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By Robert E. Moore

Synthetic spinel is proving to be a highly effective refractory for specific applications, but its cost limits applications. Formation of spinel from a raw material such as diaspore or bauxite could provide a suitable and less costly starting material. In the study reported here, finely ground (-325 mesh) diaspore from Missouri and bauxite from Guyana and China are combined with hardburned MgO (-325 mesh) in appropriate proportions to yield spinel and spinel with secondary phases. A classical sintering and creep study was completed, accompanied by a microstructure study to determine completeness of the reactions and morphologies of the reaction products.

Jan 1, 1991

By A. A. el-Geassy

High-grade iron ore fines rejected from the DRl plants (>96%Fe20) were isothermally reduced in 30-60%COIH2 gas mixtures at 973-1273K. The freshly reduced reaction products were then subsequently carburised in either H2/CO or H2/CO/S mixtures at 823-1073K for 30-120 min. The thermogarvimetric technique was used to follow up both of reduction and carburisation reactions as a function of time. The carburised samples were characterized by X-ray and Mossbauer techniques. Chemical and carbon analyses were also applied. The influence of temperature and gas composition on the reduction behavior was investigated. The calculated values of apparent activation energy, application of gas-solid mathematical formulations were correlated with the microstructures to predict the reduction mechanism, The influence of carburization time, temperature, CO contents in H2/CO or H2/CO/S were investigated. A conversion extent of Fe to Fe3C was taken as a measurable index for the efficiency of carburization reaction under the different experimental conditions.

Jan 1, 2003

By Xue Wang, Callie Babbitt, Chelsea Bailey, Matt Ganter, Gabrielle Gaustad, Brian Landi

"Current trends, motivated by fossil fuel dependence and unprecedented greenhouse gas (GHG) emissions, show lithium-ion batteries (LIBs) emerging as a competitive energy storage technology due to higher power and energy densities compared to Pb-acid and Ni-metal hydride chemistries. These trends may be of concern, however, as environmental impacts are not well understood for either the LIB itself, or for the nanoparticles consumed or released during the battery's production, use, or end-of-life. This study combines economic modeling, dynamic material flow analysis, and fundamental material characterization methods in order to quantify some of the economic and environmental trade-offs for LIBs at their end-of-life. As expected, results show that as chemistries transition from Li-Co based cathodes to Li based Fe, Mn, and S cathodes, LIB recovery value correlates to the value of the raw materials used. These initial results aim to inform collection policies being proposed currently as well as enable future deployment of novel recycling techniques.IntroductionGlobal fossil fuel dependence and unprecedented GHG emissions have led to increasing attention on energy alternatives, for both electricity production and personal transportation. However, development of renewable energy systems is contingent on concurrent technological development of energy storage systems, primarily batteries used for power grid load-leveling, renewable energy storage, and hybrid and battery electric vehicles. In this sector, lithium-ion batteries (LIBs) are emerging as a competitive technology due to higher power and energy densities compared to lead-acid and nickelmetal hydride chemistries[!]. LIBs represent close to 20% of the total rechargeable battery market and 75% of the portable rechargeable battery market, which is the fastest growing segment of the rechargeable battery market, with a 20% global growth in 2008 [2].This surge in production ofLIBs indicates a looming waste problem; total waste from Li-ion batteries has likely grown substantially from the 500 metric tons estimated in 2003 [3]. Figure IA shows the substantial increase in world-wide lithium production that has occurred in the last several decades with batteries making up the largest share of applications (Figure lB). California and New York state legislators have attempted to proactively address this looming waste by issuing diposal bans on rechargeable batteries in their states[4, 5]. However, quantification of the costs involved in collection, transportation, and processing of these materials has not been examined in depth."

Jan 1, 2012

By Michael Zinigrad

The quality of metallic materials depends on their composition and structure and these are determined by various physico-chemical and technological factors. To effectively prepare materials with required composition, structure and properties it is necessary to carry out a research in two parallel directions: Comprehensive analysis of thennodynamics, kineties and mechanisms of the processes taking place at the solid-liquid-gaseous phase interface during welding processes and development of mathematical models of the specific welding technologies. We have developed unique method of mathematical modeling of phase interaction at high temperatures. This method allows us to build models taking into account the thennodynamic characteristics of the processes, the influence of the initial composition and temperature on the equilibrium state of the reactions, the kinetics of heterogeneous processes, the influence of the temperature, composition, hydrodynamic and thennal factors on the velocity of the chemical and diffusion processes. The model can be implemented in the optimization of various technological processes in welding, surfacing, casting as well as in manufacturing of steels and non-ferrous alloys, materials refining, alloying with special additives, removing of non-metallic inclusions.

Jan 1, 2003

By Qiang Guo, Zongliang Zuo, Mengqi Wei, Qingbo Yu, Qin Qin

Activated carbons, derived from waste ion-exchange resin by CO2 physical activation, were applied to separate CO2 from flue gas against global warming. The BET specific surface areas of activated carbons at different activation temperatures and times were investigated. The CO2 adsorption capacity was tested under non-isothermal and isothermal conditions. The experimental results show that when keeping the activation temperature constant, the specific surface area increases firstly and then decreases with increasing activation time. For the given activation time, the specific surface area rises firstly and then declines with increasing activation temperature. The adsorption capacity decreases with increasing temperature. The maximum adsorption capacity is 51.46 mg/g under the condition of 298 K and pure CO2. Fractional order kinetic model is the best one to describe the kinetics of CO2 adsorption. The activated carbons show the potential to be an effective adsorbent for the removal of CO2 from flue gas.

Mar 1, 2018

By In-Ho Chi

In copper metallization, resistivity of copper seed layer is very important since the thickness of seed layer is less than 200iun. Conventionally MOCVD has been used for this purpose however electroless copper plating is simple process and the resistivity of copper deposit is less than that of copper prepared by MOCVD. In this study eIectroless depositions of copper were conducted on different substrate to find optimum conditions of electroless copper plating for electronic applications. To find optimum conditions, the effects and selectivity of activation method on several substrates were investigated. The effects of copper bath composition on morphology were investigated. The effects of pH and stabilizer on deposition rate was investigated. The resistivity of copper with thickness was also measured.

Jan 1, 2001

By Junfu Chen, Jiann-Yang Hwang, Yong Zhou, Lijun Lu, Likun Lia, Jixiong Liu

The sheet-like NiS-ZnS heterostructured composites were prepared by the microwave hydrothermal. The fabrication of the heterojunctions broadened the range of light response of ZnS. The photoexcited electrons of ZnS migrated to the redox potential of NiS/Ni2S under visible light irradiation, which can facilitate the effective separation of photogenerated electrons and holes in space. The visible photocatalytic activity towards hydrogen production for NiS/ZnS nanosheet heterostructed composites without co-catalyst achieved 0.28 mmol h–1, and the quantum efficiency was up to 18.6% under the wavelength with 420 nm visible light irradiation.

Jan 1, 2015

By Tadashi Aiura, Yasuhiro Miura

"A small amount(0.2mass%) of Scandium(Sc) was added to the 7.NOl and 5083 Al alloys as a refiner and stabilizer of microstructure, and the resulting microstructures were discussed in comparison with the effects of the conventional additives. The followings are summarized: 1) in the as-solidified structure, a ·decreased tendency of constitutional supercooling and increased solubility of Mg were recognized for the Sc-added 5083 alloy. Sc is a -better microstructure refiner for the 7N01 alloy than Zr, in a sense that it does not suppress the favorable effect of· coexisting Ti. 2) Sc effectively suppresses recrystallization both in the 5083 and 7N01 alloys. 3) The rod like primary Al3Sc crystals formed during solidification, as well as the fine dispersion of Al3Sc precipitates formed by subsequent heat treatment, can act as a strong recrystallization suppresser. IntroductionThe 7N01 and 5083 alloys are the most popular industrial Al alloys and they are widely' used for various structures because of their superior properties. Fine macro and micro structures of the materials are required for obtaining acceptable sec resistance,consistent appearance of anodized surface and good weldability, as well as good mechanical properties. In order to produce fine grain structures, transition metals, such as Cr, Zr, and Mn, have been conventionally added.It has been reported that Sc is an efficient refiner [l, 2] and can be an alternative for the conventional and also suppresses recrystallization in Al alloys [3,4]. Scandium is the lightest transition element and forms an equilibrium intermetallic phase. The equilibrium phase, Ll2-Al3Sc, is coherent with the matrix, and of _spherical shape. A fine dispersion of the spherical precipitates is obtained by quenching and aging after solutionizing annealing. The authors have already reported a part of the experimental results on the effect of Sc on the as homogenized microstructure of the 5083 alloy [5]. In the present study, the effects of Sc on the macro and micro structures of the industrial high strength Al alloys(7N01 and 5083) for extrusion are investigated, and the superior role of Sc as a grain refiner is shown"

Jan 1, 2000

By S. M. I Kytö, J .. K. Mäkinen, K. Saarhelo

"At the Outokumpu Oy Harjavalta Copper Smelter the control philosophy of the flash smelting process has been changed from the slow feed-back control to feed-forward control. This is important as the fluctuations in the flash smelting furnace matte grade and slag temperature are desired to be minimized.The system is based on a specially designed automatic sampling device and the Outokumpu Courier 20 on-stream X-ray fluorescence analyzer. A microcomputer-based Analyzer Operator Station (AOP) controls the system and calculates the process parameters for the furnace from the analyzed chemical composition and other existing data.A considerable reduction in the deviation of the matte grade and slag temperature has been gained. This has resulted in conservation of energy and refractories, lower copper losses and higher through-put in the flash smelting furnace and converters.1.0 IntroductionThe flash smelting technology for copper concentrates was developed at the Outokumpu Oy Harjavalta Smelter soon after the World War II. The incentive for this development was shortness and high price of any form of energy. The fact that smelting can be carried out autogenously, without external energy by utilizing the latent heat of sulfide combustion was known decades before, but Outokumpu Oy was the first company to take the advantage of this knowledge in practical operation. A further advantage of this technology was that the SO2 containing gases suited well for sulfuric acid production, thus minimizing the detrimental effects on the environment (1).The very heart of the flash smelting process is the reaction shaft of the flash smelting furnace (see Appendix I). Heating up of the dried feed mixture, dissociation of several compounds, ignition and oxidation of the feed take place very intensively in the reaction shaft during 2 - 3 seconds, which the fine grained particles reside in the reaction shaft. A very accurate control of the amounts of the feed materials as well as of oxidizing gases, fuel, etc. is of primary importance."

Jan 1, 1989

By A. D. Damodaran

Batch scale and continuous rotary kiln carbothermic metallisation of ilmenite followed by different down-stream treatments such as catalytic rusting, acidic chloride leaching, oxidation-leaching etc. has given rise to a high grade synthetic rutile (98% TiO2). Rotary reactor metallisation experiments had concurrently given important information with respect to mean residence time, dispersion number, hold-up and axial velocity profiles of the solids bed. A mathematical model based on law of additive reaction times has indicated that Boudouard reaction becomes faster than reduction reaction at higher conversions. A possible use of high grade synthetic rutile in paint industry and metallised ilmenite as welding electrode flux material are discussed.

Jan 1, 1992

By J. G. Zafiratos

The leaching of a Greek low-grade manganese dioxide ore, not amenable to conventional mineral processing operations, was studied using a mixed culture of Thiobacillus sp. bacteria. The experiments were carried out in specially designed continuously aerated and stirred tank reactors arranged in two-tank series. The first tank of each series was loaded with an elemental sulfur culture suspension while the second was loaded with a manganese ore high density slurry. The bacterial culture had been previously adapted to grow on elemental sulfur and also in the presence of manganese ore and dissolved manganous ion. A two level full factorial design was constructed in order to study the effects of the ferric ion concentration in the leach solution, the "elemental sulfu weight to ore weight" ratio, the ore pulp density and the composition of the dispersed gas. The responses which were investigated included percentage manganese recovery, co-dissolution of iron and manganese dissolution rate. Parameters with constant values throughout the experiments were the leach solution pH, the nutrient medium composition, the dilution rate and the ore and sulfur grain sizes. It was found that the ferric ion concentration was the most significant factor and had a positive effect on the final percentage extraction of manganese from the ore and also on the rate of manganese solubilization from the ore. The effects of the other factors studied are discussed in detail.

Jan 1, 1997

By Robert Mensah-Biney

The loading characteristics of gold-tetrabromide species onto a weak-base resin, PAZ-4, were evaluated using a completely mixed batch reaction system. The time. to attain equilibrium loading was substantial, on the order of several days. However, abnormally high loading capacity values of 15 to 20 meq Au/g dry resin (1000 to 1300 kgAu/tonne) were attainable in 24 hours. The loading of gold-bromo species by P AZ-4 was visualized as consisting of two processes: (i) the rapid adsorption of [AuBr4r species by simple ion exchange mechanisms and (ii) reduction of [AuBr4r to metallic gold by an electron exchange mechanism. Elution of gold from loaded resin was feasible provided the resin had not been loaded to high capacity values. If loading is carried to high levels, complete elution becomes impractical and the gold may be recovered by ashing the loaded resin. For the high loading capacities observed this option would appear to be cost effective.

Jan 1, 1991

By Honglei Zhang, Wuguo Xiang, Xinhao Huang, Guotao Xu, Xilai Chen

"The service behavior of refractories used in hot air pipeline for hot air stoves in a 3200 M3 blast furnace of WISCO was analyzed. The damage factors can be concluded as the poor quality of and alusite based bricks, the severe thermal shock damage, the more porosity in structures, loose bonding capability, and the unreasonable choice of materials and design of bricks. By analysis, the service life of hot air stoves can be enhanced by the measurements such as the reasonable choice of materials and their match, the use of light-weight refractories, the improvement of brick type, etc. Thereafter, the normal production operation of hot air stoves is guaranteed.IntroductionThe No.7 blast furnace of WISCO has been used for about 5 years and it was mid-repaired in March, 2012. The top phenomena of worn hot air pipelines are brick drop, breakage, severely local wear and deformation, existing hidden danger, so the worn hot air pipelines were renewed. Investigations have been done on the stove damage and design [1,2]. In order to clarify the wear mechanism, the used refractories for hot air pipelines were sampled and analyzed, the properties and structures of worn materials and reused materials are relatively studied."

Jan 1, 2013

By Clemens Schmetterer, Patrick J. Masset

"The surface tension represents an important property for the modelling of high temperature processes. In this study the surface tension of two Al2O3 – CaO – SiO2 model slags and the influence of the admixture of 5 up to 30 wt.% FeO were studied. The surface tension measurements were carried out using the sessile drop technique on BN substrates under Ar atmosphere (10-6 atm O2) up to 1500 °C.IntroductionThe aim of VIRTUHCON1 is the virtualization of high temperature conversion processes, a task that requires thorough understanding of these processes. In many of these conversion processes slag plays an important role to control the properties of the product, to protect the reactor lining or simply as waste. Slag surface tension is one of the materials properties that is needed for the description of such processes, since it influences the interactions between the components in the reactor, e.g. at the slag – Fe interface in the blast furnace.Surface and interfacial tensions have thus received considerable attention in research, but the number of investigations in this particular pseudo-quaternary system is surprisingly low. Furthermore, the literature data are subject to different measurement conditions and techniques which complicates the data analysis and comparison.The slag atlas [1] offers a compilation of the available literature until 1986 (shown in Table I), but literature search has not revealed more recent studies of this system until now. For example, Elliott and Mounier [2] determined the surface tension of ACSF slags using the double tube maximum bubble pressure technique at 1200 °C. They kept their slags in contact with Cu-S-F mattes, and the slag therefore contained a certain amount of sulphur which acts as a surfactant and lowers the surface tension. The compositions of their slags were scattered over a wide composition range and they did not use a common ACS base mixture for their tests, either. The surface tension values vary between 417 and 446 mN/m, but due to the reasons just mentioned no trend in the measurements can be observed and the influence of FeO admixture on the surface tension cannot be deduced. Further information including the temperature dependence is available from Pavlov et al. [3], Ishchanov and Shushkov [4] and Murav’eva and Kaplun [5]; the diagram on page 446 in Ref. [1] has been drawn from these sources. Both positive and negative temperature coefficients are reported in these works. SiO2 is the only pure constituent that has a positive temperature coefficient [6], but a correlation of the temperature coefficient with the SiO2 content was not found to be conclusive."

Jan 1, 2011

By Michael L. Sorokin

The various methods of converter slag cleaning operation are analysed from the thermodynamk point of view: cleaning using coal, cleaning using combustion products of natural gas and cleaning in presence of matte. All calculations were done, applying the developing computer procedure based on the free energy minimisation algorithm. Three-suffix Margules equations were used to calculate thermodynamic properties of melts; The calculations resulted in recommendations for the practical appliance.

Jan 1, 1995

By F. J. J. van Loo, J. K. Kivilahti, M. Paulasto

"Activation mechanism and interfacial reactions in brazing of ShN4 with different AgCuTi filler alloys has been investigated thermodynamically and experimentally. During brazing the AgCuTi filler alloy is divided into two liquids Ll and L2, where the (Cu,Ti)-rich liquid L2 gathers at the ShN4 interface and reacts with it. The concentration of Ti in L2 is high, but due to the strong attractive interaction between Cu and Ti, the activity of Ti in L2 is considerably low. In reaction between ShN4 and Cu-containing brazes a Ti-Cu-Si-N compound is typically formed at the interface. In absence of Cu, in joints brazed with AgTi based filler alloys, extremely Ti-rich solution reacts with ShN4 and as reaction products TiN and TisSh[N] are formed. IntroductionAdvanced ceramics like silicon nitride are increasingly used as structural components in demanding applications as well as in electronics industry. Complex, multicomponent structures for engineering applications generally require interconnections and therefore joinability of ceramics largely determines the possibilities of metal-ceramic structures to enable demanding functions. Brazing with active filler metals, most of which are based on the Ag-Cu-Ti system, has been commonly employed for joining of ShN4 to other ceramics and metals. The interfacial microstructures formed when ShN4 is brazed with Ag-Cu-Ti braze alloys have been discussed in several recent studies [1-7]. However, some inconsistencies exist in the reported results. The formation of layers of TiN and titanium silicides, possibly TisSh, next to the ShN4 has been reported in several studies [1-5], while in another investigation, a layer of an orthorhombic TiSi- Cu-N phase was found beyond the TiN layer [6]. In few investigations the thermodynamics of the ShN4-Ti system has been considered, but no detailed thermodynamic analysis of the chemical interactions between the braze and ShN4 has been provided. In order to resolve which chemical reactions are possible under various joining conditions and thereby to be able to control the brazing of ShN4 the reactions in brazing has to be studied using both microstructural and thermodynamic analysis."

Jan 1, 1996

By Lauri Holappa

Copper converting is mostly performed in Peirce-Smith converters. The process is still very similar to the original one developed in the early 20th century. It is a batch process in a horizontal cylindrical reactor with air blowing via tuyeres along the length of the reactor side. The Peirce-Smith converter has its roots in Bessemer's inventions in the 1850's as he tested both horizontal and vertical vessels for steel converting. However, for steel making a vertical pear-shaped converter with air bottom-blowing was established. In the course of time, there was a distinct necessity for oxygen usage instead of air due to harmful effects of nitrogen to steel properties and its cooling effect. In-bath blowing of oxygen did not succeed, however, and top-blown oxygen converter with oxygen lance (LD or BOF) was first developed in he 1950's and emerged rapidly to a dominating position. Somewhat later oxygen bottom-blowing via special shrouded tuyeres was developed (OBM or Q-BOP) but has attained only fractional share. Bottom-blowing technique had, however, impact on the current combined blown converters which adopted the benefits of both top and bottom blowing. In copper converting Peirce-Smith type converters have kept their position until today although new processes have been introduced and at least few of them seem to be emerging. In one respect copper converting has a clear leading position i.e. in the progress of continuous converting processes (Mitsubishi, Ausmelt). These processes utilise top-blowing lances instead of in-bath blowing tuyeres. A different principle for continuous converting is flash converting by Kennecott Outokumpu, which makes smelting and converting independent of each others. Solid ground matte is used as a feed for flash converting in a reactor shaft similar to Outokumpu matte flash smelting. A comparable process has been presented by Inco too. The paper discusses principal physico-chemical and process technical similarities and differences in copper and steel converting. Although these processes are metallurgically quite different it seems that during the modem history of ferrous and non-ferrous metallurgy, starting from the 1850's, the exchange of knowledge between these disciplines has been quite intensive. In long-term perspective, many similarities in the development can be found but also divergences due to different ambient circumstances.

Jan 1, 2003

By Kun Wang, Xinhui Li, Huaqing Xie, Qingbo Yu, Qin Qin

"Three typical model compounds of bio-oil (ethanol, acetone and phenol) were studied in the steam reforming process for hydrogen production. In the thermodynamic analysis, the three componds showed the similar trends. The hydrogen yields increased with the increase of steam/carbon (S/C) ratios, and the temperatures of the maximum hydrogen yields moved afterward to low temperature zone. However, the hydrogen contents were just about 70%. For improving hydrogen yield, a new system for steam reforming of bio-oil with site CO2 capture was put forward. This system required the catalst with the larger granularity having greater mechanical strength and higher abrasion resistance. So, six Ni-base catalysts loaded on Al2O3 particles prepared were used and among them, Mg-Ni/Co catalyst showed the best catalytic performance. For the simulated bio-oil (the mixture of the compounds), the hydrogen yield can attain 63% with Mg-Ni/Co catalyst with the good stability and regeneration ability.IntroductionCurrently the interest in the use of hydrogen as a clean energy carrier is increasing, and the main way for producing hydrogen is steam reforming of fossil fuels, containing steam reforming of nature gas, naphtha and coal. But this way caused substantial amounts of CO2 emitted, and these sources of hydrogen which are non-renewable energy will eventually be used up [1, 2]. As a kind of renewable energy, biomass is recognized as an attractive alternative to fossil fuels, because of its neutral CO2 emissions [3]. There are mainly two thermochemical processes using biomass to produce hydrogen, gasification and flash pyrolysis followed by steam reforming (SR) of the biooil produced in the flash pryolysis process [4]. The latter was known as one of the most promising and economically viable methods for hydrogen production [5]. In the last decades, the biomass flash pyrolysis technology was adequately developed and fairly mature [6]. But the steam reforming of bio-oil is still at the research stage and yet has been leading to more and more concerns by the researchers. In their research, the catalysts were widely studied and yet mainly were powdery[7-10], and the reactors manily were fixed bed reactors[11-13], readly causing the carbon deposition and the catalyst deactivation, against the continuous running. In this paper, a new systerm was put forward and could realize continuous production of hydrogen, yet needed catalysts with the larger granularity having greater mechanical strength and higher abrasion resistance, as well as powdery CO2 sorbents which mainly calcium oxide based ones.In this paper, the thermodynamic analysis of the steam reforming processes of three typical bio-oil model compounds (ethanol, acetone, phenol) was performed, and the effect of S/C ratio and temperature on the hydrogen yield and the compositions of gaseous products were investigated. Then, a new systerm for steam reforming of bio-oil with site CO2 capture was put forward, and the catalysts with a certain granularity were prepared and studied."

Jan 1, 2014

By Eiji Iwamura

"Two types of diamond-like carbon (DLC) films with different microstructures were prepared by unbalanced magnetron sputtering, and the tribological properties of the nanoscaled DLC multilayer coatings consisting of alternating layers of graphitelike and amorphous-like microstructures were examined. The DLC microstructure was characterized by certain features of graphite-like clusters, in that some of them had onion-like structures. The films filled with the clusters were obtained in a condition with an incidence of high influx of energetic electrons, and the other films without apparent cluster structures were formed in a condition with ion bombardment controlled by negative bias voltage applied to substrates. Stacking each film layer-by-layer, the nanoscaled multilayered coatings showed superior tribological properties to individual single-layered films due to the combination of properties induced by the difference of microstructures.IntroductionIn various tribologiql applications, it is necessary for diamond like carbon (DLC) coatings to have adequate adhesion, significant hardness and a concomitant low friction coefficient. A number of deposition techniques and coating structures have been proposed to achieve suitable DLC properties [1-3]. However it is still difficult to obtain a satisfactory level of combination of the properties particularly desirable for engineering applications.In this study, the features of unbalanced magnetron sputtering were demonstrated with the effect of ion and electron bombardment. Two types of microstructures , namely amorphous-like and graphite-like, were prepared by changing the condition of the charged particles bombardment during deposition. Using the difference of properties induced by the microstructures, nanoscaled DLC multilayered structures were examined in an attempt to improve tribological properties."

Jan 1, 2000

By Eren Hüseyin Obuz

In this study, the leaching kinetics of rare-earth elements were investigated using HCl and HNO3 solutions. A standard crushed complex ore was utilized as raw material. The complex ore (particle size of under 54 μm) contains REE (Ce, La, Nd, Pr, etc.). Different leaching durations were selected for the kinetic studies. The highest leaching efficiency was obtained in HCl solution, and the leaching mechanism was identified to diffusion through a product layer. The rate constants of Ce, La, Nd, and Pr were calculated as 1.08 × 10−2, 0.86 × 10−2, 1.87 × 10−2, and 1.34 × 10−2 h−1, respectively.