Crystallization process and some properties of novel transparent machinable calcium-mica glass-ceramics

Bulk glass having a calcium-mica composition (Ca_0.5Mg₃AlSi₃O₁₀F₂) is homogeneous glass. The crystallization mechanism of the mica is surface crystallization and transparency is lost completely when crystallization occurs on the surface. In this study, by decreasing SiO₂ and increasing CaO and Al₂O₃ from the chemical composition of Ca_0.5Mg₃AlSi₃O₁₀F₂, and moreover by replacing a small amount of K₂O instead of CaO, the phase separation appears in the glasses. Because of this phase separation, the mica begins to be crystallized not only on the surface but also in the bulk at lower temperatures. Consequently, the novel transparent machinable mica glass-ceramic can be obtained by heating the glasses having the chemical composition of Ca_0.6Mg₃Al_1.2Si_2.8O₁₀F₂ and K_0.01Ca_0.595Mg₃Al_1.2Si_2.8O₁₀F₂. As a larger amount of calcium-mica is separated, the bending strength decreases and the fracture toughness increases. Furthermore, by replacing K⁺ ion instead of Ca²⁺ ion in the interlayer of calcium-mica, the interlayer bonding strength becomes high, resulting in the increase of the bending strength.     

Synthesis and characterization of clinopyroxene based glasses and glass-ceramics along diopside (CaMgSi2O6)-jadeite (NaAlSi2O6) join

The crystallization behavior and mechanical characterization of glasses based upon the compositions along diopside (CaMgSi₂O₆)-jadeite (NaAlSi₂O₆) join has been investigated. Six glasses were obtained by the melt-quenching technique. Structural and thermal behaviors of these glasses were investigated by density and molar volume, infrared spectroscopy (FTIR) and dilatometry. The crystallization behavior of glasses was investigated by using differential scanning calorimetry (DSC). Sintering and crystallization behavior of the glass-ceramics were investigated under non-isothermal heating conditions up to temperatures of 850 °C. Mechanical characterization of glasses was investigated by using the measurement of Vickers indentation hardness and elastic constants such as Young's modulus (E), shear modulus (G), bulk modulus (K) and Poisson's ratio (ν). These data of the glasses were correlated with the structure of glasses, nature and role played by glass forming cations.     

Effects of nitrogen and fluorine on crystallisation of Ca-Si-Al-O-N-F glasses

The effect of nitrogen and fluorine substitution on the crystallisation of a new generation of oxyfluoronitride glasses in the Ca-Si-Al-O-N-F system has been studied. Glasses were nucleated for 5 h at the nucleation temperature of Tg + 50 °C and crystallised for 10 h at the maximum crystallisation temperature (900-1050 °C depending on the glass composition) determined from differential thermal analysis. For the oxide glass, crystallisation results in formation of wollastonite (CaSiO₃), gehlenite (Ca₂Al₂SiO₇) and anorthite (CaAl₂Si₂O₈) along with a small amount of residual glass. For crystallisation of oxyfluoride glasses (0 equiv.% N), when fluorine content increases, cuspidine (Ca₄Si₂O₇F₂) is the major crystalline phase at the expense of gehlenite while in oxyfluoronitride glasses containing 20 equiv.% N, gehlenite is always the dominant crystalline phase at different fluorine contents. At constant fluorine content (5 equiv.%), an increase in nitrogen content favours the formation of gehlenite rather than anorthite or wollastonite suggesting that this phase may be able to accommodate N into its crystal structure. While a small amount of nitrogen substitution for oxygen can be assumed in the gehlenite structure, the residual glass in the glass-ceramic is expected to be very N-rich. In terms of properties, hardness is shown to be more sensitive to changes in microstructure, phase morphology and crystal size compared with elastic modulus which is related to the amounts of constituent phases present.     

Combination of Brazilian test and digital image correlation for mechanical characterization of refractory materials

Flexibility of refractories is an interesting property to improve thermal shock resistance of refractories. It can often be obtained by promoting a nonlinear mechanical behaviour which reduces brittleness. Among industrial refractory materials developed in this aim, magnesia hercynite is of a particular interest for cement industry. As linings for rotary kilns, magnesia hercynite can be submitted to tensile and compressive stresses. Since tensile strength is usually much lower than compressive one for brittle materials, the mechanical characterization is, in such case, more significant in tension than in compression. To overcome difficulties involved by direct tensile test, an indirect tensile test (Brazilian test) has been applied here and combined to digital image correlation in order to measure kinematic fields on the surface of the sample during loading. This combination has allowed to accurately measure initial elastic properties (Young’s modulus and Poisson ratio), to detect crack initiation and to analyze fracture process.     

Effects of Al2O3 addition on microstructure and luminescence of transparent germanosilicate glass-ceramics with incorporated spinel Ga-oxide nanocrystals

Ga-oxide spinel nanocrystals are wide band gap systems, which can be incorporated in a glass matrix by phase separation mechanisms. In suitable conditions, this kind of processes can give rise to transparent nanostructured glass-ceramics with UV excitation and luminescence properties potentially interesting in several technological areas. Nanophase size dispersion and volume fraction have been demonstrated to be controllable, at some extent, by suitable thermal treatments for nucleation and nano-crystallization in low-alkali gallium germanosilicate system. Here we report the results on the role of Al₂O₃ additions on the microstructure and optical response of the glass-ceramics fabricated in this system. Data of differential scanning calorimetry, X-ray diffraction, transmission electron microscopy, absorption and fluorescence spectroscopy show that Al₂O₃ addition, up to 4.5 mol%, turns out to have a considerable impact on the size and number density of precipitated nanocrystals, which are solid solutions of γ-Ga_2-xAl_xO₃ resulting from the partial incorporation of Al³⁺ ions into the crystalline phase. We show that the use of Al₂O₃ as an additive in the composition of gallium germanosilicates facilitates glass melting and leads to glass-ceramics with significantly modified photoluminescence characteristics such as decay lifetime and integrated intensity of light emission. The possible reasons are discussed.     

Preparation of machinable bioactive mica diopside-fluoroapatite glass-ceramics

Abstract

A fluorphlogopite based glass powder was added to a bioactive glass-ceramic in the system CaO-MgO-P₂O₅ (Fe₂O₃)-SiO₂ in order to improve its machinability. The sinterability of compacted mixtures, their crystallisation behaviour during sintering and their mechanical properties were evaluated and compared with the extreme ends compounds. According to results, fluoroapatite crystallised as a new phase only in the mixtures of the two glasses, its constituents originated by counter diffusion of two glasses components. Fracture toughness and microhardness of the best sample were higher than twice of the fluorphlogopite glass-ceramic composition. The machinability of samples was evaluated by naked eye observation and determination of brittleness factor.     

PMMA composite bone cement containing bioactive and ferrimagnetic glass-ceramic particles: Effect of temperature and of the additional phase on some physical and mechanical properties

In this work, PMMA-based composite bone cements, embedding bioactive and ferrimagnetic glass-ceramic particles, have been prepared and characterized. Bioactivity, wettability, density, curing parameters, viscoelastic behaviour, bending strengths and creep have been investigated at 37 °C. The growth of a layer of HA on the samples surface after immersion in SBF has been confirmed. The presence of glass-ceramic particles improved the wetting behaviour of the composite cements. Shorter curing times and lower maximum temperatures for the three composite cements, in comparison to the plain one, have been detected. Almost unaffected mechanical properties of the composite bone cements have been found in comparison to those of the plain commercial cement both at room and at 37 °C. A little increase of the viscous flow has been evidenced in the composite samples at 37 °C. Radiographic imaging confirmed the intrinsic radiopacity of the composite cements.     

Calcium aluminate cement source evaluation for Al2O3-MgO refractory castables

Alumina-magnesia refractory castables are commonly bonded with calcium aluminate cements. At temperatures above 1200 °C, these materials present an expansive behavior due to the in situ spinel (MgAl₂O₄) formation and the CA₂ and CA₆ ones. One alternative to control the volumetric stability is by replacing the typical cements used (30 wt.% CaO) for another containing less lime (20 wt.% CaO). Nevertheless, when changing the cement sources, the castable's properties would be affected. Among them, the most relevant are the green mechanical strength, the drying behavior, the properties at intermediate and high temperatures, the expansion behavior, the hot modulus of rupture and creep. Considering these aspects, the objective of this work was to evaluate the impact of different cement sources in the processing steps and properties of alumina-magnesia castables. The results pointed out specific behaviors for each cement source during the whole processing stages, highlighting the importance of its proper selection in order to attain the required properties in working conditions.     

Growth behavior,morphology and properties of lithium aluminosilicate glass ceramics with different amount of CaO,MgO and TiO2 additive

Li₂O–Al₂O₃–SiO₂ glass with CaO, MgO and TiO₂ additive were investigated. With more CaO + MgO addition, the crystallization temperature (T_p) and the value of Avrami constant (n) decreased, the activation energy (E) increased. The mechanism of crystallization of the glass ceramics changed from bulk crystallization to surface crystallization. With more TiO₂ addition, the crystallization temperature decreased, E and n had a little change. The crystallization of the glass ceramics changed from surface crystallization to two-dimensional crystallization. Plate-like, high mechanical properties spodumene-diopside glass ceramics were obtained. The mechanical properties related with crystallization and morphology of glass ceramics.     

Effect of sintering temperature on mechanical properties of magnesia partially stabilized zirconia refractory

The optimized sintering conditions for a 3.5 wt% magnesia partially stabilized zirconia (Mg-PSZ) refractory were proposed in our recent research. The influence of the sintering temperature on the development of phase composition, microstructure, densification, thermal expansion and mechanical strength was studied in detail by X-ray diffraction (XRD), scanning electron microscope (SEM), He-pycnometer, high temperature dilatometry and three-point bending test. The samples sintered at 1670 °C had the highest bend strength, the maximum densification, the lowest thermal expansion coefficient (CTE), a homogeneous microstructure and a linear change in thermal expansion.     

Suppressing the effect of cullet composition on the formation and properties of foamed glass

The process of foaming glass is very dependent on the chemical composition of the glass. In this study we used a foaming-agent/oxidizing-agent couple and a crystallization inhibitor to foam cullets of flat, container and CRT-panel glass. Foamed glass with a density of 110–120?kg?m^–3, a thermal conductivity of 50–52?mW?m^–1 K^–1 and a homogeneous pore structure was obtained from a mixture of panel glass, 0.33?wt% carbon and 4.45?wt% Fe₂O₃. We also showed that it is possible to fabricate foamed glass with the same density or pore structure as mentioned above by adding up to 50?wt% container cullet or 70?wt% flat glass to the mixture. In the foamed samples with a low content of panel glass, crystals form, resulting in an increased open porosity, density and inhomogeneous pore structure. The crystallization can, however, be inhibited by adding calcium phosphate, so enabling the preparation of high-quality foamed glass from flat glass or flat/container-glass mixture. The pore gas is predominantly CO₂ and the pressure inside the pores is 0.36–0.47?bar. The reduced effect of the composition on the foaming process suggests that there is a great potential for stabilizing the production of foamed glass and ensuring the product's quality.     

Effect of A2O3 (A = La,Y, Cr,Al) on thermal and crystallization kinetics of borosilicate glass sealants for solid oxide fuel cells

Influence of various intermediate oxides on thermal, structural and crystallization kinetics of 30BaO–40SiO₂–20B₂O₃–10A₂O₃ (A = Y, La, Al, Cr) glasses has been studied. The highest glass transition temperature (T_g) with high thermal stability is observed in Y₂O₃ containing glasses as compared to other glasses. The thermal expansion coefficient (TEC) increases with increasing heat treatment duration in all the glasses. The maximum increase in TEC is observed in Cr₂O₃ containing glass ceramics. FTIR study showed that transmission bands due to silicate and borate chains become sharper with splitting after heat treatment. A selected glass sample (BaCr) has been tested for interaction and adhesion with Crofer 22 APU interconnect material for its application as a sealant in solid oxide fuel cell.     

Effect of substitution of ZrO2 by SnO2 on crystallization and properties of environment-friendly Li2O–Al2O3–SiO2 system (LAS) glass-ceramics

In this study, a transparent and environmentally friendly Li₂O–Al₂O₃–SiO₂ (LAS) glass-ceramic was prepared by melt-quenching and two-step heat treatment. The influence of the substitution amount of ZrO₂ by SnO₂ on the crystallization, microstructure, transparency, and mechanical properties of LAS glass and glass-ceramics was investigated by means of differential scanning calorimetry (DSC), X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Ultraviolet–visible Spectrophotometer, three-point bending strength test, and microhardness test. The results indicate that the main crystalline phase of LAS glass ceramics was a β-quartz solid solution when heat treated at 780 °C for 2 h and 870 °C for 1.5 h. When the substitution amount of ZrO₂–SnO₂ increased from 0.4 mol% to 2.5 mol%, the grain size and thermal expansion coefficient of LAS glass-ceramics first decreased and then increased, and the crystallinity first increased and then decreased. When the substitution amount of ZrO₂–SnO₂ was 0.8 mol%, the transparency of the LAS glass-ceramics was maximum, the bending strength was 96 MPa, and the Vickers hardness was 10.9 GPa.     

Thermal expansion and heat capacities of holmium and erbium orthotantalates ceramics

Monoclinic M-orthotantalates of holmium and erbium ceramics were obtained by co-precipitation and annealing at 1773 K and characterized by X-ray powder diffraction, scanning electron microscopy, and chemical analysis. Using the high-temperature X-ray diffraction method, the temperature dependence of the monoclinic lattice parameters of both ceramics were determined at range 298-1273 K. The molar heat capacity of M-HoTaO₄ and M-ErTaO₄ were measured by adiabatic (7-350 K) and differential scanning (320-1350 K) calorimetry. Standard thermodynamic function (entropy, enthalpy change, and reduced Gibbs energy) were calculated on the smoothed values of molar capacity, without taking into account contribution of low-temperature interval: 0-7 K for M-HoTaO₄ and 0-8 K for M-ErTaO₄. The general shape of the anomalous Schottky contribution to the molar heat capacity was determined.     

Influence of brick pattern interface structure on mechanical properties of continuous carbon fiber reinforced lithium aluminosilicate glass-ceramics matrix composites

Continuous carbon fiber reinforced lithium aluminosilicate glass-ceramic matrix composites have been fabricated by sol-gel process and hot pressing technique. The results show that the Cf/β-eucryptite composites hot pressed at 1300 °C and Cf/β-spodumene composites hot pressed at 1400 °C form weak interface with brick pattern characteristics, leading to high mechanical performance. The maximum flexural strength and fracture toughness reach 571 ± 32 MPa and 9.8 ± 0.6 MPa m^1/2 for Cf/β-eucryptite composites and 640 ± 72 MPa and 19.9 ± 1.8 MPa m^1/2 for Cf/β-spodumene composites. On increasing the hot pressing temperature, the active chemical diffusion consumes brick pattern interface layer, which leads to the formation of strong bonding between carbon fiber and the matrix. As a result, the composites exhibit brittle fracture behavior and the mechanical properties decrease significantly.     

Synthesis and thermal properties of inorganic polymers (geopolymers) for structural and refractory applications from volcanic ash

The volcanic ash occurring as an abundant and readily accessible natural resource in the Central African country of Cameroon was used to synthesize aluminosilicate geopolymers using sodium hydroxide as the sole alkaline activator. Both the curing conditions and the Na₂O/SiO₂ molar ratio were found to influence the development of compressive strength of the geopolymer cement paste, which achieved a maximum strength of 55 MPa at Na₂O/SiO₂ = 0.3. The formation of a mortar by the addition of 40 wt% sand to the optimized geopolymer cement composition reduced the compressive strength to 30 MPa, still within the useful range for construction applications. The geopolymers consist largely of X-ray amorphous material with a small content of crystalline phases. Scanning electron microscopy showed a homogenously distributed mixture of lath-shaped and agglomerated morphologies, with a homogeneous distribution of Si, Al and O in the geopolymer matrix. The geopolymers are relatively stable to heat, shrinking only slowly and retaining about 60% of their as synthesized compressive strength on heating to 900 °C. The FTIR spectra of both the as synthesized and heated geopolymers show two broad absorbance bands, between 820-1250 cm⁻¹ and 450-730 cm⁻¹ assigned to the internal vibrations of Si-O-Si, and Si-O-Al respectively. The compressive strengths and the thermal stability of these materials suggest their suitability for building applications and low-grade refractories.     

Improvement on the phase stability,mechanical properties and thermal insulation of Y2O3-stabilized ZrO2 by Gd2O3 and Yb2O3 co-doping

Gd₂O₃ and Yb₂O₃ co-doped 3.5 mol% Y₂O₃–ZrO₂ and conventional 3.5 mol% Y₂O₃–ZrO₂ (YSZ) powders were synthesized by solid state reaction. The objective of this study was to improve the phase stability, mechanical properties and thermal insulation of YSZ. After heat treatment at 1500 °C for 10 h, 1 mol% Gd₂O₃–1 mol% Yb₂O₃ co-doped YSZ (1Gd1Yb-YSZ) had higher resistance to destabilization of metastable tetragonal phase than YSZ. The hardness of 5 mol% Gd₂O₃–1 mol% Yb₂O₃ co-doped YSZ (5Gd1Yb-YSZ) was higher than that of YSZ. Compared with YSZ, 1Gd1Yb-YSZ and 5Gd1Yb-YSZ exhibited lower thermal conductivity and shorter phonon mean free path. At 1300 °C, the thermal conductivity of 5Gd1Yb-YSZ was 1.23 W/m K, nearly 25% lower than that of YSZ (1.62 W/m K). Gd₂O₃ and Yb₂O₃ co-doped YSZ can be explored as a candidate material for thermal barrier coating applications.     

Factors controlling the mechanical behavior of alumina–magnesia–carbon refractories in air

This work analyzes the mechanical behavior of alumina-magnesia-carbon (AMC) refractories in air up to 1260 °C. AMC refractory bricks are used on sidewalls and bottoms working linings of steel-making ladles. In plant, AMC bricks are exposed to air atmosphere during the periods of time when the ladle is empty, such as preheating. Stress–strain relationships were determined in compression, and the following parameters were calculated from these curves: strength, apparent Young's modulus, fracture strain and yield strength. Young's modulus at room temperature was also determined by the impulse excitation technique. To identify the main determining factors, the tested specimens were analyzed by apparent porosity measurements, X-ray diffraction and scanning electron microscopy coupled with X-ray dispersive energy. Thermodynamic simulations of the AMC refractories were also performed using FactSage software, so as to understand the mineralogical changes that occur in the refractories as temperature increases.     

Influence of rare earth additives and boron component on electrical conductivity of sodium rare earth borate glasses

Sodium rare earth borate glasses (Na₂O)_35.7(RE₂O₃)_7.2(B₂O₃)_57.1 (RE = Sm, Gd, Dy, Ho, Y, Er, and Yb), were prepared from a mixture of Na₂CO₃, RE₂O₃ and B₂O₃, and their properties as an Na⁺ ionic conductor were investigated. Density increased with increasing atomic weight of RE. Crystallization temperature and crystal melting temperature of the present borate system was lower than that of the previously reported silicate and germanate system. Results of the ¹¹B NMR measurement suggested that half of all boron atoms are coordinated by four oxide ions to give a [BO₄] tetrahedral unit and the others are coordinated by three oxide ions to give a [BO₃] planar triangular unit. The electrical conductivity slightly decreased with increasing the ionic radius of RE³⁺. (Na₂O)_35.7(Y₂O₃)_7.2(B₂O₃)_57.1 glass exhibited the electrical conductivity which is about one order of magnitude lower than those of the previously reported (Na₂O)_35.7(Y₂O₃)_7.2(SiO₂)_57.1 and (Na₂O)_35.7(Y₂O₃)_7.2(GeO₂)_57.1 glasses. It was assumed that this lower electrical conductivity is due to the lower content of Na⁺ ions as conduction species in the former glass, compared with the latter two glasses.     

Thermal and tensile properties of polysialate composites

Polysialate, or geopolymer, composites have gained interest due to their inherent high temperature resistance, low density and ease of manufacturing. These characteristics also suggest that polysialate composites have significant potential as materials in high temperature structures, although little is known about their thermal and mechanical properties. This study aimed to determine relevant thermal and mechanical properties over a representative temperature range. The results show that polysialate composites can exhibit stable thermal properties up to 1000 °C. Tensile properties up to 760 °C highlight a significant reduction in stiffness, but a retention of strength, at these temperatures. The thermal and mechanical results achieved provide strong evidence that polysialate composites can be suitable for use in high temperature structures, whilst subsequently providing an understanding of their limitations. In addition to this, the values ascertained also provide the data required for the design and modelling of next generation high temperature structures.