• 한국재료학회지
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• 제22권5호
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• pp.243-248
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• 2012

ZrN nanoparticles were prepared by an exothermic reduction of $ZrCl_4$ with $NaN_3$ in the presence of NaCl flux in a nitrogen atmosphere. Using a solid-state combustion approach, we have demonstrated that the zirconium nitride nanoparticles synthesis process can be completed in only several minutes compared with a few hours for previous synthesis approaches. The chemistry of the combustion process is not complex and is based on a metathesis reaction between $ZrCl_4$ and $NaN_3$. Because of the low melting and boiling points of the raw materials it was possible to synthesize the ZrN phase at low combustion temperatures. It was shown that the combustion temperature and the size of the particles can be readily controlled by tuning the concentration of the NaCl flux. The results show that an increase in the NaCl concentration (from 2 to 13 M) results in a temperature decrease from 1280 to $750^{\circ}C$. ZrN nanoparticles have a high surface area (50-70 $m^2/g$), narrow pore size distribution, and nano-particle size between 10 and 30 nm. The activation energy, which can be extracted from the experimental combustion temperature data, is: E = 20 kcal/mol. The method reported here is self-sustaining, rapid, and can be scaled up for a large scale production of a transition metal nitride nanoparticle system (TiN, TaN, HfN, etc.) with suitable halide salts and alkali metal azide.

• 자원환경지질
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• 제29권5호
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• pp.545-559
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• 1996

Rare metal (Nb-Zr-REE) ore deposits are located in the Chungju area. Geotectonically, the rare metal ore deposits are situated in the transitional zone between Kyeonggi massif and Okcheon belt. The rare metal deposits are distributed in Kyemyeongsan Formation which consist of schist and alkaline igneous rocks. Alkali granite has suffered extensive post-magmatic metasomatism and hydrothermal processes. The ore contains mainly Ce-La, Ta-Nb, Y, Y-Nd, Nd-Th group minerals. More than 15 RE and REE minerals are found in the ore deposits. Allanite, one of the Ce-La rich REE minerals belonging to the epidote group, is the most common mineral in the studied area. The allanite- bearing rocks may be devided into seven types by features of occurrence and mineral associations; zircon type (ZT), allanite-vein type (AT), feldspar type (KT), fluorite type (FT), quartz-mica type (QT), iron-oxide type (MT), and amphibole type (HT). The allanite veins (AT) and zircon rich rocks (ZT) contain the highest total REE contents. Differences in REE abundance can be interpreted in terms of varying portions of magmatic hydrothermal fluid. Petrographical and chemical data are presented for allanites which were collected from different types. The allanites show wide variations in optical properties, due in part to differences in their chemical composition (depending on the types) and to the degree of crystallinity of the individual specimens. Allanite metamicts in biotite are generally surrounded by well developed pleochroic haloes. Usually, allanite is accompanied by zircon and other REE-bearing minerals. CaO and total REE contents $({\sum}RE_2O_3)$ range from 9.29 to 18.79% and 11.66 to 26.31%, respectively. Also, SiO, (28.87~32.61%), $Al_2O_3$ (8.30~16.88%), and $Fc_2O_3$ (16.74~24.38%) contents show varying contents from type to type. The ${\sum}RE_2O_3$ of allanite has positive relationships with $Fe_2O_3$ and negative relaton with CaO, $SiO_2$, and $Al_2O_3$ Backscattered electron microscope images (BEl) of allanite shows that the its mineral composition and texture is very complex. The allanite-bearing hosts show distinct light REE enrichment with strong negative Eu anomaly except for HI. The HT has an almost flat REE distribution pattern with a small negative Eu anomaly. The chemical variation of the allanites with occurrences and mineral association can be related to condition of temperature and oxidation states in precipitation environment.

• 자원환경지질
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• 제32권4호
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• pp.385-398
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• 1999

The Narim gold mine is located approimately 200km southeast of Seoul within the Muju mineralized district of the Sobaegsan gneiss complex, Korea. Environmental geochemistry were undertaken for various kinds of water (surface, ground and mine water) collected of April, September and November in 1998 from the narim mine creek. Hydrogeochemical compositions of water samples are characterized by the relatively significant enrichment of Na+K, alkali ions, $HCO_{3}$, $NO_{3}$, Cl and F in groundwater, wheras the mine and surface waters are relatively enriched in Ca+Mg, hea표 metals and $SO_{4}$. Therefore, the groundwaters belong to the (Na+Ca)-( $HCO_{3}+SO_{4}$) type, respectively. The pH and EC values of the non-mining creek surfers are relatively lower compared with those of the surface water of the mine and ore dump area. The d values ($\delta$D-8$\delta^{18}$O) of all kinds of water from the Narim mine creek are 5.8 to 13.1 The range of $\delta$D and $\delta^{18}$O values (relative to SMOW) are shown in distinct two groups as follows: for the April waters of -64.8 to -67.8$\textperthousand$ and -9.6 to -10.0$\textperthousand$(d value=10.1 to 13.1), and for the November waters of -65.9 to -70.2$\textperthousand$ and -9.3 to -9.6$\textperthousand$ (d value=5.8 to 7.9), respectively. This range variation indicates that two group water were composed of distinct waters with seasonal difference. Geochemical modeling showed that mostly toxic metals (As, Fe, Mn, Ni, Pb, Zn) may exist largery in the from of metal $(M2^+)$ and metal-sulfate $(MSO_4\;^{2-$\mid$),\; and \;SO_4^{2-$\mid$}$ concentration influenced the speciation of heavy metals in the meteoric water. These metals in the groundwater could be formed of $CO_3 \;and \;(OH)_3$ complex ions. Using computer program, saturation index of albite, calcite, dolomite in meteoric water show undersaturated and progreddively evolved toward the saturation state, however, ground and mine water are nearly saturated. The gibbsited water-mineral reaction and stabilities suggest that the weathering of silicate minerals may be stable kaolinite, illite and Nasmectite. The clay minerals will be transformed to more stable kaolinite owing to the contiunous reaction.

• Bulletin of the Korean Chemical Society
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• 제32권8호
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• pp.2643-2647
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• 2011

Efficient ditopic receptor, uranyl(II) N,N'-(ethylenedioxy)benzenebis(salicylideneimine) (3) for beryllium ion has been obtained upon functionalization of 1,2-ethylenedioxybenzene (1) with a uranyl-salphen (salphen = N,N'-phenylenebis(salicylideneimine)) unit. Binding affinities of the receptor, 3 in AN-DMSO (v/v 95:5) solution have been measured for alkali and alkaline earth metal ions by conductometry comparing 1. The results showed that both monotopic 1 and ditopic receptor 3 were selective for $Be^{2+}$ ions over other cations, while especially 3 that can complex both with cations (coordinated to basic oxygen of ethylenedioxybenzene) and anions (coordinated to the Lewis acidic uranyl center) results in an increase of the stability constants by a factor of $10^{2.42}$ with respect to 1. Furthermore, the $Be^{2+}$-3 interactions are demonstrated by $^1H$ NMR experiments in highly polar solvent medium, DMSO-$d_6$. Higher selectivities were also observed for $Be^{2+}$ when the ditopic receptor, 3 was incorporated into PVC membranes and tested as ion selective electrodes at neutral pH.

• 분석과학
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• 제37권1호
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• pp.47-62
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• 2024

Abu Gurdi area is located in the South-eastern Desert of Egypt which considered as volcanic massive sulfide deposits (VMS). The present work aims at investigating the ore mineralogy of Abu Gurdi region in addition to the effectiveness of the hydrometallurgical route for processing these ores using alkaline leaching for the extraction of Zn, Cu, and Pb in the presence of hydrogen peroxide, has been investigated. The factors affecting the efficiency of the alkaline leaching of the used ore including the reagent composition, reagent concentration, leaching temperature, leaching time, and Solid /Liquid ratio, have been investigated. It was noted that the sulfide mineralization consists mainly of chalcopyrite, sphalerite, pyrite, galena and bornite. Gold is detected as rare, disseminated crystals within the gangue minerals. Under supergene conditions, secondary copper minerals (covellite, malachite, chrysocolla and atacamite) were formed. The maximum dissolution efficiencies of Cu, Zn, and Pb at the optimum leaching conditions i.e., 250 g/L NaCO₃ - NaHCO₃ alkali concentration, for 3 hr., at 250 ℃, and 1/5 Solid/liquid (S/L) ratio, were 99.48 %, 96.70 % and 99.11 %, respectively. An apparent activation energy for Zn, Cu and Pb dissolution were 21.599, 21.779 and 23.761 kJ.mol^-1, respectively, which were between those of a typical diffusion-controlled process and a chemical reaction-controlled process. Hence, the diffusion of the solid product layer contributed more than the chemical reaction to control the rate of the leaching process. High pure Cu(OH)₂, Pb(OH)₂, and ZnCl₂ were obtained from the finally obtained leach liquor at the optimum leaching conditions by precipitation at different pH. Finally, highly pure Au metal was separated from the mineralized massive sulfide via using adsorption method.

• 분석과학
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• 제9권3호
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• pp.279-291
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• 1996

미량 금속이온을 선택적으로 분리, 농축 및 회수하기 위해 물리적 특성이 서로 다른 XAD-2, 4 및 16 다공성 수지에 2-(2-thiazolylazo)-p-cresol(TAC) alc 4-(2-thiazolylazo)orcinol(TAO)을 화학적으로 결합시켜 킬레이트 수지를 합성하고 뱃치법으로 U(VI) 등 10개 금속이온들의 흡착 특성을 조사 비교하였다. 킬레이트 수지의 합성률은 XAD-16-TAC형 수지는 0.60 mmol/g이었고 XAD-16-TAO형은 0.68mmol/g으로서 수지의 표면적이 큰 XAD-16형 수지가 XAD-2, 4형 수지보다 높은 합성률을 나타내었다. XAD-16-TAC와 XAD-16-TAO 킬레이트 수지는 1~5M 의 $HNO_3$, HCl 및 NaOH 등의 산과 염기성 용액에서 비교적 안정하였다. 그리고 U(VI) 이온을 10회 이상 반복적으로 흡착 및 탈착을 시킨 결과 연속적으로 재사용할 수 있는 안정한 내구성을 가지고 있음을 확인하였다. XAD-16-TAC 및 XAD-16-TAO형 수지에 대한 금속 이온의 최척 흡착조건과 흡착 특성을 조사한 결과는 금속이온이 킬레이트 수지에 흡착될 때 평형에 도달하는 시간은 약 1시간 정도였으며, XAD-16형 수지에서 흡착률이 가장 높았다. 그리고 금속이온들의 흡착률에 미치는 pH의 영향을 보면 U(VI)을 비롯한 대부분의 금속이온들은 pH 5~6 범위에서 최대로 흡착됨으로써 최척 pH 를 5로 정하였다. 또한 U(VI) 이온의 흡착에 미치는 공존이온의 영향을 보면 음이온인 $Cl^-$, $NO{_3}^-$, ${SO_4}^{2-}$, $CH_3COO^-$ 이온 및 $Na^+$, $K^+$, $Mg^{2+}$ 및 $Ca^{2+}$과 같은 양이온들은 흡착에 거의 영향을 미치지 않았다. 그러나 $CO{_3}^{2-}$는 $UO{_2}^{2+}$와 $[UO_2(CO_3)_3]^{4-}$의 안정한 착물을 형성하므로 U(VI) 이온의 흡착능을 크게 감소시켰다. 선택적인 특정 금속이온의 분리를 위하여 EDTA, CDTA 및 NTA 등과 같은 가리움제를 첨가하여 그 영향을 조사한 결과 NTA에 의한 가리움 효과가 10가지 혼합 금속이온 중 U(VI) 이온에 대하여 가장 큰 것으로 나타났다.

• 청정기술
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• 제27권2호
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• pp.168-173
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• 2021

도금폐수의 처리는 폐수의 pH, 중금속 및 시안(CN)함유에 따라 다양하고 복잡한 공정이 적용된다. 이중 시안(CN)의 처리는 차아염소산(NaOCl)을 이용한 알칼리 염소 처리법이 일반적으로 많이 사용되고 있다. 그러나, 암모니아성 질소(NH₃-N)와 시안(CN)이 동시에 함유될 경우 암모니아성 질소(NH₃-N)의 처리를 위해 차아염소산(NaOCl) 이 과다하게 소비되는 문제가 있다. 이러한 문제를 해결하기 위하여 본 연구는 시안(CN)처리에 있어서 1) 알칼리염소법에서 암모니아성 질소(NH₃-N)농도에 따른 차아염소산(NaOCl)의 소모량을 조사하고 2) ferrate (VI)가 시안(CN)을 선택적으로 처리할 수 있는지를 평가하였다. 모의폐수를 이용한 실험결과 알칼리염소법에서는 암모니아성 질소(NH₃-N)농도가 높을수록 시안(CN)의 제거율이 감소하였으며 차아염소산(NaOCl)의 소비량이 암모니아성 질소(NH₃-N) 농도에 따라 선형적으로 증가하였다. Ferrate (VI)를 이용한 시안(CN) 제거에서는 암모니아성 질소(NH₃-N) 농도에 관계없이 시안(CN)의 제거를 확인하였으며 이때 암모니아성 질소(NH₃-N)의 제거율은 낮아 ferrate (VI)가 시안(CN)을 선택적으로 제거함을 확인하였다. Ferrate (VI)의 시안(CN) 제거효율은 pH가 낮을수록 높게 나타났고 ferrate (VI) 주입량에 관계없이 99% 이상을 보였다. 실제 도금폐수에 적용한 결과에서는 ferrate (VI)와 시안(CN)의 투입 몰비 1:1에서 99% 이상의 높은 제거율을 보였으며 이는 화학양론 반응식의 몰비와 일치하는 결과로 모의 폐수와 동일하게 암모니아성 질소(NH₃-N) 및 기타오염물질이 함유된 실제 폐수에서도 선택적으로 시안(CN)을 제거하는 것으로 확인되었다.

• 분석과학
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• 제9권4호
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• pp.336-344
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• 1996

뇨시료 중 혼적량의 코발트, 구리, 니켈, 카드뮴, 납 및 아연을 흑연로 원자흡수분광 광도법으로 정량하기 위한 dithizone이 포함된 chloroform으로의 용매추출에 관하여 연구하였다. 실험조건인 시료의 전처리 과정, 추출용액의 pH, 킬레이트제인 dithizone의 농도, 역추출할 때 사용하는 산의 종류와 농도에 관하여 최적화하였다. 유기물의 방해를 제거하고자 뇨시료 100.0mL에 진한 질산 30mL를 가하고 30% 과산화수소 50mL를 5.0mL씩 단계적으로 가하면서 가열하여 유기물질을 분해하였다. 삭힌 뇨시료를 100mL로 만들어 분별 깔때기에 넣고 시판용 완충용액으로 pH가 8이 되게 조절한 다음 0.1% dithizone을 포함하는 chloroform 15.0mL를 가했다. 진탕기(shaker)를 이용하여 90분 동안 흔들어 준 후 상분리시켜 용매층을 분리하였다. 카드뮴, 납, 아연은 0.2M 질산용액 10.0mL로 역추출하여 직접 정량하였고, 이런 조건으로 역추출되지 않은 코발트, 구리, 니켈은 유기 용매를 증발 건고시킨 다음 잔류물을 $HNO_3$ $H_2O_2$로 녹이고, 정확히 10.0mL가 되게 탈염수로 묽혀서 정량하였다. 최적의 추출조건을 찾기 위하여 인공 뇨시료를 제조하여 검토하였고, 얻은 최적조건으로 검정곡선을 작성하였다. 삭힌 각 시료에 일정량 첨가된 원소를 정량하여 얻은 회수율은 77 내지 109%였고, 검출한계는 Cd(II) 0.09, Pb(II) 0.59, Zn(II) 0.18, Co(II) 0.24, Cu(II) 1.3, Ni(II) 1.7ng/mL였다. 이로써 본 방법이 과량의 유기물과 알칼리 및 알칼리 토금속이 포함된 뇨시료에서 혼적량 원소들을 정량적으로 분리 분석할 수 있음 을 알았다.