Effect of Slag Basicity on Alumina Dissolution and Diffusivity:A High-temperature Confocal Laser Scanning Microscopy Study

Alumina is one of the crucial and extensively utilized refractory components.As the refractory wear due to dissolution at elevated temperatures during operation is a major threat to refractory lifespan,quantifying dissolution is important for developing cost-effective and resource-efficient refractories.This study investigated the dissolution of alumina particles in two silicate and one calcium aluminate slags at 1450,1500,and 1550°C using high-temperature confocal laser scanning microscopy(HT-CLSM).Dissolution was quantified in terms of diffusivity,with all influencing factors,including Stefan flow and bath movement,incorporated into the determination process.The trends observed in total dissolution time and diffusivity in three slags at three experimental temperatures could not be explained solely on the basis of slag basicity.Two parameters,considering the influencing factors,were introduced to explain these trends.Furthermore,the linear trend observed in Arrhenius plots of diffusivities supports the diffusivity results.Additionally,good agreement between the diffusivities of alumina in one silicate slag obtained via CLSM and rotating finger test investigations verified the reliability of the results.

In situ observation of the dissolution kinetics of Al_(2)O_(3) particles in CaO–Al_(2)O_(3)–SiO_(2) slags using laser confocal scanning microscopy

The dissolution kinetics of Al_(2)O_(3) in CaO-Al_(2)O_(3) SiOslags was studied using a high-temperature confocal scanning laser microscope at 1773 to 1873 K.The results show that the controlling step during the Al_(2)O_(3) dissolution was the diffusionin molten slag.It was found that the dissolution curves of Al_(2)O_(3) particles were hardly agreed with the traditional boundary layer diffusion model with the increase of the CaO/Al_(2)O_(3) ratio of slag.A modified diffusion equation considering slag viscosity was developed to study the dissolution mechanism of Al_(2)O_(3) in slag.Diffusion coefficients of Al_(2)O_(3) in slag were calculated as 2.8×10to 4.1×10m~2/s at the temperature of 1773-1873 K.The dissolution rate of Al_(2)O_(3) increased with higher temperature,CaO/Al_(2)O_(3),and particle size.A new model was shown to be v_(Al_(2)O_(3))=0.16×r_(0)^(1.58)×x^(3.52)×(T-T_(mp))^(1.11)to predict the dissolution rate and the total dissolution time of Al_(2)O_(3) inclusions with various sizes,where vAl_(2)O_(3) is the dissolution rate of Al_(2)O_(3) in volume,μm^(3)/s;x is the value of CaO/Al_(2)O_(3) mass ratio;R_(0) is the initial radius of Al_(2)O_(3),μm;T is the temperature,K;T_(mp) is the melting point of slag,K.

Dissolution and diffusion of TiO_2 in the CaO-Al_2O_3-SiO_2 slag

The dissolution of TiO2 in the CaO-Al2O3-SiO2 slag under static conditions was studied in the temperature range from 1643 K to 1703 K. After TiO2 dissolved, the microstructure of the interface between TiO2 and the slag was observed by scanning electron microscopy, and the concentration profiles of Ti4＋and other ions across the TiO2/slag interfaces were analyzed by energy-dispersive X-ray spectroscopy. On the basis of these results, the dissolution behavior of TiO2 was evaluated, and the diffusivity of Ti4＋in the bulk slag was estimated. Ac-cording to the Stokes-Einstein relation, the viscosity calculated by a previously reported model gave a diffusivity of Ti4＋ions greater than that estimated by the concentration profiles of Ti4＋ions. The mechanism of TiO2 dissolution in the CaO-Al2O3-SiO2 slag is discussed in de-tail.

Adsorption Thermodynamics and Diffusion Kinetics of PX over Na Y Zeolite Synthesized by In-Situ Crystallization from Kaolin Microsphere

Para-xylene was chosen as the probe molecule to study adsorption thermodynamics and diffusion kinetics on NaY zeolite and composite structured NaY zeolite synthesized by in-situ crystallization from kaolin microsphere(designated as Na Y/kaolin composites) separately, using a high precision intelligent gravimetric analyzer(IGA). The adsorption isotherms showed normal Langmuir type-Ⅰ behaviors. The increased adsorption heat with an increasing p-xylene coverage supported a mechanism of phase transition, diffusion and re-arrangement of p-xylene molecules during the adsorption process. The rearrangement seemed to be most pronounced at an adsorption loading of 2.13 and 2.29 mmol/g for Na Y zeolite and Na Y/kaolin composites respectively. Compared with Na Y zeolite, a 2—3 times higher in the diffusion coefficient of p-xylene was observed on Na Y/kaolin composites when the pressure was more than 50 Pa. Temperature-programmed desorption(TPD) of p-xylene on two samples from room temperature to 450 ℃ at a special loading has also been investigated by IGA. Results showed only single desorption peak appeared for Na Y zeolite, indicating that adsorption can only occur in the super-cage structure. Comparably, there were two different peaks for in-situ synthesized Na Y zeolite, corresponding to the two thermo desorption processes in both super-cage structure and the channels provided by kaolin, respectively.Key words:

Dissolution kinetics and mechanism of gibbsitic bauxite and pure gibbsite in sodium hydroxide solution under atmospheric pressure

The crystal structure, morphology, dissolution kinetics and mechanism of gibbsitic bauxite and pure gibbsite in Na OH solution under atmospheric pressure were systematically investigated by XRD and SEM. The results show that the size of single crystal of gibbsite in gibbsitic bauxite is smaller than that in pure gibbsite, but the interplanar distance is larger than that of pure gibbsite, which result in more defects in the crystal and less energy needed to dissolve in alkaline solution for the gibbsitic bauxite. The dissolution kinetic equations of gibbsitic bauxite and pure gibbsite were established, and the corresponding activation energies were calculated to be 99.144 and 115.149 k J/mol, respectively.

Influence of ammonium sulfate on the corrosion behavior of AZ31 magnesium alloy in chloride environment

Electrochemical corrosion of AZ31 magnesium alloy in the NH_(4)^(+)-SO_(4)2−-Cl−environment is studied.Effect of NH_(4)^(+)overshadows that of Cl−as the(NH_(4))_(2)SO_(4) concentration is 0.005 M or higher,yielding an evolution from localized corrosion to uniform corrosion.Acceleration effect of NH_(4)^(+)can be attributed to that(i)NH_(4)^(+)dissolves the inner MgO and hinders the precipitation of Mg(OH)_(2) and(ii)the buffering ability of NH_(4)^(+)provides H+,enhances the hydrogen evolution,and expedites the corrosion process.The latter is demonstrated as the dominant factor with the results in unbuffered and buffered environments.The severe corrosion and hydrogen process in NH_(4)^(+)-containing solution results in a high Hads coverage and yields an inductive loop within the low frequency.Meanwhile,SO_(4)^(2−)is helpful in generating cracked but partially protective corrosion products,while Cl−could broaden the corrosion area beneath the corrosion product.

Solvent transport dynamics and its effect on evolution of mechanical properties of nitrocellulose(NC)-based propellants under hot-air drying process

Appropriate drying process with optimized controlling of drying parameters plays a vital role in the improvement of the quality and performance of propellant products.However,few research on solvent transport dynamics within NC-based propellants was reported,and its effect on the evolution of mechanical properties was not interpreted yet.This study is conducted to gain a comprehensive understanding of hot-air drying for NC-based propellants and clarify the effect of temperature on solvent transport behavior and further the change of mechanical properties during drying.The drying kinetic curves show the drying time required is decreased but the steady solvent content is increased and the drying rate is obviously increased with the increase of hot-air temperatures,indicating hot-air temperatures have a significant effect on drying kinetics.A modified drying model was established,and results show it is more appropriate to describe solvent transport behavior within NC-based propellants.Moreover,two linear equations were established to exhibit the relationship between solvent content and its effect on the change of tensile properties,and the decrease of residual solvent content causes an obvious increase of tensile strength and tensile modulus of propellant products,indicating its mechanical properties can be partly improved by adjustment of residual solvent content.The outcomes can be used to clarify solvent transport mechanisms and optimize drying process parameters of double-based gun propellants.

Mitigating kinetic hindrance of single-crystal Ni-rich cathodes through morphology modulation,nickel reduction,and lithium vacancy generation achieved by terbium doping

Single crystallization has proven to be effective in enhancing the capacity and stability of Ni-rich LiNi_(1-x-y)Co_(x)Mn_(y)O_(2)(SNCM)cathode materials,particularly at high cut-off voltages.Nevertheless,the synthesis of high-quality single-crystal particles remains challenging because of severe particle agglomeration and irregular morphologies.Moreover,the limited kinetics of solid-phase Li^(+)diffusion pose a significant concern because of the extended diffusion path in large single-crystal particles.To address these challenges,we developed a Tb-doped single-crystal LiNi_(0.83)Co_(0.11)Mn_(0.06)O_(2)(SNCM-Tb)cathode material using a straightforward mixed molten salt sintering process.The Tb-doped Ni-rich single crystals presented a quasi-spherical morphology,which is markedly different from those reported in previous studies.Tb^(4+)oping significantly enhanced the dynamic transport of Li^(+)ions in the layered oxide phase by reducing the Ni valence state and creating Li vacancies.A SNCM-Tb material with 1 at%Tb doping shows a Li^(+)diffusion coefficient up to more than 9 times higher than pristine SNCM in the non-diluted state.In situ X-ray diffraction analysis demonstrated a significantly facilitated H1-H2-H3 phase transition in the SNCM-Tb materials,thereby enhancing their rate capacity and structural stability.SNCM-Tb exhibited a reversible capacity of 186.9 mA h g^(-1)at 5 C,retaining 94.6%capacity after 100 cycles at 0.5 C under a 4,5 V cut-off.Our study elucidates the Tb^(4+)doping mechanisms and proposes a scalable method for enhancing the performance of single-crystal Ni-rich NCM materials.

Water molecules and oxygen-vacancy modulation of vanadium pentoxide with fast kinetics toward ultrahigh power density and durable flexible all-solid-state zinc ion battery

Aqueous zinc ion battery(ZIB)with many virtues such as high safety,cost-effective,and good environmental compatibility is a large-scale energy storage technology with great application potential.Nevertheless,its application is severely hindered by the slow diffusion of zinc ions in desirable cathode materials.Herein,a technique of water-incorporation coupled with oxygen-vacancy modulation is exploited to improve the zinc ions diffusion kinetics in vanadium pentoxide(V_(2)O_5)cathode for ZIB.The incorporated water molecules replace lattice oxygen in V_(2)O_5,and function as pillars to expand interlayer distance.So the structural stability can be enhanced,and the zinc ions diffusion kinetics might also be promoted during the repeated intercalation/deintercalation.Meanwhile,the lattice water molecules can effectively enhance conductivity due to the electronic density modulation effect.Consequently,the modulated V_(2)O_5(H-V_(2)O_5)cathode behaves with superior rate capacity and stable durability,achieving 234 mA h g^(-1)over 9000 cycles even at 20 A g^(-1).Furthermore,a flexible all-solid-state(ASS)ZIB has been constructed,exhibiting an admirable energy density of 196.6 Wh kg^(-1)and impressive power density of 20.4 kW kg^(-1)as well as excellent long-term lifespan.Importantly,the assembled flexible ASS ZIB would be able to work in a large temperature span(from-20 to 70℃).Additionally,we also uncover the energy storage mechanism of the H-V_(2)O_5 electrode,offering a novel approach for creating high-kinetics cathodes for multivalent ion storage.

Physical Simulation and Experimental Examination of ε-Cu Particles Dissolution Evolution During Welding of Copper Precipitation Strengthening Steel

The kinetics of ε-Cu particles dissolution in the matrix during welding of a copper-precipitation strengthening steel was determined by a combination of GleebleTM physical simulation, TEM examination and hardness meas urement. The ε-Cu particles underwent a coarsening and part dissolution and then complete dissolution reaction as the peak temperature increased from 750 to 1 000℃, which resulted in the decrease in the number density of ε-Cu particles and hardness in the heat affected zone （HAZ）. The results can be used to understand the evolution of this transformation and a softening behavior of the HAZ during welding of this type of steel.

Effect of Temperature and Phase Constitution on Kinetics of La Diffusion

The diffusion of La in ε-Fe 2～3N(ε)and γ′-Fe 4N (γ′)phases produced by plasma nitriding was studied. It is found that with increasing nitriding time, the ε phase continuously decomposes into γ′ one under employed experimental conditions and compared with γ′ phase or ε+γ′ ones, the mono one ε has an impedient effect on depth of La diffusion. The growth of La layer in dual phases and mono one follows an approximate exponential law and a parabolic one, respectively, and this kinetics law does not change with increasing temperature. The effect of increasing temperature in the range of 520 to 560 ℃ on La diffusion depth is less than that of phase constitution change such as the decomposition of ε phase into γ′ one.

The Study of Dissolution Kinetics of K_2SO_4 Crystal in Aqueous Ethanol Solutions with a Statistical Rate Theory

Dissolution kinetics of K2SO4 crystal in aqueous ethanol solutions was studied on-line with ion selective electrode. The concentration of K2SO4 was calculated from the determined electromotive force in which the activity coefficient of components in the liquid phase was calculated with the Pitzer equation. Dissolution kinetic parameters in the modified statistical rate theory were regressed. The correlation results show that dissolution rate of K2SO4 is slower in aqueous ethanol solutions than that in aqueous solutions. The two most important reasons are as follows: (1) The solubility of K2SO4 in aqueous ethanol solutions is lower than that in aqueous solutions, which causes a decrease of the driving force of mass transfer. (2) The process of surface reaction of K2SO4 became slower due to the addition of ethanol, so that the whole process is mainly dominated by the surface reaction instead of mass transfer.

Early Cooling History of Eclogites from the Dabie-Sulu Orogen: Constraints from Diffusion Kinetics of Garnet

For the first time, we apply different geospeedometric models to garnet zoning patterns that were obtained in this study from detailed EMP analyses for garnets from eclogites and granulite in the Dabie-Sulu orogen. Various zonings of cation diffusion were preserved in the garnets, enabling the acquirement of average cooling rates for the high-to ultrahigh-pressure rocks without using geochronological approaches. The coesite-bearing hot eclogites yield fast cooling rates of about 20 to 30℃/Ma subsequent to peak metamorphic temperatures, whereas the cold eclogite gives a relatively slow cooling rate of 8℃/Ma at its initial exhumation. A very slow cooling rate of <0.3℃/Ma is obtained for the granulite at Huangtuling, suggesting that the granulite may not be involved in the continental deep subduction.

Dissolution kinetics and removal mechanism of kaolinite in diasporic bauxite in alkali solution at atmospheric pressure

A new chemical pre-desilication process of kaolinite in diasporic bauxite in alkali solution at atmospheric pressure was proposed.The dissolution kinetics and mechanism were studied by chemical analysis,XRD and SEM.The kinetic results of dissolution process show that the kaolinite is symbiotic with diaspore but without cladding.The dissolution ratio of kaolinite is close to 100%at 100℃for 90 min.The dissolution kinetic equation is 1-(1-α)^1/3=7.88×10^6 exp[-64434/(RT)]t.With the low L/S(L/S=10:1),the dissolution ratio of kaolinite decreases to 55%.This is due to the formation of lamellar hydroxyl-sodalite(OH-SOD)which is deposited on the surface of kaolinite and hinders the further dissolution of kaolinite.Under the optimum conditions,the A/S(mass ratio of Al2 O3 to SiO2)of dissolved residues is increased to 8.55,while the A/S of the bauxite is only 4.97.

Dissolution kinetics and behavior of δ phase in Inconel 718

Dissolution kinetics of δ phase in Inconel 718 at 980, 1 000 and 1 020 ℃ respectively was established using the quantitative X-ray diffraction(XRD) method. Microstructure evolution during dissolution process was analyzed with scanning electron microscopy(SEM). Dissolution rate of δ phase during high temperature heating keeps at a high level at the beginning stage, and then decreases gradually with the increase of heating time. A dynamic equilibrium state approaches after being heated at 980 ℃ for more than 30 min and at 1 000 ℃ for more than 2 h, and the equilibrium mass fraction are 3% and 0.6% respectively. δ phase fully dissolves into the austenitic matrix after being heated at 1 020 ℃ for more than 2 h. The dissolution and fracture effects cause the morphology evolution of δ phase from long needle shape to short bars or particles at high temperature.

Removal of Vand Fe from spent denitrification catalyst by using oxalic acid:Study of dissolution kinetics and toxicity

The selective dissolution of V and Fe from spent denitrification catalyst(SDC)with oxalic acid was investigated to minimise their environmental effects.The dissolution kinetics of different elements from SDC by using 0.1–1.5 mol L^(-1) oxalic acid concentration was studied at 60℃–90℃.V and Fe were preferentially released(65%and 81%)compared with Al,Ti and W within 5 min due to the redox reactions of oxalic acid.The dissolved fractions of Fe,V,Al,Wand Ti increased with the increase of oxalic acid concentration and reaction temperature.The dissolution kinetic experiments were analysed and controlled diffusion with n<0.5 according to the Avrami dissolve reaction model(R^(2)>0.92).The Arrhenius parameters of the Ea values of Ti,W,V,Fe and Al from SDC with oxalic acid were 30,26,20,19 and 11 kJ mol^(-1),respectively.The obtained Avrami equation of V and Fe was successfully used to predict their leaching behaviour in oxalic acid.Toxicity characteristic leaching procedure revealed that the toxicity risk of Vand Fe metals from SDC after leaching with oxalic acid decreased to below 5 mg kg^(-1) residua.Overall,the leaching residua by oxalic acid indicated its safety for the environment.

UV/visible spectroscopic analysis of CO^(3+) and CO^(2+) during the dissolution of cobalt from mixed Co-Cu oxidized ores

The leaching of cobalt from four-mixed Co-Cu oxidized ores containing cobalt at levels ranging from 0.5wt% to 34wt% was studied and the results has been reported. Conventional dissolution of these oxidized Co-Cu ores with diluted H2SO4 and SO2 as a reducing agent resulted in a substantial improvement in the solution based recovery of cobalt. UV/visible spectroscopic analysis of the leached solu-tions indicated that the increased cobalt content in the solution was a result of flushing the acidified cobalt leaching solution with SO2. Fur-thermore, UV/visible spectroscopy confirmed that as SO2 was flushed into the acidified leaching solution, Co3＋ bearing minerals were re-duced to the readily soluble Co2＋ bearing minerals, and this resulted in the increase of total cobalt in the collected solution. The mechanism of the reduction of Co3＋ to Co2＋ bearing minerals when SO2 is flushed during the leaching of mixed Co-Cu oxidized ores, including the stability trends of Co3＋, Co2＋, and Cu2＋ complexes, as shown by their UV/visible spectra, are also discussed.

ADSORPTION OF 1,2,4-ACID BY WEAKLY BASIC RESIN: ISOTHERMS, THERMODYNAMICS AND KINETICS

The adsorption properties, including the adsorption isotherms, thermodynamics and kinetics, of 1-amino-2- naphthol-4-sulfonic acid (1,2,4-acid) onto weakly basic resin ND900 are investigated. Both the Langmuir and Freundlich equations can give a good fit to the adsorption isotherms, which indicates an endothermic and a favorable adsorption in our study range. A high yield in elimination of about 45.21 %-97.28% is obtained for the tested adsorption systems. The capacity and affinity of the adsorption increase with temperature, due to the phenomena of 'solvent-motivated' effects. The value of is 51.59 kJ/mol, which indicates a chemical adsorption and then expects the poor desorption property of ND900. The negative value of indicates the spontaneous nature of the adsorption process, and the positive value of shows the increased randomness at the solid/solution interface during the adsorption process. The value of the adsorption rate constant lower than 0.013 min-1 is indicative of a slow adsorption rate. The intra-particle diffusion must be one of the rate limiting steps.

Formation and Growth Kinetics of Intermediate Phases in Ni-Al Diffusion Couples

Formation and growth of the intermediate phases in the Ni-Al diffusion couples prepared by pouring technique were investigated. Electron probe microanalysis, scanning electron microscopy and X-ray diffraction were used to characterize the product phases in the joints. The results show that two intermediate phases form in the sequence of NiAl3 and Ni2Al3 during solidification. After annealed, Ni2Al3 and NiAl3 still exist in the joints of the couples. The reasons for the formation of Ni2Al3 and NiAl3, as well as the absence of NiAl, Ni5Al3 and Ni3Al were discussed, respectively. The growth kinetics of both product phase layers indicates that their growth obeys the parabolic rate law. The activation energies and frequency factors for NiAl3 and Ni2Al3 phases were also calculated according to the Arrhenius equation.

Diffusion of Chloride Ions in Soils: Ⅱ. Kinetic and Thermodynamic Characteristics

The amounts of chloride ions diffused in four soils of different textures at the same water content under different temperature and at varied time were measured by the diffusion cell method using 36Cl-labelled CaCl2 solution. Five kinetic models were used to fit the dynamic process of the diffusion of chloride ions in the soils. It was found that Elovich equation or power function equation was the best model to describe the process. The pseudothermodynamic parameters, i. e. the net reaction energyl the activation entropy,activation enthalpy and activation free energy of the diffusion, were derived from the absolute reaction-rate theory. The results showed that these parameters decreased in the order of loessal soil > black in soil >lou soil > yellow cinnamon soil, which indicated that the force and the heat-energy barrier to be overcome for diffusion decreased, the diffusion rate increased and the disorder of the soil-solution-ion system due to diffusion decreased successively with the texture becoming heavier in the four soils.