Evolution of Phase Composition and Microstructure of Al_2O_3-Si-Al Composite at High Temperatures in Reducing Atmosphere

Al2 O3-Si-Al composite specimens with the size of 25 mm × 25 mm × 125 mm were prepared using fused alumina （as aggregates and fines）,ultra-fine α-Al2O3,Si and Al powders as starting materials,liquid phenol formaldehyde resin as the binder,pressing and heating at 800-1 500 ℃ for 3 h under carbon embedded condition.Evolution of phase composition and microstructure of Al2 O3-Si-Al composite during heating from 800 to 1 500 ℃ under carbon embedded condition were studied.The results show that：（1） Al4 C3,AlN and SiC are initially formed at 800-900 ℃ due to reactions of Al and Si with C or CO and N2 ; （2） at 1 000-1 300 ℃,the amounts of Al4C3,AlN and SiC increase with temperature rising and their crystals grow; （3） at 1 400-1 500 ℃,Al4 C3 and AlN disappear,and minor SiAlON crystals are observed; the nonoxide crystals develop well and they are interlaced in the corundum skeleton structure,which creates strengthening and toughening

Effect of High Temperature Calcination on Structure and Properties of Bauxite-based Homogeneous Clinkers

In this paper,the effect of high temperature calcination on the structure and properties of bauxite-based homogeneous clinkers calcined at different temperatures for different durations was studied.The results show that with the rising of calcination temperature and the prolonging of holding time,the volume density of bauxite-based homogeneous clinkers increases and the apparent porosity decreases.After high temperature calcination,the linear expansion of bauxitebased homogeneous clinker is smaller than that of the non-calcined ones.Whether calcined at high temperatures or not,the thermal shock resistance of bauxite-based homogeneous clinkers is good.The crystalline phases of bauxite-based homogeneous clinkers are mainly mullite and corundum.There is more glass phase in the bauxite-based homogeneous clinkers without calcination.After calcination at high temperatures the glass phase content decreases significantly,and the mullite crystals develop better forming the cross-network structure.

Molten salt synthesis,morphology modulation,and lithiation mechanism of high entropy oxide for robust lithium storage

High entropy oxides(HEOs)with ideal element tunability and enticing entropy-driven stability have exhibited unprecedented application potential in electrochemical lithium storage.However,the general control of dimension and morphology remains a major challenge.Here,scalable HEO morphology modulation is implemented through a salt-assisted strategy,which is achieved by regulating the solubility of reactants and the selective adsorption of salt ions on specific crystal planes.The electrochemical properties,lithiation mechanism,and structure evolution of composition-and morphology-dependent HEO anode are examined in detail.More importantly,the potential advantages of HEOs as electrode materials are evaluated from both theoretical and experimental aspects.Benefiting from the high oxygen vacancy concentration,narrow band gap,and structure durability induced by the multi-element synergy,HEO anode delivers desirable reversible capacity and reaction kinetics.In particular,Mg is evidenced to serve as a structural sustainer that significantly inhibits the volume expansion and retains the rock salt lattice.These new perspectives are expected to open a window of opportunity to compositionally/morphologi cally engineer high-performance HEO electrodes.

Effect of water loss during curing on hydration reaction and hydrates conversion in calcium aluminate cement-bonded castables

Free water available in calcium aluminate cement(CAC)-bonded castables is crucial for the hydration of CAC and the conversion of hydration products in the curing and drying processes,as both the hydration and conversion reactions are dissolution–precipitation reactions.To elucidate the effect of different levels of free water loss upon the hydration of CAC,the conversion of hydration products and the mechanical strength of the CAC-bonded castables,the CAC-bonded castables were subjected to sealed and unsealed curing conditions at 50°C and drying at 110°C.The results demonstrate that the fast removal of free water during unsealed curing would hinder the conversion from 2CaO·Al_(2)O_(3)·8H_(2)O to 3CaO·Al_(2)O_(3)·6H_(2)O and consequently prevent the deterioration of strength.As a comparison,although sealed-cured samples have less water loss and high degree of hydration of CAC,they still show lower strength than the unsealed samples after curing.The following drying process further accelerates the hydration of residual calcium aluminate clinkers for both the sealed and unsealed samples,but still does not favor the conversion from 2CaO·Al_(2)O_(3)·8H_(2)O to 3CaO·Al_(2)O_(3)·6H_(2)O in the unsealed-cured samples.

Effect of CaO Impurity on Mullite Formation from SiO_(2) Gel and Al_(2)O_(3) Powders

To broaden the application of SiO_(2) sol-bonded castables,using micro-or nano-Al_(2)O_(3) powder and SiO_(2) gel powder as the main raw materials,the effects of CaO impurity on the formation of mullite by the reaction of Al_(2)O_(3) and SiO_(2) at different temperatures(1350,1400,1500,and 1600℃)in different atmospheres(oxidation atmosphere and reduction atmosphere)were studied.The results show that in the oxidizing atmosphere,the introduction of CaO can promote the formation of mullite.When the temperature increases from 1350℃to 1600℃,the amount of mullite formed gradually increases.In the reducing atmosphere,the introduction of CaO is not conducive to the formation of mullite,and the amount of mullite decreases with the increasing temperature.The smaller the particle size of Al_(2)O_(3),the more easily it reacts with SiO_(2) gel powder to form mullite.

Effect of Zircon Addition on Properties of Corundum Porous Materials

This paper aims to improve the corrosion resistance of dispersive purging plugs.White fused corundum particles and fine powder,α-Al_(2)O_(3) micropowder,Cr_(2)O_(3) micropowder,Guangxi clay and zircon powder were used as the main raw materials.The mass ratio of white fused corundum particles and fine powder was fixed at 85:15,and 0,1%,2%,or 3%(by mass)of zircon fine powder was added to replace the same amount of white fused corundum fine powder.The corundum porous material was prepared by the particle stacking pore-forming method at 1650℃for 3 h.The effect of the zircon addition on the properties and microstructure of porous materials was investigated.The results show that:after adding zircon,the permeability of the porous material increases,the cold and hot strengths increase obviously,and the expansion rate after firing decreases.When the addition of zircon is 2%,the comprehensive performance of the specimen is optimal with the smallest linear change rate and the highest permeability.

Some Aspects in the Development of High Performance Refractories for Iron and Steel Making in China

In the past 25 years in China, to meet with the rapid increase in steel production accompanied by adoption of advanced metallurgical technologies, there has been fast development of China＇ s refractories industry in production capacity, in quality improvement and in development of new products. Sophisticated high performance refractory materials mainly based on our rich reserves of magncsite, bauxite and flake graphite have been developed, such as carbon-bonded products, high purity oxide products, bauxite-based low creep and high strength high alumina bricks and LC, ULC and ZC castables. They have been used in blast furnaces, BOFs, EAFs, secondary refining and continuous casting with considerable improvement in service pecformance.

Effect of Curing Temperature on Intermediate Temperature Properties of Calcium Aluminate Cement Bonded Corundum Castables

In order to study the effect of the curing temperature on the intermediate temperature properties of calcium aluminate cement bonded corundum castables,the prepared castables were cured at 5,10,25,40 and 50℃,respectively,dried at 110℃ for 24 h and heat treated at 800 and 1100 ℃,respectively.Then the apparent porosity,the cold modulus of rupture and the cold crushing strength were measured.The phase composition of castable matrix specimens treated under the same conditions and the influence of the curing temperature on the intermediate temperature strength of the castables were also analyzed.The results show that with the increase of the curing temperature,the hydration degree of calcium aluminate cement increases,which promotes the uniform distribution of hydration products with AI203 after decomposition,thus enhancing the intermediate temperature strength of castables.

Effect of Andalusite Aggregate Pre-fired at Different Temperatures on Properties of Al2O3-SiC-C Castables

This work investigates the effect of the pre-firing temperature of andalusite aggregate(5-3 mm)on the conversion of andalusite,the volume stability,the thermal shock resistance and the slag resistance of Al2O3-SiC-C castables.The results show that the volume stability and the thermal shock resistance of the castables could be adjusted at different pre-firing temperatures of andalusite aggregates.There was no noticeable difference in the slag resistance between the specimens without andalusite and those with andalusite aggregate pre-fired at different temperatures.

Preparation and properties of Ba_3Zn_ZCo_(2-Z)Fe_(24)O_(41)/SiO_2 microcrystalline glass ceramics

Ba 3Zn Z Co 2 Z Fe 24 O 41 /SiO 2 ( Z varies from 0.0 to 1.2 in step of 0.4) microcrystalline glass ceramics were prepared by citrate sol gel process at 1 200 ℃ in the system of BaO Fe 2O 3 CoO ZnO SiO 2. The samples were characterized by X ray diffraction (XRD) and scanning electron microscopy (SEM). The complex dielectric constant and complex permeability of Ba 3Zn Z Co 2 Z Fe 24 O 41 /SiO 2 microcrystalline glass ceramics were measured in the range of 0.16.0 GHz by transmission/reflection coaxial line method. The natural resonance phenomenon was observed in μ ″ spectra for all the Ba 3Zn Z Co 2 Z Fe 24 O 41 /SiO 2 microcrystalline glass ceramics, which was closely affected by the substitution of Zn 2+ ion.

NiCoP/NiOOH nanoflowers loaded on ultrahigh porosity Co foam for hydrogen evolution reaction under large current density

Developing user-friendly electrodes for efficiently producing hydrogen from water to substitute non-renewable fossil fuels is one of the challenges in the hydrogen energy field.For the first time,we have prepared self-supporting ultrahigh porosity cobalt foam loaded with NiCoP/NiOOH nanoflowers(NiCoP/CF)via freeze-drying and phosphorization.The as-prepared hierarchical NiCoP/CF electrodes showed superior catalytic activity for hydrogen evolution reaction(HER)in alkaline media.The one resulted from phosphorization at 350℃(NiCoP/CF-350)only required overpotential of-47,and-126 mV to deliver geometrical current density of-10 mA cm^(-2) and-100 mA cm^(-2),respectively,demonstrating improved catalytic activity than the electrodes prepared using a commercial nickel foam as a support.Moreover,it could retain its superior stability at a current density higher than-500 mA cm^(-2) for 16 h.Such an outstanding performance can be attributed to the ultrahigh porosity of Co foam support,optimal adsorption energies of HER intermediates(H^(*)),facile water dissociation on the NiCoP/NiOOH heterointerfaces,and the assistance of NiOOH facilitating the electrons transfer from the Co foam inside to the NiCoP outside.The work would provide a new strategy for future design of advanced HER electrocatalysts.

Binder Effect on Properties of Cr_(2)O_(3)-bearing Corundum-based Refractory Castables

Cr_(2)O_(3)-bearing castables bonded with reactive MgO(RM)or calcium aluminate cement(CAC)were studied to evaluate the binder effect on their performance in corrosive environments.The properties of the as-prepared castables were compared with respect to the differences in phase composition and microstructure.The corrosion behavior of the as-prepared castables by CaO-Al_(2)O_(3)-Fe_(2)O_(3)-SiO_(2)-based slag was systematically compared viarefractory cup testing at 1600℃with respect to the differences in phase composition and microstructure.The analysis indicates that RM bonded castables show higher apparent porosity,lower bulk density and strengths after drying at 110℃and firing at 1300℃,and higher permanent linear change after firing at 1300℃,but better slag corrosion and infiltration resistance compared with CAC bonded castables.

Performance of Adsorbents for NO_(2) in Furnace Flue Gas

To meet the emission standard of nitrogen oxides(NOx)in the flue gas of batch furnaces through dry adsorption,a calcium-silica inorganic adsorbent was prepared with limestone and quartz as raw materials.Sample Cu-BTC 1#was obtained by solvothermal synthesis,drying and purification in vacuum at 120℃using trimesic acid(H3BTC)and copper nitrate trihydrate(Cu(NO_(3))2·3H_(2)O)as raw materials;likewise,sample Cu-BTC 3#was obtained at 200℃.Sample Cu-BTC 2#was obtained by hydrothermal synthesis,drying and purification in air(metal-organic frameworks,1,3,5-benzene tricarboxylic acid copper).The two types of materials were tested in terms of the NO_(2) adsorption,and then the specific surface area,pore volume,NO_(2) adsorption performance,phase composition,microstructure and thermal stability of the adsorbent materials were exploredvia N_(2) physical adsorption-desorption,SEM,XRD and TG characterization.The results show that:(1)the Cu-BTC samples have higher adsorption capacity than the calcium-silica adsorbent,in which sample Cu-BTC 3#has the largest specific surface area and pore volume,thus adsorption capacity for NO_(2);(2)the calcium-silica adsorbent has better thermal stability and lower total mass loss during the entire process than the Cu-BTC samples;sample Cu-BTC 2#has the best thermal stability among the three Cu-BTC samples,and the metal Cu active sites of the Cu-BTC samples can be exposed at least above 150℃.

Foam-gelcasting preparation of porous Si C ceramic for high-temperature thermal insulation and infrared stealth

Porous SiC ceramics(PSCs)are promising lightweight and efficient thermal insulators that can evade infrared detection by reducing the surface temperature of the protected object,which plays a crucial role in the development of new military equipment.However,the controllable synthesis of PSCs with both hierarchical pore structure and thermal/mechanical stability remains challenging.In this work,such PSCs were prepared by a facile foam-gelcasting/solid-state reaction method,using silicon powders and glucose-derived carbon as starting materials.The favorable dispersibility and wettability of hydrophilic carbon microspheres and the in-situ formed SiC guarantee the highly porous structure(92.8%porosity),comparable bulk density(0.20 g·cm^(-3))and reasonable mechanical property of the product.The designed PSCs performed outstanding high-temperature performance,especially thermal insulation in both oxidizing and inert atmospheres.More importantly,the composite architecture of PSCs and low emissivity layer(Al foil)exhibited desirable infrared stealth property(at a temperature up to 1100℃),significantly extending the operating temperature range of thermal camouflage material.The unique combination of excellent properties would make PSCs a potential candidate material for future thermal protection and infrared stealth applications in an extreme environment.

Preparation of ZrB_(2)-ZrO_(2)-SiC Composite Powder by Carbothermal Reduction from Zircon

Using zircon,boric acid and carbon black as starting materials,ZrB_(2)-ZrO_(2)-SiC composite powder was synthesized by calcining at 1500℃in flowing argon atmosphere.The effects of the soaking time(3,6 and 9 h)and the addition of additive AlF_(3)(0,0.5%,1.0%,1.5%,2.0%and 2.5%,by mass)on the phase composition and the microstructure of the synthesized products were investigated.The results show that:(1)ZrB_(2)-ZrO_(2)-SiC composite powder can be synthesized by carbothermal reduction at 1500℃in flowing argon atmosphere;ZrB_(2) and ZrO_(2) are granular-like,and SiC crystals are fiberous;(2)with the soaking time increasing,the amount of ZrB_(2) increases,the amounts of m-ZrO_(2) and SiC decrease,and the total amount of non-oxides ZrB_(2),SiC and ZrC gradually increases;the optimal soaking time is 3 h;(3)compared with the sample without AlF_(3),the sample with 0.5% AlF_(3) has decreased m-ZrO_(2)amount,noticeably increased ZrB_(2) amount but decreased SiC amount;however,when the addition of AlF_(3) increases from 0.5%to 2.5%,the m-ZrO_(2) amount increases,the ZrB_(2)amount decreases,and the SiC amount changes slightly;the optimum AlF_(3)addition is 0.5%.

Manufacture of Zn-Co Substituted Y-Type Barium Hexagonal Ferrites by Citrate Precursor Route and Their Microwave Properties

Ba2ZnxCo2-xFe12O22 hexaferrites with x = 0.0, 0.4, 0.8, 1.2, 1.6 and 2.0 were prepared by citrate sol-gel process. The complex dielectric constant and complex permeability of hexaferrites were studied as functions of the measuring frequency, composition and sintering temperature in the range 100 MHz similar to 6 GHz. The natural resonance phenomenon is observed in mu' spectrum for all Y-type hexaferrites, which resonance frequency is dependent on zinc content and firing temperature. The natural resonance frequencies Of Co2Y hexaferrite were calculated, which is in agreement with the measuring results. The reflection loss of those ferrites is measuring frequency as well as absorber thickness dependent, and the higher the frequency and the thickness are, the higher the reflection loss is.

Progress in Research and Development of Refractory Oxide-Nonoxide Composites

Some of the progress made in our laboratories in collaboration with industry in research and development work on high performance oxide-nonoxide composites for metallurgical applications has been reviewed. （1） SiAlON bonded corundum composites for blast furnace usage have been produced by reduction-nitridation sinte-ring at high temperature, using bauxite instead of alu-mina in the matrix. （2） Low carbon Al2O3 - SiAlON slide plate materials successfully used in high quality steel continuous casting have been developed in which most or all of the graphite in Al2O3 - C brick is replaced by bauxite-based β-SiAlON. （3） A1/Si metal bonded A12 03 - C material characterized by low carbon content, low firing temperature and in-situ formation of carbides and nitrides at high temperature during service are found to possess very high hot strength and very good thermal shock resistance and have also been successfully used as slide plates in ladles and tundishes for high quality steel casting.

Effects of Nano Calcium Carbonate on Strength and Microstructure of Corundum-based Castables

The castables specimens were prepared using white fused alumina particle and powder, α-Al2O3 micropowder, hydrated alumina, nano calcium carbonate or calcium aluminate cement as starting materials. Effects of nano calcium carbonate addition on phase compositions, strength and microstructure of corundum based castables were studied. The calcium aluminate cement-containing corundum based castables with the same CaO amount was also tested for comparison. The results show that, when temperature is higher than 900 ℃ , the phase compositions of nano CaCO3-containing mixture and the calcium aluminate cement containing mixture are the same, but the forming mechanism, modality and distribution of new phases in the castables are different. With temperature rising, the hydration cement dehydrates and reacts inside cement forming calcium aluminate until the alumina in cement is not enough for the reaction （ternperature is 91 400 ℃ ） , then reacts with the surrounding alumina forming cluster CA6 in the castables. The change process of nano CaCO3 in corundum based enstables is that nano calcium carbonate decomposes to CaO after firing at 800℃ which reacts with Al2O3 forming amorphous calcium aluminate that causes an in-situ bonding. With temperature rising, the formed calcium aluminate reacts with Al2O3 in matrix and wholly forms tabular CA6 at 1 600 ℃ , which distributes uniformly in the castables. The cold and hot strength of the castables with nano calcium carbonate are obviously higher than those of the castables without nano calcium carbonate, especially at 800 -1 000 ℃ due to smaller size and higher dispersion of the nano calcium carbonate and its different reaction mechanism with Al2O3.

Surface functionalized N-C-TiO_(2)/C nanocomposites derived from metal-organic framework in water vapour for enhanced photocatalytic H generation

Surface-functionalized nitrogen/carbon co-doped polymorphic TiO_(2) phase junction nanoparticles uniformly distributed in porous carbon matrix were synthesized by a simple one-step pyrolysis of titanium based metal-organic framework(MOF),NH_(2)-MIL^(-1)25(Ti) at 700℃ under water vapour atmosphere.Introducing water vapour during the pyrolysis of NH_(2)-MIL^(-1)25(Ti) not only functionalizes the derived porous carbon matrix with carboxyl groups but also forms additional oxygen-rich N like interstitial/intraband states lying above the valence band of TiO2 along with the self-doped carbo n,which further narrows the energy band gaps of polymorphic TiO2 nanoparticles that enhance photocatalytic charge transfer efficiency.Without co-catalyst,sample N-C-TiO2/CArW demonstrates H_(2) evolution activity of 426 μmol gcat-1h^(-1),which remarkably outperforms commercial TiO_(2)(P-25) and N-C-TiO_(2)/CAr with a 5-fold and 3-fold H_(2) generation,respectively.This study clearly shows that water vapour atmosphere during the pyrolysis increases the hydrophilicity of the Ti-MOF derived composites by functionalizing porous carbon matrix with carboxylic groups,as well as enhancing the electrical conductivity and charge transfer efficiency due to the formation of additional localized oxygen-rich N like interstitial/intraband states.This work also demonstrates that by optimizing the anatase-rutile phase composition of the TiO2 polymorphs,tuning the energy band gaps by N/C co-doping and functionalizing the porous carbon matrix in the N-C-TiO2/C nanocomposites,the photocatalytic H_(2) generation activity can be further enhanced.

Three-dimensional graphitic carbon sphere foams as sorbents for cleaning oil spills

Frequent offshore oil spill accidents, industrial oily sewage, and the indiscriminate disposal of urban oily sewage have caused seri- ous impacts on the human living environment and health. The traditional oil-water separation methods not only cause easily environmental secondary pollution but also a waste of limited resources. Therefore, in this work, three-dimensional (3D) graphitic carbon sphere (GCS) foams (collectively referred hereafter as 3D foams) with a 3D porous structure, pore size distribution of 25-200 μm, and high porosity of 62vol% were prepared for oil adsorption via gel casting using GCS as the starting materials. The results indicate that the water contact angle (WCA) of the as-prepared 3D foams is 130°. The contents of GCS greatly influenced the hydrophobicity, WCA, and microstructure of the as-prepared samples. The adsorption capacities of the as-prepared 3D foams for paraffin oil, vegetable oil, and vacuum pump oil were approximately 12-15 g/g, which were 10 times that of GCS powder. The as-prepared foams are desirable characteristics of a good sorbent and could be widely used in oil spill accidents.