxide glasses through high resolution K-edge spectra : information from pre-edge. Sol. Stat. Com., 48 625-629. DOI:10.1016/0038-1098(83)90530-6
[52] M. Wilke, F. Farges, P.E. Petit, G.E. Brown, Jr., F. Martin. Oxidation state and coordi-nance of Fe minerals: an Fe K-XANES spectroscopic study. (2001) Am. Mineral., 86 714 –730. DOI: 10.2138/am-2001-5-612
[53] D.R. Neuville, M.R. Cicconi, Losq C. How measure a redox state? Magma Redox Geo-chemistry. Magma Redox Geochemistry. AGU Geophysical Monography Series eds Moretti and Neuville. – DOI : 10.1002/9781119473206.ch13
[54] Giuli, G., Cicconi, M. R., & Paris, E. (2012). The Fe3+–O distance in synthetic kimzeyite garnet, Ca3Zr2 [Fe2SiO12]. European Journal of Mineralogy, 24(5), 783-790. DOI: 10.1127/0935-1221/2012/0024-2206
[55] Cicconi, M. R., Giuli, G., Ertel-Ingrisch, W., Paris, E., & Dingwell, D. B. (2015). The effect of the [Na/(Na+ K)] ratio on Fe speciation in phonolitic glasses. American Mineralogist, 100(7), 1610-1619. DOI: 10.2138/am-2015-5155
[56] Neuville D.R., G.S. Henderson and D. de Ligny (2014) Advances in Raman Spectrosco-py Applied to Earth and Material Sciences. In Henderson G.S, Neuville D.R., Down B. (2014) "Spectroscopic methods in Mineralogy and Material Sciences" Review in Mineral-ogy and Geochemistry, Vol 78, 509-541. DOI: 10.2138/rmg.2013.78.13
[57] D.R. Neuville. Viscosity, structure and mixing in (Ca, Na) silicate melts. Chem. Geol., 229 (2006) 28-42. DOI: 10.1016/j.chemgeo.2006.01.008
[58] Pereira L., Linard Y., Wadsworth F.B., Vasseur J., Moretti R., Dingwell D.B., Neuville D.R. (2024) non stoichiometric nano-crystallization in magmas: the impact of composition changes on viscosity. Journal of Volcanology and Geothermal Research. 10.1016/j.jvolgeores.2024.108039
[59] F. Farges. Crystal-chemistry of Fe in natural grandidierites: a XAFS spectros¬copy study at the Fe K-edge. Phys. Chem. Minerals, 28 (2001) 619–629. DOI: 10.1007/s002690100170
[60] U. Bucheneau, M. Prager, N. Nücker, A.J. Dianoux, N. Ahmad, W.A. Phillips. Low-frequency modes in vitreaous silica, Phys. Rev.B. 34 (1986) 5665-5673. DOI: 10.1103/PhysRevB.34.5665
[61] B. Hehlen, E. Courtens, R. Vacher, A. Yamanka, M. Kataoka, K. Inoue. Hyper-raman scattering observation of the boson peak in vitreous silica. Phys. Rev. 84(23) (2000) 5355–5358. DOI: 10.1103/PhysRevLett.84.5355
[62] B. Hehlen, E. Courtens, A. Yamanka, K. Inoue. Nature of the Boson peak of silica glass-es from hyper-Raman scattering. J. Non-Cryst. Solids 307-310 (2002) 87–91. DOI: 10.1016/S0022-3093(02)01444-8
[63] B. Hehlen, D.R. Neuville. Raman response of Network Modifier Cations in alumino-silicate glasses. J. Phys. Chem. B, 119 (2015) 4093-4098. DOI: 10.1021/jp5116299
[64] G. Simon, B. Hehlen, R. Vacher, E. Courtens. Nature of the hyper-Raman active vibra-tions of Lithium borate glasses. J. Phys. Condens. Matter. 20(15) (2008) 155103 DOI: 10.1088/0953-8984/20/15/155103
[65] D.R. Neuville, P. Courtial, D.B. Dingwell, P. Richet. Thermodynamic and rheological properties of rhyolite and andesite melts.Contrib. Mineral. Petrol., 113 (1993) 571-581.
[66] Sukenaga S., Cicconi M.R., Yamada H., Wakihara T., Ohara K., Shibata H. and Neuville D.R (2024) Iron redox effect on the structure and viscosity of silicate glasses and melts. The Journal of Chemical Physics. DOI: 10.1063/5.0243427
[67] D. Di Genova, R.A. Brooker, H.M. Mader, J.W.E. Drewitt, A. Longo, J. Deubener, D.R. Neuville, S. Fanara, O. Shebanova, S. Anzellini, F. Arzilli, E.C. Bamber, L. Hennet, G. La Spina, N. Miyajima. In situ observation of nanolite growth in volcanic melt: a driving force for explosive eruptions. Sciences Advances. (2020) – DOI : 10.1126/sciadv.abb041
[68] P. McMillan, B. Piriou. Raman spectroscopy of calcium aluminate glasses and crystals. J. Non-Cryst. Solids 55(2) (1983) 221–242. DOI: 10.1016/0022-3093(83)90672-5
[69] B.N. Meera, J. Ramakrishna. Raman spectral studies of borate glasses J. Non-Cryst. Solids 159 (1993) 1–21. DOI: 10.1016/0022-3093(93)91277-A
[70] B.C. Bunker, D.R. Tallant, R.J. Kirkpatrick, G.L. Turner. Multinuclear nuclear magnetic resonance and Raman investigation of sodium borosilicate glass structures. Phys. Chem. Glasses. 31(1) (1990) 30–41.
[71] E.I. Kamitsos, M.A. Karakassides, G.D. Chryssikos. Vibrational study of lithium borate glasses with high Li2O content. Phys. Chem. Glasses. 28(5) (1987) 203–209.
[72] E.I. Kamitsos, M.A. Karakassides, G.D. Chryssikos. Structure of borate glasses. I: Ra-man study of caesium, rubidium and potassium borate glasses. Phys. Chem. Glasses, 30(6) (1989) 229-234.
[73] L. Cormier, O. Majérus, D. Neuville, G. Calas, Temperature‐Induced Structural Modifica-tions Between Alkali Borate Glasses and Melts. Journal of the American Ceramic Socie-ty, 89(1) (2006) 13-19. DOI: 10.1111/j.1551-2916.2005.00657.x
[74] D.B. Dingwell. Viscosity-temperature relationships in the system Na2Si2O5-Na4Al2O5. Geochim. Cosmochim. Acta, 50 (1986) 1261-1265. DOI: 10.1016/0016-7037(86)90409-6
[75] Drewitt J.W.E, Barnes, A.C., Jahn S., Brooker R., Hennet L., Neuville D.R., Fisher H.E. (2023) Direct measurement of iron coordination in levitated liquid FeAl2O4 using neutron diffraction with isotope substitution. Philosophical Transaction of the Royal Society A. https://doi.org/10.1098/rsta.2022.0351
[76] Cormier L., Neuville D.R. and G. Calas (2000) Structure and properties of low-silica cal-cium aluminosilicate glasses. J. Non-Crystal. Solids.274, 110-114. DOI: 10.1016/S0022-3093(00)00209-X
[77] Téqui C., Robie R.A., Hemingway B.S., Neuville D.R. and Richet P. (1991) Melting and thermodynamic properties of pyrope (Mg3Al2Si3O12). Geochim. Cosmochim. Acta., 55, 1005-1011.DOI: 10.1016/0016-7037(91)90158-2
[78] D. Virgo, B.O. Mysen, I. Kushiro. Anionic constitution of silicate melts quenched at 1 atm from Raman spectroscopy: Implications for the structure of igneous melts. Science, 208 (1980) 1371–1373. DOI: 10.1126/science.208.4450.1371
[79] D. Virgo, B.O. Mysen, F.A. Seifert. Relationship between the oxidation state of iron and structure of silicate melts. Year B. Carnegie. Inst. Wash., 80 (1981) 308- 311.
[80] D. Virgo, B.O. Mysen, P.A. Danckwerth. Redox equilibria and the anionic structure of Na2O.xSiO2-Fe-O melts: effects of oxygen fugacity. Year B. Carnegie. Inst. Wash., 82 (1983) 305-309. DOI : 10.1016/0016-7037(88)90095-6
[81] D. Virgo, B.O. Mysen. The structural state of iron in oxidized vs. reduced glasses at 1 atm: A 57Fe Mössbauer study. Phys. Chem. Min., 12 (1985) 65-76. DOI: 10.1007/BF01046829
[82] J.A. Duffy, M.D. Ingram. An interpretation of glass chemistry in terms of the optical ba-sicity concept. Journal of Non-Crystalline Solids, 21 (1976) 373-410 DOI: 10.1016/0022-3093(76)90027-2
Published
How to Cite
Issue
Section
License
Copyright (c) 2026 Rawan El Hayek, Frédérique Ferey, Alexander Pisch, Maria Rita Cicconi, Delphine Vantelon, Daniel Neuville
This work is licensed under a Creative Commons Attribution 4.0 International License.
Accepted 2024-12-31
Published 2026-05-06