Open Access
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Minerals, volume 9, issue 10, pages 615

Crystallization and Thermal Stability of the P-Doped Basaltic Glass Fibers

Publication type: Journal Article
Publication date: 2019-10-07
Journal: Minerals
scimago Q2
wos Q2
SJR: 0.495
CiteScore: 4.1
Impact factor: 2.2
ISSN: 2075163X
Geotechnical Engineering and Engineering Geology
Geology
Abstract

The present research focuses on the influence of phosphorus oxide additives on the structure and thermal properties of the basalt glasses, produced in the form of fibers, i.e. at very high quenching speed. Basaltic glass fibers with various P2O5 contents were produced in two stages. In the first stage, the bulk glasses were prepared by adding variable amounts of (NH4)4P2O7 to milled natural andesitic basalt in order to obtain samples containing 2, 4, and 6 wt % P2O5. In the second stage, the glass fibers were obtained using a laboratory-scale system. Basalt glass fibers were characterized by Raman spectroscopy to obtain information on the structure of the obtained fibers, and by DSC-TG and XRD analyses to determine the change in crystallization mechanism of basaltic fibers. The hydrostatic weighing was used for the determination of glasses density. An increase in the content of P2O5 to 6 wt % leads to a decrease in the density of glass fibers due to the polymerizing effect of phosphorus oxide. The obtained X-ray diffraction patterns indicate that all samples are X-ray amorphous. The Raman results show that the decrease in the intensity of the line corresponding to vibrations of the structural units Q2 (about 920 cm–1) with respect to the line corresponding to Q3 (about 1125 cm–1) is related to an increase of P2O5 content. This also indicates the increase in polymerization degree of glass structure. DSC and XRD data also found out the change of phase transformations order with an increase of phosphorus oxide. The crystallization in natural and modified basalt glass fibers begins with spontaneous spinel-like phase formations that become nucleation sites for the precipitation of monoclinic pyroxene as a major phase. With an increase in the P2O5 content, there is a tendency to a decrease in the pyroxene at higher temperature, as a result of which, the hematite crystallizes at lower temperatures. That is associated with the activation of liquation processes, accompanied by the formation of amorphous phases with different viscosities with an increase in the concentration of P2O5. In conclusion, all the obtained data indicate the prospect of using the proposed approach to obtain basalt glass fibers with enhanced thermal and mechanical stability.

Found 29
By date By citations
Elsevier
Structural, chemical and mechanical properties of phosphate glass fibers
Saloumi N., El Bouchti M., Tamraoui Y., Manoun B., Hannache H., Cherkaoui O.
Journal of Non-Crystalline Solids scimago Q2 wos Q2 , 
2019-10-01,  citations by CoLab: 10 ,  Abstract  
Phosphate glasses with the compositions of (53-x)P 2 O 5 -11K 2 O-25CaO-11MgO-X; (X: ZnO, CoO, Fe 2 O 3 ) were prepared and subsequently transformed into fibers by a monofilament extruder. The compositions and amorphous nature of the glasses were confirmed by XRD, Raman and infrared spectroscopies. The SEM shows that the elaborated fibers at a spinning speed of 500 m/min have a diameter of 17 μm. The degradation study in aqueous solution at 37 °C showed a decrease of 99% in degradation rate with the addition of ZnO, CoO and Fe 2 O 3 elements. This confirmed that the chemical durability of the glasses had increased. DSC showed an increase in T g values by addition ZnO, CoO and Fe 2 O 3 contents. The tensile properties show that the phosphate glass fibers have good mechanical properties, the highest tensile strength obtained is 1321 ± 50 MPa. The density measured revealed an increase from 2.54 to 2.7 g.cm −3 .
Springer Nature
The glass formation and crystallization studies on iron phosphate–silicate glasses
Kuczek J., Sułowska J., Lach R., Szumera M.
Journal of Thermal Analysis and Calorimetry scimago Q2 wos Q2 , 
2019-07-13,  citations by CoLab: 11 ,  Abstract  
The assessment of impact of incorporation of various amount of Fe2O3 at the expense of MgO and CaO on the glassy phase formation and thermal stability exhibited in P2O5–SiO2–K2O–MgO–CaO–Fe2O3 system was carried out. The characteristic temperatures for iron phosphate–silicate glasses and glass-crystalline materials were designated from associated DSC curves. Selected samples were subjected to the process of induced crystallization, and products combined with particular exothermic effects were identified. Combination of DSC, XRD and SEM–EDS methods enabled to collect invaluable data concerning the course of crystallization of not only iron phosphate–silicate glasses subjected to the process of induced crystallization, but also glass-crystalline materials obtained directly through melt-quenched technique. The amount of particular crystalline products associated with selected devitrificates was determined via Rietveld technique. Results of the conducted study indicated that Fe2O3 addition conduces to the decrease in crystallization temperatures and thermal stability which was reflected in calculated values of ΔT and KW parameters. Concomitantly, glass with 20 mol% iron (III) oxide addition exhibited significantly improved, distinctive thermal stability among the materials in the analyzed series. The connection of crystalline phases with gradual alterations in polymerization degree of glass matrix was also established. The performed study is a contribution to the knowledge of iron phosphate glasses family and associated glass-crystalline materials.
Springer Nature
Correlation between glass transition effect and structural changes in multicomponent iron phosphate-silicate glasses
Kuczek J., Jeleń P., Sułowska J., Szumera M.
Journal of Thermal Analysis and Calorimetry scimago Q2 wos Q2 , 
2019-06-21,  citations by CoLab: 10 ,  Abstract  
Iron phosphate-silicate glasses from P2O5–SiO2–K2O–MgO–CaO–Fe2O3 system were subjected to the thermal and spectroscopic studies in order to gain information about their structure and thermal behavior in the range of glass transition effect. Research includes results obtained via DSC, MIR and DRIFT spectroscopy. Designated values of glass transition temperature and specific heat change slightly increases with Fe2O3 incorporation. Spectra collected during thermal treatment of glasses containing 2 and 30 mol% Fe2O3 exhibited various changes. Fe2O3 addition affected the glass structure by its reinforcement and led to its preservation during thermal treatment. The connection between density, molar volume, oxygen packing density and the chemical composition’s alteration were also established because of the direct dependence of physical properties and the structure. Obtained results supported thermal and spectroscopic studies. Conducted research is considered as a contribution to the knowledge about the family of iron phosphate glasses, which are known from their interesting properties and widely used applications.
Elsevier
Influence of vibration on basalt fiber crystallization at high temperature
Gutnikov S.I., Pavlov Y.V., Zhukovskaya E.S.
Journal of Non-Crystalline Solids scimago Q2 wos Q2 , 
2018-12-01,  citations by CoLab: 4 ,  Abstract  
The influence of low-frequency vibrational treatment on the crystallization of basalt wool fibers was studied. In this work, three series of samples were investigated. The first sample set was only one-sided heated at temperatures from 300 °C to 900 °C for 24 h. The second sample set was after only vibrational treatment with a frequency of 50 Hz and oscillations amplitude of 1 mm for 6–48 h. The third sample set was after simultaneous treatment of one-sided heating and vibration at temperatures from 300 °C to 600 °C with a frequency of 50 Hz and oscillations amplitude of 1 mm for 24 h. It is shown that at temperatures close to the glass transition temperature, vibration can influence on the relaxation processes in glasses and accelerate them. Mechanism of glass structure transformation in the basalt fiber does not change, but it starts at a slightly lower temperature. That is a consequence of an additional low-energy vibrational treatment. The vibrational treatment intensifies the crystallization process in basalt fibers and decreases the service temperature of the material by at least 40–50 °C.
Elsevier
Fe in P-doped basaltic melts: A Mössbauer spectroscopy study
Tarrago M., Garcia-Valles M., Martinez S., Pradell T., Bruna P.
Materials Letters scimago Q2 wos Q2 , 
2018-10-01,  citations by CoLab: 3 ,  Abstract  
The addition of P to a basalt causes a change in the environment of Fe. At low P contents iron is located in the glass structure and the Fe3+/Fe2+ ratio is about 80/20. Further addition of P causes a collapse of the glass structure related to a phase separation that triggers the crystallization of a more reduced iron-containing phosphate phase with a crystalline structure similar to that of stanfieldite, and Mossbauer parameters similar to those of the alluaudite group, together with the formation of a Fe3+-Fe2+ disordered phase. Their presence increases the viscosity of the melt.
Elsevier
Phosphorus solubility in basaltic glass: Limitations for phosphorus immobilization in glass and glass-ceramics
Tarrago M., Garcia-Valles M., Martínez S., Neuville D.R.
Journal of Environmental Management scimago Q1 wos Q1 , 
2018-08-01,  citations by CoLab: 15 ,  Abstract  
The composition of sewage sludge from urban wastewater treatment plants is simulated using P-doped basalts. Electron microscopy analyses show that the solubility of P in the basaltic melt is limited by the formation of a liquid-liquid immiscibility in the form of an aluminosilicate phase and a Ca-Mg-Fe-rich phosphate phase. The rheological behavior of these compositions is influenced by both phase separation and nanocrystallization. Upon a thermal treatment, the glasses will crystallize into a mixture of inosilicates and spinel-like phases at low P contents and into Ca-Mg-Fe phosphate at high P contents. Hardness measurements yield values between 5.41 and 7.66 GPa, inside the range of commercial glasses and glass-ceramics. Leaching affects mainly unstable Mg2+-PO43- complexes.
Wiley
Raman spectroscopy of various phosphate minerals and occurrence of tuite in the Elga IIE iron meteorite
Litasov K.D., Podgornykh N.M.
Journal of Raman Spectroscopy scimago Q2 wos Q2 , 
2017-02-10,  citations by CoLab: 97 ,  Abstract  
The Raman spectra of phosphate minerals: apatite, merrillite, panethite, brianite, czochralskiite, maricite, new phosphate with composition of Na2Fe(Mg,Ca)(PO4)2 and high‐pressure phase tuite from the Elga IIE iron meteorite are characterized. Panethite, brianite, czochralskiite and new Na‐Fe phosphate were described for the first time. The basic features of all studied phosphates include strong ν1 symmetric stretching mode of PO43− ions at 950–990 cm−1, antisymmetric ν3 vibrations in the 1000–1175 cm−1 region and weak bands in the 400–500 cm−1 region, which correspond to ν2 bending mode and in the 550–640 cm−1 region, related to ν4 bending mode. Weak bands at less than 300 cm−1 represent lattice modes. Most of the studied phosphates have three non‐equivalent positions of phosphorus atoms in the crystal structures and can be derived from glaserite, K3Na(SO4)2, arrangement. Two or three of non‐equivalent [PO4] tetrahedra typically correspond to two or three strong bands in the region of ν1 vibrations. High‐pressure mineral tuite has similar composition and was formed after merrillite. P‐O vibrations in equivalent [PO4] tetrahedra produce major Raman band of tuite at 972 cm−1. The Elga parent‐body experienced a shock pressure of at least 12–15 GPa according to minimum pressures of tuite formation in the static high‐pressure experiments. This is the first finding of tuite in iron meteorites and the only second finding of high‐pressure mineral in them. Copyright © 2017 John Wiley & Sons, Ltd.
Elsevier
Crystallization of zirconia doped basalt fibers
Lipatov Y.V., Arkhangelsky I.V., Dunaev A.V., Gutnikov S.I., Manylov M.S., Lazoryak B.I.
Thermochimica Acta scimago Q2 wos Q2 , 
2014-01-01,  citations by CoLab: 22 ,  Abstract  
Abstract Crystallization of basalt fibers containing 0–7 wt% ZrO 2 was studied. Fibers were drawn from basalt glasses and annealed in air at different temperatures. Phase composition of obtained samples was determined by XRD. Kinetics of crystallization processes was investigated by DSC. Kinetic models and parameters were estimated for crystallization of spinel-like phase, pyroxene and plagioclase using model-free analysis. It was found that doping of fibers with 1–3 wt% ZrO 2 increased Arrhenius parameters of aluminosilicate crystallization. When the zirconia content was 5–7 wt% the crystallization mechanism significantly changed. This phenomenon resulted in increasing of fiber thermal stability.
Crystallization mechanism of basalt glass fibers in air
Manylov M.S., Gutnikov S.I., Pokholok K.V., Lazoryak B.I., Lipatov Y.V.
Mendeleev Communications scimago Q3 wos Q3 , 
2013-11-22,  citations by CoLab: 33 ,  Abstract  
As found by differential thermal analysis, X-ray diffraction and Mossbauer spectroscopy, the heat treatment of basalt glass fibers in air leads to complete iron oxidation and the bulk growth of superparamagnetic magnesioferrite particles which act as nucleation sites for pyroxene crystallization.
Elsevier
Effect of the initial stage of annealing on modeling of enthalpy relaxation in a hyperquenched glass
Zhang Y., Guo X., Yue Y.
Journal of Non-Crystalline Solids scimago Q2 wos Q2 , 
2013-10-01,  citations by CoLab: 4 ,  Abstract  
One of the major challenges in glass relaxation study is to establish a universal model describing the enthalpy relaxation in both the hyperquenched glass (HQG) (i.e., far from equilibrium) and the partially annealed hyperquenched glass (AHQG). In particular, the detailed features of the enthalpy relaxation in both HQG and AHQG during the initial stage of both the sub- T g and above- T g annealing cannot be captured by the existing models. In this Letter we show that the combination of a modified stretched exponential equation [M. Peyron, et al., J. Magn. Reson, Series A 118 (1996) 214] and the recently proposed composite relaxation function [L. Hornboell, et al., Chem. Phys. Lett. 1-3 (2010) 37] is a reasonable approach for describing those features. In addition, our modeling results imply that the structural heterogeneity plays a crucial role in relaxation of HQG. • We study the importance of initial annealing process to the enthalpy relaxation. • A model combining MSE with CRF is proposed for describing enthalpy relaxation. • The model stresses the importance of two neighboring states to relaxation. • The model can capture the evolvement of the enthalpy in HQG during annealing.
Elsevier
Effect of the reduction treatment on the basalt continuous fiber crystallization properties
Gutnikov S.I., Manylov M.S., Lipatov Y.V., Lazoryak B.I., Pokholok K.V.
Journal of Non-Crystalline Solids scimago Q2 wos Q2 , 
2013-05-01,  citations by CoLab: 65 ,  Abstract  
Basalt continuous fibers were treated in H 2 /Ar atmosphere at 650 °С and 700 °C. The 57 Fe Mössbauer spectroscopy indicated that after the treatment at 650 °C all ferric cations reduced to ferrous. Reduction at higher temperature leads to metallic iron formation. DSC and XRD data indicated that crystallization process in reduced basalt fibers carried slower. Glass transition temperature decreases after the reduction due to the increase of amount of ferrous cations, that act as modifiers. Due to Fe 2 + /Fe 3 + ratio changing spinel-like phase crystallization ability decreases. Crystallization in reduced basalt fibers starts at lower temperature. The tensile strength of reduced fibers is higher than the tensile strength of basalt continuous fibers that were annealed at the same condition in air. • Basalt continuous fibers were reduced in H 2 atmosphere. • Due to Fe 2 + /Fe 3 + ratio changing crystallization mechanism changes. • Crystallization process in the reduced basalt fibers carries slower. • The tensile strength loss of the reduced fibers is 40.4%.
Elsevier
Enthalpy relaxation in hyperquenched glasses of different fragility
Hornbøll L., Yue Y.
Journal of Non-Crystalline Solids scimago Q2 wos Q2 , 
2008-04-01,  citations by CoLab: 18 ,  Abstract  
The enthalpy relaxation in hyperquenched (HQ) glasses with a wide range of fragilities is studied by performing annealing and differential scanning calorimetric (DSC) experiments. In this work, the enthalpy relaxation behavior of annealed HQ glasses is characterized in terms of the excess heat capacity ( C p ,exc ) given by the difference between the first and the second DSC measurements on the HQ glasses. The shape of the C p ,exc curves depends on the fragility of the glass system, which implies that during annealing the mechanism of the structural relaxation of the HQ strong systems differs from that of the HQ fragile systems. The details of the fragility dependence of the C p ,exc curves have been discussed in terms of the energy landscape and the structure of the liquids.
Elsevier
Sinter-crystallization of a glass obtained from basaltic tuffs
Karamanov A., Ergul S., Akyildiz M., Pelino M.
Journal of Non-Crystalline Solids scimago Q2 wos Q2 , 
2008-01-01,  citations by CoLab: 28 ,  Abstract  
Glass-ceramic materials, obtained by sinter-crystallization of melted alkaline-olivine basaltic tuffs, were investigated. The kinetics of bulk crystallization was evaluated by differential thermal analysis (DTA) at different heating rates. The phase formation and the sintering behavior of glass powders (
Elsevier
Crystallization behaviour, structure and properties of sintered glasses in the diopside–Ca-Tschermak system
Goel A., Tulyaganov D.U., Agathopoulos S., Ribeiro M.J., Ferreira J.M.
Journal of the European Ceramic Society scimago Q1 wos Q1 , 
2007-01-01,  citations by CoLab: 28 , 
Elsevier
The structural behavior of ferric and ferrous iron in aluminosilicate glass near meta-aluminosilicate joins
Mysen B.O.
Geochimica et Cosmochimica Acta scimago Q1 wos Q1 , 
2006-05-01,  citations by CoLab: 79 ,  Abstract  
Iron-57 resonant absorption Mossbauer spectroscopy was used to describe the redox relations and structural roles of Fe3+ and Fe2+ in meta-aluminosilicate glasses. Melts were formed at 1500 °C in equilibrium with air and quenched to glass in liquid H2O with quenching rates exceeding 200 °C/s. The aluminosilicate compositions were NaAlSi2O6, Ca0.5AlSi2O6, and Mg0.5AlSi2O6. Iron oxide was added in the form of Fe2O3, NaFeO2, CaFe2O4, and MgFe2O4 with total iron oxide content in the range ∼0.9 to ∼5.6 mol% as Fe2O3. The Mossbauer spectra, which were deconvoluted by assuming Gaussian distributions of the hyperfine field, are consistent with one absorption doublet of Fe2+ and one of Fe3+. From the area ratios of the Fe2+ and Fe3+ absorption doublets, with corrections for differences in recoil-fractions of Fe3+ and Fe2+, the Fe3+/ΣFe is positively correlated with increasing total iron content and with decreasing ionization potential of the alkali and alkaline earth cation. There is a distribution of hyperfine parameters from the Mossbauer spectra of these glasses. The maximum in the isomer shift distribution function of Fe3+, δFe3+, ranges from about 0.25 to 0.49 mm/s (at 298 K relative to Fe metal) with the quadrupole splitting maximum, ΔFe3+, ranging from ∼1.2 to ∼1.6 mm/s. Both δFe3+ and δFe2+ are negatively correlated with total iron oxide content and Fe3+/ΣFe. The dominant oxygen coordination number Fe3+ changes from 4 to 6 with decreasing Fe3+/ΣFe. The distortion of the Fe3+–O polyhedra of the quenched melts (glasses) decreases as the Fe3+/ΣFe increases. These polyhedra do, however, coexist with lesser proportions of polyhedra with different oxygen coordination numbers. The δFe2+ and ΔFe2+ distribution maxima at 298 K range from ∼0.95 to 1.15 mm/s and 1.9 to 2.0 mm/s, respectively, and decrease with increasing Fe3+/ΣFe. We suggest that these hyperfine parameter values for the most part are more consistent with Fe2+ in a range of coordination states from 4- to 6-fold. The lower δFe2+-values for the most oxidized melts are consistent with a larger proportion of Fe2+ in 4-fold coordination compared with more reduced glasses and melts.
Found 4
By date By citations
Elsevier
Mechanical degradation of basalt fiber at elevated temperatures (300∼360 °C) studied through semi-quantitative analysis of X-ray photoelectron spectrometry
Wang Z., Liu X., Luo H., Zhang L., Jiang H.
Journal of Non-Crystalline Solids scimago Q2 wos Q2 , 
2025-01-01,  citations by CoLab: 0 , 
Elsevier
Quantification of high temperature stability of mineral wool for fire-safe insulation
Jensen P.G., Belmonte L., Solvang M., Yue Y.
Journal of Non-Crystalline Solids scimago Q2 wos Q2 , 
2023-12-01,  citations by CoLab: 4 ,  Abstract  
Mineral wool, particularly stone wool, is a widely applied thermal insulation material that plays a critical role both in saving energy and in slowing the spread of fire in buildings owing to its high-temperature stability (HTS). However, so far there has been a lack of a universal method to accurately quantify HTS of mineral wool on a small scale. Here, we established a universal method, which is based on measuring the variation of the silhouette area of a cylindrical wool fiber pellet during heating by a hot-stage microscope. Using this method, we detected two main stages of shrinking: 1) the first-stage shrinking related to viscous deformation; 2) the second-stage shrinking caused by melting. Minimizing the first stage shrinking is the key to ensure the fire barrier role of stone wool. The origin of the HTS differences among different types of wool products was clarified by X-ray diffraction, differential scanning calorimetry and thermal expansion.
Wiley
New insights about the role of Na–K ratio on the vibrational dynamics of synthetic‐basalt glasses
Cassetta M., Zanatta M., Biesuz M., Giarola M., Mariotto G.
Journal of Raman Spectroscopy scimago Q2 wos Q2 , 
2022-01-05,  citations by CoLab: 4 ,  Abstract  
Basalts are among the most abundant igneous rocks on Earth. Originated from the rapid cooling of magma erupted by volcanoes, they are increasingly used as raw materials in glass and ceramic technology due to their unique physico-chemical properties. The characteristics of basalts, like the glass transition temperature, are strongly controlled by their structure, which is a function of composition. Therefore, the investigation of the interplay between the intimate structure and the mechanical and physical properties of basalt glasses is of paramount importance in view of their industrial exploitation. Here, we present a Raman study of a set of synthetic-basalt glasses in which the occurrence of small chemical variations appreciably affects their glass transition temperature. We analyzed the Raman spectra focusing on both the spectral regions of the so-called nonbridging oxygens and of the boson peak. We show the existence of a scaling law for the boson peak of four synthetic-basalt glasses, and we infer from its breakdown the occurrence of a deep reorganization of the glass structure resulting from the Na–K replacement in the network, despite small variations of the other major elements.
Elsevier
Effects of high-temperature treatment and iron reduction index on tensile strength of basalt continuous fiber
Wang Q., Zhang Q., Luo L., Yan T., Liu J., Ding L., Jiang W.
Journal of Non-Crystalline Solids scimago Q2 wos Q2 , 
2021-07-01,  citations by CoLab: 14 ,  Abstract  
• The tensile strengths of BFs at high temperatures were studied • BFs with higher IRIs retained better tensile strengths at high temperatures • A CaO-based crystal layer was formed on the surface of BFs • BFs with lower IRIs formed more ferric tetrahedral structures at high-temperature Iron plays an important role in enhancing the tensile strength of basalt fibers (BFs); however, the origins of tensile-strength variation at high temperatures are not well understood. In this work, we prepared BFs with different iron reduction indices (IRI = Fe 2+ /Fe total ) and explored the effects of high temperature and IRI on tensile strength. The results show that BFs with higher IRIs retained better tensile strength after high-temperature treatment at 600°C for 1 h. The surface morphology was analyzed by scanning electron microscopy to observe the nanocrystalline layers on the surface of BFs with higher IRIs, and the main composition of the crystals was CaO. The formation of nanocrystalline layers increased the tensile strength of the BFs. Moreover, results from transmission 57 Fe Mössbauer spectroscopy and Fourier transform infrared spectroscopy indicate that BFs with lower IRIs formed more ferric tetrahedral structures (Fe 3+ (tet)) after high-temperature treatment, which depolymerized Si(Al)-O-Si(Al) tetrahedral structures, resulting in lower tensile strength. A better understanding of the origin of microstructures in different iron coordination states and the tensile strength of BFs at high temperatures will assist in the development of advanced iron-bearing glass fiber products suitable for high-temperature environments.

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