• Resources Recycling
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• v.31 no.1
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• pp.29-36
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• 2022

The hydrogen reduction behavior of molybdenum oxides was studied using a horizontal-tube reactor. Reduction was carried out in two stages: MoO₃ → MoO₂ and MoO₂ → Mo. In the first stage, a mixed gas composed of 30 vol% H₂ and 70 vol% Ar was selected for the MoO₃ reduction because of its highly exothermic reaction. The temperature ranged from 550 to 600 ℃, and the residence time ranged from 30 to 150 min. In the second step, pure H₂ gas was used for the MoO₂ reduction, and the temperature and residence time ranges were 700-750 ℃ and 30-150 min, respectively. The hydrogen reduction behavior of molybdenum oxides was found to be somewhat different between the two stages. For the first stage, a temperature dependence of the reaction rate was observed, and the best curve fittings were obtained with a surface reaction control mechanism, despite the presence of intermediate oxides under the conditions of this study. Based on this mechanism, the activation energy and pre-exponential were calculated as 85.0 kJ/mol and 9.18 × 10⁷, respectively. In addition, the pore size within a particle increases with the temperature and residence time. In the second stage, a temperature dependence of the reaction rate was also observed; however, the surface reaction control mechanism fit only the early part, which can be ascribed to the degradation of the oxide crystals by a volume change as the MoO₂ → Mo phase transformation proceeded in the later part.

• Applied Chemistry for Engineering
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• v.19 no.5
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• pp.477-483
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• 2008

$La_{0.7}Sr_{0.3}Co_{0.2}Fe_{0.8}O_{3-{\delta}$ oxide was synthesized by a citrate method and a typical dense membrane of perovskite oxide has been prepared using as-prepared powder by pressing and sintering at $1300^{\circ}C$. Precursor of $La_{0.7}Sr_{0.3}Co_{0.2}Fe_{0.8}O_{3-{\delta}$ prepared by citrate method was investigated by TGA and XRD. Metal-citrate complex in precursor was decomposed into perovskite oxide in the temperature range of $260{\sim}410^{\circ}C$ but XRD results showed $SrCO_3$ existed as impurity at less than $900^{\circ}C$. Electrical conductivity of membrane increased with increasing temperature but then decreased over $700^{\circ}C$ in air atmosphere ($Po_2=0.2atm$) and $600^{\circ}C$ in He atmosphere ($Po_2=0.01atm$) respectively due to oxygen loss from the crystal lattice. The oxygen permeation flux increased with increasing temperature and maximum oxygen permeation flux of $La_{0.7}Sr_{0.3}Co_{0.2}Fe_{0.8}O_{3-{\delta}$ membrane with 1.6 mm thickness was about $0.31cm^3/cm^2{\cdot}min$ at $950^{\circ}C$. The activation energy for oxygen permeation was 88.4 kJ/mol in the temperature range of $750{\sim}950^{\circ}C$. Perovskite structure of membrane was not changed after permeation test of 40 h and the membrane was stable without secondary phase change with 0.3 mol Sr addition.

• Proceedings of the Korean Vacuum Society Conference
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• 2016.02a
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• pp.77-77
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• 2016

Thin films synthesized by plasma processes have been widely applied in a variety of industrial sectors. The structure control of thin film is one of prime factor in most of these applications. It is well known that the structure of this film is closely associated with plasma parameters and species of plasma which are electrons, ions, radical and neutrals in plasma processes. However the precise control of structure by plasma process is still limited due to inherent complexity, reproducibility and control problems in practical implementation of plasma processing. Therefore the study on the fundamental physical properties that govern the plasmas becomes more crucial for molecular scale control of film structure and corresponding properties for new generation nano scale film materials development and application. The thin films are formed through nucleation and growth stages during thin film depostion. Such stages involve adsorption, surface diffusion, chemical binding and other atomic processes at surfaces. This requires identification, determination and quantification of the surface activity of the species in the plasma. Specifically, the ions and neutrals have kinetic energies ranging from ~ thermal up to tens of eV, which are generated by electron impact of the polyatomic precursor, gas phase reaction, and interactions with the substrate and reactor walls. The present work highlights these aspects for the controlled and low-temperature plasma enhanced chemical vapour disposition (PECVD) of Si-based films like crystalline Si (c-Si), Si-quantum dot, and sputtered crystalline C by the design and control of radicals, plasmas and the deposition energy. Additionally, there is growing demand on the low-temperature deposition process with low hydrogen content by PECVD. The deposition temperature can be reduced significantly by utilizing alternative plasma concepts to lower the reaction activation energy. Evolution in this area continues and has recently produced solutions by increasing the plasma excitation frequency from radio frequency to ultra high frequency (UHF) and in the range of microwave. In this sense, the necessity of dedicated experimental studies, diagnostics and computer modelling of process plasmas to quantify the effect of the unique chemistry and structure of the growing film by radical and plasma control is realized. Different low-temperature PECVD processes using RF, UHF, and RF/UHF hybrid plasmas along with magnetron sputtering plasmas are investigated using numerous diagnostics and film analysis tools. The broad outlook of this work also outlines some of the 'Grand Scientific Challenges' to which significant contributions from plasma nanoscience-related research can be foreseen.

• Korean Journal of Materials Research
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• v.5 no.7
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• pp.775-780
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• 1995

Thin films of titanium nitride are formed using the tetrakis-dimethyl-amino-titanium (TDMAT(Ti[N($CH_3$)$_2$]$_4$)) under various conditions. The formation of TiN films has been obtained from the thermal decomposition of the Ti-precursor and the gas phase reaction between TDMAT and ammonia(NH$_3$). The resistivity of the MOCVD film can be attributed to their impurity. Especially the curve fitting graph of XPS data is revealed that main impurities in the films as carbon and oxygen make various interstitial compounds which has influenced physical and electrical properties of the film. In the contact hole with the aspect ratio of 3:1 and the diameter of 0.5${\mu}{\textrm}{m}$, the SEM morphology shows that the step coverage is more decreased in the films formed y flowing ammonia additionally than the films formed by pyrolysis of TDMAT and the phenomenon is probably related with the activation energy.

• Journal of the Korean Chemical Society
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• v.34 no.3
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• pp.239-247
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• 1990

The gas-phase S_N2$ reactions can be classified into neutral bimolecular, solvated, and ionic reactions; the neutral bimolecular reaction proceeds via retention mechanism whereas the ionic reaction produces inversion products. In the reaction of solvated nucleophile with one solvent molecule, a six-center transition state (TS) is formed and the two processes i.e., retention and inversion, are found to compete with a favored path depending on the electronic effect of the nucleophile and substituents in the substrate and on the steric requirement. In the ionic reaction, the difference in the energy barrier between the two processes reduces to a small value when the substrate methyl group is made bulky, leaving ability of the leaving group is improved and at the same time the negative charge of the nucleophile is dispersed. When the reaction center atom in the $S_N2$ reaction is changed to a larger sized second row elements, the activation barrier decreases since the steric crowding in the penta-coordinated TS is relieved. However within the same row, the barrier was found to increase as the atomic size decreased. For the boron, B, the barrier height was the least since in addition to the relatively large atomic size compared to C and N, it forms tetra-coordinated TS so that the steric crowding becomes nearly negligible.

• Korean Journal of Materials Research
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• v.8 no.8
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• pp.757-765
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• 1998

This study was performed to investigate the influence of fuel/oxygen ratio (F/O= 3.2, 3.0, 2.8) on the oxidation behavior of two kinds of (20wt%NiCr claded $\textrm{Cr}_{3}\textrm{C}_{2}$, and 7wt%NiCr mixed $\textrm{Cr}_{3}\textrm{C}_{2}$) composite powder with different manufacturing method. The results show that the oxidation behavior between the 20wt% NiCr claded $\textrm{Cr}_{3}\textrm{C}_{2}$ and 7wt% NiCr mixed $\textrm{Cr}_{3}\textrm{C}_{2}$ coating was widely different. The surface morphology of the coating composed of 7wt% NiCr mixed $\textrm{Cr}_{3}\textrm{C}_{2}$ was changed to porous with F/O ratio by the aggressive evolution of gas phases($\textrm{CO}_2$, CO and $\textrm{CrO}_3$) and the oxide cluster composed of Ni and Cr were grown after oxidation at $1000^{\circ}C$ for 50 hours. But the surface morphology of the coating composed of 20wt% NiCr claded $\textrm{Cr}_{3}\textrm{C}_{2}$ was not changed to porous after oxidation at $1000^{\circ}C$ for 50 hours. Therefore, the reason for high oxidation rate is due to activation of $\textrm{Cr}_{3}\textrm{C}_{2}$ to oxidation by entrapped oxygen gases within coating layer, and to closely relate with the decomposition of $\textrm{Cr}_{3}\textrm{C}_{2}$ to $\textrm{Cr}_{7}\textrm{C}_{3}$ phase. Accordingly, On the evidence of these results, the study about the oxidation behavoir of the HVOF sprayed $\textrm{Cr}_{3}\textrm{C}_{2}$ coating depending on hydrogen flow rate must be done.

• Korean Journal of Materials Research
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• v.9 no.3
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• pp.244-250
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• 1999

MOCVD TiN films were prepared from a new TiN precursor, tetrakis(etylmethylamino)titanium (TEMAT) and ammonia. Deposition of TiN films from a single precursor, TEMA T yielded the growth rates of $70 to 1050\AA$/min, depending on the deposition temperature. Furthermore, the excellent bottom coverage of -90% over $0.35\mu\textrm{m}$ contacts was obtained at $275^{\circ}C$. The addition of ammonia to TEMA T lowered the resistivity of as- deposited TiN film to ~ $800\mu\omega-cm$ from $3500~6000\mu\omega-cm$ and improved the stability of TiN film in air. Examination of the films by Auger electron spectroscopy(AES) showed that the oxygen and carbon contents decreased with the addition of ammonia. However, increasing ammonia flow rate decreased the bottom coverage of TiN films over $0.5\mu\textrm{m}$ contacts, probably due to the high sticking coefficient of intermediate species produced from the gas phase reaction of TEMA T and ammonia. Based on the byproduct gases detected by the quadrupole mass spectrometer (QMS), the transammination reaction was proposed to be responsible for TiN deposition. In addition, XPS analysis revealed that the carbon in the films made from TEMA T and ammonia was metallic carbon, suggesting that $\beta$-hydrogen activation process occurs competitively with the transammination reaction.

• Applied Chemistry for Engineering
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• v.35 no.1
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• pp.1-7
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• 2024

Mn-M/Al₂O₃ (M = Cu, Fe, Co, and Ce) catalysts were prepared for simultaneous oxidation of NO, CO, and CH₄, and their oxidation activities were compared. The Mn-Cu/ Al₂O₃ catalyst with the best simultaneous oxidation activity was characterized by XRD, Raman, XPS, and O₂-TPD analysis. The result of XRD indicated that Mn and Cu existed as complex oxides in the Mn-Cu/Al₂O₃ catalyst. Raman and XPS results showed that electron transfer between Mn ions and Cu ions occurred during the formation of the Mn-O-Cu bond in the Mn-Cu/Al₂O₃ catalyst. The XPS O 1s and O₂-TPD analyses showed that the Mn-Cu/Al₂O₃ catalyst has more adsorbed oxygen species with high mobility than the Mn/Al₂O₃ catalyst. The high simultaneous oxidation activity of the Mn-Cu/Al₂O₃ catalyst is attributed to these results. Gas-phase NO promotes the oxidation reactions of CO and CH₄ in the Mn-Cu/Al₂O₃ catalyst while suppressing the NO oxidation reaction. These results were presumed to be because the oxidized NO was used as an oxidizing agent for CO and CH₄. On the other hand, the oxidation reactions of CO and CH₄ competed on the Mn-Cu/Al₂O₃ catalyst, but the effect was not noticeable because the catalyst activation temperature was different.