Development and characterisation of a Y2Ti2O7-based glass-ceramic as a potential oxidation protective coating for titanium suboxide (TiOx)

A silica-based glass-ceramic, with Y₂Ti₂O₇ as the major crystalline phase, is designed, characterised and tested as an oxidation-protective coating for a titanium suboxide (TiO_x) thermoelectric material at temperatures of up to 600 °C. The optimised sinter-crystallisation treatment temperatures are found to be 1300 °C and 855 °C for a duration of 30 min, and this treatment leads to a glass-ceramic with cubic Y₂Ti₂O₇ and CaAl₂Si₂O₈ as crystalline phases. An increase of ~270 °C in the dilatometric softening temperature is observed after devitrification of the parent glass, thus further extending its working temperature range.Excellent adhesion of the glass-ceramic coating to the thermoelectric material is maintained after exposure to a temperature of 600 °C for 120 h under oxidising conditions, thus confirming the effectiveness of the T1 glass-ceramic in protecting the TiO_x material.     

Effect of sintering temperature on solidification and migration of non-volatile and volatile heavy metals in glass-ceramic

Using tailings as material to prepare glass-ceramic is an excellent way to achieve the resource utilization of solid waste. However, at present, researches on the solidification and migration of heavy metals are limited. Therefore, in this study, ten groups of samples were prepared by controlling sintering temperatures. The solidification, migration, and leaching behavior of non-volatile and volatile heavy metals were studied. The research showed that, with the increase of temperature, the properties of the samples were improved. Fe participated in the phase transformation and evolved into insoluble iron pyroxenes solid solution, while Pb was homogeneously distributed in the glass matrix of glass-ceramics. The leaching concentrations of Fe and Pb in the glass-ceramics were 0.055 mg/L ～0.087 mg/L and 0.074 mg/L ～0.140 mg/L, which were far below the threshold value. The results showed that heavy metals can be effectively solidified in glass-ceramics and have good environmental benefits.     

Synergistic effect of glass fibre and Al powder on the mechanical properties of glass-ceramics

To explore the synergistic effect of glass fibre and Al powder on the mechanical properties of glass-ceramics, blast furnace slag was chosen as the main material, and glass fibre and Al powder as reinforcement materials. The phase compositions, microstructures, compressive properties, and apparent density of the glass-ceramics with varying quantities of glass fibre and Al powder were investigated. The experimental results indicated that Al powder could exist as a simple substance in glass-ceramics and form a dense net coating on the surface of blast furnace slag to improve the plasticity of the glass-ceramic. The glass fibre had better reinforcement effect than Al powder because of its extremely high mechanical strength. The plasticity of glass-ceramics, however, severely decreased; the glass-ceramics exhibited brittle failure during compression. A slight increase in the content of CaSi₂ and SiO₂ in the glass-ceramics was closely related to the addition of glass fibre. Considering safety and economy, glass-ceramics with 6% Al and 14% glass fibre (S4) have the best mechanical properties. The compressive strength, strain at maximum force, and apparent density were 40?MPa, 19% and 1.974?g/cm³, respectively.     

The impact of heat-treatment protocol on the grain size and ionic conductivity of NASICON glass-ceramics

Na₂AlTi(PO₄)₃ (NATP) and Na_1.8Al_0.8Ge_1.2(PO₄)₃ (NAGP) NASICON (Na-Superionic Conductor) glass-ceramics are obtained by applying different single (SHT) and double (DHT) heat treatments on the respective precursor glass to evaluate its effect on the microstructure and in turn, on the total ionic conductivity. The grain and grain boundary contributions are also analyzed in the NATP composition. SHT with longer crystallization times favors the development of well-defined grains in both compositions and also promotes the grain growth in NAGP samples. This behavior causes a decrease in the activation energy of the grain boundary, which enhances the total ionic conductivity. Regarding DHT samples, microstructure with larger grains and higher ionic conductivity were obtained with shorter nucleation times for NATP and NAGP compositions. Finally, the microstructural variation generated by the different thermal treatments causes the total conductivity to increase up to two times.     

Precipitating spinel into precursor glass and its assistance in crystallization

The crystallization phenomena of spinel in CaO-MgO-Al₂O₃-SiO₂-Fe₂O₃ glass have received much attention due to the particular role in preparation of glass-ceramic materials, which represent an effective option to manage hazardous waste. In this study, both preliminary spinel and secondary spinel were precipitated in the precursor glass. The formation of these spinel was meticulously assessed by a combination of X-ray diffractometry and scanning electron microscopy. The structure of the microenvironment in the precursor glass was characterized by Raman spectrums. These advanced techniques highlight the potential for one-step crystallization of the glass. The investigation, which focused on one-step crystallization, demonstrated the growth of pyroxene on spinel accompanying a migration of chromium. The results also show the microstructure of the obtained glass-ceramic was very dependent on the heat-treat temperature. This study not only unambiguously reveals the precipitation mechanisms of spinel but also provides more documentation for one-step crystallization in the glass-ceramics field.     

Effect of ZnO content on the physical,mechanical and chemical properties of glass-ceramics in the CaO–SiO2–Al2O3 system

The objective of this study was to evaluate the effect of ZnO content on the physical, mechanical and chemical properties of CaO–Al₂O₃–SiO₂ (CAS) glass-ceramics produced from Colombian wastes, such as fly ash, granulated blast furnace slag and glass cullet. The CaO/SiO₂ molar ratio of the mixtures was held constant (0.36). ZnO was added to the mixtures in proportions of 4, 7 and 10 wt%. The glass-ceramics were produced by the controlled crystallization of a parent glass. The values of crystallization temperature (T_p) show a fall up to 7 wt% and then shoots up with 10 wt% concentration of ZnO, but in general, ZnO addition lowers the temperature required for the formation of crystalline phases. In general, anorthite (CaAl₂Si₂O₈) is the main phase observed in all heat treated samples, in addition to albite (Na(AlSi₃O₈)) and labradorite (Na_0.45 Ca_0.55 Al_1.55 Si_2.45 O₈). The crystalline phases hardystonite (Ca₂ZnSi₂O₇) and willemite (Zn₂SiO₄) were also identified in the samples with 7 and 10 wt% ZnO. The densities of the glass-ceramics were between 2658 and 2848 kg/m³, and it was found that ZnO helps to increase the density of glass-ceramics. The elastic modulus was in the 100–105 GPa range, the fracture toughness was between 0.45 and 0.64 MPa m^1/2, and the Vickers microhardness was between 632 and 653 MPa. With regards to the durability, the weight loss of the glass-ceramics immersed in alkaline solution (NaOH) did not exceed 1.5 wt% after immersion for 6 h at 80 °C. The results of this study confirm that the vitrification process is a favorable option to utilize these industrial wastes.     

Preparation and characterization of fully waste-based glass-ceramics from incineration fly ash,waste glass and coal fly ash

Municipal solid waste incineration (MSWI) fly ash (FA) is a typical hazardous waste due to its high contents of toxic heavy metals, and hence its disposal has attracted global concern. In this work, it was recycled into environmental-friendly CaO–Al₂O₃–SiO₂ system glass-ceramics via adding coal fly ash (CFA) and waste glass (WG). The effects of CaO/SiO₂ ratios and sintering temperatures on the crystalline phases, morphologies, mechanical and chemical properties, heavy metals leaching and potential ecological risks of glass-ceramics were investigated. The results showed that wollastonite (CaSiO₃), anorthite (CaAl₂Si₂O₈) and gehlenite (Ca₂Al₂SiO₇) were the dominant crystals in the glass-ceramics, which were not affected by CaO/SiO₂ ratio and sintering temperature. The compressive strength increased, while the Vickers hardness and microhardness decreased as increasing the sintering temperatures from 850 to 1050 °C, which reached their maximum values of 660.69 MPa, 6.14 GPa, and 7.43 GPa, respectively. However, the increase of CaO/SiO₂ ratio resulted into the reduction of the three mechanical parameters. As varying CaO/SiO₂ ratio from 0.48 to 0.86, the maximum compressive strength, Vickers hardness and microhardness were 611.80 MPa, 5.43 GPa, and 6.56 GPa, respectively. Besides, all the glass-ceramics exhibited high alkali resistance of >97%. The extremely low heavy metals leaching concentrations and low potential ecological risk of glass-ceramics further revealed its environmentally friendly property and potential application feasibility.     

Crystallization behavior and mechanical properties of high strength mica-containing glass-ceramics from granite wastes

The high-strength mica-containing glass-ceramics were prepared from granite wastes by bulk crystallization. The influences of SiO₂/Al₂O₃ molar ratio (S/A = 7.72, 9.62, 12.58, 17.82 and 29.67) on the crystallization behavior, microstructure, mechanical properties and machinability of glass-ceramics were investigated. The results demonstrated that the polymerization degree of the glass network decreased with the S/A ratio increasing, which further caused the decrease in glass transition temperature and crystallization temperatures. The increase in the S/A ratio promoted the precipitation of diopside, hectorite, kalsilite and tainiolite in glass-ceramics when the samples were heated at 750 °C, while inhibiting the precipitation of forsterite. For the glass-ceramics crystallized at 800 and 900 °C, the main crystalline phases transformed from diopside, forsterite, and nepheline to diopside, kalsilite, and tainiolite, with the S/A ratio increasing. As the SiO₂ gradually replaced Al₂O₃, the morphology of crystals changed from lamellar to granular, while the mean size of crystals reduced. The Vickers-Hardness values of glass-ceramics crystallized at 800 and 900 °C ascended with S/A ratio rising, and the values were above 6.30 GPa. The bending strength of most glass-ceramics is stable between 90 and 140 MPa, among which the maximum bending strength is 133.28 ± 14.81 MPa. The fracture toughness of the glass-ceramic crystallized at 800 and 900 °C declined, while that at 700 °C increased with a larger S/A ratio. Glass-ceramics after heat-treated at 900 °C with S/A ratio of 9.62 had the largest fracture toughness of 3.28 ± 0.15 MPa m^1/2. In preliminary tests of machinability, glass-ceramic after heat-treated at 900 °C with S/A ratio of 9.62 showed better results.     

电解锰渣制备微晶玻璃正交实验研究

将煅烧后的电解锰渣作为单一的实验原料,采用烧结法,制备微晶玻璃,通过正交实验对锰渣微晶玻璃的热处理方案及性能进行探讨。实验通过DSC、XRD、SEM等方法对样品的性能进行表征,并测试了样品的体积密度、抗弯强度等性能。结果显示:不同的热处理条件下的锰渣微晶玻璃的主晶相均为透辉石(含铁),次晶相为普通辉石相。在800℃/0.5 h+980℃/1 h的热处理条件下得到的锰渣微晶玻璃的综合性能最优,其抗弯强度为106.82 MPa;体积密度为2.68 g/cm^3;维氏硬度为4.43 GPa;耐酸度为0.71%;耐碱度为0.07%。此外,锰渣微晶玻璃用作建筑材料,有非常大的应用潜力。     

The effect of lithium fluoride on the thermal stability and thermoluminescence properties of borosilicate glass and glass-ceramics

The oxyfluoride glass and glass-ceramics from the LiF-B₂O₃-SiO₂ system are developed. The stable glass can be produced in the range of 20–40 mol% LiF. The effect of LiF admixture on the thermal stability of the glass as well as the thermoluminescence (TL) properties such as glow curves shape is studied. The results show that the increase of lithium fluoride content in the borosilicate glass causes efficiency enhancement of the thermoluminescence signal. We have clearly stated that the process of controlled crystallization of the oxyfluoride glasses can lead again to increased intensity of the TL process. The glass-ceramics with 40 mol% LiF reveals similar level of TL signal to commercially used doped LiF material and can be considered as active material for alpha and beta radiation detectors.