Cleavage Plane Of Calcite Research Articles

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.

Impact of long-range attraction on desorption kinetics.

Desorption of molecules from surfaces is widespread both in nature and technology. Despite its omnipresence and conceptual simplicity, fundamental details can be surprisingly complex and are often poorly understood. In many cases, first-order kinetics is assumed, which implies that the adsorbates do not interact with each other and desorption is the rate-limiting process. While this might be a good approximation in some cases, it is far from reality in the case of adsorbates that form ordered structures. Here, we study the desorption of a submonolayer film of 3-nitrophenol from the natural cleavage plane of calcite kept in ultrahigh vacuum. Interestingly, two distinctly different desorption regimes are observed during isothermal desorption monitored by dynamic atomic force microscopy. Initially, at high coverages, the coverage decreases almost linearly in time, indicating a constant desorption rate. Beyond this linear regime, at low coverages, a drastic increase in desorption rate is observed until the surface is completely empty. The transition between these two regimes is associated with a critical island width. We propose an existence of a long-range attractive interaction between the molecules as a possible explanation for the sudden increase in the desorption rate when a critical island width is reached. The herein observed phenomenon of two different desorption regimes is expected to be of general nature when interactions beyond next-neighbour attraction are present.

How water desorbs from calcite.

Calcite is the most abundant carbonate mineral in Earth's crust. Upon cleavage, the (10.4) plane with a rectangular unit cell is exposed. Interestingly, several experiments suggest a (2 × 1) surface reconstruction. However, clear experimental evidence and a theoretical confirmation were long missing. Recently, convincing indication for a (2 × 1) reconstruction has been given by atomic force microscopies taken at 5 K. Here, we show temperature-programmed desorption (TPD) experiments of water and ethanol desorbing from calcite (10.4) around room temperature. The TPD curves fit excellently to a kinetic model considering two different adsorption sites, as expected in case of a (2 × 1) reconstruction. This finding applies to the desorption of water and ethanol, illustrating that the effect is characteristic for the calcite cleavage plane. Our results thus show that the (2 × 1) reconstruction not only exists at room temperature but has significant impact on the interfacial properties of calcite.

Structure-Dependent Dissolution and Restructuring of Calcite Surfaces by Organophosphonates

Organophosphonates are well-known to strongly interact with the surfaces of various minerals, such as brucite, gypsum, and barite. In this work, we study the influence of six systematically varied organophosphonate molecules (tetraphosphonates and diphosphonates) on the dissolution process of the (10.4) surface of calcite. In order to pursue a systematic study, we have selected organophosphonates that exhibit similar structural features, but also systematic architectural differences. The effect of this class of additives on the dissolution process of the calcite (10.4) surface is evaluated using in situ dynamic atomic force microscopy. For all of the six organophosphonate derivatives, we observe a pronounced restructuring of the (10.4) cleavage plane of calcite, demonstrated by the formation of characteristically shaped etch pits. To elucidate their specific influence on the dissolution process of calcite (10.4), we vary systematically the number of functional end groups (two for the tetraphosphonates and...

Generic nature of long-range repulsion mechanism on a bulk insulator?

Dynamic atomic force microscopy measurements are reported that provide evidence for the presence of long-range repulsion in molecular self-assembly on a bulk insulator surface. We present the structures formed from four different benzoic acid derivatives on the (10.4) cleavage plane of calcite kept in ultra-high vacuum. These molecules have in common that they self-assemble into molecular stripes when deposited onto the surface held at room temperature. For all molecules tested, a detailed analysis of the stripe-to-stripe distance distribution reveals a clear deviation from what would be expected for randomly placed, non-interacting stripes (i.e., geometric distribution). When excluding kinetic effects during growth, this result gives evidence for a long-range repulsion mechanism acting during the assembly of these stripes. The fact that this finding is robust against changes in the molecular structure indicates a generic nature of the observed mechanism, implying a ubiquitous origin such as electrostatic repulsion. Finally, we discuss parameters that might affect the unambiguous observation of this generic repulsion under specific experimental conditions.

X-ray scattering of calcite thin films deposited by atomic layer deposition: Studies in air and in calcite saturated water solution

Carbonates are one of the most abundant groups of minerals in earth systems and are important in many geological settings and industrial processes. Calcite (CaCO3) thin films produced by atomic layer deposition offer a method to evaluate the surficial properties of carbonates as well as interactions at the carbonate–fluid interface. Using synchrotron X-ray reflectivity and X-ray diffraction, these films are observed to be porous, polycrystalline, and have crystallites oriented with the major (104) calcite cleavage plane parallel to the surface of the z-cut single crystal quartz substrate. An Al2O3 buffer layer, present between quartz and the calcite film, does not affect the as-deposited film, but does influence how the films reorganize in contact with fluid. Without a buffer layer, calcite reorients its crystallites to have populations of (006) and (030) parallel to the substrate, while those with an Al2O3 buffer layer become more amorphous. Amorphous films may represent an analog to amorphous calcium carbonate and provide insights into that material's thermophysical behavior. Due to a higher percentage of pore spaces available for fluid infiltration, films deposited at higher temperature make the calcite thin films more susceptible to amorphization. These films are chemically similar, but structurally dissimilar to bulk natural calcite. Nevertheless, they can be a complementary system to traditional single crystal X-ray surface scattering studies on carbonates, particularly for important but less common minerals, to evaluate mineral–fluid interfacial interactions.

Controlled Activation of Substrate Templating in Molecular Self-Assembly by Deprotonation

Templated assembly of organic molecules constitutes a promising approach for fabricating functional nanostructures at surfaces with molecular-scale control. Using the substrate template for steering the adsorbate growth enables creating a rich variety of molecular structures by tuning the subtle balance of intermolecular and molecule–surface interactions. On insulating surfaces, however, surface templating is largely absent due to the comparatively weak molecule–surface interactions compared to metallic substrates. Here, we demonstrate the activation of substrate templating in molecular self-assembly on a bulk insulator by controlled deprotonation of the adsorbed molecules upon annealing. Upon deposition of 4-iodobenzoic acid onto the natural cleavage plane of calcite held at room temperature, high molecular mobility is observed, indicating a small diffusion barrier. Molecular islands only nucleate at step edges. These islands show no commensurability with the underlying substrate, clearly indicating the absence of surface templating. Upon annealing the substrate, the molecules undergo a transition from the protonated to the deprotonated state. In the deprotonated state, the molecules adopt a well-defined adsorption position, resulting in a distinctly different, substrate-templated molecular structure that is stable at room temperature. Our work, thus, demonstrates the controlled activation of substrate templating by changing the molecule–surface interaction upon annealing.

How deprotonation changes molecular self-assembly – an AFM study in liquid environment

We study the influence of Alizarin Red S deprotonation on molecular self-assembly at the solid–liquid interface of the natural cleavage plane of calcite immersed in aqueous solution. To elucidate the adsorption details, we perform pH dependent high-resolution atomic force microscopy measurements. When Alizarin Red S is deposited onto calcite(10.4) in a liquid environment at an acidic pH of 5, weakly bound, ordered islands with a (3 × 3) superstructure are observed. A sharp structural transition is revealed when increasing the pH above 8. Above this pH, stable needle-like structures oriented along the [01.0] direction form on the surface. Comparing these results with potentiometric titration data allows for unambiguously assigning the two molecular structures to the single and two-fold deprotonated moieties of Alizarin Red S. Our work, thus, illustrates the decisive impact of the protonation state on molecular self-assembly.

Substrate Templating upon Self‐Assembly of Hydrogen‐Bonded Molecular Networks on an Insulating Surface

Molecular self-assembly on insulating surfaces, despite being highly relvant to many applications, generally suffers from the weak molecule-surface interactions present on dielectric surfaces, especially when benchmarked against metallic substrates. Therefore, to fully exploit the potential of molecular self-assembly, increasing the influence of the substrate constitutes an essential prerequisite. Upon deposition of terephthalic acid and trimesic acid onto the natural cleavage plane of calcite, extended hydrogen-bonded networks are formed, which wet the substrate. The observed structural complexity matches the variety realized on metal surfaces. A detailed analysis of the molecular structures observed on calcite reveals a significant influence of the underlying substrate, clearly indicating a substantial templating effect of the surface on the resulting molecular networks. This work demonstrates that choosing suitable molecule/substrate systems allows for tuning the balance between intermolecular and molecule-surface interactions even in the case of typically weakly interacting insulating surfaces. This study, thus, provides a strategy for deliberately exploiting substrate templating to increase the structural variety in molecular self-assembly on a bulk insulator at room temperature.

Clear Signature of the (2 × 1) Reconstruction of Calcite (101̅4)

Calcite is a mineral of fundamental importance that plays a crucial role in many fields of research such as biomineralization, biomolecule adsorption, and reactivity as well as industrial and daily life applications. Consequently, the most stable cleavage plane of calcite has been studied extensively using both direct imaging techniques such as atomic force microscopy as well as spectroscopic and diffraction techniques. Several surface structures have been reported for the (1014) cleavage plane of calcite differing from the simple bulk-truncated structure and an ongoing controversy exists in literature whether the cleavage plane exhibits a (2 x 1) reconstruction or not. We study the (1014) cleavage plane using high-resolution noncontact atomic force microscopy (NC-AFM) under ultrahigh vacuum conditions and obtain a clear signature of the (2 x 1) reconstruction. This reconstruction is observed in very narrow tip-surface distance ranges only, explaining why in some experiments the reconstruction has been observed and in others not. Moreover, as all sample preparation is performed in ultrahigh vacuum, the possibility of the (2 x 1) reconstruction being adsorbate-induced appears rather unlikely. Additionally, tip-induced surface changes are ruled out as origin for the observed reconstruction either. In conclusion, our study suggests that the (2 x 1) reconstruction is a true surface property of the (1014) cleavage plane of calcite.

Toward Molecular Nanowires Self-Assembled on an Insulating Substrate: Heptahelicene-2-carboxylic acid on Calcite (101̅4)

Molecular self-assembly is employed for creating unidirectional molecular nanostructures on a truly insulating substrate, namely the (101̅4) cleavage plane of calcite. The molecule used is racemic heptahelicene-2-carboxylic acid, which forms structures, well-aligned along the [010] crystallographic direction and stable at room temperature. Precise control of both molecule−substrate and molecule−molecule interaction is required, leading to the formation of such wire-like structures of well-defined width and lengths exceeding 100 nm. This subtle balance is governed by the heptahelicene-2-carboxylic acid used in this study, allowing for both hydrogen bond formation as well as π−π stacking.

True Atomic-Resolution Imaging of (101̅4) Calcite in Aqueous Solution by Frequency Modulation Atomic Force Microscopy

Calcite (CaCO3) is one of the most abundant minerals on earth and plays an important role in a wide range of different fields including, for example, biomineralization and environmental geochemistry. Consequently, surface processes and reactions such as dissolution and growth as well as (macro)molecule adsorption are of greatest interest for both applied as well as fundamental research. An in-depth understanding of these processes requires knowledge about the detailed surface structure in its natural state which is quite often a liquid environment. We have studied the most stable cleavage plane of calcite under liquid conditions using frequency modulation atomic force microscopy. Using this technique, we achieved true atomic-resolution imaging, demonstrating the high-resolution capability of frequency modulation atomic force microscopy in liquids. We could reproduce contrast features reported before using contact mode atomic force microscopy, originating from the protruding oxygen atom of the carbonate groups. Besides this contrast, however, our results, indeed, indicate that we obtain more detailed structural information, revealing the calcium sublattice of the (1014) cleavage plane.

Modeling the Competitive Adsorption of Water and Methanoic Acid on Calcite and Fluorite Surfaces

Atomistic simulation techniques were used to investigate the interaction between the minerals calcite and fluorite with water and methanoic acid. The relative adsorption energies suggest that methanoic acid preferentially adsorbs onto fluorite surfaces, while adsorption of water is energetically preferred over methanoic acid on the calcite cleavage plane in agreement with experiment. The coverage and configuration of adsorbed methanoic acid on the surfaces depends largely on lattice spacing between the cations, and bridging between surface calcium atoms is highly favored. These findings have given an insight into interactions at the atomic level which indicate that modeling techniques should be capable of predicting adsorption behavior and designing collector molecules, which is of central importance to the mineral processing technique of flotation.

Incorporation of growth-inhibiting diphosphonates into steps on the calcite cleavage plane surface

The interaction between the calcite cleavage plane surface and three different diphosphonate molecules has been studied employing methods based on interatomic potentials. The diphosphonates studied include 1-hydroxyethylidene-1,1-diphosphonate (HEDP) (which is known empirically to poison crystal growth) together with two more symmetrical analogues. We show that the diphosphonate molecules enter into a calcite surface or step (to which they are more strongly bound) by replacing two carbonate ions, provided that the carbonate–carbonate distance matches the distance between the phosphonate groups reasonably well. We suggest a microscopic mechanism of growth inhibition on the basis of calculations of the binding energy for a calcium carbonate unit in the vicinity of the inhibitor.

In-Situ Atomic Force Microscope Imaging of Calcite Etch Pit Morphology Changes in Undersaturated and 1-Hydroxyethylidene-1,1-diphosphonic Acid Poisoned Solutions.

Morphology changes in etch pits formed on the (1014) cleavage plane of calcite were induced by varying the ratio of [Ca2+] to [CO32-] in the bulk solution as well as through the addition of the crystal poison 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP). Three distinct morphologies were noted: symmetric rhombic, asymmetric rhombic, and triangular with a rough curved hypotenuse. The latter represents a transient morphology which is only observed during the actual dissolution process, while the former morphologies persist after dissolution is halted.

A study of the calcite cleavage plane using the atomic force microscope

A study of the calcite cleavage plane using the atomic force microscope

True Atomic Resolution by Atomic Force Microscopy Through Repulsive and Attractive Forces

The (1014) cleavage plane of calcite has been investigated by atomic force microscopy in water at room temperature. True lateral atomic-scale resolution was achieved; the atomic-scale periodicities as well as the expected relative positions of the atoms within each unit cell were obtained. Along monoatomic step lines, atomic-scale kinks, representing point-like defects, were resolved. Attractive forces on the order of 10(-11) newton acting between single atomic sites on the sample and the front atoms of the tip were directly measured and provided the highest, most reliable resolution on a flat, well-ordered surface.

AFM images of dissolution and growth on a calcite crystal

We present atomic-force-microscope (AFM) images of aqueous dissolution and growth of monolayers on the cleavage plane of calcite. These processes were observed in real time and in situ. Dissolution in 0.015N NaOH occured primarily by faceting and expansion of pre-existing surface pits and by removal of islands. No new dissolution sites were observed to nucleate during this process. We also observed a simple growth sequence wherein CaCO 3 monolayers were deposited on the calcite surface by uniformly advancing steps. Atomic resolution was readily obtained, even at larger-scale features such as steps and etch pits. This shows the potential of the AFM to study deposition and removal of individual molecules on a crystal surface in solution.

Dynamic etching of natural rhombohedral calcite cleavage planes

AbstractDynamic etching of natural rhombohedral calcite cleavage plane in low concentration of monocarboxylic acid (such as formic, acetic and propionic acids) is studied and interesting results are obtained. Eccentricity of rhombic etch pits increase indefinitely as stirring rate increase in low concentration of monocarboxylic acids, whereas peak value of eccentricity is obtained with stirring rate when there is a change in etch pit morphology. Change in etch pit morphology and change in eccentricity with stirring rate is explained with the help of lateral reaction rates along various directions. Eccentricity variation with stirring rate is compared with concentration variation with concentration of different monocarboxylic acids.

Fine Structure of Metallic Surfaces with the Electron Microscope

Several techniques for producing surface replicas to be used in the transmission electron microscope are briefly discussed and compared on the basis of experience with them in this laboratory. A new two-step replica process is described which utilizes molded polystyrene as the first replica and evaporated silica as the second, thin film replica. The high mobility of condensing silica vapor on polystyrene is pointed out and it is shown that such evaporated films tend to fill in small surface irregularities and so produce a replica of fine surface structure which appears to be reliable. A table is included which gives an idea of the amounts of silica required for several surfaces of different ``roughness'' to yield films that are of about the same quality for use in the electron microscope. Electron micrographs of replicas so prepared are exhibited illustrating some pearlitic structures in a 0.98 C, hot roll steel, precipitation in a Cu–Be alloy, and a calcite cleavage plane. Excellent resolution can be obtained in such replicas and a resolution of approximately 50A is demonstrated in the calcite cleavage plane.