Phase evolution and microstructure analysis of CaZrTi2O7 zirconolite in glass

The internal crystallization of CaZrTi₂O₇ zirconolite in a sodium alumino-borosilicate glass has been investigated with powder X-ray diffraction (XRD), scanning electron microscopy and energy dispersion spectroscopy (SEM-EDS), transmission electron microscopy (TEM) and selected area electron diffraction (SAED) techniques. The samples have been prepared using a soft chemistry route and ceramic phase evolution has been observed with sintering time. Zirconolite as the dominant phase at 1 h sintering gradually changes to baddeleyite structured materials for longer sintering times. XRD shows that one dominant phase belongs to zirconolite at 3 h sintering, however, SEM-EDS reveals that the dominant ceramic phase is actually baddeleyite phase, which is enclosed by zirconolite phase. TEM and SAED patterns also confirm the crystallization of zirconolite phase in glass. The addition of CaO enhances the formation of zirconolite (i.e. impedes baddeleyite phase) with CaO to glass weight ratio ≤ 35:100.     

Novel method to synthesis of single phase zirconolite ceramic

Single phase zirconolite (CaZrTi₂O₇) was synthesised by a novel method using acid corrosion to treat zirconolite–diopside mixture powders (2CaZrTi₂O₇–Mg2Si₂O₆). The mixture powders were prepared by solid state reaction method at 1200°C for 2 h. Single phase zirconolite powders were obtained by acid corrosion method with 5% hydrofluoric acid on the zirconolite–diopside Synroc mixture powders and washed with 10% acetic acid.     

Phase and structural evolution of zirconolite ceramics prepared by solid-state reaction sintering

The evolution of phase assemblage and microstructure of stoichiometric zirconolite (CaZrTi₂O₇) ceramics, prepared by a solid-state reaction sintering route, was systematically investigated as a function of sintering temperature. Using powder XRD and quantitative phase analysis data, it was determined that the formation of zirconolite was a one-step reaction, without formation of intermediate phases. The accompanying fractions of secondary CaTiO₃ and ZrO₂ phases were reduced to approximately 2 wt % each after sintering at 1200 °C, with zirconolite formed as the major phase (> 99 wt%) after reaction at 1300 °C. Notable product densification only occurred at T ≥ 1400 °C, at which it was possible to achieve a relative density of 96.97% which is highly desirable for applications as a nuclear wasteform. The zirconolite-2M polytype structure (space group: C2/c) was formed in all products as expected, confirmed by combined high resolution TEM-ED analyses.     

X-Ray Diffraction Analysis of Phase Formation in Synthesis of Actinide Matrices

The products of synthesis of crystalline matrices promising for immobilization of actinides were studied by the method of x-ray phase analysis. The experiments were performed on compositions corresponding to the phase stoichiometry of structural types of zirconolite (CaZrTi₂O₇) and pyrochlore (CaCeTi₂O₇, Gd₂Ti₂O₇, Gd₂Zr₂O₇). The experiments were carried out within a temperature range of 800 – 1600°C for a sintering time of 5 – 50 h, in air and in an oxygen temperature. The phase formation conditions in matrices of different compositions are identified. Practical recommendations are issued.     

The effects of temperature and Ce-dopant concentration on the synthesis of zirconolite glass-ceramic

Zirconolite based glass-ceramic has been deemed as a promising waste form for high-level waste (HLW). In this study, the zirconolite (nominally CaZrTi₂O₇) glass-ceramic based on a SiO₂-B₂O₃-Na₂O-CaO-ZrO₂-TiO₂-Al₂O₃ system was sought to be synthesized by two-step thermal treatment. The temperature effects such as nucleation temperature and cooling rate were studied. The influence of the Ce-dopant concentration on crystallization behavior was also investigated. For characterization, powder X-ray diffraction (XRD), thermogravimetry-differential scanning calorimeter (TG-DSC) and scanning electron microscopy (SEM) were applied. Our results illustrate that homogeneous zirconolite with the particle size of 1.8?μm can be the target phase when the glass matrix underwent a rapid cooling process and the nucleation temperature was controlled at around 860?°C. Besides, the results also indicate that the distribution of the zirconolite along with its lattice parameters change regularly as the increase of CeO₂ concentration. A larger crystal size of zirconolite phase and some trace amounts of precipitated phases are observed when the CeO₂ concentration exceed 3?wt%. This work emphasizes the synthesis of zirconolite glass-ceramic in a SiO₂-B₂O₃-Na₂O-CaO-ZrO₂-TiO₂-Al₂O₃ system, which is expected to provide basic technical data for underground disposal of HLW.     

Preparation of glass–ceramic glazes for fast firing applications by CaF2 substitution with B2O3 in the CaO–CaF2–Al2O3–SiO2 system

The present work aims to obtain glass–ceramic glazes for floor tile applications. In this regard, CaF₂ was gradually replaced by B₂O₃ in the glass compositions belonging to the CaO–CaF₂–Al₂O₃–SiO₂ system. This substitution led to a noticeable decrease of crystallization peak temperatures and to an alteration of the crystallization trend. In the B₂O₃ bearing glazes, anorthite and gehlenite were identified as the major and minor crystalline phases, respectively. During concurrent crystallization and sintering based on the fast firing program, glass–ceramic glazes containing 9 weight parts of fluorine and 12 weight parts of boron oxide showed the most desirable sinterability. The optimized glass–ceramic glazes offered acceptable micro-hardness, whiteness and thermal expansion behavior after fast firing heat treatment.     

Investigation on low-temperature reactive viscous flow sintering behavior of lanthanum-borate glass-ceramic with BaTi4O9 ceramic filler

In this paper, the sintering behavior of the lanthanum-borate (B₂O₃-La₂O₃-MgO-TiO₂,BLMT) glass-ceramic with BaTi₄O₉ filler composite was investigated in terms of the wetting behavior, interfacial reaction, sinter-shrinkage process, sintering activation energy, as well as phase and microstructure evolution with change in filler contents and sintering temperature. Our research suggested that the glass is unable to wet the filler material within a temperature up to 1000 °C, indicating that the densification process of composites is dominated by viscous flow of glass matrix. The increase in filler content that performs as a rigid particle in composite causes the rise in the sinter-shrinkage-onset and -end temperature, thereby proving that the viscous-flow densification of the composites with x≤ 30 wt% filler content is accomplished before the crystallization of BLMT glass, whereas the composites with x≥ 40 wt% cannot. After densification, a chemical reaction that almost synchronizes with the glass crystallization occurred between glass and ceramic, which not only imposes significant influence on the crystallization behavior, but eradicates the closed pore formed by the viscous flow and the induced crystallization porosity. The densification process of the BaTi₄O₉ filler-BLMT glass composite was referred to as two-stage reactive assisted viscous flow sintering process which consists of viscous flow of glass, of the crystallization process of glass, and/or of the chemical reaction between glass and filler.     

Different microstructure BaO–B2O3–SiO2 glass/ceramic composites depending on high-temperature wetting affinity

In this work, we propose a simple but effective method to fabricate BaO–B₂O₃–SiO₂ glass/ceramic composites with different microstructures that depend on the high-temperature wetting affinity. The experimental results showed that the wetting affinity between oxide ceramic and the BaO–B₂O₃–SiO₂ glass matrix could strongly affect the driving force of densification and crystallization and finally the microstructure of the glass/ceramic composites. It was found that suitable amounts of alumina powders could obviously increase the driving force for sintering of glass by increasing the capillary pressure. In this case, the contact angle between alumina and glass matrix is about 24° at high temperature and a densified and homogeneous microstructure of glass/alumina composite was obtained. On the contrary, rutile powders additive was found to result in higher phase separation and crystallization during the sintering of glass/rutile composites. In this case, the contact angle between rutile and glass matrix is about 124° at high temperature, and the sintered body has a lower dielectric loss than the sample with alumina additive. Therefore, the microstructure and dielectric property of glass/ceramic composites could be controlled by adjusting the ceramic composition and wetting affinity between ceramic additive and glass matrix in our study.     

Phase evolution and microstructural studies in CaZrTi2O7 (zirconolite)–Sm2Ti2O7 (pyrochlore) system

From the characterization of a series compositions with general stoichiometry as Ca_1−xZr_1−xSm_2xTi₂O₇ (0.00 ≤ x ≤ 1.00), the phase evolution between zirconolite (CaZrTi₂O₇) and pyrochlore type Sm₂Ti₂O₇ has been elucidated. All the compositions were prepared by high temperature solid state reaction and characterized by powder X-ray diffraction (XRD) and electron probe for microanalyses (EPMA). Three major phase fields, namely two layer (2-M) or four layer (4-M) monoclinic zirconolite and cubic pyrochlore structure types were observed in this system. In addition, a feeble amount of perovskite type phase is found to coexist with zirconolite phase. 4-M zirconolite phase is observed as single phase field at the composition with x = 0.30 and 0.35, while cubic pyrochlore phase is observed as single phase at the compositions with x ≥ 0.60. Further, the composition and microstructure of coexisting phases are verified by back scattered electron image and EPMA studies.     

SHS/QP Synthesis and Characterization of Ce‐Bearing Zirconolite‐Rich Waste Forms Using MoO3 as the Oxidant

In this study, zirconolite (CaZrTi₂O₇)/Mo composite was rapidly synthesized by self‐propagating high‐temperature plus quick pressing (SHS/QP) technique using MoO₃ as the oxidant. As the surrogate of tetravalent actinide nuclides, up to 50 at.% CeO₂ (about 17.5 wt% of the raw material) was introduced to substitute the Zr site of zirconolite. Perovskite (CaTiO₃) and rutile TiO₂ were inevitably produced after the incorporation of CeO₂. The raw CeO₂ was partially reduced to trivalent state, which promotes the substitution of Ce into the Ca sites of perovskite and zirconolite. The aqueous durability of Ce‐bearing waste form was investigated with normalized leaching rates (42 d) of Ce in moderate value of about 10^?2 g m^?2 d^?1.     

Sintering of sodium conducting glass ceramics in the Na2O-Y2O3-SiO2-system

A solid electrolyte is a core component for the development of low temperature sodium batteries with metallic Na-anode. The Na₅YSi₄O₁₂ (N5) composition in the Na₂O-Y₂O₃-SiO₂ system shows a high ionic conductivity comparable to NASICON or β-Al₂O₃. Up to date glass ceramic solid electrolytes of this type have been mainly prepared by crystallization of monolithic, molten glass components. We show that this material can be processed via the glass-ceramic powder route starting with a glass powder. A glass with a composition according to the stoichiometry of the Na₅YSi₄O₁₂-phase and tailored by addition of P₂O₅ allows the separation of sintering and crystallization of the glass powder resulting in dense microstructure. Thermophysical properties and phase content have been correlated with ionic conductivity. The densification and crystallization are completed at temperatures below 1100 °C. Grain conductivities up to 0,18 mS cm^?1 at room temperature in sintered glass ceramic microstructures are demonstrated.     

Pyrochlore glass-ceramics fabricated via both sintering and hot isostatic pressing for minor actinide immobilization

Pyrochlore glass-ceramics (GCs) have been investigated with samples fabricated via both sintering and hot isostatic pressing (HIPing) of a mixed oxide precursor. It has been demonstrated that sintering at 1200°C in air is necessary to obtain well-crystallized pyrochlore crystals in a sodium aluminoborosilicate glass through a one-step controlled cooling. The crystallization, structure, and microstructure of Eu₂Ti₂O₇ pyrochlore as the major phases in residual glass were confirmed with X-ray diffraction (XRD), scanning electron microscopy-energy dispersive spectroscopy, transmission electron microscopy, and Raman spectroscopy. The structures of major Eu₂Ti₂O₇ pyrochlore and minor [Eu_4.67O(SiO₄)₃] apatite in both sintered and HIPed samples were refined using synchrotron XRD data. While the processing atmosphere did not appear to affect the cell parameter of the main pyrochlore phase, very small volume expansion (~0.3%) was observed for the minor apatite phase in the HIPed sample. In addition, static leaching of the HIPed sample confirmed that pyrochlore GCs are chemically durable. Overall, pyrochlore GCs prepared via both sintering and HIPing with the Eu partitioning factor of ~23 between ceramics and the residual glass are suitable waste forms for minor actinides with processing chemicals.     

Influence of Al2O3 and B2O3 on Sintering and Crystallization of Lithium Silicate Glass System

This article reports on the effect of Al₂O₃ and B₂O₃ added as dopants on the preparation of glass‐ceramics (GCs) belonging to the lithium silicate glass system. The GCs are prepared by sintering route using glass powders. The reasons for the crystallization of the metastable crystalline phase lithium metasilicate (LS) are discussed and the impact of the dopants on the thermodynamics and kinetics of crystallization is investigated. The addition of dopants modifies the thermodynamic equilibrium of the system and this change is mainly entropy driven and also slowdown the kinetics of crystallization. Differential thermal analysis and hot‐stage microscopy are employed to investigate the glass‐forming ability, sintering, and crystallization behavior of the studied glasses. The crystalline phase assemblage studied under nonisothermal heating conditions in the temperature range of 800°C–900°C in air. Well sintered and dense glass‐ceramics are obtained after sintering of glass powders at 850°C–900°C for 1 h featuring crystalline phase assemblage dominated by lithium disilicate (LS₂).     

Phase Evolution of SiO2–Al2O3–ZnO–CaO–ZrO2–TiO2‐Based Glass with Added Y‐PSZ Particles

Yttria partially stabilized zirconia Y‐PSZ/glass‐ceramic composites were prepared by reaction sintering using powder mixtures of a SiO₂–Al₂O₃–ZnO–CaO–ZrO₂–TiO₂‐based glass and yttria partially stabilized zirconia (Y‐PSZ). The glass crystallized during sintering at temperatures of 1173, 1273, and 1373 K to give a glass‐ceramic matrix for high‐temperature protecting coatings. With the increasing firing time, the added zirconia reacted with the base glass and a glass‐ceramic material with dispersed zircon particles was prepared in situ. Furthermore, the added zirconia changed the crystallization behavior of the base glass, affecting the shape, amount, and distribution of zircon in the microstructure. The bipyramid‐like zircon grains with imbedded residual zirconia particles turned out to have two growth mechanisms: the inward growth and the outward growth, and its rapid growth was mainly dominated by the later one. For comparison, the referenced glass‐ceramic was prepared by sintering using exclusive glass granules and its crystallization behavior at 1173–1373 K was examined as well. Scanning electron microscopy (SEM), energy dispersive X‐ray spectroscopy (EDS), transmission electron microscopy (TEM), and X‐ray diffraction (XRD) were used to characterize the crystallization behavior of the base glass and the phase evolution of the Y‐PSZ/glass‐ceramic composites.     

Preparation of surface-crystallized optical glass-ceramics SrO · 2B<Subscript>2</Subscript>O<Subscript>3</Subscript>

The physicochemical features of the phase formation upon crystallization of monolithic glasses of the strontium diborate stoichiometric composition are investigated. It is demonstrated that the first phase crystallizing on the surface of the SrO · 2B₂O₃ glass is the strontium borate Sr₄B₁₄O₂₅, which plays the role of a precursor for the subsequent crystallization of the SrB₄O₇ borate. The temperature corresponding to the maximum crystal nucleation rate on the surface and the time of complete “operation” of nuclei are determined using differential thermal analysis. The optical glass-ceramics prepared by the two-stage crystallization are surface-crystallized glasses in which the filling density of the surface is approximately equal to 30% and the content of the main phase SrB₄O₇ is as high as ∼ 70%. No second harmonic generation of neodymium laser radiation in the glass-ceramics is observed because of both the absence of the preferred orientation of SrB₄O₇ nonlinear optical crystals and the small crystal sizes (considerably smaller than the coherence length of the SrB₄O₇ crystal) in the direction perpendicular to the glass surface.     

Glass–ceramics and composites containing aluminum borate whiskers

Glass–ceramics and composites containing aluminum borate whisker crystals were developed using two different approaches: crystallization of an aluminum borosilicate glass or addition of an aluminum borate precursor powder to a glass frit. Two different glass frits were used, a commercially available borosilicate glass or the same aluminum borosilicate glass used in the crystallization experiments. X-ray diffraction analysis showed that Al₄B₂O₉ or Al₁₈B₄O₃₃ whiskers formed in all samples, indicating that the glass crystallized significantly with increasing heating temperature, and that the precursor can be effectively be used to generate in situ aluminum borate crystals within glass matrices. However, the samples produced by mixing the aluminum precursor with glass frits contained porosity after processing, indicating that pressureless viscous sintering was not efficient. The hardness of the glass–ceramic did not vary significantly with processing temperature, but the (indentation) fracture toughness measured showed a >100% increase (after heating at 1200 °C), demonstrating that whisker-shaped crystals are effective in increasing the mechanical toughness of the glass matrix. The hardness of the composites showed a dependence on the amount of aluminum borate crystals present.     

Low temperature sintering and characterization of La2O3-B2O3-CaO glass-ceramic/LaBO3 composites for LTCC application

An interesting attempt to develop low temperature sintering glass-ceramic/ceramic composite based on La₂O₃-B₂O₃-CaO (LBC) glass-ceramic and LaBO₃ ceramic, which was reported to be the main crystalline phase precipitated from La₂O₃-B₂O₃-based glass-ceramics, has been taken. The sintering behavior, phase evolution, microstructures and dielectric properties of LBC/LaBO₃ composites have been studied. The densification of LBC/LaBO₃ composite is achieved by partially reactive sintering. The LaBO₃ filler is directly involved in the sintering process of glass/ceramic composite as additional liquid phase provider at high sintering temperature, and it will suppress the formation of other crystalline phases so that the produced LBC/LaBO₃ composites exhibit unusual simple phase structures, which is beneficial to regulate the performance of composites. LBC/LaBO₃ composite with 50 wt% LaBO₃ sintered at 950 ºC for 2 h has a dielectric constant ε_r = 10.12, a dielectric loss tanδ = 1.82 × 10^―3, a Q × f = 9312 GHz (at 16.95 GHz), and shows good chemical compatibility while co-firing with Ag electrode. This indicates that LBC glass/LaBO₃ ceramic composites have a potential to meet the requirements of microwave LTCC applications.     

Effect of MgO addition on the crystallization and in vitro bioactivity of glass ceramics in the CaO–MgO–SiO2–P2O5 system

CaO–MgO–SiO₂–P₂O₅ glass ceramics were successfully prepared by sintering the sol–gel-derived powders. The effects of MgO addition on the samples crystallization and structure were investigated by means of differential thermal analysis (DTA), X-ray diffraction (XRD) and scanning electron microscopy (SEM). In addition, samples degradation and in vitro bioactivity assays were also evaluated. With more MgO addition, the glass ceramics crystallization kinetics under non-isothermal conditions changed from bulk crystallization to surface crystallization, and new crystal phases of Ca₂MgSi₂O₇ and SiO₂ were induced. In addition, it is observed that with increasing MgO concentration, the glass ceramics degradability gradually decreased and the formation of apatite was delayed.     

A Novel Glass‐Ceramic with Ultra‐Low Sintering Temperature for LTCC Application

In this paper, the phase compositions and the dielectric properties of 3ZnO–2B₂O₃ glass‐ceramic prepared by solid‐state method were investigated. The X‐ray diffraction patterns show that all sintered samples consist of Zn₃B₂O₆ and α‐Zn(BO₂)₂. The dielectric properties changed significantly with the sintering temperature. After sintering at 650°C for 30 min, the glass‐ceramic exhibits optimum dielectric properties: a dielectric constant of 7.5 and a dielectric loss of 0.6 × 10^?3 at 10 MHz. The chemical compatibility with Ag electrode under the co‐fired process illustrates a potential application in low temperature co‐fired ceramic field for the glass‐ceramic.     

Sealing Glass‐Ceramics with Near Linear Thermal Strain,Part I: Process Development and Phase Identification

A widely adopted approach to form matched seals in metals having high coefficient of thermal expansion (CTE), e.g. stainless steel, is the use of high CTE glass‐ceramics. With the nucleation and growth of Cristobalite as the main high‐expansion crystalline phase, the CTE of recrystallizable lithium silicate Li₂O–SiO₂–Al₂O₃–K₂O–B₂O₃–P₂O₅–ZnO glass‐ceramic can approach 18 ppm/°C, matching closely to the 18 ppm/°C–20 ppm/°C CTE of 304L stainless steel. However, a large volume change induced by the α‐β inversion between the low‐ and high‐ Cristobalite, a 1^st order displacive phase transition, results in a nonlinear step‐like change in the thermal strain of glass‐ceramics. The sudden change in the thermal strain causes a substantial transient mismatch between the glass‐ceramic and stainless steel. In this study, we developed new thermal profiles based on the SiO₂ phase diagram to crystallize both Quartz and Cristobalite as high expansion crystalline phases in the glass‐ceramics. A key step in the thermal profile is the rapid cooling of glass‐ceramic from the peak sealing temperature to suppress crystallization of Cristobalite. The rapid cooling of the glass‐ceramic to an initial lower hold temperature is conducive to Quartz crystallization. After Quartz formation, a subsequent crystallization of Cristobalite is performed at a higher hold temperature. Quantitative X‐ray diffraction analysis of a series of quenched glass‐ceramic samples clearly revealed the sequence of crystallization in the new thermal profile. The coexistence of two significantly reduced volume changes, one at ~220°C from Cristobalite inversion and the other at ~470°C from Quartz inversion, greatly improves the linearity of the thermal strains of the glass‐ceramics, and is expected to improve the thermal strain match between glass‐ceramics and stainless steel over the sealing cycle.