• Journal of Korean Society of Occupational and Environmental Hygiene
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• v.9 no.1
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• pp.56-72
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• 1999

Airborne concentrations of welding fumes in which 13 different metals such as Al, Cd, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Si, Sn, Ti, and Zn were analyzed were measured at 18 factories including automobile assembly and manufactures, steel heavy industries and shipyards. Air samples were collected by personal sampler at each worker's worksite(n=339). Blood levels of Cd, Cu, Fe, Mn, Pb and Zn were also measured from samples taken from 447 welders by atomic absorption spectrometry and compared with control values obtained from 127 non-exposed workers. The results were as follows ; 1. Among various welding types, $CO_2$ welding 70.2 % were widely used, shielded metal arc welding(SMAW) 22.1 % came next, and rest of them were metal inert gas(MIG) welding, submerged arc welding(SAW), spot welding(SPOT) and tungsten inert gas(TIG) welding. 2. Welding fume concentration was $0.92mg/m^3$($0.02{\sim}15.33mg/m^3$) at automobile assembly and manufactures, $4.10mg/m^3$($0.02{\sim}70.75mg/m^3$) at steel heavy industries and $5.59mg/m^3$($0.30{\sim}91.16mg/m^3$) at shipyards, respectively, showing significant difference among industry types. Workers exposed to high concentration of welding fumes above Korean Permissible Exposure Limit(KPEL) amounted to 7.9 % and 12.5 %, in $CO_2$ welding and in SMAW at automobile assembly and manufactures and 62.7 % in $CO_2$ welding, and 12.5 % in SMAW at shipyards, and 66.2 % in $CO_2$ welding and 70.6 % in SMAW at steel heavy industries. 3. Geometric mean of airborne concentration of each metal released from welding fumes was below one 10th of KPEL in all welding types. Percentage of workers, however, exposed to airborne concentration of metals above KPEL amounted to 16.8 % in Mn and 7.6 % in Fe in $CO_2$ welding; 37.5 % in Cu in SAW, 30 % in Cu in TIG; and 25 % in Pb in SPOT welding. As a whole, 76 Workers(22.4%) were exposed to high concentration of any of the metals above KPEL. 4. There were differences in airborne concentration of metals such as Al, Cd, Cr, Cu. Fe. Mn, Mo, Ni, Pb, Si, Sn, Ti and Zn by industry types. These concentrations were higher in shipyards and steel heavy industries than in automobile assembly and manufactures. Workers exposed to higher concentration of Pb above KPEI amounted to 7.4 % of workers(7/94) in automobile assembly and manufactures. In shipyards, 19.2 % of workers(19/99) were over-exposed to Mn and 7.1 % (7/99) to Fe above KPEL. In steel heavy industries, 14.4 %(21/146), 7.5 %(11/146) and 13 %(19/146) were over-exposed to Mn, Fe and Cu, respectively. As a whole, 76 out of 339 workers(22.4%) were exposed to any of the metals above KPEL. 5. Blood levels of Cd, Cu, Fe, Mn, Pb, and Zn in welders were $0.11{\mu}g/100m{\ell}$, $0.84{\mu}g/m{\ell}$, $424.4{\mu}g/m{\ell}$, $1.26{\mu}g/100m{\ell}$, $5.01{\mu}g/100m{\ell}$ and $5.68{\mu}g/m{\ell}$, respectively, in contrast to $0.09{\mu}g/100m{\ell}$, $0.70{\mu}g/m{\ell}$, $477.2{\mu}g/m{\ell}$, $0.73{\mu}g/100m{\ell}$, $3.14{\mu}g/100m{\ell}$ and $6.15{\mu}g/m{\ell}$ in non-exposed control groups, showing significantly higher values in welders but Fe and Zn.

• Applied Chemistry for Engineering
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• v.9 no.3
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• pp.394-398
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• 1998

An optimum synthetic condition was studied for the MCS used as a silicone monomer. The contact mixture was made from the four component catalyst system($CuCl/ZnCl_2/Sn/Cd$) and silicon particles. The contact mass was used for a series of experiments with methyl chloride, which were designed and done to explore the optimum condition for MCS synthesis by an experimental design method. The optimum temperature and MeCl flow rate, which were obtained using 50g contact mass at 60rpm and 1 atm, were in the range of $300-305^{\circ}C$ and of 70-80ccm. Also a continuous run was performed to confirm the conditions. The results showed that the average reaction rate and selectivity were 170(g-MCS/hr.kg-Si) and 0.05 respectively at 67% conversion of MeCl and 92% silicon utilization rate. Also the parameters of overall reaction rate equation and a total pressure were estimated on the basis of the results of the continuous run.

• Proceedings of the Materials Research Society of Korea Conference
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• 2012.05a
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• pp.65-65
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• 2012

Copper zinc tin sulfide ($Cu_2ZnSnS_4$, CZTS) is a very promising material as a low cost absorber alternative to other chalcopyrite-type semiconductors based on Ga or In because of the abundant and economical elements. In addition, CZTS has a band-gap energy of 1.4~1.5eV and large absorption coefficient over ${\sim}10^4cm^{-1}$, which is similar to those of $Cu(In,Ga)Se_2$(CIGS) regarded as one of the most successful absorber materials for high efficient solar cell. Most previous works on the fabrication of CZTS thin films were based on the vacuum deposition such as thermal evaporation and RF magnetron sputtering. Although the vacuum deposition has been widely adopted, it is quite expensive and complicated. In this regard, the solution processes such as sol-gel method, nanocrystal dispersion and hybrid slurry method have been developed for easy and cost-effective fabrication of CZTS film. Among these methods, the hybrid slurry method is favorable to make high crystalline and dense absorber layer. However, this method has the demerit using the toxic and explosive hydrazine solvent, which has severe limitation for common use. With these considerations, it is highly desirable to develop a robust, easily scalable and relatively safe solution-based process for the fabrication of a high quality CZTS absorber layer. Here, we demonstrate the fabrication of a high quality CZTS absorber layer with a thickness of 1.5~2.0 ${\mu}m$ and micrometer-scaled grains using two different non-vacuum approaches. The first solution-processing approach includes air-stable non-toxic solvent-based inks in which the commercially available precursor nanoparticles are dispersed in ethanol. Our readily achievable air-stable precursor ink, without the involvement of complex particle synthesis, high toxic solvents, or organic additives, facilitates a convenient method to fabricate a high quality CZTS absorber layer with uniform surface composition and across the film depth when annealed at $530^{\circ}C$. The conversion efficiency and fill factor for the non-toxic ink based solar cells are 5.14% and 52.8%, respectively. The other method is based on the nanocrystal dispersions that are a key ingredient in the deposition of thermally annealed absorber layers. We report a facile synthetic method to produce phase-pure CZTS nanocrystals capped with less toxic and more easily removable ligands. The resulting CZTS nanoparticle dispersion enables us to fabricate uniform, crack-free absorber layer onto Mo-coated soda-lime glass at $500^{\circ}C$, which exhibits a robust and reproducible photovoltaic response. Our simple and less-toxic approach for the fabrication of CZTS layer, reported here, will be the first step in realizing the low-cost solution-processed CZTS solar cell with high efficiency.

• Resources Recycling
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• v.10 no.5
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• pp.29-35
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• 2001

This study was carried out to recover gold, silver and valuable metals from the printed circuit boards (PCBs) of waste computers. PCBs samples were crushed under 1 mm by a shredder and separated into 30% conducting and loft nonconducting materials by an electrostatic separator. The conducting materials contained valuable metals which were then used as feed materials for magnetic separation. 42% of magnetic materials from the conducting materials was removed by magnetic separation as nonvaluable materials and the others, 58% of non magnetic materials, was used as leaching samples containing 0.227 mg/g Au and 0.697 mg/g Ag. Using the materials of leaching from magnetic separation, more than 95% of copper, iron, zinc, nickel and aluminium was dissolved in 2.0M sulfuric acid solution, added with 0.2M hydrogen peroxide at $85^{\circ}C$. Au and Ag were not extracted in this solution. On the other hand, more than 95% of gold and 100% of silver were leached by the selective leaching with a mixed solvent (0.2M($NH_4$)$_2$$S_2$$O_3$,0.02M $CuSO_4$,0.4M $NH_4$OH). Finally, the residues were reacted with a NaCl solution to leach Pb whereas sulfuric acid was used to leach Sn. Recoveries reached 95% and 98% in solution, respectively.

• KSBB Journal
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• v.14 no.1
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• pp.96-102
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• 1999

Marine bacterium Bacillus cereus ASK202 produced an extracellular agarase (E.C.3.2.1.81) which showed a high level of enzyme activity in the presence of agar and agarose. In the optimal culture conditions, the agarase production increased 7.7 folds compared with the one obtained from the basal medium. Agarase production reached upto 160 units/L after 24hr of cultivation in a modified marine medium at $25^{\circ}C$. The degree of purification increased 31.5 folds with 27.8% yield through freeze drying, DEAE Sepharose CL-6B and Superose 6HR 10/30 column chromatography. The molecular weight of the purified agarase was determined to be 90,000 daltons by gel-permeation filteration. Optimal temperature and pH for the enzyme activity were $40^{\circ}C$ and 7.8, respectively. The enzyme was stable up to $50^{\circ}C$ and at a broad pH range of 5.0-10.0. The $\beta$-agarase was activated by $Zn(NO_3)_2$, and was inhibited by $CuSO_4$ and $SnCl_2$. The Km and Vmax values of this enzyme for agarose as a substrate was $2.4mg/m\ell$ and 13.6 mg/m$\ell$, respectively.

• Journal of Electrochemical Science and Technology
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• v.9 no.4
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• pp.308-319
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• 2018

Single step electrodeposition of $Cu_2ZnSnS_4$ (CZTS) for solar cell applications was studied using an aqueous thiocyanate based electrolyte. The sodium thiocyanate complexing agent was found to decrease the difference in the deposition potential of the elements. X-ray diffraction analysis of the samples indicates the formation of kesterite phase CZTS. UV-vis studies reveal the band gap of the deposits to be in the range of 1.2 - 1.5 eV. The thickness of the deposit was found to decrease with increase in pH of the electrolyte. Nearly stoichiometric composition was obtained for CZTS films coated at pH 2 and 2.5. I-V characterization of the film with indium tin oxide (ITO) substrate in the presence and the absence of light source indicate that the resistance decrease significantly in the presence of light indicating suitability of the deposits for solar cell applications. Results of electrochemical impedance spectroscopic studies reveal that the cathodic process for sulfur reduction is the slowest among all the elements.

• Korean Journal of Heritage: History & Science
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• v.51 no.4
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• pp.224-233
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• 2018

Thirty-three Early Iron Age bronzes at the sites of Hoam-dong in Chungju and Cheongsong-ri in Buyeo were investigated in order to study the manufacturing technique and the provenance of lead. Chemical analysis using X-ray fluorescence showed that 33 bronzes consist of copper(Cu), tin(Sn) and lead(Pb) served as major elements. Major and minor elemental analyses by EPMA were performed on two mirrors and 2 weapons of the bronzes investigated. The results shows that bronze mirrors from Chungju and Buyeo were high-tin bronzes(> 30 wt%). And 20% of tin and 5% of lead were founded in bronze weapons. Iron, zinc, arsenic, silver, nickel, sulfur and cobalt detected in four bronzes as minor and trace elements. The four bronzes were alloyed considering their function and were not heat treated after casting due to their high tin content. Lead isotope analysis using TIMS indicates that thirty-three bronzes were distributed southern Korea peninsula except Zone 1. As a result, lead raw materials came from various regions in Korean Peninsula not from Gyeongsang-do regions. The manufacturing techniques of bronze ware generalized at this age, and bronze was produced in various sites using raw materials from various sources.

• Restorative Dentistry and Endodontics
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• v.22 no.1
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• pp.1-33
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• 1997

The objective of this study was to analyze the in vitro and in vivo corrosion products of low and high copper amalgams. The four different types of amalgam alloy used in this study were Fine cut, Caulk spherical, Dispersalloy, and Tytin. After each amalgam alloy and Hg were triturated according to the directions of the manufacturer by means of the mechanical amalgamator(Amalgam mixer. Shinhung Co. Korea), the triturated mass was inserted into a cylindrical metal mold which was 12mm in diameter and 10mm in height. The mass was condensed by 150Kg/cm compressive force. The specimen was removed from the mold and aged at room temperature for about seven days. The standard surface preparation was routinely carried out by emery paper polishing under running water. In vitro amalgam specimens were potentiostatically polarized ten times in a normal saline solution at $37^{\circ}C$(potentiostat : HA-301. Hukuto Denko Corp. Japan). Each specimen was subjected to anodic polarization scan within the potential range -1700mV to+400mV(SCE). After corrosion tests, anodic polarization curves and corrosion potentials were obtained. The amount of component elements dissolved from amalgams into solution was measured three times by ICP AES(Inductive Coupled Plasma Atomic Emission Spectrometry: Plasma 40. Perkim Elmer Co. U.S.A.). The four different types of amalgam were filled in occlusal and buccal class I cavities of four human 3rd molars. After about five years the restorations were carefully removed after tooth extraction to preserve the structural details including the deteriorated margins. The occlusal surface, amalgam-tooth interface and the fractured surface of in vivo amalgam corrosion products were analyzed. In vivo and in vitro amalgam specimens were examined and analyzed metallographically by SEM(Scanning Electron Microscope: JSM 840. Jeol Co. Japan) and EDAX(Energy Dispersive Micro X-ray Analyser: JSM 840. Jeol Co. Japan). 1. The following results are obtained from in vitro corrosion tests. 1) Corrosion potentials of all amalgams became more noble after ten times passing through the in vitro corrosion test compared to first time. 2) After times through the test, released Cu concentration in saline solution was almost equal but highest in Fine cut. Ag and Hg ion concentration was highest in Caulk spherical and Sn was highest in Dispersalloy. 3) Analyses of surface corrosion products in vitro reveal the following results. a)The corroded surface of Caulk spherical has Na-Sn-Cl containing clusters of $5{\mu}m$ needle-like crystals and oval shapes of Sn-Cl phase, polyhedral Sn oxide phase. b)In Fine cut, there appeared to be a large Sn containing phase, surrounded by many Cu-Sn phases of $1{\mu}m$ granular shapes. c)Dispersalloy was covered by a thick reticular layer which contained Zn-Cl phase. d)In Tytin, a very thin, corroded layer had formed with irregularly growing Sn-Cl phases that looked like a stack of plates. 2. The following results are obtained by an analysis of in vivo amalgam corrosion products. 1) Occlusal surfaces of all amalgams were covered by thick amorphous layers containing Ca-P elements which were abraded by occlusal force. 2) In tooth-amalgam interface, Ca-P containing products were examined in all amalgams but were most clearly seen in low copper amalgams. 3) Sn oxide appeared as a polyhedral shape in internal space in Caulk spherical and Fine cut. 4) Apical pyramidal shaped Sn oxide and curved plate-like Sn-Cl phases resulted in Dispersalloy. 5) In Tytin, Sn oxide and Sn hydroxide were not seen but polyhedral Ag-Hg phase crystal appeared in internal space which assumed a ${\beta}_l$ phase.

• Restorative Dentistry and Endodontics
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• v.21 no.1
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• pp.87-105
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• 1996

The purpose of this study is to investigate the characteristics of the compositions and phases of amalgam alloys and amalgams by using EMPA and X-ray diffractometer. Each specimen was made from Caulk Fine Cut Clow copper lathe cut amalgam), Caulk Spherical (low copper spherical amalgam), Tytin (high copper unicorn position amalgam), Dispersally (high copper admixed amalgam) and Valiant (Palladium enriched amalgam). For preparing amalgam alloys, Tytin and Valiant were used as powder forms and the others were used as tablet forms after being polished with polishing machine. For preparing amalgams, each amalgam alloy and Hg were measured, and triturated by mechanical amalgamater according to user's instructions. After triturating, the triturated mass was inserted to cylindrical metal mold and simultaneously adapted by cylindrical condenser with same diameter and condensed by Instron universal testing machine with 80kg pressure & 1mm/min speed. Each specimen was removed from the metal mold and stored at room temperature for a week. The specimen was polished with the same polishing machine for amalgam alloy. For observation of microstructure and analysis of composition of amalgam alloys and amalgams, EMPA was used to get secondary electron images, backscattered images and characteristic X-ray images of Ag, Sn, Cu, Zn, Hg. To analyze compositions of amalgam alloys and amalgams, X-ray diffractometer was used. Amalgam alloys were scanned at the range of 2${\theta}$ of 30-$85^{\circ}$ and the speed of $4^{\circ}$/min with Cuka line and amalgams were scanned at the range of 2${\theta}$ of 28-$44^{\circ}$ and the speed of $4^{\circ}$/min with Cuka line. By comparing obtained d(distance between surfaces) and d of expected phases and atoms in amalgam alloys and amalgams in ASTM card, phases and atoms were identified. The results were as follows, 1. In Caulk Fine Cut amalgam alloy typical ${\gamma}$ phase was shown, and in amalgam, ${\gamma}$, ${\gamma}_1$ and ${\gamma}_2$ phases were observed. 2. In Caulk Spherical amalgam alloy ${\gamma}$, Ag, Cu and $\varepsilon$ phases were shown, and in amalgam ${\gamma}$, ${\gamma}_1$, ${\gamma}_2$ and $\eta$ phases were observed. 3. In Tytin amalgam alloy ${\gamma}$, Cu and $\varepsilon$ phases were shown, and in amalgam ${\gamma}$, ${\gamma}_1$, $\eta$ and $\varepsilon$ phases were observed. 4. In Dispersalloy ${\gamma}$, Ag, Cu and $\varepsilon$ phases were shown, and in amalgam ${\gamma}$, ${\gamma}_1$, $\eta$ and $\varepsilon$ phases were observed. 5. In Valiant alloy ${\gamma}$, Cu and e phases were shown, and in amalgam ${\gamma}$, ${\gamma}_1$, $\eta$ and $\varepsilon$ phases were observed.

• Proceedings of the Materials Research Society of Korea Conference
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• 2012.05a
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• pp.99.1-99.1
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• 2012

The thin-film photovoltaic absorbers (CdTe and $Cu(In,Ga)Se_2$) can achieve solar conversion efficiencies of up to 20% and are now commercially available, but the presence of toxic (Cd,Se) and expensive elemental components (In, Te) is a real issue as the demand for photovoltaics rapidly increases. To overcome these limitations, there has been substantial interest in developing viable alternative materials, such as $Cu_2ZnSnS_4$ (CZTS) is an emerging solar absorber that is structurally similar to CIGS, but contains only earth abundant, non-toxic elements and has a near optimal direct band gap energy of 1.4 - 1.6 eV and a large absorption coefficient of ~104 $cm^{-1}$. The CZTS absorber layers are grown and investigated by various fabrication methods, such as thermal evaporation, e-beam evaporation with a post sulfurization, sputtering, non-vacuum sol-gel, pulsed laser, spray-pyrolysis method and electrodeposition technique. In the present work, we report an alternative aqueous chemical approach based on chemical bath deposition (CBD) method for large area deposition of CZTS thin films. Samples produced by our method were analyzed by scanning electron microscopy, X-ray diffraction, transmission electron microscopy, absorbance and photoluminescence. The results show that this inexpensive and relatively benign process produces thin films of CZTS exhibiting uniform composition, kesterite crystal structure, and some factors like triethanolamine, ammonia, temperature which strongly affect on the morphology of CZTS film.