Effects of ZnO,FeO and Fe_(2)O_(3)on the spinel formation,microstructure and physicochemical properties of augite-based glass ceramics

Augite-based glass ceramics were synthesised using ZnO,FeO,and Fe_(2)O_(3)as additives,and the spinel formation,matrix structure,crystallisation thermodynamics,and physicochemical properties were investigated.The results showed that oxides resulted in numerous preliminary spinels in the glass matrix.FeO,ZnO,and Fe_(2)O_(3)influenced the formation of spinel,while FeO simplified the glass network.FeO and ZnO promoted bulk crystallisation of the parent glass.After adding oxides,the grains of augite phase were refined,and the relative quantities of augite crystal planes were also influenced.All samples displayed good mechanical properties and chemical stability.The 2wt%ZnO-doping sample displayed the maximum flexural strength(170.3 MPa).Chromium leaching amount values of all the samples were less than the national standard(1.5 mg/L),confirming the safety of the materials.In conclusion,an appropriate amount of zinc-containing raw material is beneficial for the preparation of augite-based glass ceramics.

Crystallization characteristics of iron-rich glass ceramics prepared from nickel slag and blast furnace slag

The crystallization process of iron-rich glass-ceramics prepared from the mixture of nickel slag（NS） and blast furnace slag（BFS） with a small amount of quartz sand was investigated.A modified melting method which was more energy-saving than the traditional methods was used to control the crystallization process.The results show that the iron-rich system has much lower melting temperature,glass transition temperature（Tg）,and glass crystallization temperature（Tc）,which can result in a further energy-saving process.The results also show that the system has a quick but controllable crystallization process with its peak crystallization temperature at 918°C.The crystallization of augite crystals begins from the edge of the sample and invades into the whole sample.The crystallization process can be completed in a few minutes.A distinct boundary between the crystallized part and the non-crystallized part exists during the process.In the non-crystallized part showing a black colour,some sphere-shaped augite crystals already exist in the glass matrix before samples are heated to Tc.In the crystallized part showing a khaki colour,a compact structure is formed by augite crystals.

Development of Glass Ceramics Made From Ferrous Tailings and Slag in China

A great amount of ferrous tailings and slag cause severe damage to the ecological environment, which must be reclaimed and utilized. The composition, type, and characteristics of ferrous tailings and slag in China were introduced. The research status and the application outlook of glass ceramics made from ferrous tailings and slag were discussed. Glass ceramics made from ferrous tailings and slag can be applied to various fields, and it will be environmentally conscious materials in the 21st century.

Effect of TiO_2 on Crystallization of the Glass Ceramics Prepared from Granite Tailings

The effect of TiO2 on the crystallization behaviors of the glass ceramics prepared from granite tailings was investigated by differential scanning calorimetry （DSC）, X-ray diffraction （XRD）, and field emission scanning electron microscopy （FESEM）. The results showed that the crystallization peak temperature decreased firstly, and then increased with the increase of TiO2 content. The optimum addition amount of TiO2 was 8 wt%. With a single-step heat treatment at 924 ℃ for I h, augite precipitated as the only crystalline phase both on the surface and in the interior. The avrami parameter of the sample was 3.25, suggesting a two- dimensional crystallization mechanism. The activation energies for phase separation and crystallization of augite were 321.75 and 698.83 kJ/mol, respectively.

Local vibration around rare earth ions in alkaline earth fluorosilicate transparent glass and glass ceramics using Eu^(3+) probe

By heat treating the alkaline earth fluorosilicate glass, transparent glass ceramics containing alkaline earth fluoride nanocrystallites were prepared. The luminescence spectra and phonon sideband associated with the Eu^3＋：^5D2→^7F0 in glass and glass ceramics were investigated to analyze the local environment around Eu^3＋. Judd-Ofelt parameters were also calculated from emission spectra, which indicated that the Eu^3＋ ions entered the precipitated CaF2, SrF2, and BaF2 nanocrystallites. Heat treating could not pledge Eu^3＋ ions to coordinate with F^- in the precipitated MgF2 nanocrystallites, owing to the smaller radius of Mg^2＋ than that of Eu^3＋.

Phase, magnetism and thermal conductivity of glass ceramics from iron ore tailings

In order to develop the applications of ore tailings, the glass ceramics were prepared by using a conventional melting-quenching-sintering process. The phase component, microstructures, magnetic properties and thermal conductivities of the prepared glass ceramics were investigated by using X-ray diffractometer, scanning electron microscopy, vibrating sample magnetometer and thermophysical properties tester, respectively. The results show that orthorhombic olivine-type phase and triclinic sunstone-type phase formed when the glass was annealed at 700 oC, the concentration of olivine-type and sunstone-type phases decreased, the spinel-type cubic phase occurred and the amount increased when the annealing temperatures increased. The magnetic properties from the cubic spinel ferrites were detected in the glass ceramics, and the related saturation magnetization increased with the annealing temperature increasing. The porous glass ceramics with magnetic property showed much lower thermal conductivity, compared with the non-magnetic porous glass-ceramic and the dense glass-ceramics.

Phase evolution and properties of glass ceramic foams prepared by bottom ash,fly ash and pickling sludge

Municipal solid waste incineration products of bottom ash(BA),fly ash(FA),and pickling sludge(PS),causing severe environ-mental pollution,were transformed into glass ceramic foams with the aid of CaCO3 as a pore-foaming agent during sintering.The effect of the BA/FA mass ratio on the phase composition,pore morphology,pore size distribution,physical properties,and glass structure was investigated,with results showing that with the increase in the BA/FA ratio,the content of the glass phase,Si-O-Si,and Q3Si units decrease gradually.The glass transmission temperature of the mixture was also reduced.When combined,the glass viscosity decreases,causing bubble coalescence and uneven pore distribution.Glass ceramic foams with uniform spherical pores are fabricated.When the content of BA,FA,and PS are 35wt%,45wt%,and 20wt%,respectively,contributing to high performance glass ceramic foams with a bulk density of 1.76 g/cm3,porosity of 56.01%,and compressive strength exceeding 16.23 MPa.This versatile and low-cost approach provides new insight into synergistically recycling solid wastes.

An investigation on crystallization property, thermodynamics and kinetics of wollastonite glass ceramics

Wollastonite glass ceramics were prepared using the reactive crystallization sintering method by mixing waste glass powders with gehlenite.The crystallization property,thermodynamics,and kinetics of the prepared wollastonite glass ceramics were determined by X-ray diffraction analysis,scanning electron microscopy,energy-dispersive spectroscopy,high-resolution transmission electron microscopy,and differential thermal analysis.Results showed that crystals of wollastonite and alumina could be found in the gehlenite through its reaction with silicon dioxide.The wollastonite crystals showed a lath shape with a certain length-to-diameter ratio.The crystals exhibited excellent bridging and reinforcing effects.In the crystallization process,the aluminum ions in gehlenite diffused into the glass and the silicon ions in the glass diffused into gehlenite.Consequently,the three-dimensional frame structure of gehlenite was partially damaged to form a chain-like wollastonite.The results of crystallization thermodynamics and kinetics indicated that crystallization reaction could occur spontaneously under a low temperature(1173 K),with 20 wt%gehlenite added as the reactive crystallization promoter.The crystallization activation energy was evaluated as 261.99 kJ/mol by using the Kissinger method.The compression strength of the wollastonite glass ceramic samples(7.5 cm×7.5 cm)reached 251 MPa.

THE STRUCTURE AND PROPERTIES OF Li_2O-Al_2O_3-SiO_2LOW EXPANSION GLASS CERAMICS CONTAINING B_2O_3

Through measuring the coefficient of linear expansion, the structure and properties of the Li2O-Al2O3-SiO2 low expansion glass ceramics containing B2O3 are studied by JR and XRD. It is shoutn that the IR method is efficient in the study of the glass-ceramics structure. There is a " Boron abnormality" in the system which has an important influence on the properties of the glass-ceramics.

Preparation and Luminescence of Er^(3+) Doped Oxyfluoride Glass Ceramics Containing LaF_3 Nanocrystals

Er^3＋ doped transparent oxyfluoride glass ceramics version and near infrared luminescence behavior of Er^3＋ in containing LaF3 nanocrystals were prepared and the up-conglasses heat-treating time and temperature, the size （varied from 0 to 19 and glass ceramics were investigated. With increasing nm） and crystallinity （varied from 0 to 47%） of LaF3 nanocrystals in the glass ceramics are increased. The up-conversion luminescence intensity of Er^3＋ ions in the glass ceramics is much stronger than that in the glasses The near infrared emission of Er^3＋ ions in and increased significantly with increasing heat-treating time and temperature the glass ceramics is found to be similar to that in the glasses.

Microstructure and microwave dielectric properties of lead borosilicate glass ceramics with Al_2O_3

The effects of Al2O3 addition on both the sintering behavior and microwave dielectric properties of PbO-B203-SiO2 glass ceramics were investigated by Fourier transform infrared spectroscope （FTIR）, differential thermal analysis （DTA）, X-ray diffraction （XRD） and scanning electron microscopy （SEM）. The results show that with the increase of Al2O3 content the bands assigned to [SiO4] nearly disappear. Aluminum replaces silicon in the glass network, which is helpful for the formation of boron-oxygen rings. The increase of the transition temperature Tg and softening temperature Tf of PbO-B2O3-SiO2 glass ceramics leads to the increase of liquid phase precipitation temperature and promotes the structure stability in the glasses, and consequently contributes to the decreasing trend of crystallization. Densification and dielectric constants increase with the increase of Al2O3 content, but the dielectric loss is worsened. By contrast, the 3% （mass fraction） Al2O3-doped glass ceramics sintered at 725℃ have better properties of density p=2.72 g/cm3, dielectric constant Er=6.78, dielectric loss tan8=2.6×10^-3 （measured at 9.8 GHz）, which suggest that the glass ceramics can be applied in multilayer microwave devices requiring low sintering temperatures.

Glass ceramic of high hardness and fracture toughness developed from iron-rich wastes

A study has been carried out on the feasibility of using high iron content wastes, generated during steel making, as a raw material for the production of glass ceramic. The iron-rich wastes were mixed and melted in different proportions with soda-lime glass cullet and sand. The devitrification of the parent glasses produced from the different mixtures was investigated using differential thermal analysis, X-ray diffraction, and scanning electron microscopy. The mechanical properties of the glass-ceramic were assessed by hardness and indentation fracture toughness measurement. A glass ceramic with mixture of 60 wt pct iron-rich wastes, 25 wt pct sand, and 15 wt pct glass cullet exhibited the best combination of properties, namely, hardness 7.9 CPa and fracture toughness 3.75 MPa·m^1/2, for the sake of containing magnetite in marked dendritic morphology. These new hard glass ceramics are candidate materials for wear resistant tiles and paving for heavy industrial floors.

Sintering,crystallization and dielectric properties of CaO-B_2O_3-SiO_2 system glass ceramics

CaO-B203-SiO2 （CBS） glass powders are prepared by conventional glass melting method at different melting temperatures whose properties and microstructures are characterized by X-ray diffraction （XRD） and scanning electron microscopy （SEM）. It is found that there are SiO2 and some unknown phases in CBS glass melting liquid from 1 300 ℃ to 1 500 ℃ and the amount of these phases decreases with the increase of the melting temperature. The CBS glass melted at 1 450 ℃ could be sintered from 830 ℃ to 930 ℃ and the bulk densities of the samples are all higher than 2.4 g/cm^3. From the points of the properties and energy conservation, the melting temperature of 1 450 ℃ is the optimal melting temperature. The glass ceramic sintered at 850 ℃ exhibits better dielectric properties： er=6.33, tan6=2.2×10^-3 at 10 GHz, and the major phases of the samples are CaSiO3, CaB2O4 and SiO2.

Fabrication,microstructure,and optical properties of nanocrystalline transparent LAST glass ceramics containing CeO_2

In the present research, the effect of CeO2 dopant on the fabrication of transparent lithium aluminosilicate titanate （LAST） glass ceramics was investigated. Nanocrystallineβ-quartz solid solution （s.s.） was observed to be the main phase crystallized in this system. Com-parable refractive indices of the glassy matrix andβ-quartz s.s., as well as the incorporation of very fine grains size were determined as the main reasons for retaining the transparency of the glass ceramics. CeO2 was introduced as a suitable optical agent, playing a role as a network modifier in the glass ceramics, because it does not accelerate the growth process and retards the extended growth of crystals. Optical investi-gations indicate that the Fermi energy level, direct and indirect band gaps, and Urbach energy decrease with increasing nanocrystal content in the glassy matrix of specimens, which can be related to the expansion of conduction band, the enhancement of ionic bonds in the crystal lat-tice, and the enhancement of structural arrangement degree, respectively.

Effect of Y_2O_3 on the crystallization kinetics of TiO_2 nucleated LAS glass for the production of nanocrystalline transparent glass ceramics

Crystallization kinetics of metastable B-quartz solid solution as a desirable phase for the production of trans- parent lithium aluminosilicate （LAS） glass ceramics was investigated in the presence of Y203. Accordingly, differential thermal analysis scans were performed thoroughly to study the mechanism of crystallization kinetics. The aim of this investigation is to discover the complicated mechanism of crystallization process in the presence of co-additives and ac- cordingly find a way for increasing the transparency of glass ceramics. It is shown that the bulk （3D） growth is intensively increased by the enhancement of Y203. Then again, reducing nucleation and increasing growth mechanisms were recog- nized for the LAS system in the presence of Y2O3. Results of the investigation illustrate that when co-additives are added to glasses, it is necessary to nucleate the optical component separately before the growth process.

Nanocrystal formation and structure in oxyfluoride glass ceramics

The up-conversion luminescent property of the oxyfluoride glass ceramics 30SiO2·15Al2O3· （50-x）PbF2·xCdF2 doped with 4ErF3·1YbF3 has been investigated. Up-conversion luminescent intensity of Er^3＋ ions increased obviously after heat-treatment due to co-doping with CdF2. The structure model of nanocrystals PbxCdl-xF2 was determined and the effect of CdF2 in oxyfluoride glass ceramics was explained by the analysis of x-ray diffraction data. Different nucleation temperatures of samples with different compositions were obtained by differential thermal analysis curves and the results showed the growth process of different nanocrystals in glass ceramics.

Spectroscopic properties and mechanism of Tm^(3+)/Er^(3+)/Yb^(3+) co-doped oxyfluorogermanate glass ceramics containing BaF_2 nanocrystals

Transparent Tm^3＋/Er^3＋/yb^3＋ co-doped oxyfluorogermanate glass ceramics containing BaF2 nanocrystals are prepared. Under excitation of a 980-nm laser diode （LD）, compared with the glass before heat treatment, the Tm^3＋/Er^3＋/yb^3＋ co-doped oxyfluorogermanate glass ceramics can emit intense blue, green and red up-conversion luminescence and Stark- split peaks; X-ray diffraction （XRD） and transmission electron microscope （TEM） results show that BaF2 nanocrystals with an average diameter of 20 nm are precipitated from the glass matrix. Stark splitting of the up-conversion luminescence peaks in the glass ceramics indicates that Tm^3＋, Er^3＋ and （or） Yb^3＋ ions are incorporated into the BaF2 nanocrystals. The up-conversion luminescence intensities of Tm^3＋, Er^3＋ and the splitting degree of luminescence peaks in the glass ceramics increase significantly with the increase of heat treat temperature and heat treat time extension. In addition, the possible energy transfer process between rare earth ions and the up-conversion luminescence mechanism are also proposed.

Study on crystallization and microstructure of Li_2O-Al_2O_3-SiO_2 glass ceramics

Lithium aluminosilicate （LAS） glasses are generally difficult to prepare because of their high melting temperature. In this study, the preparation of LAS glasses was achieved at a relatively low melting temperature. The batch containing MgO-ZnO-LiEO- Al2O3-SiO2 was melted in a platinum crucible at 1550℃ for 2 h and was then followed by two- or three-step heat treatment processes for nucleation and crystal growth. The characterizations were carried out by differential thermal analysis, X-ray diffraction, infrared spectroscopy, scanning electron microscopy, and UV-Vis-NIR scanning spectrophotometry. The hexagonal stuffed β-eucryptite solid solution crystallized at 840-960℃. Most of the hexagonal β-eucryptite solid solution transformed into the tetragonal β-spodumene solid solution at 1100℃. Almost all the aluminum atoms entered into the tetrahedral sites in the aluminosilicate network of the 6- eucryptite/β-quartz solid solution. All of the Al atoms did not belong to the aluminosilicate network of the β-spodumene solid solution. The glass ceramic with a mean grain size of 10-20 nm is transparent, the transmittance reaches -85% in the visible light wavelength.

Synthesis of glass ceramics from kaolin and dolomite mixture

Cordierite- and anorthite-based binary glass ceramics of the CaO-MgO-Al2O3-SiO2 （CMAS） system were synthesized by mixing local and abundant raw minerals （kaolin and doloma by mass ratio of 82/18）. A kinetics study reveals that the activation energy of crystalli- zation （Ea） calculated by the methods of Kissinger and Marotta are 438 kJ·mol^-1 and 459 kJ·mol^-1, respectively. The Avrami parameter （n） is estimated to be approximately equal to 1, corresponding to the surface crystallization mechanism. X-ray diffraction （XRD） analysis shows that the anorthite and cordierite crystals are precipitated from the parent glass as major phases. Anorthite crystals first form at 850℃, whereas the μ-cordierite phase appears after heat treatment at 950℃. Thereafter, the cordierite allotropically transforms to α-cordierite at 1000℃. Complete densification is achieved at 950℃; however, the density slightly decreases at higher temperatures, reaching a stable value of 2.63 kg·m^-3 between 1000℃ and 1100℃, The highest Vickers hardness of 6 GPa is also obtained at 950℃. However, a substantial decrease in hardness is recorded at 1000℃; at higher sintering temperatures, it slightly increases with increasing temperature as the ct-cordierite crystallizes.

Microstructure and fracture behavior of SiO_2 glass ceramic and TC4 alloy joint brazed with TiZrNiCu alloy

Vacuum brazing of SiO2 glass ceramic and TC4 alloy using a commercially available TiZrNiCu foil was investigated. The interfacial microstructure and the fractures were examined with an optical microscope （OM） and an S-4700 scanning electron microscope （SEM） equipped with an energy dispersive spectrometer （EDS） and an electron probe X-ray microanalyzer （EPMA）. The structure of joint interface was identified by XRD （JDX-3530M）. Meanwhile, the fracture paths of the joints were comprehensively studied. The results show that processing parameters, especially the brazing temperature, have a significant effect on the microstructure and mechanical properties of joints. The typical interface structure is SiO2/Ti2O＋Zr3Si2＋Ti5Si3/（Ti,Zr）＋Ti2O＋ TiZrNiCu/Ti（s.s）/TiZrNiCu＋Ti（s.s）＋Ti2（Cu,Ni）/TC4 from SiO2 glass ceramic to TC4 alloy side. Based on the mechanical property tests, the joints brazed at 880 ℃ for 5 rain has the maximum shear strength of 23 MPa.