• Journal of the Korean Ceramic Society
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• v.39 no.12
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• pp.1143-1148
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• 2002

Precipitated calcium carbonate is one of the most versatile mineral fillers and is consumed in an wide range of products including paper, paint, plastics, rubber, textiles, sealants, adhesives and printing ink and can be produced by several methods. Calcium carbonate has three isomorphism; vaterite, aragonite and calcite, with numerous variations of morphology in the natural mineral or organism. Formation process of vaterite in the reaction of system $Ca(OH)_2-CH_3OH-H_2O-CO_2$ were investigated by measuring the electrical conductivity, $Ca^{2+}$ ion concentration, pH in the slurries and by means of X-ray diffraction and electron microscopic observation. It was clearly established that the reaction temperature is important variable in the carbonation process; in general over 50${\circ}C$, the vaterite was precipitated with the calcite and aragonite. SEM and XRD observations revealed that the vaterite formation could be prepared the temperature range of 40 to 50${\circ}C$ and mean size of particles in this range is controlled from 0.5 to 0.8 ${\mu}m$.

• Korean Journal of Mineralogy and Petrology
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• v.33 no.4
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• pp.439-450
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• 2020

Global warming caused by the emission of greenhouse gases into the atmosphere is being treated as a major problem for the human life, and mineral carbonation is drawing attention as one of many countermeasures against this situation. In this study, mineral carbonation experiments using autoclaved lightweight concrete (ALC) were performed under various conditions to determine its potential as a carbonation material. ALC can be regarded as a promising material for carbonation because it contains about 27 wt.% of CaO, a major component of mineral carbonation. The CaCO3 content produced as a result of the carbonation of ALC calculated on the assumption that all of the CaO content participates in mineral carbonation is about 40 wt.%. The optimum conditions for the mineral carbonation reaction from ALC are the solid-liquid ratio of 0.01 and the reaction time of 180 minutes when calcite is considered as a single product, or 0.06 and 180 minutes when mixture of calcite and vaterite can be considered. The coexistence of vaterite with calcite at solid-liquid ratio of 0.06 or higher was interpreted to be the case where vaterite formed in the later stage and did not change to calcite until the reaction was completed.

• Proceedings of the Korean Ceranic Society Conference
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• 2003.04a
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• pp.30.2-30
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• 2003

• Korean Chemical Engineering Research
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• v.57 no.5
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• pp.666-671
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• 2019

Calcium carbonate involves three phases such as calcite, vaterite, and aragonite. Calcite and aragonite were more thermodynamically stable than vaterite. The synthesis of aragonite crystals by the reaction with sodium carbonate and calcium chloride solutions was investigated focusing on the effect of temperature and rpm in continuous crystallizer. In the batch crystallization test, calcite was synthesized by a relatively low temperature (under $40^{\circ}C$), but aragonite was formed at high temperature. In the continuous process with 100 rpm, no aragonite was found regardless of reaction temperature. But as increasing the stirring rate to 300 rpm and 500 rpm, the ratio of aragonite to calcite increased as increasing the temperature.

• Economic and Environmental Geology
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• v.56 no.3
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• pp.217-227
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• 2023

Crystalline calcium carbonate (CaCO₃) occurs in various geological and aqueous environments as calcite, aragonite, and vaterite. These minerals also have practical applications in engineered settings. Synthetic methods of calcium carbonate have been developed for scientific research and technical applications. For example, these methods have become widely adopted for studying the formation of CaCO₃ minerals and (geo-)chemical processes involving these minerals in natural and engineered systems. Furthermore, these methods have the potential to be applied in various technical and biomedical fields. Water-based synthesis is particularly important for simulating the formation of calcium carbonate minerals in natural aqueous environments. This review paper describes the procedures and experimental conditions for water-based synthetic methods of each calcium carbonate polymorph, compares the morphological and structural features of the resulting crystals, and analyzes the crystallization mechanisms.

• Journal of the Mineralogical Society of Korea
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• v.17 no.1
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• pp.11-21
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• 2004

Crystallization of CaC $O_3$ from the solutions of various degrees of supersaturation was carried out by a spontaneous precipitation method. The solution was kept at $25^{\circ}C$ and pH 6.9∼8.8. The solution compositions were varied in two ways: (1) The total carbonate, [C $O_3$]$_{Τ}$, to total calcium. [Ca]$_{Τ}$, ratios vary as ; [C $O_3$]$_{Τ}$/[Ca]$_{Τ}$ >1. [C $O_3$]$_{Τ}$/[Ca]$_{Τ}$=1, and [C $O_3$]$_{Τ}$/[Ca]$_{Τ}$<1. (2) The total calcium concentration, [Ca]$_{Τ}$, held at 0.02 mo1/d $m^3$, 0.2 mo1/d $m^3$, and 0.4 mo1/d $m^3$. We found that the CaC $O_3$ phase crystallized from the solutions of [C $O_3$]$_{Τ}$/[Ca]$_{Τ}$ $\geq$ 1 was mostly calcite with less than 1% of vaterite, while the CaC $O_3$ crystals precipitated from low carbonate concentration toward calcium concentration, [C $O_3$]$_{Τ}$/[Ca]$_{Τ}$ < 1, were dominated by vaterite crystals. It appears that the polymorph of CaC $O_3$ precipitate was mainly controlled not by the calcium concentration but by the carbonate concentration during the spontaneous precipitation. Also, we found that the surface roughness of vaterite increased with decreasing carbonate concentration from 0.8 or 0.5 of [C $O_3$]$_{Τ}$/[Ca]$_{Τ}$ ratios and the surface area of vaterite increased from 5.64∼7.34 $\mu\textrm{m}$ to 8.39∼10.3 $\mu\textrm{m}$.

• Proceedings of the Korea Association of Crystal Growth Conference
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• 1996.06b
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• pp.3-27
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• 1996

분체의 입자 배열이 불규칙한 경우뿐만 아니라 입자 크기가 극미세하여 X선회절분석이 불가능한 경우에도 비정질물질이라 한다. 수용액 속에서 이런 비정질 물질을 합성하기 위해서는 합성용액의 과포화도를 높여 계속 유지시킴에 따라 극미세 1차핵 생성의 지속적인 유도에 따른 입자 성장을 최대한 억제시켜야만 한다. 본 연구에서는 흡습제, 칼슘제 및 식품 첨가제 등으로 이용되는 비정질 탄산칼슘을 계에서 합성하고, 이때 생성된 비정질 상태의 겔을 수용액 환경을 변화시켜가면서 따라 결정화를 유도하고 탄산칼슘의 동질이상을 관찰하였다. CO2의 유속을 11/min, 교반속도를 600rpm으로 고정시키고, Ca(OH)2의 양을 10g에서 50g까지 변화시켜가면서 겔 상태의 비정질 탄산칼슘을 합성하였다. 이때 전기전도도는 CO2의 용해와 더불어 Ca(OH)2의 용해도가 증가함에 따라 변화하였으며, 반응종반부에는 겔화가 시작될 때까지 거의 일정하였다. 따라서, 이러한 사실들로부터 현탁액 내에서의 전기전도도의 변화는 Ca이온의 영향을 받는 것으로 사료된다. 비정질 탄산칼슘은 수용액에서 불안정하여 CO2 가스를 방출하면서 급격히 결정화되는데, 본 연구에서는 Ca(OH)2의 양을 20g으로 하여 위의 방법에 의해 얻어진 겔을 수용액의 종류와 농도 및 결정화 온도, 교반속도를 달리하면서 결정화시켰다. 교반속도를 100rpm으로 하여 물의 온도변화에 다라 결정화시킨 경우 전 온도범위에서 칼사이트상이었으며, 물의 온도가 5$^{\circ}C$일 경우에는 미세한 입자들이 응집된 형태였으나, 그 외의 온도변화조건에서는 모두 평균입경 0.4$\mu\textrm{m}$정도의 비교적 균일하 능면체 형태였다. 또한 교반속도를 500rpm으로 증가시켰을 경우에는 8$0^{\circ}C$에서 침상의 아라코나이트가 소량생성되었음을 SEM사진으로 관찰할 수 있었으며, 소량의 바테라이트도 혼재되어 결정화되었음을 XRD결과로 알 수 있었다. 교반속도를 100rpm으로 한 NH4Cl 0.5mol/l 수용액에서는 입자의 형태와 크기가 불규칙한 칼사이트로 결정화되었으며, MgCl2 0.05mol/l 수용액의 경우에는 순수한 H2O의 경우에서와는 달리 2$0^{\circ}C$에서는 모서리가 무딘 매우 균일한 크기의 칼사이트 입자가 관찰되었으며, 6$0^{\circ}C$부터는 아라고나이트가 생성됨을 관찰할 수 있었다. 따라서, 고온(8$0^{\circ}C$)의 농도 MgCl2 수용액(0.1, 0.2 mol/l)에서 교반속도를 높여(800rpm) 겔을 결정화시킨 결과 아라고나이트의 생성수율이 증가되는 것을 확인할 수 있었다.

• Clean Technology
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• v.29 no.2
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• pp.95-101
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• 2023

An experiment was conducted to produce vaterite-type precipitated calcium carbonate from waste oyster shells in order to use them as recyclable resources. Calcined oyster shells containing calcium oxide as their main component were prepared at a temperature of 800℃ for 24 h. The oyster shells were dissolved in nitric acid or hydrochloric acid solution to make 0.1 M calcium nitrate or calcium chloride aqueous solution, and a carbonation reaction was performed using a 0.1 M sodium carbonate aqueous solution under various experimental conditions, which included varying the amount of aspatic acid additive, the amount of NH₄OH added, the reaction time, the reaction temperature, the stirring speed, and the type of dissolved acid. The XRD, SEM, and size distributions were analyzed and the vaterite content was calculated. Spherical precipitated calcium carbonate with a vaterite content of 95.9% was synthesized by adding 0.1 mol aspatic acid/1 mol CaO and 2 cm³ of NH₄OH, and reacting for 1 h at 25℃ while stirring at 600 rpm. The average particle diameter was found to be 12.11 ㎛. Calcium carbonate contatining high vaterite is used as high value added calcium carbonate for medical, food, inke additiver, etc.

• Journal of the Mineralogical Society of Korea
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• v.28 no.1
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• pp.39-49
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• 2015

Recently, carbon capture and storage (CCS) techniques have been globally studied. This study was conducted to use waste cement powder as an efficient raw material of mineral carbonation for $CO_2$ sequestration. Direct aqueous carbonation experiment was conducted with injecting pure $CO_2$ gas (99.9%) to a reactor containing $200m{\ell}$ reacting solution and the pulverized cement paste (W:C = 6:4) having particle size less than 0.15 mm. The effects of two additives (NaCl, $MgCl_2$) in carbonation were analyzed. The characteristics of carbonate minerals and carbonation process according to the type of additives and pH change were carefully evaluated. pH of reacting solution was gradually decreased with injecting $CO_2$ gas. $Ca^{2+}$ ion concentration in $MgCl_2$ containing solution was continuously decreased. In none $MgCl_2$ solution, however, $Ca^{2+}$ ion concentration was increased again as pH decreased. This is probably due to the dissolution of newly formed carbonate mineral in low pH solution. XRD analysis indicates that calcite is dominant carbonate mineral in none $MgCl_2$ solution whereas aragonite is dominant in $MgCl_2$ containing solution. Unstable vaterite formed in early stage of experiment was transformed to well crystallized calcite with decreasing pH in the absence of $MgCl_2$ additives. In the presence of $MgCl_2$ additives, the content of aragonite was increased with decreasing pH whereas the content of calite was decreased.

• Journal of the Mineralogical Society of Korea
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• v.31 no.2
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• pp.113-121
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• 2018

Baekasan Acheon cave located in Hwasun-gun, Jeollanam-do is a natural limestone cave only found in this province. In this study, the mineralogical and geochemical characteristics of speleothems collected from Baekasan Acheon cave were identified and the capability of carbonate mineral formation by aerobic microorganisms enriched from the cave and the mineralogical and geochemical characteristics of carbonate minerals formed by the microorganisms were investigated. The samples of sediments (clay) and speleothems (shelfstone and cave coral) were collected at three sites in the cave. The samples of shelfstone and cave coral were identified mainly as carbonate mineral, Mg-rich calcite, and clay minerals were composed of quartz, muscovite, and vermiculite by X-ray diffraction (XRD) analysis. To cultivate the carbonate forming microorganisms, parts of the sediment and speleothems were placed in D-1 medium containing urea, respectively, and the growth of microorganisms was observed under the aerobic condition at room temperature. The capability of carbonate mineralization of the cultured Baekasan Acheon cave microorganisms was examined through adding 1% (v/v) of the cultured microorganisms and calcium sources, Ca-acetate or Ca-lactate, into the D-1 medium. XRD analysis showed that the microorganisms cultured in cave deposits formed calcium carbonate ($CaCO_3$) under all conditions, and these microbial carbonate minerals included calcite and vaterite. The morphological characteristics and chemical composition of biologically formed minerals were observed by SEM-EDS showed various crystal forms such as rhomboid, spherical, perforated surface with Ca, C, and O of major chemical components. The existence of such microorganisms in the cave can contribute the formation of carbonate minerals, and it is likely to affect the geochemical cycles of carbon and calcium in the cave.