• 공학논문집
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• 제6권1호
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• pp.97-109
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• 2004

CaO의 첨가량에 따라 $CO_2$가스를 불어넣고 반응시간 변화에 따라 용매로 $C_2 H_5 OH$을 사용하여 에틸렌글리콜을 첨가한 CaO-$C_2 H_5 OH$-$CO_2$계의 기.액반응으로부터 비정질 $CaCO_3$의 합성과 결정구조를 전기전도도, X-선회절 및 주사전자현미경으로 조사하였다. 이 반응에서 900ml의 $C_2 H_5 OH$에 에틸렌글리콜 100ml를 첨가하고 CaO의 양을 10~40g으로 하여 $CO_2$가스를 1$\ell$/min의 유속으로 흡입시켜 얻은 합성분말의 겔형 물질을 신속히 여과, 감압하의 $60^{\circ}C$에서 건조하여 1${\mu}m$이하의 구형 vaterite상과 무정형인 비정질 $CaCO_3$을 얻었다. 그리고 비정질 $CaCO_3$의 일부는 중간생성물로서 연쇄형 calcite로 변화하는 것을 알 수 있었고 침강성 $CaCO_3$의 생성보다 먼저 초기 반응생성물은 비정질 $CaCO_3$이었고 이 경우 생성역역은 pH 7-9의 범위로 상당한 영향을 준다. 또한 비정질 $CaCO_3$은 용액 속에서 불안정하여 용해반응으로 인해서 결국 calcite로 결정화한다. 특히 비정질 $CaCO_3$은 CaO-$C_2 H_5 OH$-$CO_2$계의 반응에 의해서 침강되어 생성되거나 또는 gel상으로 된다.

• 한국세라믹학회지
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• 제39권4호
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• pp.327-335
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• 2002

Experiments were conducted to investigate the synthesis characteristics of Precipitated Calcium Carbonate(for short PCC) in Ca(OH)$_2-CO_2-H_2O$ system by the continuous drop method of Ca(OH)$_2$ slurry into the solution containing $CO_2$(aq). When the flow rate of $CO_2$(g) increases and the concentration of Ca(OH)$_2$ slurry become low, the absorption rate of $CO_2$(g) become faster than the dissolution rate of Ca(OH)$_2$. Consequently, the growth of the calcite crystal plane is facilitated resulting in synthesis of $1.0{\mu}m$ of rhombohedral calcite. On the other hand, when the flow rate of $CO_2$(g) decreases and the concentration of Ca(OH)$_2-CO_2-H_2O$ slurry become high, new nuclei is created along with the crystal growth resulting in synthesis of $0.1{\mu}m$ of prismatic calcite. Maintaining 1.0wt% of Ca(OH)$_2-CO_2-H_2O$ slurry, 120 drops/min of drop rate and $25^{circ}C$ of temperature, the shape of PCC shows colloidal and spherical agglomerate at 100 mL/min of the flow rate of $CO_2$(g); the mixture of rhombohedral and plate-shaped calcite, at 200∼500 mL/min. Therefore, as the flow rate of $CO_2$(g) increases, the shape of PCC changes from colloidal and rhombohedral calcite to plate-shaped calcite. Maintaining 500 mL/min of the flow rate of $CO_2$(g), 120 drops/min of the drop rate of Ca(OH)$_2$ slurry, and $25^{circ}C$ of temperature, the shape of PCC shows the plate-shaped calcite at 1.0∼3.0 wt% of Ca(OH)$_2$ slurry; the hexagonal plate-shape calcite of the thickness of $0.1{\mu}m$ and the width of $1.0{\mu}m$, at 4.0 wt%.

• 한국세라믹학회:학술대회논문집
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• 한국세라믹학회 2003년도 춘계총회 및 연구발표회 초록집
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• pp.30.2-30
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• 2003

• 한국환경과학회지
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• 제9권6호
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• pp.505-509
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• 2000

The purpose of this study was to evaluate the effects of $Ca(OH)_2$ and $CO_2$ additions on the corrosion of metal coupons(ductile iron, galvanized steel, copper and stainless steel). Corrosion rate and released metal ion concentration of ductile iron and galvanized steel decreased by adjusting alkalinity, calcium hardness and pH with $Ca(OH)_2$ & $CO_2$ additions on copper and stainless steel were less than those on ductile iron and galvanized steel. When ductile iron coupon was exposed to water treated with Ca(OH)$_2$&$CO_2$, additions, the main components of corrosion product formed on its surface were $CaCO_3$ and $Fe_2 O_3 or Fe_2 O_4$ which often reduce the corrosion rate by prohibiting oxygen transport to the metal surface.

• 한국표면공학회지
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• 제47권1호
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• pp.39-47
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• 2014

The peculiar feature of cathodic protection in seawater has the capability to form mineral calcareous deposits such as magnesium and calcium on metal surfaces. It is assumed that $OH^-$ ions are generated close to the metal surface as a result of cathodic protection and generated $OH^-$ ions increases the pH of the metal/seawater interface outlined as the following formulae. (1) $O_2+2H_2O+4e{\rightarrow}4OH^-$, or (2) $2H_2O+2e{\rightarrow}H_2+2OH^-$. And high pH causes precipitation of $Mg(OH)_2$ and $CaCO_3$ in accordance with the following formulae. (1) $Mg^{2+}+2OH^-{\rightarrow}Mg(OH)_2$, (2) $Ca^{2+}+CO{_3}^{2-}{\rightarrow}CaCO_3$. The focus of this study was to increase the amount of $CO{_3}^{2-}$ with the injection of $CO_2$ gas to the solution for accelerating process of the following formulae. (1) $H_2O+CO_2{\rightarrow}H_2CO_3$, (2) $HCO^{3-}{\rightarrow}{H^+}+CO{_3}^{2-}$. Electrodeposit films were formed by an electro-deposition technique on steel substrates in solutions of both natural seawater and natural seawater dissolved $CO_2$ gas with different current densities, over different time periods. The contents of films were investigated by scanning electron microscopy(SEM) and X-ray diffraction(XRD). The adhesion and corrosion resistance of the coating films were evaluated by anodic polarization. From an experimental result, only $CaCO_3$ were found in solution where injected $CO_2$ gas regardless of current density. In case of injecting the $CO_2$ gas, weight gain of electrodeposits films hugely increased and it had appropriate physical properties.

• 한국마린엔지니어링학회:학술대회논문집
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• 한국마린엔지니어링학회 2005년도 후기학술대회논문집
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• pp.196-197
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• 2005

Cathodic protection is one of the successful ways to prevent corrosion of steel structures in marine environments. The unique feature of cathodic protection in seawater is the formation of calcareous deposits on cathodic metal surface. The formation principles of calcareous deposit seawater had been known for a long time. That is, cathodic reduction reactions associated with cathodic protection in seawater generate $OH^-$ at the metal surface in accordance with the formular ; 1/2 $O_2$ + $H_2O$ + $2e^-$ $2OH^-$ and $2H_2O$ + $2e^-$ ${\rightarrow}$ $H_2$ + $2OH^-$. These reactions increase the pH at the metal / seawater interface. The high pH causes precipitation of $Mg(OH)_2$ and $CaCO_3$ in accordance with the formular ; $Mg^{2+}$ + $2(OH)^-$ ${\rightarrow}$ $Mg(OH)_2$ and $Ca^{2+}$ + $HCO_3^-$ + $OH^-$ ${\rightarrow}$ $H_2O$ + $CaCO_3$. These are typically the main compounds in calcareous deposits. It obviously has several advantages compared to the conventional coatings, since the environment-friendly calcareous deposit coating is formed by the elements($Mg^{2+}$, $Ca^{2+}$) naturally present in seawater. In this study, environmental friendly calcareous deposit films were prepared on steel plates by electro plating technic in natural seawater. The influence of current density on composition ratio, structure and morphology of the coated films were investigated by scanning electron microscopy formation process of calcareous deposits films in natural seawater. And we confirmed the properties of all the films can be improved greatly by controlling the material structure and morphology with effective use of the electroplating method in natural seawater.

• Korean Chemical Engineering Research
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• 제57권6호
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• pp.812-825
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• 2019

국내에서 채광되는 백운석(dolomite, $CaMg(CO_3)_2$)을 회분식 형태의 마이크로웨이브 소성로($950^{\circ}C/60min$)에 의해 소성하여 경소백운석($CaO{\cdot}MgO$)을 제조하였다. 국내에서 산출된 두 개의 백운석 시료를 대상으로 경소백운석($CaO{\cdot}MgO$) 제조 후 수화 특성을 규명한 결과 반응성이 다름을 규명하였다. 경소백운석($CaO{\cdot}MgO$)의 수화 특성의 반응성을 이용하여 강산성 양이온 교환수지와 반응 시켜서 MgO를 분리하는 조건을 실시하였다. 분리 실험 조건은 경소백운석($CaO{\cdot}MgO$)과 $R-SO_3H$ (1:12 mass %)로 칼슘이온 흡착($Ca-(R-SO_3)_2$)하여 MgO를 분리하였다. 분리 후 MgO의 함량은 94 mass % 이상으로 분리되었다. 분리된 MgO를 $950^{\circ}C$, 60 min 동안 열처리 후 MgO의 순도는 96 mass %로 나타났다. 그리고칼슘 이온이 흡착된강산성 양이온교환수지($Ca-(R-SO_3)_2$)와 NaOH, $CO_2$ gas 반응에 의해서 98 mass %의 $CaCO_3$를 합성하였다.

• Korean Chemical Engineering Research
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• 제59권3호
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• pp.399-409
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• 2021

백운석을 칼슘/마그네슘 화합물 소재로 활용하기 위해 마이크로웨이브 소성로(950 ℃, 60 min)을 이용하여 소성하여 고반응성 경소백운석(CaO·MgO)을 제조하였다. Hydration test(ASTM C 110) 기준에 따라 실험을 실시하였으며 수화 반응성 결과, 중 반응성(max 74.1 ℃, 5 min)으로 분석 되었다. 경소백운석의 수화 반응에 기초하여 경소백운석과 염(MgCl₂·6H₂O) (a) 1:1, (b) 1:1.5, (c) 1:2 wt%로 실험을 진행하였다. 염 첨가 비율이 증가 할수록 경소백운석의 MgO가 Mg(OH)₂로 증가되는 것을 X-선 회절 분석 결과 확인하였다. 분리 반응 후 칼슘은 CaCl₂ 용액 상태로 80 ℃, 24 시간 동안 교반시켜 흰색 결정체인 CaCl₂가 제조 되었다. XRD 분석 결과, CaCl₂·(H₂O)x(calcium chloride hydrate)로 경소백운석과 염 첨가 반응에 의한 CaO는 CaCl₂로 분리 되는 것을 확인하였다. 그리고 CaCl₂ 용액에 NaOH 첨가 반응으로 순도 99 wt%의 Ca(OH)₂ 합성하였으며, 합성된 Ca(OH)₂를 열처리 과정을 통하여 CaO를 제조하였다. 탄산칼슘을 제조하기 위해 CaCl₂ 용액에 Na₂CO₃ 첨가 반응으로 CaCO₃를 합성하였으며, 형상은 큐빅(cubic) 형태로 순도 99 wt%로 분석 되었다.

• 한국세라믹학회지
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• 제40권12호
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• pp.1208-1212
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• 2003

CaCO$_3$ powders were synthesized by aqueous solution reaction of CaC1$_2$ㆍ2$H_2O$-(NH$_4$)$_2$CO$_3$ system with NH$_4$OH at 45$^{\circ}C$ and pHs 8, 9, 10, and 11 and in the concentration range of 0.1∼5 M and its polymorphism, morphology and size were investigated. In order to investigate the influence of pH on nucleation, pH was adjusted before and after reaction respectively. When pH was adjusted after reaction a formation ratio of vaterite was increased with increasing pH and concentration but vaterite was formed with calcite. But, when pH was adjusted before reaction, the formation rate of vaterite was increased with increasing pH and concentration. resulting in a phase-pure vaterite with a spherical shape and 2∼5 $\mu\textrm{m}$ in size. It was found that solubility of alkaline vaterite was decreased with increasing OH- ions in the high pH solution. When pH was adjusted before nucleation in the high concentration range, in particular, decreasing of solubility disturbed transformation of initially formed numerous vaterite to calcite.

• 자원리싸이클링
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• 제4권1호
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• pp.38-45
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• 1995

본 연구는 2.$0^{\circ}C$~85.3$^{\circ}C$, 2$\times$10\ulcornerM의 상압에서 탄산칼슘의 동질이상인 calcite, aragonite, vaterite의 생성과 그 형상에 미치는 온도의 영향을 조사한 것이다. 실험된 반응은 \circled1 Ca($HCO_3$)$_2$-Air bubble, \circled2 (OH)$Ca_2$ $-CO_2$, \circled3 (OH)$Ca_2$ $-H _2$$CO_3$, \circled4 $Ca(OH)_2$$-Na_2$CO$_3$, \circled5 $Ca(OH)_2$ $-K_2$ $ CO_3$, \circled6 $Ca(OH)_2$-($NH_4$)$_2$$CO_3$, \circled7 $CaCl_2$ $-Na2$ $CO_3$, \circled8 $CaCl_2$-K$_2$$CO_3$, \circled9 $CaCl_2$-($NH_4$)$_2$$CO_3$, \circled10 Ca($NO_3$)$_2$- $Na_2$$CO_3$, ⑪ Ca($NO_3$)$_2$- $K_2$$CO_3$, ⑫ Ca($NO_3$)$_2$등 12가지이며, 얻어진 실험결과는 아래와 같다. calcite는 반응종류에 상관없이 실험된 거의 모든 온도범위($2.0^{\circ}C$~$80.0^{\circ}C$)에서 생성하며 그 생성수율은 3$0^{\circ}C$정도일 때가 가장 높았다. aragonite는 반응에 따라 약간씩 차이는 있지만 주로 41.$0^{\circ}C$~53.$0^{\circ}C$ 사이에서 생성하기 시작하며 온도는 높을수록 그 수율은 높아진다. pH 또한 aragonite의 생성수율에 영향을 미치며 반응후 모액의 pH가 10.0~11.0 사이일 경우 생성수율이 최대가 되며 12.3 이상인 경우는 aragonite가 거의 생성되지 않았다. vaterite는 4$0^{\circ}C$ 이하에서만 생성하며 상당히 불안정하기 때문에 생성후 모액속에 방치할 경우 Cl￣를 포함하지않는 반응계에서는 10~60분 경과후 완전히 calcite로 전이하고 Cl￣를 포함하는 계에서는 약 140시간만에 완전히 calcite로 전이한다.