• Journal of the Korean Chemical Society
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• v.45 no.3
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• pp.242-246
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• 2001

The quaternary thiophosphates, $A_2NiP_2S_6$ (A=Rb, Cs), have been synthesized with halide fluxes and structurally characterized by single-crystal X-ray diffraction technique. These compounds crystallize in the space group $C_{2h}^5-P2_1/n$ of the monoclinic system with two formula units in a cell of dimensions a=5.960(2), b=12.323(4), $c=7.491(3)\AA$, $\beta=97.05(3)^{\circ}$, and $V=546.0(3)\AA^3$ for Rb2NiP2S6 and a=5.957(4), b=12.696(7), $c=7.679(4)\AA$, $b=93.60(5)^{\circ}$, and $V=579.7(5)\AA^3$ for $Cs_2NiP_2S_6.$ These compounds are isostructural. The structure of $Cs_2NiP_2S_6$ is made up of one-dimensional $_\infty^1[NiP_2S_6^{2-}]$ chains along the a axis and these chains are isolated by $Cs^+$ ions. The Ni atom is octahedrally coordinated by six S atoms. These Ni$S_6$ octahedral units are linked by sharing three m-S atoms of the $[P_2S_6^{4-}]$ anions to form the infinite one-dimensional $_\infty^1[NiP_2S_6^{2-}]$ chain. For $Cs_2NiP_2S_6$, the magnetic susceptibility reveals an antiferromagnetic exchange interaction below 8K,which corresponds to the Neel temperature ($T_N$). Above $T_N$, this compound obeys Curie-Weiss law. The magnetic moment, C, and ${\theta}forCs_2NiP_2S_6$ are 2.77 B.M., 0.9593 K, and -19.02 K, respectively. The effective magnetic moment obtained from the magnetic data is agreed with the spin-only value of $Ni^{2+}d^8$(2.83 B.M.) system.

• Journal of Life Science
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• v.25 no.2
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• pp.237-242
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• 2015

The use of calcite-forming bacteria (CFB) in crack remediation and durability improvements in construction materials creates a permanent and environmentally-friendly material. Therefore, research into this type of application is stimulating interdisciplinary studies between microbiology and architectural engineering. However, the mechanisms giving rise to these materials are dependent on calcite precipitation by the metabolism of the CFB, which raises concerns about possible hazards to cement-based construction due to microbial metabolic acid production. The aim of this study was to determine target microorganisms that possibly can have bio-corrosive effects on cement mortar and to assess multi-functional CFBs for their safe application to cement structures. The chalky test was first used to evaluate the $CaCO_3$ solubilization feature of construction sites by fungi, yeast, bacterial strains. Not all bacterial strains are able to solubilize $CaCO_3$, but C. sphaerospermum KNUC253 or P. prolifica KNUC263 showed $CaCO_3$ solubilization activity. Therefore, these two strains were identified as target microorganisms that require control in cement structures. The registered patented strains Bacillus aryabhatti KNUC205, Arthrobacter nicotianae KNUC2100, B. thuringiensis KNUC2103 and Stenotrophomonas maltophilia KNUC2106, reported as multifunctional CFB (fungal growth inhibition, crack remediation, and water permeability reduction of cement surfaces) and isolated from Dokdo or construction site were unable to solubilize $CaCO_3$. Notably, B. aryabhatti KNUC205 and A. nicotianae KNUC2100 could not hydrolyze cellulose or protein, which can be the major constituent macromolecules of internal materials for buildings. These results show that several reported multi-functional CFB can be applied to cement structures or diverse building environments without corrosive or bio-deteriorative risks.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2008.06a
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• pp.239-240
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• 2008

As semiconductor devices are scaled down for better performance and more functionality, the Cu-based interconnects suffer from the increase of the resistivity of the Cu wires. The resistivity increase, which is attributed to the electron scattering from grain boundaries and interfaces, needs to be addressed in order to further scale down semiconductor devices [1]. The increase in the resistivity of the interconnect can be alleviated by increasing the grain size of electroplating (EP)-Cu or by modifying the Cu surface [1]. Another possible solution is to maximize the portion of the EP-Cu volume in the vias or damascene structures with the conformal diffusion barrier and seed layer by optimizing their deposition processes during Cu interconnect fabrication, which are currently ionized physical vapor deposition (IPVD)-based Ta/TaN bilayer and IPVD-Cu, respectively. The use of in-situ etching, during IPVD of the barrier or the seed layer, has been effective in enlarging the trench volume where the Cu is filled, resulting in improved reliability and performance of the Cu-based interconnect. However, the application of IPVD technology is expected to be limited eventually because of poor sidewall step coverage and the narrow top part of the damascene structures. Recently, Ru has been suggested as a diffusion barrier that is compatible with the direct plating of Cu [2-3]. A single-layer diffusion barrier for the direct plating of Cu is desirable to optimize the resistance of the Cu interconnects because it eliminates the Cu-seed layer. However, previous studies have shown that the Ru by itself is not a suitable diffusion barrier for Cu metallization [4-6]. Thus, the diffusion barrier performance of the Ru film should be improved in order for it to be successfully incorporated as a seed layer/barrier layer for the direct plating of Cu. The improvement of its barrier performance, by modifying the Ru microstructure from columnar to amorphous (by incorporating the N into Ru during PVD), has been previously reported [7]. Another approach for improving the barrier performance of the Ru film is to use Ru as a just seed layer and combine it with superior materials to function as a diffusion barrier against the Cu. A RulTaN bilayer prepared by PVD has recently been suggested as a seed layer/diffusion barrier for Cu. This bilayer was stable between the Cu and Si after annealing at $700^{\circ}C$ for I min [8]. Although these reports dealt with the possible applications of Ru for Cu metallization, cases where the Ru film was prepared by atomic layer deposition (ALD) have not been identified. These are important because of ALD's excellent conformality. In this study, a bilayer diffusion barrier of Ru/TaCN prepared by ALD was investigated. As the addition of the third element into the transition metal nitride disrupts the crystal lattice and leads to the formation of a stable ternary amorphous material, as indicated by Nicolet [9], ALD-TaCN is expected to improve the diffusion barrier performance of the ALD-Ru against Cu. Ru was deposited by a sequential supply of bis(ethylcyclopentadienyl)ruthenium [Ru$(EtCp)_2$] and $NH_3$plasma and TaCN by a sequential supply of $(NEt_2)_3Ta=Nbu^t$ (tert-butylimido-trisdiethylamido-tantalum, TBTDET) and $H_2$ plasma. Sheet resistance measurements, X-ray diffractometry (XRD), and Auger electron spectroscopy (AES) analysis showed that the bilayer diffusion barriers of ALD-Ru (12 nm)/ALD-TaCN (2 nm) and ALD-Ru (4nm)/ALD-TaCN (2 nm) prevented the Cu diffusion up to annealing temperatures of 600 and $550^{\circ}C$ for 30 min, respectively. This is found to be due to the excellent diffusion barrier performance of the ALD-TaCN film against the Cu, due to it having an amorphous structure. A 5-nm-thick ALD-TaCN film was even stable up to annealing at $650^{\circ}C$ between Cu and Si. Transmission electron microscopy (TEM) investigation combined with energy dispersive spectroscopy (EDS) analysis revealed that the ALD-Ru/ALD-TaCN diffusion barrier failed by the Cu diffusion through the bilayer into the Si substrate. This is due to the ALD-TaCN interlayer preventing the interfacial reaction between the Ru and Si.

• Journal of Sensor Science and Technology
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• v.6 no.4
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• pp.328-336
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• 1997

The CdSe thin films were grown on the Si(100) wafers by a hot wall epitaxy method (HWE). The source and substrate temperature are $600^{\circ}C$ and $430^{\circ}C$ respectively. The crystalline structure of epilayers was investigated by double crystal X-ray diffraction(DCXD). Hall effect on the sample was measured by the van der Pauw method and studied on the carrier density and mobility dependence on temperature. From Hall data, the mobility was increased in the temperature range 30K to 150K by impurity scattering and decreased in the temperature range 150k to 293k by the lattice scattering. In order to explore the applicability as a photoconductive cell, we measured the sensitivity(${\gamma}$), the ratio of photocurrent to darkcurrent(pc/dc), maximum allowable power dissipation(MAPD), spectral response and response time. The results indicated that the photoconductive characteristic were the best for the samples annealed in Cu vapor compare with in Cd, Se, air and vacuum vapour. Then we obtained the sensitivity of 0.99, the value of pc/dc of $1.39{\times}10^{7}$, the MAPD of 335mW, and the rise and decay time of 10ms and 9.5ms, respectively.

• Journal of Korean Society of Environmental Engineers
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• v.32 no.10
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• pp.986-993
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• 2010

In this study, sorption characteristics of thermally treated activated alumina (AA) for fluoride were investigated. Sorption experiments have been conducted in equilibrium and kinetic batch conditions. Also, effects of solution pH and anions on fluoride removal have been observed. The properties of thermally treated ( $700^{\circ}C$) activated alumina (AA700) and untreated activated alumina (UAA) were compared using field-emission scanning electron microscope, energy-dispersive spectrometry, X-ray diffractometer (XRD) analysis, and Brunauer-Emmett-Teller (BET) analysis. From the experiments using AA thermally treated at different temperatures (100, 300, 500, $700^{\circ}C$), it was found that at high fluoride concentrations (50, 100, 200 mg/L) the sorption capacity of thermally treated AA increased with increasing thermal treatment temperature. At an initial fluoride concentration of 200 mg/L, the sorption capacity of AA700 was 3.67 times greater than that of UAA. The BET analysis showed that the specific surface area of UAA was about 2 times larger than that of AA700. The XRD analysis indicated that UAA was composed of both boehmite (AlOOH) and bayerite ($Al(OH)_3$) while AA700 was $Al_2O_3$. The reason that fluoride sorption capacity of AA700 increased despite of decrease in specific surface area compared to UAA could be attributed to the change of crystal structure. The kinetic sorption test showed that fluoride sorption to AA700 arrived at equilibrium after 24 h. The equilibrium test demonstrated that the maximum sorption capacity of AA700 was 5.70 mg/g. Additional batch experiments indicated that fluoride sorption to AA700 was the highest at pH 7, decreasing at both acidic and basic solution pHs. Also, fluoride sorption to AA700 decreased in the presence of anions such as phosphate, nitrate, and carbonate. This study demonstrated that thermal treatment of AA at high temperature could increase its sorption capacity for fluoride.

• Journal of the Mineralogical Society of Korea
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• v.31 no.4
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• pp.307-323
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• 2018

The Inseong Au-Ag and base metal deposit, located in Chungchengbuk-do, Korea, consists of series of quartz veins filling fissures. The deposit occurs in Hwanggangri meta-sediment formation, a lime pebble-bearing phyllite, in the Okcheon Supergroup. Abundant ore minerals in the deposit are pyrite, arsenopyrite, sphalerite, chalcopyrite and galena. The gangue minerals are quartz, calcite and chlorite. Hydrothermal alteration such as chlorization, silicitication, sericitization and carbonitization can be observed around the quartz veins. 4 vein stages can be distinguished based on its paragenetic sequence, vein structure, alteration features and ore minerals. Microthermometry of the fluid inclusion assemblages occur in the veins are conducted to reconstruct a hydrothermal P-T evolution. Fluid inclusions in clean and barren quartz vein in stage 1 have Th of $270{\sim}342^{\circ}C$ and salinity of 1.7~6.4 (NaCl eqiv.) wt%. Euhedral quartz crystal in stage 2 have Th of $108{\sim}350^{\circ}C$ and salinity of 0.5~7.5 wt%. Barren milky quartz vein in stage 3 have Th of $174{\sim}380^{\circ}C$ and salinity of 0.8~7.5 wt%. Calcite vein in stage 4 have Th of $103{\sim}265^{\circ}C$ and salinity of 0.7~6.4 wt%. Calculated paleodepth about 0.5~1.5 km (hydrostatic pressure) indicate epithermal ore-forming condition. Shallow depth but relatively high-T hydrothermal fluids possibly create a steep geothermal gradient, sufficient for base metal precipitation in the Inseong deposit.

• Economic and Environmental Geology
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• v.53 no.6
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• pp.667-675
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• 2020

An Alum-sludge based adsorbent (ASBA) was synthesized by the hydrothermal treatment of alum sludge obtained from settling basin in water treatment plant. ASBA was applied to remove fluoride and arsenic in artificially-contaminated aqueous solutions and mine drainage. The mineralogical crystal structure, composition, and specific surface area of ASBA were identified. The result revealed that ASBA has irregular pores and a specific surface area of 87.25 ㎡ g-1 on its surface, which is advantageous for quick and facile adsorption. The main mineral components of the adsorbent were found to be quartz(SiO2), montmorillonite((Al,Mg)2Si4O10(OH)2·4H2O) and albite(NaAlSi3O8). The effects of pH, reaction time, initial concentration, and temperature on removal of fluoride and arsenic were examined. The results of the experiments showed that, the adsorbed amount of fluoride and arsenic gradually decreased with increasing pH. Based on the results of kinetic and isotherm experiments, the maximum adsorption capacity of fluoride and arsenic were 7.6 and 5.6 mg g-1, respectively. Developed models of fluoride and arsenic were suitable for the Langmuir and Freundlich models. Moreover, As for fluoride and arsenic, the increase rate of adsorption concentration decreased after 8 and 12 hr, respectively, after the start of the reaction. Also, the thermodynamic data showed that the amount of fluoride and arsenic adsorbed onto ASBA increased with increasing temperature from 25℃ to 35℃, indicating that the adsorption was endothermic and non-spontaneous reaction. As a result of regeneration experiments, ASBA can be regenerated by 1N of NaOH. In the actual mine drainage experiment, it was found that it has relatively high removal rates of 77% and 69%. The experimental results show ASBA is effective as an adsorbent for removal fluoride and arsenic from mine drainage, which has a small flow rate and acid/neutral pH environment.

• Korean Journal of Mineralogy and Petrology
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• v.35 no.2
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• pp.111-123
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• 2022

Carbonate green rust (CGR) and sulfate green rust (SGR) commonly occur in nature. In this study, CGR and SGR were synthesized through co-precipitation, and their formation mechanisms and physicochemical properties were investigated. X-ray diffraction (XRD) and Rietveld refinement showed both CGR and SGR with layered double hydroxide structure were successfully synthesized without any secondary phases under each synthetic condition. Refined structural parameters (unit cell) for two green rusts were a (=b) = 3.17 Å and c = 22.52 Å for CGR and a (=b) = 5.50 Å and c = 10.97 Å for SGR with the crystallite size 57.8 nm in diameter from (003) reflection and 40.1 nm from (001) reflections, respectively. Scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDS) results showed that both CGR and SGR had typical hexagonal plate-like crystal morphologies but their chemical composition is different in the content of C and S. In addition, Fourier transform infrared (FT-IR) spectroscopy analysis revealed that carbonate (CO₃^2-) and sulfate (SO₄^2-) molecules were occupied as interlayer anions of CGR and SGR, respectively. These SEM/EDS and FT-IR results were in good agreement with XRD results. Changes in the solution chemistry (i.e., pH, Eh and residual iron concentrations (Fe(II):Fe(III)) of the mixed solution) were observed as a function of the injection time of hydroxyl ion (OH^-) into the iron solution. Three different stages were observed in the formation of both CGR and SGR; precursor, intermediator, and green rust in the formation of both CGR and SGR. This study provides co-precipitation methods for CGR and SGR in a way of the stable synthesis. In addition, our findings for the formation mechanisms of the two green rusts and their physicochemical properties will provide crucial information with researches and industrials in utilizing green rust.

• Economic and Environmental Geology
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• v.54 no.6
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• pp.709-716
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• 2021

In this study, an adsorbent prepared by natural drying of iron hydroxide-based sludge collected from settling basin at a mine drainage treatment facility located in Gangneung, Gangwon-do was used to remove fluoride in an artificial fluoride solution and mine drainage, and the adsorption characteristics of the adsorbent were investigated. As a result of analyzing the chemical composition, mineralogical properties, and specific surface area of the adsorbent used in the experiment, iron oxide (Fe₂O₃) occupies 79.2 wt.% as the main constituent, and a peak related to calcite (CaCO₃) in the crystal structure analysis was analyzed. It was also identified that an irregular surface and a specific surface area of 216.78 m²·g^-1. In the indoor batch-type experiment, the effect of changes in reaction time, pH, initial fluoride concentration and temperature on the change in adsorption amount was analyzed. The adsorption of fluoride showed an adsorption amount of 3.85 mg·g^-1 16 hours after the start of the reaction, and the increase rate of the adsorption amount gradually decreased. Also, as the pH increased, the amount of fluoride adsorption decreased, and in particular, the amount of fluoride adsorption decreased rapidly around pH 5.5, the point of zero charge at which the surface charge of the adsorbent changes. Meanwhile, the results of the isotherm adsorption experiment were applied to the Langmuir and Freundlich isotherm adsorption models to infer the fluoride adsorption mechanism of the used adsorbent. To understand the thermodynamic properties of the adsorbent using the Van't Hoff equation, thermodynamic constants 𝚫H° and 𝚫G° were calculated using the adsorption amount information obtained by increasing the temperature from 25℃ to 65℃ to determine the adsorption characteristics of the adsorbent. Finally, the adsorbent was applied to the mine drainage having a fluoride concentration of about 12.8 mg·L^-1, and the fluoride removal rate was about 50%.

• Clean Technology
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• v.28 no.3
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• pp.218-226
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• 2022

As a result of the recent social transformation towards a hydrogen economy and carbon-neutrality, the demands for hydrogen energy have been increasing rapidly worldwide. As such, eco-friendly hydrogen production technologies that do not produce carbon dioxide (CO₂) emissions are being focused on. Among them, ammonia (NH₃) is an economical hydrogen carrier that can easily produce hydrogen (H₂). In this study, Ru/Al₂O₃ catalyst coated onmetallic monolith for hydrogen production from ammonia was prepared by a dip-coating method using a catalyst slurry mixture composed of Ru/Al₂O₃ catalyst, inorganic binder (alumina sol) and organic binder (methyl cellulose). At the optimized 1:1:0.1 weight ratio of catalyst/inorganic binder/organic binder, the amount of catalyst coated on the metallic monolith after one cycle coating was about 61.6 g L^-1. The uniform thickness (about 42 ㎛) and crystal structure of the catalyst coated on the metallic monolith surface were confirmed through scanning electron microscopy (SEM) and X-ray diffraction (XRD) analysis. Also, a numerical optimization regression equation for NH3 conversion according to the independent variables of reaction temperature (400-600 ℃) and gas hourly space velocity (1,000-5,000 h^-1) was calculated by response surface methodology (RSM). This model indicated a determination coefficient (R²) of 0.991 and had statistically significant predictors. This regression model could contribute to the commercial process design of hydrogen production by ammonia decomposition.