Thermal properties, density and structure of percalcic and peraluminus CaO–Al2O3–SiO2 glasses

doi:10.1016/j.jnoncrysol.2014.12.019

Journal of Non-Crystalline Solids

Volume 411, 1 March 2015, Pages 5-12

https://doi.org/10.1016/j.jnoncrysol.2014.12.019 Get rights and content

Highlights

•
Glass transition temperature and thermal expansion coefficient are evaluated.
•
Ionic packing factor is calculated from measured density.
•
Variations of the properties with [Al₂O₃]/[CaO] molar ratio are studied.
•
Relationship between the properties and glass structure is discussed.

Abstract

Calcium silicate and aluminosilicate glasses with various SiO₂ contents (10–76 mol%) were prepared in the wide range of [Al₂O₃]/[CaO] molar ratio from 0.10 to 4.00 by conventional melt-quenching method and an aerodynamic levitation device for a part of peraluminus glasses. Variations of glass transition temperature, the coefficient of linear expansion, and ionic packing factor derived from density measurements with [Al₂O₃]/[CaO] molar ratio were studied. The glass structures of SiO₄ three dimensional network, mixed anions of (Si, Al)O₄ tetrahedra, isolated AlO₄ and Al–O–Al linkages were evaluated by FT-IR measurements. Compositional dependences of the properties are qualitatively related to the glass structure examined by IR spectroscopy and the proportions of AlO_x (x = 4, 5, 6) species evaluated in a previous study by using ²⁷Al MQ NMR spectroscopy.

Introduction

Aluminosilicate glasses are of interest for excellent mechanical and thermal properties. Both SiO₂ and Al₂O₃ constituents contribute to the formation of network in the glasses. It is well known that Al^3 + can play different roles and can be in different coordination number, CN = 4, 5 and 6. The CN of Al depends on glass composition [1], [2], [3], [4], [5], temperature condition [4], [6], [7], pressure condition [8], [9], [10], [11], [12] and quenching rate [4], [7]. Therefore, the structural role of Al is essential for determining the properties of aluminosilicate glasses.

The role of Al depends on [Al₂O₃]/[R₂O, R′O] molar ratio where R₂O is the alkali oxide and R′O the alkaline earth oxide in terms of simple stoichiometric considerations. In order to link and share the corner between AlO₄ tetrahedra, charge compensating cations such as R⁺ or R^2 + are needed. When the charge compensating cation exists enough for Al in [Al₂O₃]/[R₂O, R′O] ≤ 1.0, all Al ideally behave as a network former for the formation of AlO₄ tetrahedra. On the other hand, when the cation is insufficient for Al in [Al₂O₃]/[R₂O, R′O] > 1.0, a part of Al may behave as a modifier, e.g., AlO₆ octahedra. Although some exceptions were reported e.g., Ca-aluminosilicate [3], [13] and aluminate glasses [14], at [Al₂O₃]/[R₂O, R′O] = 1.0, it has been ideally thought that the tectrosilicate glasses have fully polymerized network structure of SiO₄ and AlO₄ terahedra without any non-bridging oxygens.

Riebling [15] reported that the viscosity at high temperature of Na₂O–Al₂O₃–SiO₂ melt increased with increasing [Al₂O₃]/[Na₂O] molar ratio in persodic region, exhibited a maximum at [Al₂O₃]/[Na₂O] = 1.0 and then decreased in the peraluminus region. He explained that the decrease of melt viscosity in the peraluminus region is due to the formation of some AlO₆ octahedra based on analogy of the corresponding high-temperature crystalline phase in the Al₂O₃–SiO₂ binary systems. Toplis et al. [16] observed maxima in melt viscosity at the peraluminus region of [Al₂O₃]/[Na₂O] > 1.0 in Na₂O–Al₂O₃–SiO₂ melt with > 50 mol% SiO₂. They explained that the result is due to the existence of a tricluster. In the tricluster, an oxygen atom is shared between three SiO₄ and AlO₄ tetrahedral groups [17], [18]. Le Losq et al. [19] obtained the glass transition temperature T_g and the configuration entropy at T_g from measured viscosity data for Na₂O–Al₂O₃–SiO₂ glasses and melts with 75 mol% SiO₂. They explained their compositional dependences by the connectivity of network relating to the AlO₅ species with threefold coordinated oxygen atoms.

The role of Al on the short- and medium-range structures of aluminosilicate glasses has been analyzed by infrared [20], [21], [22], Raman [3], [23] and NMR [3], [24] spectroscopy. Neuville et al. reported that AlO₅ and AlO₆ species exist in the peraluminus region of [Al₂O₃]/[CaO] > 1.0 [3], [25] and the glass neutrality is maintained by Al coordination number change in CaO–Al₂O₃–SiO₂ (CAS) glasses.

In our previous study the effect of Al₂O₃ addition on thermal properties and structure was studied for percalcic CAS glasses with [Al₂O₃]/[CaO] < 1.0 [26]. In this paper CaO–SiO₂ (CS) binary and CAS ternary glasses with 10–76 mol% SiO₂ were prepared in the wide [Al₂O₃]/[CaO] range from 0.10 to 4.00. The glass transition temperature, the coefficient of linear expansion and density were evaluated for the CS and CAS glasses. The ionic packing factor [27] was derived from density measurements. The network morphologies of SiO₄ tetrahedra, mixed-anion (Si, Al)O₄ and AlO_x species (x = 4, 5, 6) were examined by IR spectra. The proportions of AlO_x evaluated by ²⁷Al MQ-MAS NMR in a previous study [3] were used to understand the variation of AlO_x species as a function of [Al₂O₃]/[CaO] molar ratio (ACMR hereinafter). We provide the first direct comparison among measured Al coordination information, thermal properties and the ionic packing factor.

Section snippets

Experimental

Fig. 1 shows the CS and CAS glass compositions studied in this work. Glass compositions examined in previous studies [21], [28] are also appeared for comparison. Moesgaard et al. [28] evaluated the intermediate-range order heterogeneity for the distribution of SiO₄ unit by using ²⁹Si NMR in the vicinity of eutectic compositions for anorthite–gehlenite–wollastonite and anorthite–wollastonite–tridymite points. A part of our glass series with 45, 50, 55 and 60 mol% SiO₂ has similar compositions of

Properties

Table 1 summarizes the measured values of T_g, α and ρ, and calculated ones of V_m and V_p in 50CaO∙50SiO₂ and CAS glasses with various SiO₂ contents. T_g tends to increase with increasing [Al₂O₃]/[CaO] molar ratio (ACMR) in all CAS glass series (Fig. 2). Moreover, T_g increases slowly for [Al₂O₃]/[CaO] ≥ 1.00. As shown in Fig. 3, α decreases with increasing both ACMR and SiO₂ content in the percalcic region and has almost constant values (4.5–5.0 × 10^− 6/°C) in the peraluminus region. These

Glass structure

For a variety of CAS glass series, differences of peak positions relating to various network components were observed in IR spectra (Figs. 6(a)–(g) and 7). The structure of CAS glasses is evaluated by IR spectra (Fig. 6) and ²⁷Al MQ NMR spectra measured in a previous study [3]. Fig. 8 shows variations of the proportions of AlO_x (x = 4, 5, 6) species as a function of ACMR for CAS glass series with 10, 33 and 50 mol% SiO₂ from the NMR data [3]. Previous NMR studies also showed the presence of

Conclusions

The CaO–SiO₂ (CS) binary and CAS ternary glasses with 10–76 mol% SiO₂ were prepared in the wide range of [Al₂O₃]/[CaO] = 0.10–4.00. The glass transition temperature T_g increases, both the coefficient of linear expansion, α, and the ionic packing factor V_p calculated from measured density decrease due to the contribution of AlO₄ formation in the percalcic region with [Al₂O₃]/[CaO] < 1.00. The result of IR spectroscopy reveals that in the percalcic region Al forms AlO₄ tetrahedra with Al–O–Al linkages

Acknowledgment

This research is partly supported by the New Energy and Industrial Technology Development Organization (NEDO), Innovative Zero-emission Coal Gasification Power Generation Project.

References (46)

C.I. Merzbacher et al.
The structure of alkaline earth aluminosilicate glasses as determined by vibrational spectroscopy
J. Non-Cryst. Solids
(1991)
D.R. Neuville et al.
Al coordination and speciation in calcium aluminosilicate glasses: effects of composition determined by ²⁷Al MQ-MAS NMR and Raman spectroscopy
Chem. Geol.
(2006)
W.J. Malfait et al.
Aluminum coordination in rhyolite and andesite glasses and melts: effect of temperature, pressure, composition and water content
Geochim. Cosmochim. Acta
(2012)
K. Kanehashi et al.
In situ high temperature ²⁷Al NMR study of structure and dynamics in a calcium aluminosilicate glass and melt
J. Non-Cryst. Solids
(2007)
J.F. Stebbins et al.
Temperature effects on non-bridging oxygen and aluminum coordination number in calcium aluminosilicate glasses and melts
Geochim. Cosmochim. Acta
(2008)
S.K. Lee et al.
Disorder and the extent of polymerization in calcium silicate and aluminosilicate glasses: O-17 NMR results and quantum chemical molecular orbital calculations
Geochim. Cosmochim. Acta
(2006)
M. Licheron et al.
Raman and ²⁷Al NMR structure investigations of aluminate glasses: (1 − x)Al₂O₃ − x MO, with M = Ca, Sr, Ba and 0.5 < x < 0.75.
J. Non-Cryst. Solids
(2011)
M.J. Toplis et al.
Peraluminous viscosity maxima in Na₂O–Al₂O₃–SiO₂ liquids: the role of triclusters in tectosilicate melts
Geochim. Cosmochim. Acta
(1997)
M. Schmücker et al.
New evidence for tetrahedral triclusters in aluminosilicate glasses
J. Non-Cryst. Solids
(2002)
C. Le Losq et al.
The role of Al^3 + on rheology and structural changes in sodium silicate and aluminosilicate glasses and melts
Geochim. Cosmochim. Acta
(2014)

M. Okuno et al.

Structure of SiO₂–Al₂O₃ glasses: combined X-ray diffraction, IR and Raman studies

J. Non-Cryst. Solids

(2005)

D.R. Neuville et al.

Al environment in tectosilicate and peraluminous glasses: a ²⁷Al MQ-MAS NMR, Raman, and XANES investigation

Geochim. Cosmochim. Acta

(2004)

A.D. Sontakke et al.

Study on Tb^3 + containing high silica and low silica calcium aluminate glasses: impact of optical basicity

Spectrochim. Acta A Mol. Biomol. Spectrosc.

(2012)

S.-.L. Lin et al.

Structure of CeO₂–Al₂O₃–SiO₂ glasses

J. Non-Cryst. Solids

(1996)

N.J. Clayden et al.

Solid state 27Al NMR and FTIR study of lanthanum aluminosilicate glasses

J. Non-Cryst. Solids

(1999)

J. Hormadaly

Empirical methods for estimating the linear coefficient of expansion of oxide glasses from their composition

J. Non-Cryst. Solids

(1986)

S.K. Lee et al.

The structure of aluminosilicate glasses: high-resolution O-17 and Al-27 MAS and 3QMAS

J. Phys. Chem. B

(2000)

D.R. Neuville et al.

Environments around Al, Si and Ca in aluminate and aluminosilicate melts by X-ray absorption spectroscopy at high temperature

Am. Mineral.

(2008)

E. Ohtani et al.

Al^3 + coordination change in liquid aluminosilicates under pressure

Nature

(1985)

J.L. Yarger et al.

Al coordination changes in high-pressure aluminosilicate liquid

Science

(1995)

S.K. Lee

Structure of silicate glasses and melts at high pressure: quantum chemical calculations and solid-state NMR

J. Phys. Chem. B

(2004)

J.R. Allwardt et al.

Al coordination and density of high-pressure aluminosilicate glasses

Am. Mineral.

(2005)

J.R. Allwardt et al.

The effect of fictive temperature on Al-coordination in high-pressure (10 GPa) Na aluminosilicate glasses

Am. Mineral.

(2005)

Cited by (88)

Synergistic effect of inorganic salt and AlN removal in the secondary aluminum dross during the roasting process
2023, Journal of Alloys and Compounds
This study investigated the synergistic transformations and interaction effects of inorganic salts with high-content (HS-SAD) and low-content (LS-SAD) and AlN in secondary aluminum dross (SAD) during the roasting process. The results demonstrated that the presence of inorganic salts significantly enhanced the oxidation of AlN in SAD. The removal efficiency of AlN in HS-SAD reached 95.8 % at 800 °C for 120 min, whereas in LS-SAD, it was 69.47 % at 1000 °C. The oxidation of AlN leads to the formation of a 25–45 nm alumina film, which hinders the further progression of the oxidation process. The presence of SO₂ and SiO₂ facilitated the low-temperature volatilization of inorganic salts, thereby limiting the formation of the alumina film. The partial melting of inorganic salts and the reaction of NaF with the alumina film, resulting in the formation of Na₂O, destroyed the dense alumina film, exposing AlN. Following roasting at 800 °C and 1000 °C, the hazardous components in both HS-SAD and LS-SAD were effectively eliminated, and 92.93 % of the inorganic salts in HS-SAD were successfully recovered. Roasting at a mixing ratio of 1:1 at 900 °C for 120 min resulted in an 86.97 % removal efficiency of AlN. These findings offer valuable insights into the removal of AlN in SAD and the comprehensive utilization of SAD residue.
Effect of Al<inf>2</inf>O<inf>3</inf>/SiO<inf>2</inf> mass ratio on the structure and properties of medical neutral boroaluminosilicate glass based on XPS and infrared analysis
2023, Ceramics International
A new medical neutral boroaluminosilicate glass with thermal and chemical stabilities conforming to international standards has been successfully prepared by the traditional melt cooling method. Based on X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectroscopy (FTIR) characterizations, the relationship between the structure and physical and chemical properties of the glass was discussed. The increase of Al₂O₃ introduction led to the continuous increase of the octahedral proportion of [AlO₆], and weakened the degree of glass network connection, which resulted in the increase of thermal expansion coefficient of the glass and the decrease of chemical stability. B³⁺ ions and Al³⁺ ions have a competition for free oxygen and basic metal ions, which caused obvious boron-aluminum anomaly. The research has certain guiding significance for the performance standard of medical glass materials and the control of industrial development cost.
Quantitative studies on the microstructure of ternary CaO–Al<inf>2</inf>O<inf>3</inf>–SiO<inf>2</inf> glasses by Raman spectroscopy, <sup>27</sup>Al MAS NMR and quantum chemistry ab initio calculation
2023, Ceramics International
To investigate the structural behaviors of Al³⁺ in aluminosilicate systems, the microstructural characteristics of CaO–SiO₂-based glassy samples with various Al₂O₃ contents were examined quantitatively by Raman spectroscopy and ²⁷Al MAS NMR. A sequence of multiple model clusters of aluminosilicate systems modified with Ca²⁺ and Na ⁺ cations was designed. Then quantum chemistry (QC) ab initio calculations were performed for geometric optimization, and Raman spectral simulations were carried out. The functional relationship between the Raman scattering cross section (RSCS) and stress index of silicon-oxygen tetrahedron (SIT) for aluminosilicates was established, which was successfully applied to calibrate experimental Raman spectra. Some fivefold coordinated aluminum (Al^Ⅴ, approximately 5%) and less than 2% sixfold coordinated aluminum (Al^Ⅵ) were detected by ²⁷Al MAS NMR, while most aluminum remained in tetrahedral sites (Al^Ⅳ). The ever-finer quantitative results of Raman spectroscopy and NMR showed a gradual production of Al^Ⅳ with the addition of Al₂O₃, along with a significant adjustment in Q_i species distribution. Specifically, Q₁, Q₂ decreased, fully polymerized Q₄ increased and Q₃ showed a nonmonotonic variation and obtained the maximum at Al₂O₃ = 12 mol%. Furthermore, the effects of aluminum on bridging oxygen bond types (T-O_b, T = Si, Al) and the degree of polymerization were discussed in detail. These structural features related to composition are essential theoretic foundations for understanding the properties of these systems.
Elevating thermal and chemical properties of aluminoborosilicate medical neutral glass via adjusting CaO, BaO and ZnO
2023, Ceramics International
For sake of enhancing dependability and broadening application of medical packing glass, this work is designed to develop a new-type aluminoborosilicate neutral glass and optimize its main performances by adjusting CaO, BaO and ZnO amounts. Based on X-ray photoelectron spectroscopy, infrared spectroscopy, nuclear magnetic resonance and performances analysis, the different effects of BaO, CaO and ZnO were interpreted. The partial replacing BaO with CaO facilitated formation of [AlO₄] and thermal stability, while entirely substitution of CaO impaired the Si group network connectivity and chemical stability. The ZnO was testified as a weak network former which reversely hindered [BO₄] and [AlO₄] formations, and boosted the water resistance specifically. In summary, a series of neutral glasses fulfilled requirements for medical packing material was prepared, and improved thermal and chemical properties were obtained whilst BaO/CaO mixed ratio reached about 0.8; the ZnO bearing glasses showed higher water resistance but faintly weaker thermal and partial chemical performances.
Review paper on thermal expansion and tribological behavior of composite materials
2023, Materials Today: Proceedings
Composite materials are cutting-edge materials with uncontrollable opportunities for modern development and material research. The designer will get help from these materials to accomplish objectives and desired conceptions. The reinforcement of metals serves as a tool to satisfy the various objectives of different metals. The use of light metals for reinforcement opens up a world of possibilities for weight reduction. Traditional materials become motivating for usage as constructional and functional materials if their property contours either do not satisfy the higher standards of explicit expectations or are the solution to the difficulty.
Traditional materials, on the other hand, become motivating for usage as constructional and functional materials if their property contours either do not reach the growing standard of explicit expectations or are the solution to the problem. The appreciating knowledge of composite materials, on the other hand, competes with other contemporary material technologies. Researchers and scientists are now interested in and active in breakthroughs relevant to metal matrix composite materials. A large number of scientists and researchers have conducted considerable research.
Light alloys are attractive as a basic matrix, according to literature, due to affordability, availability, and recycling. As basic matrixes, aluminium, copper, magnesium, iron metals, and titanium including their alloys, are commonly employed. The choice of a certain base matrix is influenced by the industrial uses of composites. Other alloys can be employed, but only for a limited number of applications.
Phase transition during nucleation process in calcium aluminate glass-ceramics manufactured from secondary aluminum dross
2022, Journal of Alloys and Compounds
Secondary aluminum dross is a solid waste discharged during aluminum processing and melting. Calcium aluminate glass-ceramics was manufactured from secondary aluminum dross without adding nucleating agent. Phase transition of glass-ceramics was studied. Nucleation temperature was set at 846 ℃ according to differential scanning calorimetry and X-ray diffraction results. Field-emission transmission electron microscopy was applied to observe microstructure of the thermally treated parent glass. During nucleation process, omphacite grew from glass network. Omphacite growth consisted of two steps: migration of silicon group and cation; growth of omphacite. After parent glass was thermally treated at 846 ℃ for 3 h, silicon group and cation migrated and formed silicon enrichment field. A little of omphacite crystal formed in silicon enrichment field. When thermal treatment time was increased to 12 h, more independent omphacite crystals grew in silicon enrichment field. The independent omphacite crystals grew larger and contacted with each other to form a large omphacite crystal. The large omphacite crystal became nucleus of glass-ceramics. Omphacite nucleation had two effects on crystallization of glass-ceramics. First, omphacite crystal became nucleus, which provided surface for growing crystals. Second, omphacite growth consumed silicon group in glass network, which decreased polymerization degree of glass network and promoted crystallization. In calcium aluminate glass-ceramics with silicon, omphacite crystal could act as the nucleus without additional nucleation agents.

View all citing articles on Scopus

View full text

Thermal properties, density and structure of percalcic and peraluminus CaO–Al2O3–SiO2 glasses

Highlights

Abstract

Introduction

Section snippets

Experimental

Properties

Glass structure

Conclusions

Acknowledgment

J. Non-Cryst. Solids

Chem. Geol.

Geochim. Cosmochim. Acta

J. Non-Cryst. Solids

Geochim. Cosmochim. Acta

Geochim. Cosmochim. Acta

J. Non-Cryst. Solids

Geochim. Cosmochim. Acta

J. Non-Cryst. Solids

Geochim. Cosmochim. Acta

J. Non-Cryst. Solids

Geochim. Cosmochim. Acta

Spectrochim. Acta A Mol. Biomol. Spectrosc.

J. Non-Cryst. Solids

J. Non-Cryst. Solids

J. Non-Cryst. Solids

The structure of aluminosilicate glasses: high-resolution O-17 and Al-27 MAS and 3QMAS

J. Phys. Chem. B

Environments around Al, Si and Ca in aluminate and aluminosilicate melts by X-ray absorption spectroscopy at high temperature

Am. Mineral.

Al3 + coordination change in liquid aluminosilicates under pressure

Nature

Al coordination changes in high-pressure aluminosilicate liquid

Science

Structure of silicate glasses and melts at high pressure: quantum chemical calculations and solid-state NMR

J. Phys. Chem. B

Al coordination and density of high-pressure aluminosilicate glasses

Am. Mineral.

The effect of fictive temperature on Al-coordination in high-pressure (10 GPa) Na aluminosilicate glasses

Am. Mineral.

Thermal properties, density and structure of percalcic and peraluminus CaO–Al₂O₃–SiO₂ glasses

Al^3 + coordination change in liquid aluminosilicates under pressure