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2025 Vol.35, Issue 4 Preview Page

Special Articles

Temperature-Dependent Phase Selectivity and Morphology of Ammonia-Induced Calcium Carbonate (CaCO3) Polymorphs

암모니아 기체 확산법에서 탄산칼슘(CaCO3) 다형체 형태와 상 선택성의 온도 의존성

DongKwon Kim1
,
Sugeun Jo2
,
Jun Lim3
,
YoungJae Kim4*
김 동권1
,
조 수근2
,
임 준3
,
김 영재4*
1Undergraduate Researcher, Division of Earth and Environmental System Sciences, Major of Environmental Geosciences, Pukyong National University
2Senior Researher, Pohang Accelerator Laboratory, Pohang University of Science and Technology (POSTECH)
3Principal Researcher, Pohang Accelerator Laboratory, Pohang University of Science and Technology (POSTECH)
4Assistant Professor, Division of Earth and Environmental System Sciences, Major of Environmental Geosciences, Pukyong National University
1국립부경대학교 지구환경시스템과학부 환경지질과학전공 학부연구생
2포항공과대학교 포항가속기연구소 선임연구원
3포항공과대학교 포항가속기연구소 수석연구원
4국립부경대학교 지구환경시스템과학부 환경지질과학전공 조교수
*Corresponding Author
31 December 2025. pp. 515-523
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Abstract

Calcium carbonate (CaCO3) occurs naturally as three main polymorphs (calcite, aragonite, and vaterite) and is used widely in many industrial and engineering applications. The ammonia diffusion method, which relies on gas–liquid reactions involving NH3(g), produces different CaCO3 polymorphs depending on the calcium concentration, the amount of NH4+-bearing solid, and the exposed solution surface area; however, the effect of temperature has not been well studied. We synthesized CaCO3 at 15–30°C using the ammonia diffusion method. The temperature-dependent phase selectivity and crystal morphology were examined using X-ray diffraction (XRD) and scanning electron microscopy (SEM). Calcite was dominant at 15°C, whereas mixtures of calcite, aragonite, and vaterite were observed at higher temperatures. Aragonite developed needle-like crystals, and vaterite formed flower-like aggregates as the temperature increased. These results suggest that temperature modulates CaCO3 supersaturation and nucleation rate in the ammonia–Ca2+ solution reaction, controlling polymorph selectivity and crystal growth. This study provides a basis for optimizing phase control and growth conditions in CaCO3 synthesis using the ammonia diffusion method.

Keywords
ammonia diffusion method
calcite
aragonite
vaterite
temperature effect

탄산칼슘(CaCO3) 광물은 자연계에서 방해석(calcite), 아라고나이트(aragonite), 바테라이트(vaterite) 세 가지 동질이상체 형태로 흔하게 존재한다. 뿐만 아니라, 다양한 산업 및 공학적 응용 분야에서 핵심적인 소재로 활용된다. 탄산칼슘 광물을 합성하는 주요한 방법 중 암모니아(NH3(g)) 확산법은 기체-액체 반응을 기반으로 한다. 암모니아 확산법을 이용한 합성에서 칼슘 용액의 농도, 반응용기 부피 대비 암모늄 이온(NH4+) 포함 고체 함량, 용액이 노출된 표면적 등 다양한 요인에 의해 합성 결과(탄산칼슘 동질이상체 간 상대적 비율, 결정 형상 등)가 크게 좌우되는 것으로 알려져 있다. 하지만 암모니아 확산법에서 온도에 의한 탄산칼슘 광물의 특성변화는 거의 알려진 바가 없다. 본 연구에서는 암모니아 확산법으로 15–30°C 범위에서 탄산칼슘을 합성하고 주사전자현미경과 X-선 회절 분석을 통해 온도에 따른 동질이상체 간 상 선택성(phase selectivity)과 결정형상 변화를 진단하였다. 15°C에서는 방해석이 우세하게 관찰되었고, 온도가 높아질수록 방해석, 아라고나이트, 바테라이트가 함께 관찰되었다. 아라고나이트와 바테라이트는 온도 상승에 따라 각각 침상(acicular)과 꽃모양(flower-like)으로 뚜렷하게 발달하였다. 이러한 결과는 온도 상승에 따른 탄산칼슘 포화도 및 핵 생성 속도 변화에 기인한 것으로 판단된다. 우리 연구는 암모니아 확산법을 통한 탄산칼슘의 상 선택성 제어 및 결정 성장 조건을 최적화하는데 기초 자료를 제공한다.

키워드
암모니아 확산법
방해석
아라고나이트
바테라이트
온도 효과
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Information
  • Publisher :Korean Society of Engineering Geology
  • Publisher(Ko) :대한지질공학회
  • Journal Title :The Journal of Engineering Geology
  • Journal Title(Ko) :지질공학
  • Volume : 35
  • No :4
  • Pages :515-523
  • Received Date : 2025-11-25
  • Revised Date : 2025-12-19
  • Accepted Date : 2025-12-22
  • DOI :https://doi.org/10.9720/kseg.2025.4.515
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