The effect of fluoride ions on the structure and crystallization kinetics of La2O3-containing diopside based oxyfluoride glasses

Oxyfluoride glasses in the system CaO–MgO–BaO–SiO₂–Al₂O₃–La₂O₃–CaF₂ were obtained by adding CaF₂ (3–8 wt%) to a parent diopside based glass composition, Ca_0.8Ba_0.1MgAl_0.1La_0.1Si_1.9O₆. The characterization of the glasses has been made by density, dilatometry and FTIR measurements. Non-isothermal crystallization kinetic studies in conjunction with XRD and SEM have been employed in order to investigate the effects of fluoride ion additions on crystallization behaviour and mechanism of glasses.     

Glass transition and crystallization of ZnO-B2O3-SiO2 glass doped with Y2O3

The effect of Y₂O₃ on the glass transition kinetics, crystallization kinetics, phase separation and crystallization behavior of 60ZnO–30B₂O₃–10SiO₂ glass has been investigated by non-isothermal differential thermal analysis, scanning electron microscopy (SEM) and X-ray powder diffraction (XRD). The glass transition activation energies E_g calculated by using both Kissinger and Moynihan model decrease from 668?kJ/mol to 573?kJ/mol for Kissinger model, and 682?kJ/mol to 587?kJ/mol for Moynihan model with the increase of yttrium oxide doping content from 0 to 6?mol%. And the glass crystallization kinetics parameters, crystallization activation energy E_c and Avrami exponent n stands for crystal growth, are also obtained on the basis of several well developed equations. Increase of about 58?kJ/mol in Ec values obtained by different theoretical equations is caused by addition of 6?mol% yttrium oxide into 60ZnO–30B₂O₃–10SiO₂ glass, and the Avrami exponent (n close to 2) suggests that crystal growth in 60ZnO–30B₂O₃–10SiO₂ glass doped with or without yttrium is mainly one-dimensional growth of crystals. The results on the phase separation and crystallization behavior occurred at 893?K and 993?K respectively for base and doped glass, are well consistent with the glass transition and crystallization kinetics results. Hence, addition of yttrium oxide into 60ZnO–30B₂O₃–10SiO₂ glass decrease the glass transition activation energy while increase the crystallization activation energy of glass, thereby the stability of glass structure is improved. Phase separation phenomenon and crystallization behavior occurred at glass surface provide some useful information for preparing glass ceramics with micro- or nano-crystals in surface.     

Synthesis and properties of lithium disilicate glass-ceramics in the system SiO2–Al2O3–K2O–Li2O

The purpose of this study was the synthesis of lithium disilicate glass-ceramics in the system SiO₂–Al₂O₃–K₂O–Li₂O. A total of 8 compositions from three series were prepared. The starting glass compositions 1 and 2 were selected in the leucite–lithium disilicate system with leucite/lithium disilicate weight ratio of 50/50 and 25/75, respectively. Then, production of lithium disilicate glass-ceramics was attempted via solid-state reaction between Li₂SiO₃ (which was the main crystalline phase in compositions 1 and 2) and SiO₂. In the second series of compositions, silica was added to fine glass powders of the compositions 1 and 2 (in weight ratio of 20/100 and 30/100) resulting in the modified compositions 1–20, 1–30, 2–20, and 2–30. In the third series of compositions, excess of silica, in the amount of 30 wt.% and 20 wt.% with respect to the parent compositions 1 and 2, was introduced directly into the glass batch. Specimens, sintered at 800 °C, 850 °C and 900 °C, were tested for density (Archimedes’ method), Vickers hardness (H_V), flexural strength (3-point bending tests), and chemical durability. Field emission scanning electron microscopy and X-ray diffraction were employed for crystalline phase analysis of the glass-ceramics. Lithium disilicate precipitated as dominant crystalline phase in the crystallized modified compositions containing colloidal silica as well as in the glass-ceramics 3 and 4 after sintering at 850 °C and 900 °C. Self-glazed effect was observed in the glass-ceramics with compositions 3 and 4, whose 3-point bending strength and microhardness values were 165.3 (25.6) MPa and 201.4 (14.0) MPa, 5.27 (0.48) GPa and 5.34 (0.40) GPa, respectively.     

Pressureless sintering and mechanical properties of SiO2–Al2O3–MgO–K2O–TiO2–F (CaO–Na2O) machinable glass–ceramics

To develop a high strength machinable glass–ceramic through pressureless sintering, the glassy compositions were obtained by mixing a mica-based frit and a frit in the SiO₂–CaO–Na₂O system. According to XRD results, the glass compositions mainly crystallized into phlogopite and diopside after sintering. The optimum sintered glass–ceramic with desirable mechanical properties, machinability and sinterability was achieved by addition of 30 wt.% SiO₂–CaO–Na₂O glass powder to 70 wt.% mica glass composition. SEM results confirmed presence of needle-like diopside crystals which played a reinforcement role to the platelet phlogopite and glassy matrix combination. The measurements showed bending strength and fracture toughness enhanced up to 144.6 ± 17.6 MPa and 1.7 ± 0.2 MPa m^1/2, respectively.     

Structural, thermal and crystallization kinetics of ZnO–BaO–SiO2–B2O3–Mn2O3 based glass sealants for solid oxide fuel cells

Glass compositions in the system 40SiO₂–30BaO–20ZnO–(x)Mn₂O₃–(10 − x)B₂O₃ glasses have been synthesized and the thermal, structural and crystallization kinetic properties characterized. The lower concentration of Mn₂O₃ in place of B₂O₃ acts as a network former and suppressed the tendency of phase separation in glasses. On the other hand, concentration of Mn₂O₃ > 7.5 mol% induce phase separation in the glass matrix. The highest activation energy for crystallization is observed in the composition without B₂O₃ (INM4) (355 kJ/mol). The values of thermal expansion coefficient (TEC) and viscosity of this glass is 8 × 10⁻⁶ K⁻¹ and 10^4.2dPa s (850 °C), respectively. After long heat treatment (800 °C for 100 h), thermodynamically stable hexacelsian and monoclinic phases are formed. These phases are not detrimental to SOFC application.     

Nanocomposite Fe2O3–SiO2 inclusion pigments from post-functionalized mesoporous silicas

High-surface mesoporous silicas with different pore sizes were employed for the first time as silicon precursors in the synthesis of reddish Fe₂O₃–SiO₂ inclusion pigments. Interestingly, the size of included Fe₂O₃ nanoparticles was partially controlled through confinement effects into silica mesopores. Notably, impregnated samples showed a more homogeneous and efficient encapsulation of smaller and monodisperse hematite nanoparticles (sizes around 10–35 nm). Moreover, they resulted in an improved reddish color at 1000 °C within a ceramic glaze. The best red shade (a* ≈ 18) was associated to nanocomposite with smaller hematite nanoparticles (around 5 nm). These promising results suggest the possibility to improve the reddish coloration and thermostability of Fe₂O₃–SiO₂ ceramic pigments through and adequate control of confinement effects into sintered mesoporous silicas.     

Phase relations and electrical properties in the pseudo-ternary La2O3–TiO2–Mn2O3 system in air

Scanning electron microscopy (SEM), electron-probe microanalysis, energy- and wavelength-dispersive X-ray analysis and X-ray powder diffraction were used to investigate the subsolidus phase relations in the pseudo-ternary La₂O₃–TiO₂–Mn₂O₃ system in air (oxygen partial pressure p_O2=0.21   atm) at 1275 °C. The addition of Mn₂O₃ to the starting La₂O₃:3TiO₂ mixture led to the formation of a La-deficient perovskite La_2/3TiO₃ compound. The oxides form two new compounds with the proposed compositions: (i) La_1.7Ti_13.0Mn_6.3O_38−x, with a davidite-like crystal structure, and (ii) La₄₉Ti₁₈Mn₁₃O₁₂₉. There were also several solid solutions existing over a wide range of concentrations.     

Abrasive wear of Al2O3–SiC and Al2O3–(SiC)–C composites with micrometer- and submicrometer-sized alumina matrix grains

The response of Al₂O₃, Al₂O₃–SiC–(C) and Al₂O₃–C nanocomposites to grinding was investigated in terms of changes of quality of ground surfaces and of the weight losses with time. The study used monolithic polycrystalline aluminas as references, and alumina-based composites with nanosized SiC and C inclusions and with alumina matrix grain size varying from submicrometer to approximately 4 μm. The studied materials can be roughly divided into two groups. Materials with submicrometer alumina matrix grains (Group 1) wear predominantly by plastic deformation and grooving. Coarse-grained materials (Group 2) wear by mixed wear mechanism involving crack initiation and interlinking accompanied by grain pull-out, plastic deformation and grooving. The wear rate of composites increases with increasing volume fraction of SiC. The Group 2 materials wear much faster then those with submicron microstructure. In all cases (with one exception) the wear resistance of composites was higher than that of pure aluminas of comparable grain sizes used as reference materials.     

Synthesis and properties of a zeolite LEV analogue from the system—Na2O–Al2O3–SiO2–N,N-dimethylpiperidine chloride–H2O

A new structure-directing agent (SDA) was firstly reported for the synthesis of a zeolite LEV analogue. N,N-dimethyl piperidine performed the SDA function, and induced the synthesis of products from a zeolite MOR with 12-ring channels to a zeolite LEV analogue with only 8-ring channels. The zeolite LEV analogue was synthesized from gels with initial compositions (5.0–6.0)Na₂O–Al₂O₃–(10–200)SiO₂–(4.0–8.0)N,N-dimethyl piperidine–400H₂O at 150 °C. The ²⁹Si NMR spectra showed that the relative intensities of the first line at −115 ppm for low Si/Al ratios were lower than that at high Si/Al ratios. Varying ion exchanges led to different acidities in the zeolite LEV analogue, with the acidity of H-LEV-HCl higher than that of H-LEV-NH₃·H₂O. Zeolite H-LEV in hydration of propene showed a higher selectivity of 1-propanol.     

Dielectric properties and microstructures of CaSiO3 ceramics with B2O3 addition

The effects of B₂O₃ additives on the sintering behavior, microstructure and dielectric properties of CaSiO₃ ceramics have been investigated. The B₂O₃ addition resulted in the emergence of CaO–B₂O₃–SiO₂ glass phase, which was advantageous to lower the synthesis temperature of CaSiO₃ crystal phase, and could effectively lower the densification temperature of CaSiO₃ ceramic to as low as 1100 °C. The 6 wt% B₂O₃-doped CaSiO₃ ceramic sintered at 1100 °C possessed good dielectric properties: _r = 6.84 and tan δ = 6.9 × 10⁻⁴ (1 MHz).     

Effect of SO2 on the catalytic activity of Ga2O3–Al2O3 for the selective reduction of NO with propene in the presence of oxygen

The effect of coexisting SO₂ on the catalytic activity of Ga₂O₃–Al₂O₃ prepared by impregnation, coprecipitation and sol–gel method for NO reduction by propene in the presence of oxygen was studied. Although the activity of Al₂O₃ and Ga₂O₃–Al₂O₃ prepared by impregnation (Ga₂O₃/Al₂O₃(I)) and coprecipitation (Ga₂O₃–Al₂O₃(CP)) was depressed considerably by the presence of SO₂, NO conversion on Ga₂O₃–Al₂O₃ prepared by sol–gel method (Ga₂O₃–Al₂O₃(S)) was not decreased but increased slightly by SO₂ at temperatures below 723 K. From catalyst characterization, SO₂ treatment was found to cause two important effects on the surface properties: one is the creation of Brønsted acid sites on which propene activation is promoted (positive effect), and the other is the poisoning of NO_x adsorption sites on which NO reduction proceeds (negative effect). It was presumed that the influence of SO₂ treatment on the catalytic activity is strongly related to the balance between the negative and positive. The activity enhancement of Ga₂O₃–Al₂O₃(S) by SO₂ was accounted for by the following consideration: (1) increase of the propene activation ability by SO₂, (2) incomplete inhibition of NO_x adsorption sites by SO₂.     

Effects of alumina on the crystallization behavior, densification and dielectric properties of BaO–ZnO–SrO–CaO–Nd2O3–TiO2–B2O3–SiO2 glass–ceramics

The alumina addition effects on the crystallization, sintering behaviors and dielectric properties of BaO–ZnO–SrO–CaO–Nd₂O₃–TiO₂–B₂O₃–SiO₂ (Ba–Zn–Sr–Ca–Nd–Ti–B–Si) glass powder were investigated using the differential thermal analyzer (DTA), thermo-mechanical analyzer (TMA), X-ray diffractometer (XRD). The results showed that the addition of alumina powder into Ba–Zn–Sr–Ca–Nd–Ti–B–Si glass changed the crystallization sequence from Nd₂Ti₄O₁₁–Nd_0.66TiO₃ to Nd₂Ti₃O_8.7–Nd₂Ti₂O₇–Nd₂Ti₄O₁₁and increased the densification activation energy due to the dissolution of Al³⁺ ions into the glass structure. Fully densified 30 vol.% alumina-added Ba–Zn–Sr–Ca–Nd–Ti–B–Si glass can be obtained via glass viscous flow before the second and third crystalline phases, Nd₂Ti₂O₇ and Nd₂Ti₄O₁₁crystallization. The 30 vol.% alumina-added Ba–Zn–Sr–Ca–Nd–Ti–B–Si glass–ceramics sintered at 900 °C exhibited a high dielectric constant of 17 and a quality factor of about 820, which provided a promising candidate for LTCC applications.     

Microstructural characterization and crystallization of (1 − x)TeO2–xCdF2 (x = 0.10, 0.15, 0.25 mol) glasses

The differential thermal analysis (DTA), X-ray diffractometer and scanning electron microscopy/energy dispersive spectrometer (SEM/EDS) techniques were used to investigate the microstructural characterization and the thermal behavior of the three (1 − x)TeO₂–xCdF₂ (x = 0.10, 0.15, 0.25 mol) glasses. The effect of the heating rate, annealing temperature and CdF₂ content on the thermal and the microstructural properties of TeO₂–CdF₂ binary glasses were enquired. DTA analysis has shown that as the CdF₂ content in the glass composition increases, the value of the glass transition and the peak crystallization temperatures shift to higher values. SEM/EDS investigations have shown that the crystal formation of α-TeO₂, γ-TeO₂ and CdTe₂O₅ crystal phases were observed when the 0.90TeO₂–0.10CdF₂ and the 0.85TeO₂–0.15CdF₂ glass samples were annealed to temperatures above the crystallization temperatures. X-ray diffraction (XRD) results illustrated clearly the transformation of the metastable γ-TeO₂ phase to stable α-TeO₂ crystalline phase as the annealing temperature was increased from 385 to 425 °C for the 0.75TeO₂–0.25CdF₂ glass.     

Formation of GdAlO3–Al2O3 composite having fine pseudo-eutectic microstructure

GdAlO₃ and Al₂O₃ powders were mixed and pulverized using ball mills. The prepared powder was sintered by SPS at 1450 °C without holding time. SEM observation of the sintered specimen showed a eutectic-like microstructure. This is called ‘pseudo-eutectic’ in this research. The microstructure formed from a powder pulverized by a tumbling ball mill for one week was much finer than that by a planetary ball mill for 5 and 10 h. The fine homogeneous eutectic-like (pseudo-eutectic) microstructures could be formed at both eutectic and off-eutectic compositions. In case of crystallization from a melt of eutectic components, homogeneous eutectic microstructures can be formed only at restricted compositions very close to the eutectic one. Coarse primary crystals generally exist in the eutectic microstructure at off-eutectic compositions. The pseudo-eutectic microstructures can be formed at any compositions because a mixing ratio of the starting powders can be varied.     

Thermodynamic evaluation of the Al2O3–H2O binary system at pressures up to 30 MPa

The behaviour of the hydrated phases in the Al₂O₃–H₂O system is of major importance in the chemistry of ceramic materials. In this work, stability and metastability relations in the Al₂O₃–H₂O system have been studied. Gibbs free energy functions of the gibbsite and boehmite phases have been critically revised and new optimized functions have been calculated. The functions obtained have been used to predict the stability and metastability relations by calculating a P–T diagram following the CALPHAD methodology. Comparison with the corresponding available experimental data is discussed.     

Low-temperature sintering and microwave dielectric properties of 3Z2B glass–Al2O3 composites

A potential low temperature co-fired ceramics system based on zinc borate 3ZnO–2B₂O₃ (3Z2B) glass matrix and Al₂O₃ filler was investigated with regard to phase development and microwave dielectric properties as functions of the glass content and sintering temperature. The densification mechanism for 3Z2B–Al₂O₃ composites was reported. The linear shrinkage of 3Z2B glass–Al₂O₃ composites exhibited a typical one-stage densification behavior. XRD patterns showed that a new crystalline phase, ZnAl₂O₄ spinel, formed during densification, indicating that certain chemical reaction took place between the 3Z2B glass matrix and the alumina filler. Meanwhile, several zinc borate phases, including 4ZnO·3B₂O₃, crystallized from the glass matrix. Both of the reaction product phase and crystallization phases played an important role in improving the microwave dielectric properties of composites. The optimal composition sintered at 850–950 °C showed excellent microwave dielectric properties: ?_r = ∼5.0, Q·f₀ = ∼8000 GHz, and τ_f = ∼−32 ppm/°C at ∼7.0 GHz.     

Low-temperature firing and microwave dielectric properties of 16CaO–9Li2O–12Sm2O3–63TiO2 ceramics with V2O5 addition

The sintering behaviors and microwave dielectric properties of the 16CaO–9Li₂O–12Sm₂O₃–63TiO₂ (abbreviated CLST) ceramics with different amounts of V₂O₅ addition had been investigated in this paper. The sintering temperature of the CLST ceramic had been efficiently decreased by nearly 100 °C. No secondary phase was observed in the CLST ceramics and complete solid solution of the complex perovskite phase was confirmed. The CLST ceramics with small amounts of V₂O₅ addition could be well sintered at 1200 °C for 3 h without much degradation in the microwave dielectric properties. Especially, the 0.75 wt.% V₂O₅-doped ceramics sintered at 1200 °C for 3 h have optimum microwave dielectric properties of Kr = 100.4, Q × f = 5600 GHz, and TCF = 7 ppm/°C. Obviously, V₂O₅ could be a suitable sintering aid that improves densification and microwave dielectric properties of the CLST ceramics.     

Mechanism of the carbonitriding reactions of SiO2–Al2O3 minerals in the Si–Al–O–N system

Ceramics of the Si–Al–O–N system and SiC have a great technological interest because of their good thermomechanical properties at high temperatures. It is possible to obtain phases such as β-SiC, Si₃N₄, β′-sialons, O′-sialons, polytype sialons, AlN, Al₂O₃ or mixtures of these phases by means of carbonitriding reactions starting from minerals such as quartz, diatomite and other aluminosilicate minerals. The knowledge of the mechanism of these reactions permits to establish the necessary conditions to achieve the desired phases in the final product. The mechanisms of the carbonitriding reactions of several minerals with increasing aluminium content are studied. Their compositions are from diatomite up to mullite. Reactions of the mineral carbon mixture were carried out at 1300–1650°C in N₂ atmosphere. The phases formed were identified by X-ray diffraction in qualitative and, in some cases, in quantitative form. Intermediate compounds such as β-SiC, X-phase, mullite, glassy phases and gaseous silicon oxide were observed. The formation and importance of these phases depend on the mineral composition as well as on the reaction conditions (temperature, time, etc.). β-SiC, the main intermediate phase, may remain in the final products and may be the major phase depending on the temperature and the carbon content used. The final products of these reactions are phases of the Si–Al–O–N system. The phases obtained were characterized by EPMA, SEM and BET techniques.     

Phase transitional behavior and piezoelectric properties of BiYbO3–Pb(Ti0.5Zr0.5)O3–LiNbO3 ceramics

Perovskite (1 − x)(0.06BiYbO₃–0.94Pb(Ti_0.5Zr_0.5)O₃)–xLiNbO₃ (BYPTZ-LN) ceramics were synthesized by the conventional ceramic processing. The effect of LiNbO₃ on the microstructure and piezoelectric properties was investigated. The perovskite phase and the Yb₂Ti₂O₇ pyrochlore phase are coexisting in the BYPTZ-LN ceramics sintered at 1140 °C. The material with perovskite structure is tetragonal at x ≤ 0.04 and becomes single rhombohedral at x ≥ 0.08. A morphotropic phase boundary between rhombohedral and tetragonal phases is found in the composition range 0.04 ≤ x ≤ 0.08. Analogous to Pb(Zr,Ti)O₃, the piezoelectric and electromechanical properties are enhanced for compositions near the morphotropic phase boundary. Piezoelectric constant d₃₃values reach 290–360 pC/N. Electromechanical coefficients k_p reach 0.38–0.55. The maximum values of d₃₃, k_p and P_r are obstained as x = 0.08, accompanying with the minimum values of Q_m and E_c. The Curie temperature T_c and the maximum value of dielectric constant decrease with increasing LiNbO₃ content. BYPTZ-LN ceramics with the high d₃₃ value and the high thermal-depoling temperatures of >320 °C are obtained.     

Synergetic effect of combined use of Cu–ZnO–Al2O3 and Pt–Al2O3 for the steam reforming of methanol

Commercial Cu–ZnO–Al₂O₃ catalysts are used widely for steam reforming of methanol. However, the reforming reactions should be modified to avoid fuel cell catalyst poisoning originated from carbon monoxide. The modification was implemented by mixing the Cu–ZnO–Al₂O₃ catalyst with Pt–Al₂O₃ catalyst. The Pt–Al₂O₃ and Cu–ZnO–Al₂O₃ catalyst mixture created a synergetic effect because the methanol decomposition and the water–gas shift reactions occurred simultaneously over nearby Pt–Al₂O₃ and Cu–ZnO–Al₂O₃ catalysts in the mixture. A methanol conversion of 96.4% was obtained and carbon monoxide was not detected from the reforming reaction when the Pt–Al₂O₃ and Cu–ZnO–Al₂O₃ catalyst mixture was used.