A simple strategy for the synthesis of well-defined bassanite nanorods

Tritschler, Ulrich; Kellermeier, Matthias; Debus, Christian; Kempter, Andreas; Cölfen, Helmut

doi:10.1039/c5ce00519a

Cited by 49 publications

(81 citation statements)

References 22 publications

(41 reference statements)

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“…This was achieved by dissolving equimolar amounts of CaCl2 and H2SO4 in dry methanol. 8,11 Similarly, we suggest that in our system the high concentration of CaSO4 within a very small volume of solvent would result in a thin interfacial fluid layer with a CaSO4:H2O ratio sufficiently high to achieve the critical value for anhydrite precipitation. This idea is also supported by noting that the equilibrium constant for the conversion of gypsum to anhydrite is highly dependent on the temperature and solvent water activity.…”

Section: Mechanism Of the Gypsum-anhydrite Transitionmentioning

confidence: 99%

“…Recent work demonstrates that full control is also achievable for calcium sulfate, 8,11 a system that has been explored to a much lesser extent. The calcium sulfate system consists of three intriguing crystal structures, with different degrees of hydration.…”

Section: Introductionmentioning

confidence: 99%

“…8,11 More broadly, there are several examples where organic solvents have been exploited to study both the mechanisms and kinetics of crystallization, as well as crystal morphology. 30,31 In this paper, a two-phase, non-miscible, liquid-liquid (water-hexane or water-dodecane) system was employed, with the aqueous phase providing a source of SO4 2-and the organic phase containing a Ca 2+ source.…”

Section: Introductionmentioning

confidence: 99%

“…[12][13][14] The most thermodynamically stable phase of calcium sulfate at room temperature is the dihydrate, gypsum (CaSO4⋅2H2O) and, as a consequence, it is highly abundant in nature. 11,[15][16][17][18][19][20][21][22] Both the hemihydrate, bassanite (CaSO4⋅0.5H2O) and the anhydrous form, anhydrite (CaSO4) are relatively thermodynamically unstable and kinetically unfavorable under ambient conditions, but each has important industrial applications. Bassanite (more commonly known as plaster of Paris), is a highly valuable building material, whereas anhydrite has applications as a binder in cements and adhesives.…”

Section: Introductionmentioning

confidence: 99%

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Microscopic Studies of Calcium Sulfate Crystallization and Transformation at Aqueous–Organic Interfaces

Ravenhill

Kirkman²,

Unwin

2016

Crystal Growth & Design

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The calcium sulfate crystal system is of considerable fundamental and practical interest, consisting of the three hydrates, gypsum (CaSO4⋅2H2O), bassanite (CaSO4⋅0.5H2O) and anhydrite (CaSO4). Each have significant applications, however, synthesis of anhydrite via conventional aqueous methods requires elevated temperatures and therefore high energy costs.Herein, we investigate calcium sulfate crystal growth across a non-miscible aqueous-organic (hexane or dodecane) interface. This process is visualized via in situ optical microscopy, which produces high magnification videos of the crystal growth process. The use of interferometry, Raman spectroscopy and X-ray diffraction allows the full range of calcium sulfate morphologies and hydrates to be analyzed subsequently in considerable detail. In the case of dodecane, gypsum is the final product, but the use of hexane in an open (evaporating) system results in anhydrite crystals, via gypsum, at room temperature. A dissolution-precipitation mechanism between neighboring microcrystals is responsible for this transformation. This work opens up a simple new crystal synthesis route for controlling and directing crystallization and transformation.3

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Section: Mechanism Of the Gypsum-anhydrite Transitionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Microscopic Studies of Calcium Sulfate Crystallization and Transformation at Aqueous–Organic Interfaces

Ravenhill

Kirkman²,

Unwin

2016

Crystal Growth & Design

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“…Considering calcium sulphate, solvent polarity, i.e., its water-withdrawing ability, has a direct bearing on the polymorph selection of bassanite and gypsum [49]. For organic crystals, the solvent composition also determines the selective nucleation of polymorphic forms [50].…”

Section: Introductionmentioning

confidence: 99%

Modulating Nucleation by Kosmotropes and Chaotropes: Testing the Waters

2017

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Abstract:Water is a fundamental solvent sustaining life, key to the conformations and equilibria associated with solute species. Emerging studies on nucleation and crystallization phenomena reveal that the dynamics of hydration associated with mineral precursors are critical in determining material formation and growth. With certain small molecules affecting the hydration and conformational stability of co-solutes, this study systematically explores the effects of these chaotropes and kosmotropes as well as certain sugar enantiomers on the early stages of calcium carbonate formation. These small molecules appear to modulate mineral nucleation in a class-dependent manner. The observed effects are finite in comparison to the established, strong interactions between charged polymers and intermediate mineral forms. Thus, perturbations to hydration dynamics of ion clusters by co-solute species can affect nucleation phenomena in a discernable manner.

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Exploiting Confinement to Study the Crystallization Pathway of Calcium Sulfate

Anduix‐Canto

Levenstein

Kim

et al. 2021

Adv Funct Materials

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Characterizing the pathways by which crystals form remains a significant challenge, particularly when multiple pathways operate simultaneously.Here, an imaging-based strategy is introduced that exploits confinement effects to track the evolution of a population of crystals in 3D and to characterize crystallization pathways. Focusing on calcium sulfate formation in aqueous solution at room temperature, precipitation is carried out within nanoporous media, which ensures that the crystals are fixed in position and develop slowly. The evolution of their size, shape, and polymorph can then be tracked in situ using synchrotron X-ray computed tomography and diffraction computed tomography without isolating and potentially altering the crystals. The study shows that bassanite (CaSO 4 0.5H 2 O) forms via an amorphous precursor phase and that it exhibits long-term stability in these nanoscale pores. Further, the thermodynamically stable phase gypsum (CaSO 4 2H 2 O) can precipitate by different pathways according to the local physical environment. Insight into crystallization in nanoconfinement is also gained, and the crystals are seen to grow throughout the nanoporous network without causing structural damage. This work therefore offers a novel strategy for studying crystallization pathways and demonstrates the significant impact of confinement on calcium sulfate precipitation, which is relevant to its formation in many real-world environments.

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A simple strategy for the synthesis of well-defined bassanite nanorods

Cited by 49 publications

References 22 publications

Microscopic Studies of Calcium Sulfate Crystallization and Transformation at Aqueous–Organic Interfaces

Microscopic Studies of Calcium Sulfate Crystallization and Transformation at Aqueous–Organic Interfaces

Modulating Nucleation by Kosmotropes and Chaotropes: Testing the Waters

Exploiting Confinement to Study the Crystallization Pathway of Calcium Sulfate

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