Comparison of the interface reaction behaviors of CaO–V_(2)O_(5) and MnO_(2)–V_(2)O_(5) solid-state systems based on the diffusion couple method

The formation mechanism of calcium vanadate and manganese vanadate and the difference between calcium and manganese in the reaction with vanadium are basic issues in the calcification roasting and manganese roasting process with vanadium slag.In this work,CaO–V_(2)O_(5) and MnO_(2)–V_(2)O_(5) diffusion couples were prepared and roasted for different time periods to illustrate and compare the diffusion reaction mechanisms.Then,the changes in the diffusion product and diffusion coefficient were investigated and calculated based on scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS) analysis.Results show that with the extension of the roasting time,the diffusion reaction gradually proceeds among the CaO–V_(2)O_(5) and MnO_(2)–V_(2)O_(5) diffusion couples.The regional boundaries of calcium and vanadium are easily identifiable for the CaO–V_(2)O_(5) diffusion couple.Meanwhile,for the MnO_(2)–V_(2)O_(5) diffusion couple,MnO_(2) gradually decomposes to form Mn_(2)O_(3),and vanadium diffuses into the interior of Mn_(2)O_(3).Only a part of vanadium combines with manganese to form the diffusion production layer.CaV_(2)O_(6) and MnV_(2)O_(6) are the interfacial reaction products of the CaO–V_(2)O_(5) and MnO_(2)–V_(2)O_(5) diffusion couples,respectively,whose thicknesses are 39.85 and 32.13μm when roasted for 16 h.After 16 h,both diffusion couples reach the reaction equilibrium due to the limitation of diffusion.The diffusion coefficient of the CaO–V_(2)O_(5) diffusion couple is higher than that of the MnO_(2)–V_(2)O_(5) diffusion couple for the same roasting time,and the diffusion reaction between vanadium and calcium is easier than that between vanadium and manganese.

VUV luminescence properties of Y_(0.95)Eu_(0.05)PO_4 phosphor derived by a modified solid-state route

A modified solid-state route was attempted to prepare Y0.95 Eu0.05PO4 PDP phosphor, involving milling a powdered mixture of YCl3, EuCl3, and （NH4）2HPO4 and calcining the milling-derived precursor. The thermal decomposition behavior of the milling-derived precursor was investigated by thermogravimetric analysis （TGA）. Phase compositions, morphologies, and luminescence properties of the prepared phosphor powder were characterized by X-ray diffraction （XRD）, scanning electron microscope （SEM）, and vacuum ultraviolet （VUV） emission spectra, respectively. The results indicated that the Y0.95Eu0.05PO4 phosphor powder obtained at a calcination temperature of 900℃ was xenotime-structured. The phosphor powder particles were uniform and spherical-shaped with a primary particle size of-200 um. In comparison with that derived by the conventional solid-state route, the phosphor powder prepared by the modified solid-state route exhibited a higher color purity, presenting a predominant emission peak at 619 nm under 147 um VUV excitation.

Facile Solid-State Synthesis Route to Metal Nitride Nanoparticles

By a facile and efficient solid-state reaction route using an organic reagent cyanamide （CN2H2） as a precursor with another one being metal oxides, we successfully synthesized seven technologically important metal nJtrJdes including cubic VN, CrN, NbN, hexagonal GaN, AIN, BN, and WN at moderate temperatures. The experimental results show that cyanamide （CN2H2） is a powerfully reducing and nitridizing reagent and the metal oxides are completely converted into the corresponding nitride nanoparticles at lower temperatures than that reported in the conventional methods. It is found that EN2H2 can exhibit some interesting condensation processes, and the final products, highly active carbon nitride species, play a crucial role in the reducing and nitridizing processes.

Kinetics of solid-state reduction of chromite overburden

The demand for alternative low-grade iron ores is on the rise due to the rapid depletion of high-grade natural iron ore resources and the increased need for steel usage in daily life.However,the use of low-grade iron ores is a constant clinical task for industry metallurgists.Direct smelting of low-grade ores consumes a substantial amount of energy due to the large volume of slag generated.This condition can be avoided by direct reduction followed by magnetic separation(to separate the high amount of gangue or refractory and metal parts)and smelting.Chromite overburden(COB)is a mine waste generated in chromite ore processing,and it mainly consists of iron,chromium,and nickel(<1wt%).In the present work,the isothermal and non-isothermal kinetics of the solid-state reduction of self-reduced pellets prepared using low-grade iron ore(COB)were thoroughly investigated via thermal analysis.The results showed that the reduction of pellets followed a firstorder autocatalytic reaction control mechanism in the temperature range of 900-1100℃.The autocatalytic nature of the reduction reaction was due to the presence of nickel in the COB.The apparent activation energy obtained from the kinetics results showed that the solid-state reactions between COB and carbon were the rate-determining step in iron oxide reduction.

Preparation of nano-sized cerium and titanium pyrophosphates via solid-state reaction at room temperature

Nano-sized cerium-titanium pyrophosphates Ce1-xTixP2O7 （with x = 0, 0.2, 0.5, 0.7, 0.9, and 1.0） were obtained by grinding a mixture of Ce（SO4）2·4H2O, Ti（SO4）2, and Na4P2O7·10H2O in the presence of surfactant PEG-400 at room temperature, washing the mixture with water to remove soluble inorganic salts, and drying at 100℃. The products and their calcined samples were characterized using ultraviolet-visible spectroscopy （UV-vis）, thermogravimetry and differential thermal analyses （TG/DTA）, X-ray powder diffraction （XRD）, and transmission electron microscopy （TEM）. The results show that nano-sized Ce1-xTixP2O7 behave as an excellent UV-shielding material. Thereinto, the CeP2O7 has the most excellent UV-shielding effect, and the amorphous state of Ce0.8Ti0.2P2O7 can keep at a higher temperature than CeP2O7. Therefore, the stabilization of the amorphous state of the cerium pyrophosphates was carded out by doping titanium. This stabilization is a significant improvement, which enables to apply these amorphous pyrophosphates not only to cosmetics and paints, but also plastics and films.

Electrochemical properties of spinel LiMn_2O_4 and LiAl_(0.1)Mn_(1.9)O_(3.9)F_(0.1) synthesized by solid-state reaction

Two types of spinel cathode powders, LiMn2O4 and LiAl0.1Mn1.9O3.9F0.1, were synthesized by solid-state reaction, X-ray diffraction （XRD） patterns of the prepared samples were identified as the spinel structure with a space group of Fd 3^- m. The cubic lattice parameter was determined from least-squares fitting of the XRD data. The LiAl0.1Mn1.9O3.9F0.1 sample showed a little lower initial capacity, but better cycling performance than the LiMn2O4 sample at both room temperature and an elevated temperature. The Vanderbilt method was used to test the electrochemical conductivity of the LiMn2O4 samples. The electrochemical impedance spectroscopy （EIS） method was employed to investigate the electrochemical properties of these spinel LiMn2O4 samples.

Strontium ferrite powders prepared from oily cold rolling mill sludge by solid-state reaction method

Oily cold rolling mill （CRM） sludge is one of the pollutants emitted by iron and steel plants. Recycling oily CRM sludge can not only reduce pollution but also bring social and environmental benefits. In this study, using oily CRM sludge as sources of iron oxide, the strontium ferrite powders were synthesized in multiple steps including vacuum distillation, magnetic separation, oxidizing roasting, and solidstate reaction. The optimal technological conditions of vacuum distillation and oxidizing roasting were studied carefully. To consider the effects of Fe203/ SrCO3 tool ratio, calcination temperature, milling time and calcination time on magnetic properties of prepared strontium ferrite powders, the orthogonal experimental method was adopted. The maximum saturation magneti- zation （62.6 mA-m2.g-1） of the synthesized strontium ferrite powders was achieved at the Fe203/SrCO3 mol ratio of 6, 5 h milling time, 1250 ~C calcination temperature, and 1 h calcination time. Strontium ferrite powders syn- thesis method not only provides a cheap, high quality raw material for the production of strontium ferrite powders, but also effectively prevents the environmental pollution.

Application-oriented hydrolysis reaction system of solid-state hydrogen storage materials for high energy density target:A review

Hydrogen storage and delivery technology is still a bottleneck in the hydrogen industry chain.Among all kinds of hydrogen storage methods,light-weight solid-state hydrogen storage(LSHS)materials could become promising due to its intrinsic high hydrogen capacity.Hydrolysis reaction of LSHS materials occurs at moderate conditions,indicating the potential for portable applications.At present,most of review work focuses on the improvement of material performance,especially the catalysts design.This part is important,but the others,such as operation modes,are also vital to to make full use of material potential in the practical applications.Different operation modes of hydrolysis reaction have an impact on hydrogen capacity to various degrees.For example,hydrolysis in solution would decrease the hydrogen capacity of hydrogen generator to a low value due to the excessive water participating in the reaction.Therefore,application-oriented operation modes could become a key problem for hydrolysis reaction of LSHS materials.In this paper,the operation modes of hydrolysis reaction and their practical applications are mainly reviewed.The implements of each operation mode are discussed and compared in detail to determine the suitable one for practical applications with the requirement of high energy density.The current challenges and future directions are also discussed.

Recent advance in high-pressure solid-state metathesis reactions

High-pressure solid-state metathesis(HPSSM)reaction is an effective route to novel metal nitrides.A recent advance in HPSSM reactions is presented for a number of examples,including 3d transition metal nitrides(ε-Fe_(3)N,ε-Fe_(3-x)Co_(x)N,CrN,and Co_(4)N_(x)),4d transition metal nitrides(MoNx),and 5d transition metal nitrides(Re_(3)N,WN_(x)).Thermodynamic investigations based on density functional theory(DFT)calculations on several typical HPSSM reactions between metal oxides and boron nitride indicate that the pressure could reduce the reaction enthalpy △H.High-pressure confining environment thermodynamically favors an ion-exchange process between metal atom and boron atom,and successfully results in the formation of well-crystalized metal nitrides with potential applications.

Chemical Reaction Route Selection Based on Green Chemical Engineering

In the preliminary stage of chemical process design, the choice of chemical reaction route is the key design decision, and the concepts of atom utilization and environmental quotient have become extremely useful tools. However, the waste quality such as chemical toxicity and other engineering factors have not been taken into account. Therefore, a synthetic route selection index, Iroute, is proposed to determine the suitability of a chemical route in this paper. Iroute considers the effects of 'extended atom economy', material renewability, chemical characteristics and some engineering factors. The extended atom economy concept regards not only the value of the desired product but also the value of byproducts. The methodology by using Iroute to compare different routes is illustrated in case study of cyclohexanone oxime and acrylonitrile manufacture.

Robust interface layers with redox shuttle reactions suppress the dendrite growth for stable solid-state Li metal batteries

Designing a durable lithium metal anode for solid state batteries requires a controllable and uniform deposition of lithium, and the metal lithium layer should maintain a good interface contact with solid state electrolyte during cycles. In this work, we construct a robust functional interface layer on the modified LiB electrode which considerably improves the electrochemical stability of lithium metal electrode in solid state batteries. It is found that the functional interface layer consisting of polydioxolane, polyiodide ion and Li TFSI effectively restrains the growth of lithium dendrites through the redox shuttle reaction of I-/I3-and maintains a good contact between lithium anode and solid electrolyte during cycles. Benefit from these two advantages, the modified Li-B anode exhibits a remarkable cyclic performance in comparison with those of the bare Li-B anode.

Effects of Solid-State Reaction Synthesis Processing Parameters on Thermoelectric Properties of Mg_2Si

The Mg_(2)Si-matrix thermoelectric material was synthesized by low temperature solid-state reaction.This paper studies the effects of holding time and reaction temperature on the particle size and the properties of the material,and also studies effects of doping elemental Sb,Te and their doping seqence on the properties of the material.The result shows that excessively high temperature and elongated holding time of solid-state reaction are harmful,there is a range of particle size to ensure optimum properties and the doping sequence of Sb or Te without influencing the properties.

Preparation of NH_4ZrH(PO_4)_2·H_2O via solid-state reaction at low heat and its catalytic performance in the synthesis of butyl acetate

Nanocrystalline NH4ZrH（PO4）2·H2O was obtained by grinding ZrOC12·8H2O and （NH4）2HPO4 in the presence of surfactant PEG-400 via solid-state reaction at room temperature. The product NH4ZrH（PO4）2·H2O and its product of thermal decomposition were characterized using thermogravimetry and differential thermal analyses （TG/DTA）, Fourier transform infrared spectroscopy （FT-IR）, X-ray powder diffraction （XRD）, and transmission electron microscopy （TEM）. Nanocrystalline NHaZrH（PO4）2·H2O with an average particle size of 17 nm was obtained when the product was kept at80℃ for 3 h. Its crystalline framework was stable at temperatures below 250℃. In addition, the catalytic performance of NH4ZrH（PO4）2·H2O in the synthesis of butyl acetate was investigated. The results show that NH4ZrH（PO4）2·H2O behaved as an excellent heterogeneous catalyst in the synthesis of butyl acetate.

Solid-state reaction of a CaO−V_(2)O_(5)mixture:A fundamental study for the vanadium extraction process

The aim of this study was to investigate the phase transformation and kinetics of the solid-state reaction of CaO−V_(2)O_(5),which is the predominant binary mixture involved in the vanadium recovery process.Thermal analysis,X-ray diffraction spectroscopy,scanning electron microscopy,and energy dispersive spectrometry were used to characterize the solid-state reaction of the samples.The extent of the solid reac-tion was derived using the preliminary quantitative phase analysis of the X-ray patterns.The results indicate that the solid reaction of the CaO−V_(2)O_(5)mixture is strongly influenced by the reaction temperature and CaO/V_(2)O_(5)mole ratio.The transformation of calcium vanadate in-volves a step-by-step reaction of CaO−V_(2)O_(5),CaO−CaV_(2)O_(6),and CaO−Ca_(2)V_(2)O7 depending on the CaO/V_(2)O_(5)mole ratio.The kinetic data of the solid reaction of the CaO−V_(2)O_(5)(1:1)mixture followed a second-order reaction model.The activation energy(Ea)and preexponential factor(A)were determined to be 145.38 kJ/mol,and 3.67×10^(8)min^(−1),respectively.

Synthesis of Nano-sized Barium Titanate Powder by Solid-state Reaction between Barium Carbonate and Titania

Size control of BaTiO3 in solid-state reaction between BaCO3 and TiO2 was demonstrated by varying the size of TiO2 and milling conditions of BaCO3. The smaller TiO2 particles had higher surface area, resulting in faster initial reaction. The mechanically milled BaCO3 particles accelerated the diffusion process and decreased the calcinations temperature. It can be deduced from the results that the size control is possible and nano-sized BaTiO3 particles with about 60 nm can be synthesized by using the conventional solid-state reaction between BaCO3 and TiO2.

Preparation of new sunscreen materials Ce_(1-x)Zn_xO_(2-x) via solid-state reaction at room temperature and study on their properties

Superfine cerium-zinc oxides Ce1-xZnxO2-x with x = 0, 0.1, 0.3, 0.5, and 1.0 were obtained by grinding Ce（SO4）2·4H2O, ZnSO4·7H2O and NH4HCO3 under the condition of surfactant PEG-400 being present at room temperature, washing the mixture with water to remove soluble inorganic salts, drying at 80°C, and calcining.The precursor and its calcined samples were characterized using thermogravimetry and differential thermal analyses（TG/DTA）, UV-vis absorption spectroscopy, X-ray powder diffraction（XRD）, and scanning electron microscopy（SEM）.The results showed that superfine Ce1-xZnxO2-x behaved as an excellent UV-shielding material.The ZnO-doped CeO2 can facilitate the formation of crystalline state CeO2.The catalytic ability of products used in air oxidation of castor oil was investigated.The results showed that the catalytic abilities of products decreased with increasing zinc amount.

Effect of Ethanol on Synthesis and Electrochemical Property of Mesoporous Al-doped Titanium Dioxide via Solid-state Reaction

Mesoporous aluminum-doped titanium dioxide(Al-TiO2) materials with high specific surface areas were prepared via a solid-state reaction route.The properties of these materials were characterized by X-ray diffraction(XRD),high resolution transmission electron microscopy(HRTEM),energy dispersive spectroscopy(EDS),N2 absorption-desorption,ultraviolet visible light spectroscopy(UV-Vis) and electrochemical spectroscopy.The results show that the mesoporous structure of the product with ethanol is composed of anatase laced crystal walls with amorphous grain boundaries formed gradually by degradation.Compared with those without ethanol,these samples possess larger crystallite size since ethanol decreases the pore size at higher temperature.With the increase of ethanol amount,however,the crystallite size will grow.The amorphous grain boundaries in the mesoporous material,with a large impedance and low incidental cyclic potential,are difficult to effectively degrade and the phase transformation temperature is changed from 500 to 550℃.The growth rate of Al-TiO2 crystallites that obeys the quadratic polynomial equation may be controlled.

Thermal kinetic analysis of a complex process from a solid-state reaction by deconvolution procedure from a new calculation method and related thermodynamic functions of Mn_(0.90)Co_(0.05)Mg_(0.05)HPO_4?3H_2O

Three individual peaks of thermal solid-state reaction processes of the synthesized Mn0.90Co0.05Mg0.05HPO4?3H2O were observed corresponding to dehydration I,dehydration II and polycondensation processes.An alternative method for the calculation of the extent of conversion was proposed from the peak area of the individual DTG peak after applying the best fitting deconvolution function(Frazer–Suzuki function).An iterative integral isoconversional equation was used to compute the values of the apparent activation energy Eαand they were found to be 65.87,78.16 and 119.32 kJ/mol for three peaks,respectively.Each individual peak was guaranteed to be a single-step kinetic system with its unique kinetic parameters.The reaction mechanism functions were selected by the comparison between experimental and model plots.The results show that the first,second and final individual peaks were two-dimensional diffusion of spherical symmetry(D2),three-dimensional diffusion of spherical symmetry(D3)and contracting cylinder(cylindrical symmetry,R2)mechanisms.Pre-exponential factor values of 3.91×106,1.35×107 and 2.15×107 s?1 were calculated from the Eαvalues and reaction mechanisms.The corresponded standard thermodynamic functions of the transition-state(activated)complexes were determined and found to agree well with the experimental data.

Effect of NH_4F and Nano-SiO_2 on Morphological Control of α-Al_2O_3 Platelets via Solid-state Reaction

Alpha-alumina(α-Al_2O_3) platelets were prepared via solid-state reaction using pseudo-boehmite as the starting material, while NH_4F and nano-SiO_2 were used as additives, and nitric acid was used as the binder. The effect of these additives on properties of the alumina platelets was determined via scanning electron microscopy, X-ray diffraction, and measurements of the surface area and silicon content. A mechanism governing their role in the synthesis process was proposed. The results indicated that NH_4F could promote the formation of highly crystalline platelets. Addition of nano-SiO_2 could lead to increase in the diameter and reduction in the thickness of the platelets, and could also prevent their transformation to α-Al_2O_3. This addition weakened the effect of NH_4F because of the reaction of nano-SiO_2 with F-species and the formation of volatile SiF_4.

Effect of Lithium Nitrate on the Structure and Property of α-Al2O3 Platelets Prepared via Solid-state Reaction

The α-Al_2O_3 platelets were prepared via solid-state reactions and the effect of the amount of lithium nitrate additive on the property of the platelets was investigated. The ICP results indicated that the high temperature calcination process resulted in a large loss of lithium species because of volatilization, but there was still a small amount of residual lithium species in the α-Al_2O_3 platelets. The SEM micrographs showed that lithium nitrate led to decrease in the thickness of α-Al_2O_3 platelets and irregular morphology of aggregates. Pore structures results exhibited that addition of lithium nitrate led to decrease in the pore size and increase in the specific surface area of aggregates of α-Al_2O_3 platelets. The XRD and IR patterns suggested that the residual lithium and aluminum oxide formed LiAl_5O_8. The existence of LiAl_5O_8 was the basic reason for the changed performance of α-Al_2O_3 platelets.