Self-assembly of carbonate-silica colloids: between living and non-living form

Hyde, Stephen T.; Carnerup, Anna M.; Larsson, Ann‐Kristin; Christy, Andrew G.; García‐Ruiz, Juan Manuel

doi:10.1016/j.physa.2004.03.045

Cited by 53 publications

(94 citation statements)

References 14 publications

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“…It is worth noting that the clusters have flat faces (see Figures 3D,E) where the nucleation start point and the first sheetlike projections can be observed. This three-dimensional crystal morphology has also been observed in strontium 21 and barium 22 carbonate biomorphs and bears a striking resemblance to natural corals ( Figure 3H). Figure 3F) in 0.1 M hydrochloric acid (dissolving all carbonate material) leaves a hollow silica "ghost" (Figure 3G).…”

Section: Optical and Electron Microscopysupporting

confidence: 65%

Inorganic Self-Organized Silica Aragonite Biomorphic Composites

Voinescu

Kellermeier

Bartel

et al. 2008

Crystal Growth & Design

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ABSTRACT:The precipitation of calcium carbonate in alkaline silica solutions results in the formation of complex curvilinear forms if aragonite formation is encouraged by growth at an elevated temperature (80°C). The resulting coralline self-assembled silica-calcium carbonate particles are "biomorphs", bearing a striking resemblance to natural coral forms. These materials, comprised of calcium carbonate nanocrystals and an amorphous silica matrix, have a complex ultrastructure, made of clusters of gathered sheets of variable curvatures formed by successive curling. The nanocrystals within these "ruled surfaces" are thin, elongated, densely packed needles of aragonite. These clusters are outgrowths from central saddlelike cores that resemble developable petaloid surfaces. The size, shape, crystallography, and chemical composition of the resulting biomorphs were examined by optical microscopy, field emission scanning electron microscopy (FE-SEM), powder X-ray diffractometry (XRD), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM and HRTEM), and energy dispersive X-ray analysis (EDX).

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Section: Optical and Electron Microscopysupporting

confidence: 65%

Inorganic Self-Organized Silica Aragonite Biomorphic Composites

Voinescu

Kellermeier

Bartel

et al. 2008

Crystal Growth & Design

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“…Comparable similarities between experiments and simulations can be seen in three dimensions for the Category 2 spherulites [102] and the floral spherulites [103] ( Figure 19). …”

Section: Disordered (''Dizzy'') Dendrites: Particles Vs M Hmentioning

confidence: 62%

“…, [102] Ó 2003 American Physical Society); (b) and (c) Qualitative PF simulations performed using the PBG model. [30] (ii) ''Floral'' spherulites: (d) Experimental image (Reproduced with permission from Hyde et al, [103] Ó 2004 Elsevier B.V.). (e) PF simulation performed using the PBG model.…”

Section: Foreign Particles Holes and Scratchesmentioning

confidence: 99%

Phase-Field Modeling of Polycrystalline Solidification: From Needle Crystals to Spherulites—A Review

Gránásy

Rátkai

Szàllàs

et al. 2013

Metall Mater Trans A

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LÁ SZLÓ GRÁ NÁ SY, LÁ SZLÓ RÁ TKAI, ATTILA SZÁ LLÁ S, BÁ LINT KORBULY, GYULA I. TÓ TH, LÁ SZLÓ KÖ RNYEI, and TAMÁ S PUSZTAI Advances in the orientation-field-based phase-field (PF) models made in the past are reviewed. The models applied incorporate homogeneous and heterogeneous nucleation of growth centers and several mechanisms to form new grains at the perimeter of growing crystals, a phenomenon termed growth front nucleation. Examples for PF modeling of such complex polycrystalline structures are shown as impinging symmetric dendrites, polycrystalline growth forms (ranging from disordered dendrites to spherulitic patterns), and various eutectic structures, including spiraling two-phase dendrites. Simulations exploring possible control of solidification patterns in thin films via external fields, confined geometry, particle additives, scratching/piercing the films, etc. are also displayed. Advantages, problems, and possible solutions associated with quantitative PF simulations are discussed briefly.

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“…These peculiar materials are composed of elongated alkaline-earth metal carbonate nanocrystals, measuring several hundreds of nanometers in length and around 50 nm across, which are interwoven and sheathed by a matrix of amorphous silica. [6][7][8][9][10][11][12][13] Notably, the arrangement of the crystallites within an aggregate, though allowing for local defects, is well defined on the mesoscale, where the rods describe a smoothly varying orientation field with respect to their long axis. [10] Beyond that, on scales of microns up to millimeters, the crystal assemblies adopt striking curvilinear ultrastructures that lack any crystallographic symmetry; a feature traditionally thought to be exclusive to animate nature.…”

Section: Introductionmentioning

confidence: 99%

Growth Behavior and Kinetics of Self‐Assembled Silica–Carbonate Biomorphs

Kellermeier

Melero‐García

Glaab

et al. 2012

Chemistry A European J

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Upon slow crystallization from silica-containing solutions or gels at elevated pH, alkaline-earth carbonates spontaneously self-assemble into remarkable nanocrystalline ultrastructures. These so-called silica biomorphs exhibit curved morphologies beyond crystallographic symmetry and ordered textures reminiscent of the hierarchical design found in many biominerals. The formation of these fascinating materials is thought to be driven by a dynamic coupling of the components' speciations in solution, which causes concerted autocatalytic mineralization of silica-stabilized nanocrystals over hours. In the present work, we have studied the precipitation kinetics of this unique system by determining growth rates of individual aggregates using video microscopy, and correlated the results with time-dependent data on the concentration of metal ions and pH acquired online during crystallization. In this manner, insight to the evolution of chemical conditions during growth was gained. It is shown that crystallization proceeds linearly with time and is essentially reaction controlled, which fits well in the proposed morphogenetic scenario, and thus, indirectly supports it. Measurements of the silica concentration in solution, combined with analyses of crystal aggregates isolated at distinct stages of morphogenesis, further demonstrate that the fraction of silica coprecipitated with carbonate during active growth is rather small. We discuss our findings with respect to the role of silica in the formation of biomorphs, and moreover, prove that the external silica skins that occasionally sheath the aggregates--previously supposed to be involved in the growth mechanism--originate from secondary precipitation after growth is already terminated.

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Self-assembly of carbonate-silica colloids: between living and non-living form

Cited by 53 publications

References 14 publications

Inorganic Self-Organized Silica Aragonite Biomorphic Composites

Inorganic Self-Organized Silica Aragonite Biomorphic Composites

Phase-Field Modeling of Polycrystalline Solidification: From Needle Crystals to Spherulites—A Review

Growth Behavior and Kinetics of Self‐Assembled Silica–Carbonate Biomorphs

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