Calcite Single Crystals Research Articles

Spatioselective Occlusion of Copolymer Nanoparticles within Calcite Crystals Generates Organic-Inorganic Hybrid Materials with Controlled Internal Structures.

Efficient occlusion of particulate additives into a single crystal has garnered an ever-increasing attention in materials science because it offers a counter-intuitive yet powerful platform to make crystalline nanocomposite materials with emerging properties. However, precisely controlling the spatial distribution of the guest additives within a host crystal remains highly challenging. We herein demonstrate a unique, straightforward method to engineer the spatial distribution of copolymer nanoparticles within calcite (CaCO3) single crystals by judiciously adjusting initial [Ca2+] concentration used for the calcite precipitation. More specifically, polymerization-induced self-assembly is employed to synthesize well-defined and highly anionic poly(3-sulfopropyl methacrylate potassium)41-block-poly(benzyl methacrylate)500 [PSPMA41-PBzMA500] diblock copolymer nanoparticles, which are subsequently used as model additives during the growth of calcite crystals. Impressively, such guest nanoparticles are preferentially occluded into specific regions of calcite depending on the initial [Ca2+] concentration. These unprecedented phenomena are most probably caused by dynamic change in electrostatic interaction between Ca2+ ions and PSPMA41 chains based on systematic investigations. This study not only showcases a significant advancement in controlling the spatial distribution of guest nanoparticles within host crystals, enabling the internal structure of composite crystals to be rationally tailored via a spatioselective occlusion strategy, but also provides new insights into biomineralization.

Spatioselective Occlusion of Copolymer Nanoparticles within Calcite Crystals Generates Organic‐Inorganic Hybrid Materials with Controlled Internal Structures

AbstractEfficient occlusion of particulate additives into a single crystal has garnered an ever‐increasing attention in materials science because it offers a counter‐intuitive yet powerful platform to make crystalline nanocomposite materials with emerging properties. However, precisely controlling the spatial distribution of the guest additives within a host crystal remains highly challenging. We herein demonstrate a unique, straightforward method to engineer the spatial distribution of copolymer nanoparticles within calcite (CaCO3) single crystals by judiciously adjusting initial [Ca2+] concentration used for the calcite precipitation. More specifically, polymerization‐induced self‐assembly is employed to synthesize well‐defined and highly anionic poly(3‐sulfopropyl methacrylate potassium)41‐block‐poly(benzyl methacrylate)500 [PSPMA41‐PBzMA500] diblock copolymer nanoparticles, which are subsequently used as model additives during the growth of calcite crystals. Impressively, such guest nanoparticles are preferentially occluded into specific regions of calcite depending on the initial [Ca2+] concentration. These unprecedented phenomena are most probably caused by dynamic change in electrostatic interaction between Ca2+ ions and PSPMA41 chains based on systematic investigations. This study not only showcases a significant advancement in controlling the spatial distribution of guest nanoparticles within host crystals, enabling the internal structure of composite crystals to be rationally tailored via a spatioselective occlusion strategy, but also provides new insights into biomineralization.

The Capture of Cadmium from Solution during the Replacement of Calcite by Apatite.

The capture of cadmium (Cd) from phosphate-containing solutions during the replacement of CaCO3 by phosphate phases such as hydroxylapatite (HAP) and tricalcium phosphate (TCP) has been studied under high and low temperature and pressure conditions using atomic force microscopy, scanning electron microscopy equipped with an X-ray spectrometer and a backscattered electron detector, Raman spectroscopy, and microprobe analysis. Starting with cubes of Carrara Marble (polycrystalline calcite) and single crystals of calcite, a new solid phosphate phase was observed to incorporate Cd from solution, formed under different pressure and temperature conditions tested. Results showed that Cd precipitated in a new phase on the surface of all samples tested. In Carrara Marble, pseudomorphic replacement of CaCO3 is restricted possibly due to kinetic limitation caused by the adsorption of Cd complexes formed in solution at reactive surface sites and the variation of fluid composition inside the sample. However, on the sample surface, this kinetic limitation is less influential, so the new phase could incorporate higher amounts of Cd faster. Furthermore, this reaction at room temperature was found to have similar and/or better Cd-uptake efficiency as HAP and CaCO3 in pure Cd solution through the precipitation of Cd-containing phosphate crystals on the sample surface. Both reactions were able to capture Cd in the precipitating phase structure and could provide a mechanism for simultaneous Cd and phosphate removal from solutions contaminated with both, in industrial or natural settings.

Interfacial processes underlying the temperature-dependence of friction and wear of calcite single crystals

HypothesisThis study posits that thermal effects play a substantial role in influencing interfacial processes on calcite, and consequently impacting its mechanochemical properties. ExperimentsThis work interrogates the temperature-dependence of friction and wear at nanoscale contacts with calcite single crystals at low air humidity (≤ 3–10 % RH) by AFM. FindingsThree logarithmic regimes for the velocity-dependence of friction are identified. BelowTc ∼ 70 °C, where friction increases with T, there is a transition from velocity-weakening (W1) to velocity-strengthening friction (S1). AboveTc ∼ 70 °C, where friction decreases with T, a second velocity-strengthening friction regime (S0) precedes velocity-weakening friction (W1). The low humidity is sufficient to induce atomic scale changes of the calcite cleavage plane due to dissolution-reprecipitation, and more so at higher temperature and 10 % RH. Meanwhile, the surface softens above Tc –likely owing to lattice dilation, hydration and amorphization. These interfacial changes influence the wear mechanism, which transitions from pit formation to plowing with increase in temperature. Furthermore, the softening of the surface justifies the appearance of the second velocity-strengthening friction regime (S0).These findings advance our understanding of the influence of temperature on the interfacial and mechanochemical processes involving calcite, with implications in natural processes and industrial manufacturing.

A natural multifunction and multiscale hierarchical matrix as a drug-eluting scaffold for biomedical applications.

Sea urchin spines are biogenic single crystals of magnesium calcite that are stiff, strong, damage tolerant and light and have a bicontinuous porous structure. Here, we showed that the removal of their intraskeletal organic matrix materials did not affect the compressive mechanical properties and generated an open porosity. This matrix was able to adsorb and release oxytetracycline, a broad-spectrum antibiotic. The drug-loaded sea urchin matrix induced bacterial cell death after 4 and 8 hours of incubation of both Gram-negative E. coli and Gram-positive S. aureus strains and this process induces an inhibition of bacterial cell adhesion. In conclusion, this study shows that thermally treated sea urchin spines are a compressive resistant and lightweight matrix able to load drugs and with potential use in spine fusion, a challenging application that requires withstanding high compressive loading.

Light-driven nucleation, growth, and patterning of biorelevant crystals using resonant near-infrared laser heating

Spatiotemporal control over crystal nucleation and growth is of fundamental interest for understanding how organisms assemble high-performance biominerals, and holds relevance for manufacturing of functional materials. Many methods have been developed towards static or global control, however gaining simultaneously dynamic and local control over crystallization remains challenging. Here, we show spatiotemporal control over crystallization of retrograde (inverse) soluble compounds induced by locally heating water using near-infrared (NIR) laser light. We modulate the NIR light intensity to start, steer, and stop crystallization of calcium carbonate and laser-write with micrometer precision. Tailoring the crystallization conditions overcomes the inherently stochastic crystallization behavior and enables positioning single crystals of vaterite, calcite, and aragonite. We demonstrate straightforward extension of these principles toward other biorelevant compounds by patterning barium-, strontium-, and calcium carbonate, as well as strontium sulfate and calcium phosphate. Since many important compounds exhibit retrograde solubility behavior, NIR-induced heating may enable light-controlled crystallization with precise spatiotemporal control.

Interfacial Supra-Assembly of Copolymer Nanoparticles Enables the Formation of Nanocomposite Crystals with a Tunable Internal Structure.

It is highly desirable but technically challenging to precisely control the spatial composition and internal structure of crystalline nanocomposite materials, especially in a one-pot synthetic route. Herein, we demonstrate a versatile pathway to tune the spatial distribution of guest species within a host inorganic crystal via an incorporation strategy. Specifically, well-defined block copolymer nanoparticles, poly(methacrylic acid)x-block-poly(styrene-alt-N-phenylmaleimide)y [PMAAx-P(St-alt-NMI)y], are synthesized by polymerization-induced self-assembly. Such anionic nanoparticles can supra-assemble onto the surface of larger cationic nanoparticles via an electrostatic interaction, forming colloidal nanocomposite particles (CNPs). Remarkably, such CNPs can be incorporated into calcite single crystals in a spatially controlled manner: the depth of CNPs incorporation into calcite is tunable. Systematic investigation indicates that this interesting phenomenon is governed by the colloidal stability of CNPs, which in turn is dictated by the PMAAx-P(St-alt-NMI)y adsorption density and calcium ion concentration. This study opens up a general and efficient route for the preparation of a wide range of crystalline nanocomposite materials with a controlled internal composition and structure.

Structural control and Ostwald ripening as essential mechanisms during the fossilization process of sea urchin (Balanocidaris? Lambert) spines from Lower Cretaceous of Southern Spain

ABSTRACT A comparative study has been made between some cidaroid fossil spines from Lower Cretaceous of southern Spain and other contemporary ones. The modern spines are a composite material formed by calcite nanocrystals oriented with their optical axes parallel to the elongated direction, which behave as a single crystal. Transmission Petrographic Microscopy (TPM) observations of the fossil spines prove that it is a calcite single crystal, whose optical axis coincides with the direction of elongation (as in the current spines). This paper presents a crystallographic approach to propose a secondary crystallisation mechanism, specifically the Ostwald ripening process, through a structural analysis that compares the spines and the conditions observed during the fossilisation process.

Starfish-Inspired Diamond-Structured Calcite Single Crystals from a Bottom-up Approach as Mechanical Metamaterials.

Inspired by knobby starfish, this work demonstrates a bottom-up approach for fabricating a calcite single-crystal (CSC) with a diamond structure by exploiting the self-assembly of the block copolymer and corresponding templated synthesis. Similar to the knobby starfish, the diamond structure of the CSC gives rise to a brittle-to-ductile transition. Most interestingly, the diamond-structured CSC fabricated exhibits exceptional specific energy absorption and strength with lightweight character superior to natural materials and artificial counterparts from a top-down approach due to the nanosized effect. This approach provides the feasibility for creating mechanical metamaterials with the combined effects of the topology and nanosize on the mechanical performance.

Phase-field modeling of coupled reactive transport and pore structure evolution due to mineral dissolution in porous media

Based on the phase-field method, a fluid–solid coupling modeling method was proposed to simulate the reaction transport in porous media at the pore scale and realize the dynamic tracking of the fluid–solid interface. We skillfully combined the phase-field module in COMSOL with the Heaviside function to realize the numerical solution of the model. The feasibility and reliability of the model are verified by comparing it with the results of previous studies on the related benchmark problems (the dissolution process of a single calcite crystal). To further explore the practicability of the model, we simulate the dissolution process in two-dimensional porous media generated by random circles under different transport conditions and reaction rates. The results show that the solute can be transported downstream of the model region under advection-dominated transport conditions, which are common in engineering applications, and the dissolution reaction in the medium takes place synchronously. When diffusion is the main transport mode which often occurs in natural conditions, and the reaction is relatively fast, the solute is difficult to transport downstream of the model region, mineral dissolution mainly occurs near the solute inlet, and mineral disappearance is carried out in a horizontal push mode. The permeability-porosity relationship is predicted by the Kozeny-Carman law for different transport conditions and reaction rates. The results show that the Kozeny-Carman law is more accurate in predicting permeability over a porosity range of 15% for advection-dominated reactive transport, considering specific surface area variation.

Coupled dissolution-precipitation and growth processes on calcite, aragonite, and Carrara marble exposed to cadmium-rich aqueous solutions

Calcium carbonate and cadmium-rich fluid interactions have been studied at the nano and microscale with fluid flow and static fluid conditions for three forms of CaCO3: calcite in single crystals of Iceland Spar, calcite in a polycrystalline Carrara marble, and aragonite single crystals. Atomic Force Microscopy (AFM) showed the nanoscale effect of cadmium on CaCO3 dissolution and growth under flow-through conditions at ambient temperature, with the modification of calcite dissolution behaviour and simultaneous precipitation of a Cd-rich phase on all the different samples. Hydrothermal experiments at 200 °C revealed that the reactivity of single calcite crystals is passivated by epitaxial growth of the less soluble Cd-rich endmember of the (Ca,Cd)CO3 solid-solution on the sample surface due to the similar crystallographic structures of calcite and otavite (CdCO3). Conversely, the presence of grain boundaries in Carrara marble or the change of crystallographic structure and reaction-induced fracturing in aragonite allowed, to some extent, the pseudomorphic replacement of Carrara marble and aragonite samples by a porous (Ca,Cd)CO3 solid-solution phase of variable composition. These phenomena have been observed in solutions undersaturated with respect to all solid phases and are the result of an interface-coupled dissolution-precipitation mechanism where the dissolving CaCO3 provides ions to supersaturate the mineral-fluid interfacial layer, leading to the precipitation of a Cd-containing phase on the samples' surfaces. This coupled dissolution-precipitation mechanism could potentially be used as a remediation process to sequester cadmium from contaminated effluents.

Tensile and compressive mechanical properties of nanocrystalline calcite with grain size effect

Abstract Calcite is one of the most main components of microbially induced calcium carbonate precipitation (MICP). With the in-depth research of MICP, the mechanical properties of nanocrystalline calcite attract much attention. In this paper, the deformation and failure behaviors of nanocrystalline calcite under a uniaxial tensile or compressive condition are studied by molecular dynamics simulation, and then the dominant deformation and failure mechanisms, as well as their grain size effect, are analyzed. The results show that the grain boundary densification dominates the elastic deformation, while the intragranular phase transition dominates the plastic deformation. Compared with single-crystal calcite, the elastic modulus of nanocrystalline calcite is significantly reduced and its ultimate strength is decreased by more than 50%. Nanocrystalline calcite has stronger plastic deformation ability in compression than in tension. Its tensile and compressive elastic moduli and peak stresses all increase with the average grain size. The effects of grain size on the limit stresses can be described by the inverse Hall–Petch equation. This study is helpful for tailoring the mechanical properties of MICP by the morphology of nanocrystalline calcite.

Recovering and Exploiting Aragonite and Calcite Single Crystals with Biologically Controlled Shapes from Mussel Shells.

Control over the shape and morphology of single crystals is a theme of great interest in fundamental science and for technological application. Many synthetic strategies to achieve this goal are inspired by biomineralization processes. Indeed, organisms are able to produce crystals with high fidelity in shape and morphology utilizing macromolecules that act as modifiers. An alternative strategy can be the recovery of crystals from biomineralization products, in this case, seashells. In particular, waste mussel shells from aquaculture are considered. They are mainly built up of single crystals of calcite fibers and aragonite tablets forming an outer and an inner layer, respectively. A simple mechanochemical treatment has been developed to separate and recover these two typologies of single crystals. The characterization of these single crystals showed peculiar properties with respect to the calcium carbonate from quarry or synthesis. We exploited these biomaterials in the water remediation field using them as substrate adsorbing dyes. We found that these substrates show a high capability of adsorption for anionic dye, such as Eosin Y, but a low capability of adsorption for cationic dyes, such as Blue Methylene. The adsorption was reversible at pH 5.6. This application represents just an example of the potential use of these biogenic single crystals. We also envision potential applications as reinforcing fillers and optical devices.

Biomineralization of ordered dolomite and magnesian calcite by the green alga Spirogyra

AbstractThe formation of ordered dolomite under Earth's surface conditions remains a challenge, although many researchers have now shown that microbes can facilitate the precipitation of this common mineral. This study provides the first evidence of dolomite biomineralization by the green alga Spirogyra (Zygnematales, Chlorophyta), a globally dispersed lacustrine genus. Microbial mats formed by Spirogyra occur in the hyperalkaline and ephemeral lake Caballo Alba, located in Central Spain and characterized by water solutions with high Mg/Ca ratios. Microscopic, geochemical, mineralogical and cytochemical studies have shown that accumulations of carbonates occur within different cells and locations of the alga. Biominerals mostly consist of single crystals of magnesian calcite and dolomite with variable proportions of Ca2+ and Mg2+. High‐resolution transmission electron microscopy and selected area electron diffraction patterns of the carbonates confirm the pervasive presence of super‐lattice reflections typical of ordered dolomite in compositions with greater than 32 mol% MgCO3. The curved surfaces of some carbonate crystals and their attachment to the organic surfaces represent imprints of a confined growth in compartments that act as a template for crystal nucleation and shape the crystals. Dyes reveal chemical differences in these compartments which explain the polymineral biomineralization and suggest that the alga do not strictly control the precipitation process. Zygnematales algae related with Spirogyra date back possibly to the Early Palaeozoic, thus suggesting that dolomite biomineralization could have been a common process through the Phanerozoic. This discovery provides new insight into the biotic formation of orderly dolomite and aids in the reconstructions of past lacustrine environments of dolomite deposition.

Metal-Organic Frameworks@Calcite Composite Crystals.

The direct incorporation of guest crystals into another type of host crystals during the formation of the latter is technically challenging due to the large difference in surface energy for different crystalline components. Nevertheless, we herein demonstrate that metal-organic frameworks (MOFs, UiO-66-NH2 as a model guest crystal) after postsynthetic modification with poly(methacrylic acid) can be efficiently incorporated into calcite single crystals, forming a unique composite structure where the MOF crystals are uniformly distributed throughout the whole calcite host crystals. Remarkably, such MOF@calcite composite crystals exhibit superior performance in fluoride removal compared with the MOF or calcite alone. Moreover, this incorporation strategy is general as it can be extended to other guest particles. In principle, this study opens up a versatile avenue for the rational design and preparation of a wide range of hybrid functional materials with controllable compositions and enhanced physicochemical properties.

Formation of Strontianite and Witherite Cohesive Layers on Calcite Surfaces for Building Stone Conservation

The formation of micrometric-thick mineral cohesive layers is a novel method to prevent the deterioration of historical buildings. Here, we study the formation of thin, cohesive, pseudomorphic shells of strontianite (SrCO3) and witherite (BaCO3) on the surface of calcite (CaCO3) single crystals reacted with aqueous solutions bearing Sr2+ and Ba2+, respectively. The reaction front moves inward from the calcite–solution interface through a dissolution–crystallization reaction, which stops before the strontianite and witherite shells are barely 40 thick. These shells consist of elongated crystallites that grow oriented on the calcite substrate, with which they share very small contact areas. The calcite–strontianite and −witherite epitaxies are mono-dimensional and involve a parallelism between (101̅4)Cal||(021)Str/Wth. Strontianite and witherite cohesive layers remain strongly attached to the calcite substrates, which appear crack-free even after 2 years of reaction time. The formation of thin, cohesive, and durable replacement layers of strontianite and witherite may provide a long-lasting protection for calcitic marbles and limestones used as building stones in cultural heritage.

Local Heating Transforms Amorphous Calcium Carbonate to Single Crystals with Defined Morphologies

AbstractThe use of amorphous calcium carbonate (ACC) as a precursor phase affords organisms with outstanding control over the formation of calcite and aragonite biominerals. Essential to this strategy is that the ACC is maintained within confined volumes in the absence of bulk water. This ensures that the ACC undergoes a pseudomorphic transformation and that the organism can independently control nucleation and growth. However, comparable control has proven hard to achieve in synthetic systems. Here, a straightforward method is demonstrated for controlling the crystallization of ACC thin films in which nucleation is first triggered using a heated probe, and then growth is sustained by incubating the film at a lower temperature. By independently controlling nucleation and growth, sub‐millimeter calcite single crystals can be generated when and where it is desired, morphologies ranging from discs to squares to serpentine strips can be created, and arrays of crystals formed. The mechanism and energetics of crystallization of the ACC are studied using in situ transmission electron microscopy and continuity between the ACC and calcite at the growth front is demonstrated. It is envisaged that this method can be applied to the formation of large single crystals of alternative functional materials that form via amorphous precursor phases.

Nanomechanical Characterization of Enzyme Induced Carbonate Precipitates

The mechanical properties of calcium carbonate minerals formed by enzyme-induced carbonate precipitation (EICP) were studied using nanoindentation. Two types of precipitates were considered: (i) a “baseline” precipitate, synthesized via urea hydrolysis in an aqueous solution of urease enzyme, urea, and calcium chloride; and (ii) a “modified” precipitate, synthesized from a similar solution, but with the inclusion of nonfat dry milk. While both precipitates predominantly comprised calcite, X-ray diffraction and Raman spectroscopy indicated broader peaks in the modified precipitate, implying differences in the crystal structure of the two precipitates. Both precipitates were polycrystalline and had a higher average indentation hardness (H) and a lower indentation modulus (M) compared with the values for single calcite crystals reported in the literature. The ductility of the precipitates was quantified by the ratio M/H. The modified precipitate had a higher average M/H, implying greater ductility. The increased ductility of the modified precipitate results in higher resistance to crack propagation. In sands biocemented using the modified EICP solution, the increased ductility of the precipitate, in addition to preferential precipitation at interparticle contacts, may contribute to relatively high unconfined compressive strengths at low carbonate contents.

Mechanical Properties of Single-Crystal Calcite and Their Temperature and Strain-Rate Effects.

Calcite is the most stable crystalline phase of calcium carbonate. It is applied or found in composite products, the food industry, biomineralization, archaeology, and geology, and its mechanical properties have attracted more and more attention. In this paper, the mechanical behaviors of single-crystal calcite under uniaxial tension in different directions were simulated with the molecular dynamics method. The obtained elastic moduli are in good agreement with the experimental results. It has been found from further research that single-crystal calcite has typical quasi-brittle failure characteristics, and its elastic modulus, fracture strength, and fracture strain are all strongly anisotropic. The tensile failure is caused by dislocation emission, void formation, and phase transition along the and directions, but by continuous dislocation glide and multiplication along the direction. The fracture strength, fracture strain, and elastic modulus are all sensitive to temperature, but only elastic modulus is not sensitive to strain rate. The effects of temperature and logarithmic strain rate on fracture strength are in good agreement with the predictions of fracture dynamics.

Velocity-weakening and -strengthening friction at single and multiasperity contacts with calcite single crystals

SignificanceThe empirical nature of rate-and-state friction (RSF) equations remains a drawback to their application to predict earthquakes. From nanoscale friction measurements on smooth and rough calcite crystals, a set of parameters is analyzed to elucidate microscopic processes dictating RSF. We infer the influence of roughness on the velocity dependence of friction in dry environment and that atomic attrition leads to stick-slip instabilities at slow velocities. In fault dynamics, stick-slip is associated with seismic slips. The aqueous environment eliminates atomic attrition and stick-slip and dissolves calcite under pressure. This yields remarkable lubrication, even more so in rough contacts, and suggests an alternative pathway for seismic slips. This work has implications for understanding mechanisms dictating fault strength and seismicity.