Preparation, Crystallization and Mechanical Properties of Potassium Aluminosilicate Glass-ceramics

In this study,transparent K_(2)O-Al_(2)O_(3)-SiO_(2)(KAS)glass-ceramics with leucite as the main crystalline phase were prepared by melting-quench method and two-step heat treatment.The effects of SiO_(2)/Al_(2)O_(3) ratio and heat treatment on crystallization and mechanical properties were studied.The crystallization kinetics and X-Ray Diffraction(XRD)results showed that SiO_(2)/Al_(2)O_(3) ratio and heat treatment system had a direct impact on the crystallization behavior of potassium aluminosilicate glass-ceramics.When heat-treated at 680℃/2 h and 780℃/1 h,cracks generated on the surface of the sample with the addition of SiO_(2)/Al_(2)O_(3)=4.8(in mol)due to the huge difference in the coefficient of thermal expansion between glass matrix and surface.When the addition of SiO_(2)/Al_(2)O_(3)(in mol)was 4,the sample with leucite as the main crystalline phase showed an excellent fracture toughness(1.46 MPa·m^(0.5))after the heat treatment of 680℃/2 h and 780℃/5 h.And there was a phase transformation from kaliophilite to leucite.The crystalline phases of the sample heat-treated at 680℃/8 h and 780℃/1 h were leucite and kaliophilite,which resulted in the visible light transmittance of 63%and the fracture toughness of 0.91 MPa·m^(0.5).Furthermore,after the heat treatment of 680℃/2 h and 780℃/5 h,the main crystalline phase of the sample with SiO_(2)/Al_(2)O_(3)=3.2(in mol)was still kaliophilite.Because leucite only grows on the surface of the sample and is hard to grow inward,it is hard to achieve the bulk crystallization of leucite in the sample with SiO_(2)/Al_(2)O_(3)=3.2(in mol).

Glass-Ceramics with High Strength and High Transmittance Obtained by Multi-Factor Controlling

The presence of Li_(2)Si_(2)O_(5) and LiAlSi_(4)O_(10) could effectively improve the elastic modulus and transmittance of lithium disilicate(LD)glass-ceramics.Through synergistically modulation of the crystal content and grain size,we obtained high strength and high transmittance of LD glass-ceramics.The optimal sample had a high transmittance of 90.3%,the hardness was 7.72 GPa,the fracture toughness was 1.07 MPa·m^(1/2),and the elastic modulus was 103.1 GPa.

Isotropic sintering shrinkage of 3D glass-ceramic nanolattices:backbone preforming and mechanical enhancement

There is a perpetual pursuit for free-form glasses and ceramics featuring outstanding mechanical properties as well as chemical and thermal resistance.It is a promising idea to shape inorganic materials in three-dimensional(3D)forms to reduce their weight while maintaining high mechanical properties.A popular strategy for the preparation of 3D inorganic materials is to mold the organic–inorganic hybrid photoresists into 3D micro-and nano-structures and remove the organic components by subsequent sintering.However,due to the discrete arrangement of inorganic components in the organic-inorganic hybrid photoresists,it remains a huge challenge to attain isotropic shrinkage during sintering.Herein,we demonstrate the isotropic sintering shrinkage by forming the consecutive–Si–O–Si–O–Zr–O–inorganic backbone in photoresists and fabricating 3D glass–ceramic nanolattices with enhanced mechanical properties.The femtosecond(fs)laser is used in two-photon polymerization(TPP)to fabricate 3D green body structures.After subsequent sintering at 1000℃,high-quality 3D glass–ceramic microstructures can be obtained with perfectly intact and smooth morphology.In-suit compression experiments and finite-element simulations reveal that octahedral-truss(oct-truss)lattices possess remarkable adeptness in bearing stress concentration and maintain the structural integrity to resist rod bending,indicating that this structure is a candidate for preparing lightweight and high stiffness glass–ceramic nanolattices.3D printing of such glasses and ceramics has significant implications in a number of industrial applications,including metamaterials,microelectromechanical systems,photonic crystals,and damage-tolerant lightweight materials.

Properties of Ultra-low Thermal Expansion LAS Transparent Glass-ceramics Prepared by Spodumene

The glass-ceramics were prepared with the spodumene mineral as the main raw material,and the effects of ZrO_(2)replacing TiO_(2)on the samples were systematically investigated.The results show that the substitution of ZrO_(2)for TiO_(2)is not conductive to precipitate𝛽β-quartz solid solution phase,but can improve the transparency and flexural strength of glass-ceramics.And the glass-ceramic with the highest visible light transmittance(87%)and flexural strength(231.80 MPa)exhibits an ultra-low thermal expansion of-0.028×10^(-7)K^(-1)in the region of 30-700℃.

Influence of aluminium nitride as a foaming agent on the preparation of foam glass-ceramics from high-titanium blast furnace slag

To effectively reuse high-titanium blast furnace slag （TS）, foam glass-ceramics were successfully prepared by powder sintering at 1000℃. TS and waste glass were used as the main raw materials, aluminium nitride （AIN） as the foaming agent, and borax as the fluxing agent. The influence of the amount of A1N added （lwt%-5wt%） on the crystalline phases, microstructure, and properties of the produced foam glass-ceramics was studied. The results showed that the main crystal phases were perovskite, diopside, and augite. With increasing A1N content, a transformation from diopside to augite occurred and the crystallinity of the pyroxene phases slightly decreased. Initially, the aver- age pore size and porosity of the foam glass-ceramics increased and subsequently decreased; similarly, their bulk density and compressive strength decreased and subsequently increased. The optimal properties were obtained when the foam glass-ceramics were prepared by adding 4wt% AIN.

Effect of sintering temperature on the microstructure and properties of foamed glass-ceramics prepared from high-titanium blast furnace slag and waste glass

Foamed glass-ceramics were prepared via a single-step sintering method using high-titanium blast furnace slag and waste glass as the main raw materials The influence of sintering temperature(900–1060℃) on the microstructure and properties of foamed glass-ceramics was studied. The results show that the crystal shape changed from grainy to rod-shaped and finally turned to multiple shapes as the sintering temperature was increased from 900 to 1060℃. With increasing sintering temperature, the average pore size of the foamed glass-ceramics increased and subsequently decreased. By contrast, the compressive strength and the bulk density decreased and subsequently increased. An excessively high temperature, however, induced the coalescence of pores and decreased the compressive strength. The optimal properties, including the highest compressive strength(16.64 MPa) among the investigated samples and a relatively low bulk density(0.83 g/cm^3), were attained in the case of the foamed glass-ceramics sintered at 1000℃.

Influence of CeO_2 addition on the preparation of foamed glass-ceramics from high-titanium blast furnace slag

Foamed glass-ceramics doped with cerium oxide（CeO_2）were successfully prepared from high-titanium blast furnace slag by one-step sintering.The influence of CeO_2 addition（1.5wt%–3.5wt%）on the crystalline phases,microstructure,and properties of foamed glass-ceramics was studied.Results show that CeO_2 improves the stability of the glass phase and changes the two-dimensional crystallization mechanism into three-dimensional one.XRD analysis indicates the presence of Ca（Mg,Fe）Si_2O_6 and Ca（Ti,Mg,Al）（Si,Al）_2O_（6 ）in all sintered samples.Added with CeO_2,Ti CeO_4 precipitates,and crystallinity increases,leading to increased thickness of pore walls and uniform pores.The comprehensive properties of foamed glass-ceramics are better than that of samples without CeO_2.In particular,the sample added with a suitable amount of CeO_2（2.5wt%）exhibits bulk density that is similar to and compressive strength（14.9 MPa）that is more than twice of foamed glass-ceramics without CeO_2.

Structural properties of residual carbon in coal gasification fine slag and their influence on flotation separation and resource utilization:A review

Coal gasification fine slag(FS)is a typical solid waste generated in coal gasification.Its current disposal methods of stockpil-ing and landfilling have caused serious soil and ecological hazards.Separation recovery and the high-value utilization of residual carbon(RC)in FS are the keys to realizing the win-win situation of the coal chemical industry in terms of economic and environmental benefits.The structural properties,such as pore,surface functional group,and microcrystalline structures,of RC in FS(FS-RC)not only affect the flotation recovery efficiency of FS-RC but also form the basis for the high-value utilization of FS-RC.In this paper,the characteristics of FS-RC in terms of pore structure,surface functional groups,and microcrystalline structure are sorted out in accordance with gasification type and FS particle size.The reasons for the formation of the special structural properties of FS-RC are analyzed,and their influence on the flotation separation and high-value utilization of FS-RC is summarized.Separation methods based on the pore structural characterist-ics of FS-RC,such as ultrasonic pretreatment-pore-blocking flotation and pore breaking-flocculation flotation,are proposed to be the key development technologies for improving FS-RC recovery in the future.The design of low-cost,low-dose collectors containing polar bonds based on the surface and microcrystalline structures of FS-RC is proposed to be an important breakthrough point for strengthening the flotation efficiency of FS-RC in the future.The high-value utilization of FS should be based on the physicochemical structural proper-ties of FS-RC and should focus on the environmental impact of hazardous elements and the recyclability of chemical waste liquid to es-tablish an environmentally friendly utilization method.This review is of great theoretical importance for the comprehensive understand-ing of the unique structural properties of FS-RC,the breakthrough of the technological bottleneck in the efficient flotation separation of FS,and the expansion of the field of the high value-added utilization of FS-RC.

A novel process of preparing glass-ceramics directly from molten steel slag

A novel process technology to prepare glass-ceramics directly from molten steel slag （MSS） is proposed in the study. The liquid-solid mixing method was used to adjust the components of the MSS and glass-ceramics was obtained. The effects of heat-treatment conditions on the microstructure ,physical and mechanical properties of samples were studied. Economical benefits of the novel process were analyzed. The results show that heat-treatment is a very effective approach to achieving crystallization. The dominant crystal phase in products is diopside [ （ Mg6Al2Fe2 ） Ca （ Si1.5 Al5 ） O2 ]. The shape of the crystallization is like a granule. The glass-ceramic samples exhibited good mechanical properties and presented chemical stability. The economic benefits of the process are remarkable due to less energy consumption compared with conventional glass-ceramics production methods.

Glass-ceramics made from arc-melting slag of waste incineration fly ash

Grate fly ash and fluidized bed fly ash mixed with glass cullet additive respectively were melted in the electronic arc-furnace. The product, arc-melting slag, was further treated by crushing, pressing and heat treatment in order to make the glass-ceramics. The crystallization behaviors of the produced glass-ceramics were examined by differential thermal analysis （DTA）, X-ray diffractometry （XRD） and scanning electron microscopy （SEM）. Results show that main crystalline phase of the glass-ceramics fi＇om grate fly ash is wollastonite （CaSiO3） with small amount of diopside （Ca（Mg,Al）（Si,Al）206）, and that from fluidized bed fly ash is diopside （Ca（Mg,Al）（Si,Al）206）. It is found that the glass-ceramics sintered at 850 ℃and 1 000℃ from grate fly ash and fluidized bed fly ash respectively have the optimal physical, mechanical and chemical characteristics. Glass-ceramics samples, produced from incinerator fly ash with desirable properties and the low leaching concentration of heavy metals, can be the substitute of nature materials such as marble, granite and porcelain tiles.

Effect of electrical parameters and slag system on macrostructure of electroslag ingot

To investigate the influence of electric parameters and slag system on the solidification quality of electroslag ingot during electroslag remelting,different power supply modes,current strengths and remelting slag systems were used to conduct electroslag remelting experiments on 304L austenitic stainless steel,and the macrostructure of electroslag ingots was analyzed.The results indicate that the depth of the metal pool decreases with the reduction of remelting frequency in the low frequency power supply mode.The effects of different power supply modes,such as low-frequency,direct current straight polarity(DCSP),and direct current reverse polarity(DCRP),on reducing the depth of the metal pool increase in that order.By reducing the remelting current strength in the same power supply mode,the depth of metal pool is reduced.When compared to the binary slag system of 70%CaF2+30%Al2O3,the ternary slag system of 60%CaF2+20%Al2O3+20%CaO is more effective in reducing the depth of the metal pool during remelting.Utilizing the 60%CaF2+20%Al2O3+20%CaO ternary slag system results in a shallower and flatter metal pool,with columnar crystal growth occurring closer to the axial crystal.This effect is observed for both low frequency and direct current(DC)power supply modes.

Effect of Fe_2O_3 on the crystallization behavior of glass-ceramics produced from naturally cooled yellow phosphorus furnace slag

CaO–Al2O3–SiO2(CAS) glass-ceramics were prepared via a melting method using naturally cooled yellow phosphorus furnace slag as the main raw material. The effects of the addition of Fe2O3on the crystallization behavior and properties of the prepared glass-ceramics were studied by differential thermal analysis, X-ray diffraction, and scanning electron microscopy. The crystallization activation energy was calculated using the modified Johnson–Mehl–Avrami equation. The results show that the intrinsic nucleating agent in the yellow phosphorus furnace slag could effectively promote the crystallization of CAS. The crystallization activation energy first increased and then decreased with increasing amount of added Fe2O3. At 4wt% of added Fe2O3, the crystallization activation energy reached a maximum of 676.374 kJ·mol−1. The type of the main crystalline phase did not change with the amount of added Fe2O3. The primary and secondary crystalline phases were identified as wollastonite (CaSiO3) and hedenbergite (CaFe(Si2O6)), respectively. © 2017, University of Science and Technology Beijing and Springer-Verlag Berlin Heidelberg.

Experimental study on glass-ceramics preparation from hot steel slag

When liquid steel slag produced from steelmaking process was treated into the post-cold slag by conventional methods,the great deal of slag heat was dissipated into the environment,causing a lot of energy waste and environmental pollution.In this study,a novel approach of direct utilization of hot steel slag as a raw material and slag heat for the production of glass-ceramics was proposed and experimentally tested.In order to simulate liquid slag from steelmaking electric furnace,40%water-quenched slag was remelted at 1 450℃and then mixed with 60%melting additives(silica powder,alumina powder and sodium oxide, etc.)and subsequently melted together at 1 500℃for 1 h into modified liquid slag which was cast,heat-treated, annealed and transformed into glass-ceramics.The heat-treated glass samples were investigated using differential thermal analysis(DTA),X-ray diffraction(XRD),and scanning electron microscopy(SEM). The results show that dominant crystalline phase is diopside[CaFe(SiO_3)_2]and the shape of the crystal is like the granule,diameter is about 0.2 -0.6μm.A glass-ceramic with nucleation temperature of 695℃for two hours and crystallization temperature of 893℃for one hour and 1 163℃for half-hour exhibited the best combination of properties.This method of slag mixed with melting additives to adjust the composition of the parent glass is important for the industrial production of glass-ceramics by direct utilization of hot steel slag.

Interphase migration and enrichment of lead and zinc during copper slag depletion

An interphase migration and enrichment model of lead and zinc during molten copper slag depletion was established.The occurrence of various components in copper slag was predicted using sulfur-oxygen potential calculations and confirmed through high-temperature experiments.The recovery rate of copper can reach 90.13%under the optimal conditions of 1200°C,an iron to silicon mass ratio of 1.0,3 wt.%ferrous sulfide,and a duration of 45 min.Lead(54.07 wt.%)and zinc(17.42 wt.%)are found in the flue dust as lead sulfate,lead sulfide,and zinc oxide,while copper matte contains lead(14.44 wt.%)and zinc sulfide(1.29 wt.%).The remaining lead and zinc are encapsulated as oxides within the fayalite phase.

Corrosion behavior of co-gasification slag of furfural residue and coal on alumina-silica refractories

Gasification of furfural residue with coal can realize its efficient and clean utilization.But the high alkali metal content in furfural slag is easy to cause the corrosion of gasifier refractory.Two gasification coals with different silica alumina ratio and a furfural residue were selected in the study.The effects of furfural residue additions on corrosion of silica brick,corundum brick,high alumina brick and mullite brick were investigated by using XRD,SEM-EDS and Factsage Software,and the corrosion mechanism was analyzed.With increasing furfural residue addition,the permeability of the slags to high-aluminium-bearing refractories first decreases and then increases,while the permeability on silica brick shows a slight decrease trend.Leucite(KAlSi_(2)O_(6))with high-melting temperature is generated from the reaction of K_(2)O and SiO_(2)in slag with Al_(2)O_(3)in refractories after furfural residue is added,which hinders the infiltration of slag in refractories.Kaliophilite(KAlSiO_(4))of low-melting point is formed when K_(2)O content increases,and this contributes to the infiltration of slag in refractories.The acid-base reaction between slag and silica brick is distinctly occurred,more slag reacts with SiO_(2)in the silicon brick,resulting in a decrease in the amount of slag infiltrating into the silicon brick as furfural residue is added.The corrosion of silica brick is mainly caused by the acid-base reaction,while the corrosion of three alumina based refractory bricks of corundum,mullite and high alumina brick is determined by slag infiltration.A linear correlation between the percolation rate and slag viscosity is established,the slag permeability increases with decreasing viscosity,resulting in stronger permeability for the high Si/Al ratio slag with lower viscosity.

Detection of Al, Mg, Ca, and Zn in copper slag by LIBS combined with calibration curve and PLSR methods

The precise measurement of Al, Mg, Ca, and Zn composition in copper slag is crucial for effective process control of copper pyrometallurgy. In this study, a remote laser-induced breakdown spectroscopy(LIBS) system was utilized for the spectral analysis of copper slag samples at a distance of 2.5 m. The composition of copper slag was then analyzed using both the calibration curve(CC) method and the partial least squares regression(PLSR) analysis method based on the characteristic spectral intensity ratio. The performance of the two analysis methods was gauged through the determination coefficient(R^(2)), average relative error(ARE), root mean square error of calibration(RMSEC), and root mean square error of prediction(RMSEP). The results demonstrate that the PLSR method significantly improved both R^(2) for the calibration and test sets while reducing ARE, RMSEC, and RMSEP by 50% compared to the CC method. The results suggest that the combination of LIBS and PLSR is a viable approach for effectively detecting the elemental concentration in copper slag and holds potential for online detection of the elemental composition of high-temperature molten copper slag.

Phase equilibria relations in the V_(2)O_(5)-rich part of the Fe_(2)O_(3-)TiO_(2)-V_(2)O_(5) system at 1200℃ related to converter vanadium-bearing slag

The efficient recycling of vanadium from converter vanadium-bearing slag is highly significant for sustainable development and circular economy.The key to developing novel processes and improving traditional routes lies in the thermodynamic data.In this study,the equilibrium phase relations for the Fe_(2)O_(3)-TiO_(2)-V_(2)O_(5)system at 1200℃in air were investigated using a high-temperature equilibrium-quenching technique,followed by analysis using scanning electron microscopy-energy dispersive X-ray spectrometer and X-ray photoelectron spectroscopy.One liquid-phase region,two two-phase regions(liquid-rutile and liquid-ferropseudobrookite),and one three-phase region(liquid-rutile-ferropseudobrookite)were determined.The variation in the TiO_(2)and V_(2)O_(5)contents with the Fe_(2)O_(3)content was examined for rutile and ferropseudobrookite solid solutions.However,on further comparison with the predictions of FactSage 8.1,significant discrepancies were identified,highlighting that greater attention must be paid to updating the current thermodynamic database related to vanadium-bearing slag systems.

Breaking the Fe_(3)O_(4)-wrapped copper microstructure to enhance copper-slag separation

The precipitation of Fe_(3)O_(4)particles and the accompanied formation of Fe_(3)O_(4)-wrapped copper structure are the main obstacles to copper recovery from the molten slag during the pyrometallurgical smelting of copper concentrates.Herein,the commercial powdery pyrite or anthracite is replaced with pyrite-anthracite pellets as the reductants to remove a large amount of Fe_(3)O_(4)particles in the molten slag,resulting in a deep fracture in the Fe_(3)O_(4)-wrapped copper microstructure and the full exposure of the copper matte cores.When 1wt%composite pellet is used as the reductant,the copper matte droplets are enlarged greatly from 25μm to a size observable by the naked eye,with the copper content being enriched remarkably from 1.2wt%to 4.5wt%.Density functional theory calculation results imply that the formation of the Fe_(3)O_(4)-wrapped copper structure is due to the preferential adhesion of Cu_(2)S on the Fe_(3)O_(4)particles.X-ray photoelectron spectroscopy,Fourier transform infrared spectrometer(FTIR),and Raman spectroscopy results all reveal that the high-efficiency conver-sion of Fe_(3)O_(4)to FeO can decrease the volume fraction of the solid phase and promote the depolymerization of silicate network structure.As a consequence,the settling of copper matte droplets is enhanced due to the lowered slag viscosity,contributing to the high efficiency of copper-slag separation for copper recovery.The results provide new insights into the enhanced in-situ enrichment of copper from mol-ten slag.

Copper slag assisted coke reduction of phosphogypsum for sulphur dioxide preparation

The reduction of phosphogypsum(PG)to lime slag and SO_(2)using coke can effectively alleviate the environmental problems caused by PG.However,the PG decomposition temperature remains high and the product yield remains poor.By adding additives,the decomposition temperature can be further reduced and PG decomposition rate and product yield can be improved.However,the use of current additives such as Fe_(2)O_(3)and SiO_(2)brings the problem of increasing economic cost.Therefore,it is proposed to use solid waste copper slag(CS)as a new additive to reduce PG to prepare SO2,which can reduce the cost and meet the environmental benefits at the same time.The effects of proportion,temperature and thermostatic time on PG decomposition are investigated by experimental and kinetic analysis combined with FactSage thermodynamic calculations to optimize the roasting conditions.Finally,the reaction mechanism is proposed.It is found that adding CS to the coke and PG system can increase the rate of PG decomposition and SO_(2)yield while lowering the PG decomposition temperature.For example,when the CS/PG mass ratio increases from 0 to 1,PG decomposition rate increases from 83.38%to 99.35%,SO_(2)yield increases from 78.62%to 96.81%,and PG decomposition temperature decreases from 992.4℃to 949.6℃.The optimal reaction parameters are CS/PG mass ratio of 1,Coke/PG mass ratio of 0.06 at 1100℃for 20 min with 99.35%PG decomposition rate and 96.81%SO_(2) yield.The process proceeds according to the following reactions:2CaSO_(4)+ 0.7C + 0.8Fe_(2)SiO_(4)→0.8Ca_(2)SiO_(4)+ 0.2Ca_(2)Fe_(2)O_(5)+ 0.4Fe_(3)O_(4)+2SO_(2)+ 0.7CO_(2)Finally,a process for decomposing PG with coke and CS is proposed.

Multiscale analysis of fine slag from pulverized coal gasification in entrained-flow bed

Fine slag(FS)is an unavoidable by-product of coal gasification.FS,which is a simple heap of solid waste left in the open air,easily causes environmental pollution and has a low resource utilization rate,thereby restricting the development of energy-saving coal gasification technologies.The multiscale analysis of FS performed in this study indicates typical grain size distribution,composition,crystalline structure,and chemical bonding characteristics.The FS primarily contained inorganic and carbon components(dry bases)and exhibited a"three-peak distribution"of the grain size and regular spheroidal as well as irregular shapes.The irregular particles were mainly adsorbed onto the structure and had a dense distribution and multiple pores and folds.The carbon constituents were primarily amorphous in structure,with a certain degree of order and active sites.C 1s XPS spectrum indicated the presence of C–C and C–H bonds and numerous aromatic structures.The inorganic components,constituting 90%of the total sample,were primarily silicon,aluminum,iron,and calcium.The inorganic components contained Si–O-Si,Si–O–Al,Si–O,SO_(4)^(2−),and Fe–O bonds.Fe 2p XPS spectrum could be deconvoluted into Fe 2p_(1/2) and Fe 2p_(3/2) peaks and satellite peaks,while Fe existed mainly in the form of Fe(III).The findings of this study will be beneficial in resource utilization and formation mechanism of fine slag in future.