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Abstract: Dissolution kinetics at the aqueous solution-calcite interface at 50 °C were investigated using in situ atomic force microscopy (AFM) to reveal the influence of magnesium concentration and solution saturation state on calcite dissolution kinetics and surface morphology. Under near-equilibrium conditions, dissolved displayed negligible inhibitory effects on calcite dissolution even at concentrations of . Upon the introduction of , the solution saturation state with respect to calcite, , acted as a “switch” for magnesium inhibition whereby no significant changes in step kinetics were observed at , whereas a sudden inhibition from was activated at . The presence of the -switch in dissolution kinetics indicates the presence of critical undersaturation in accordance with thermodynamic principles. The etch pits formed in solutions with exhibited a unique distorted rhombic profile, different from those formed in Mg-free solutions and in de-ionized water. Such unique etch pit morphology may be associated with the anisotropy in net detachment rates of counter-propagating kink sites upon the addition of . [ABSTRACT FROM AUTHOR]

Abstract: In situ Atomic Force Microscopy (AFM) and Lateral Force Microscopy (LFM) studies on dolomite (101̄4) were performed during exposure to supersaturated aqueous solutions (supersaturated in dolomite, calcite, aragonite, vaterite, huntite and magnesite) at pH = 9 at various Ca2+/Mg2+ aqueous ion activity ratios. At high saturation ratios, rapid growth of a single layer (∼3 Å thick) of a carbonate followed by much slower growth of a second layer was observed. Growth of the second layer was highly inhibited, suggesting that the first layer was essentially self-limited, and inhibited further layer-by-layer growth. The growth of the first layer was observed over a wide range of Ca2+/Mg2+ ratios, suggesting that the dolomite surface is favorable to formation of a range of Ca-Mg carbonates. LFM data revealed contrast in the tip-surface frictional forces on the first grown layer, but this contrast was only observed in layers grown from middle to high Ca2+/Mg2+ solutions. Thus, LFM may have detected or responded to differences in the structure and/or composition between the first layer relative and the dolomite substrate. Dissolution of the first layer occurred from significantly supersaturated solutions relative to ordered stoichiometric dolomite permitting an estimate of the excess interfacial strain energy of up to 10 mJ/m2. [Copyright &y& Elsevier]

Magnesite (104) dissolution kinetics were studied in acidic aqueous solutions (2.0 < pH < 4.2) at temperatures between 60 and 90°C by atomic force microscopy (AFM). Comparison of dissolution fluxes obtained by AFM and chemical methods revealed six to seven times larger dissolution fluxes obtained by chemical analysis. Corresponding empirical activation energies were found to be 74 ±22 kJ/mol and 41 ± 4 kJ/mol (at pH 4.2) for the AFM and chemical methods, respectively. The empirical reaction order with respect to proton concentration was 0.36 ± 0.13 and 0.47 ± 0.03 for AFM and chemical methods, respectively. These comparisons suggest that the two experimental measurement methods differ as a result of the different sampling length scales associated with the methods. Negligible changes in step dissolution velocity with changes in bulk pH were found, suggesting that the principal source of increasing dissolution flux with decreasing pH is an increase in step density. However, the observed stable step orientation, which is dependent on pH, suggests that more than one proton adsorption equilibrium should be used to describe the surface chemistry of magnesite in acidic solution. [Copyright &y& Elsevier]

Presents a design of a contact atomic force microscope (AFM) for aqueous solution imaging. Features of the AFM; Advantages of the design; Details on the unit-cell scale vertical resolution of the AFM.

The rate of growth of ionic minerals from solutions with varying aqueous cation:anion ratios may result in significant errors in mineralization rates predicted by commonly-used affinity-based rate equations. To assess the potential influence of solute stoichiometry on barite growth, step velocities on the barite (0 0 1) surface have been measured at 108 °C using hydrothermal atomic force microscopy (HAFM) at moderate supersaturation and as a function of the aqueous barium:sulfate ratio ( r ). Barite growth hillocks at r ∼ 1 were bounded by 〈 1 2 0 〉 steps, however at r < 1, kink site densities increased, steps followed a direction vicinal to 〈 1 2 0 〉 , and the [0 1 0] steps developed. At r > 1, steps roughened and rounded as the kink site density increased. Step velocities peaked at r = 1 and decreased roughly symmetrically as a function of r , indicating the attachment rates of barium and sulfate ions are similar under these conditions. We hypothesize that the differences in our observations at high and low r arise from differences in the attachment rate constants for the obtuse and acute 〈 1 2 0 〉 steps. Based on results at low r , the data suggests the attachment rate constant for barium ions is similar for obtuse and acute steps. Based on results at high r , the data suggests the attachment rate constant for sulfate is greater for obtuse steps than acute steps. Utilizing a step growth model developed by Stack and Grantham (2010) the experimental step velocities as a function of r were readily fit while attempts to fit the data using a model developed by Zhang and Nancollas (1998) were less successful. [ABSTRACT FROM AUTHOR]

Step velocities on the celestite (0 0 1) surface have been measured as a function of temperature (23–45 °C), saturation state ( S = 1.1–2.2), ionic strength ( I = 0.01, 0.06, and 0.1 M), and aqueous strontium:sulfate ratio ( r = 0.01–100) using atomic force microscopy (AFM). Celestite growth hillocks were flanked by [0 1 0]-aligned step edges, which are polar, and step edges vicinal to 〈1 2 0〉, which are non-polar. [0 1 0] step velocities increased with temperature and saturation state, however step velocities did not vary significantly with ionic strength. Step velocities were non-linear with saturation state, suggesting a change in mechanism at high S as compared with low S. At constant S , the step velocities were maximized at r = 1 and decreased significantly at extreme r , demonstrating the governing role of solute stoichiometry. We successfully fit the step velocity data as a function of r using the Stack and Grantham (2010) nucleation and propagation model. Based on the results as a function of ionic strength and r , the mechanism at low S is likely ion-by-ion attachment to the step with an activation energy of 75 (±10) kJ mol −1 . At high S the mechanism is a combination of the one at low S and possibly attachment of a neutral species such as an ion pair with an activation energy of 43 (±9) kJ mol −1 . [ABSTRACT FROM AUTHOR]

Abstract: The purpose of this work was to examine the effects of polished crystal-surface orientation and degree of solution undersaturation on the dissolution kinetics of calcite. Crystallographic surface orientations utilized in this study included natural calcite specimens polished approximately parallel to the (104) plane, giving rise to surfaces with flat terraces with few steps, as well as fully kinked surfaces created by sectioning approximately parallel to the (001) plane. Results from inductively coupled plasma optical emission spectroscopy (ICP-OES) and vertical scanning interferometry (VSI) investigations revealed how crystallographic orientations of calcite with initially higher energy surface morphologies were associated with greater extent of reaction, greater surface retreat, and therefore, greater initial transient dissolution rates than those with lower energy initial surface morphologies. However, both the ICP-OES and atomic force microscopy (AFM) results confirm that the effects of crystal orientation become minimal under long-term conditions because (1) variously oriented calcite surfaces exhibited similar “long-term” rates and (2) orientations with high initial reactive site densities developed lower energy morphologies. Estimating a step rate coefficient from the experimental data from a miscut sample suggest that these coefficients may be highly morphology dependent. Results from this study are significant for predicting long term calcite dissolution rates because they suggest that the “long-term” dissolution rate of calcite will be governed by the rates of the rhombohedral faces and microfacets and the time-scale for approaching such conditions is of the order of days at room temperature and slightly alkaline solution conditions. [Copyright &y& Elsevier]

Abstract: A computer algorithm was developed to automatically track the displacement of straight step edges between sequential scanning probe microscopy images of single-crystal surfaces. The program utilizes the Canny edge detection algorithm followed by the Hough Transform of the edge map to identify step edges according to their direction, relative to the image axes, and according to their displacement, relative to the image origin. The tracking of individual steps is facilitated by the fact that straight edges in general maintain their direction and therefore, steps of similar displacement but different direction can be sorted. The algorithm is based on the assumption that the rate of image acquisition is much greater than the rate of (mono)layer growth/dissolution, requiring that changes in step displacement are small in successive images. The change in step displacement in sequential images leads directly to the calculation of the step speed. By tabulating all changes in step displacement through a sequence of images, a statistical representation of the step edge data is produced. The program was evaluated using a sequence of 20 atomic force microscopy images from a calcite (104) surface growing from a supersaturated aqueous solution. The program required, in total, 5 CPU-minutes running on a Pentium 4 processor to compute the mean step speed with 60% precision whereas the equivalent number of measurements performed “by hand” required 6 person-hours at 70% precision. For comparable output, the computer program therefore represents a factor of about 100 decrease in required effort. [Copyright &y& Elsevier]

Abstract: Dissolution of celestite (001) was studied by atomic force microscopy as a function of solution undersaturation. In solutions near saturation with respect to celestite, dissolution of the mineral took place exclusively by removal of ions from existing step edges. The onset of etch pit nucleation was observed at a critical saturation state of . Below this saturation state, dissolution took place both at existing step edges and via the creation of new steps surrounding the etch pits. The dissolution rates of celestite exhibited a non-linear dependence on saturation state. Basic crystal dissolution/growth models were inadequate to describe the non-linearity, but a model that incorporates a critical undersaturation provided an improved fit to data collected at high undersaturation. A simple model for dissolution at low undersaturation also fit the rate data well, but in light of the conditions necessary to produce new step edges, the rate coefficient in this model is poorly constrained due to the effects of sample surface history. Consideration of the process of topographic relaxation, consisting of changes in the surface microtopography (i.e., step density) resulting from changes in solution conditions, led to predicted relaxation times on the order of days for the celestite–water interface. [Copyright &y& Elsevier]

Abstract: Plasma-assisted functional films have significant potential in various engineering applications. They can be tailored to impart desired properties by bonding specific molecular groups to the substrate surface. The aim of this investigation was to develop a fundamental understanding of the atomic level growth, coverage and functional effectiveness of plasma nano-films on flat surfaces and to explore their application-potential for complex and uneven shaped nano-materials. In this paper, results on plasma-assisted nano-scale fluorocarbon films, which are known for imparting inertness or hydrophobicity to the surface, will be discussed. The film deposition was studied as a function of time on flat single crystal surfaces of silicon, sapphire and graphite, using microwave plasma. X-ray photoelectron spectroscopy (XPS) was used for detailed study of composition and chemistry of the substrate and coating atoms, at all stages of deposition. Atomic force microscopy (AFM) was performed in parallel to study the coverage and growth morphology of these films at each stage. Combined XPS and AFM results indicated complete coverage of all the substrates at the nanometer scale. It was also shown that these films grew in a layer-by-layer fashion. The nano-films were also applied to complex and uneven shaped nano-structured and porous materials, such as microcellular porous foam and nano fibers. It was seen that these nano-films can be a viable approach for effective surface modification of complex or uneven shaped nano-materials. [Copyright &y& Elsevier]

To better understand the role of spectator ions in barite growth, the kinetics of step edge growth on barite (001) surfaces were studied under various salt solutions. Hydrothermal atomic force microscopy (HAFM) was used to investigate the effect of background electrolytes (NaCl, NaBr, and NaNO3) as a function of saturation index and ionic strength (I) on barite growth sourced at dislocations at 108 °C. Results demonstrate that hillock morphology is affected by I, as well as type of anion, where the prevalence of steps aligned on the [010] direction is highest under Cl-. There is a modest increase in kinetic coefficient of 55-130% with a 10-fold increase in I for each salt. In comparing the kinetic coefficients of the salts at low ionic strength (0.01 M), there is a moderate difference, suggesting that the anion may play a role in barium attachment. [ABSTRACT FROM AUTHOR]

Abstract: Direct measurements of calcite faces were performed using in situ atomic force microscopy (AFM) to reveal the dissolution processes as a function of solution saturation state and temperature. Time-sequential AFM images demonstrated that step velocities at constant temperature increased with increasing undersaturation. The anisotropy of obtuse and acute step velocities appeared to become more significant as solutions approached equilibrium and temperature increased. At saturation state Ω >0.02, a curvilinear boundary was formed at the intersection of two acute steps and the initially rhombohedral etch pit exhibited a nearly triangular shape. This suggests that the and steps may not belong to the calcite-aqueous solution equilibrium system. Further increase in the saturation state (Ω ⩾0.3) led to a lack of etch pit formation and dissolution primarily occurred at existing steps, in accordance with . Analysis of step kinetics at different temperatures yielded activation energies of 25±6kJ/mol and 14±13kJ/mol for obtuse and acute steps, respectively. The inconsistencies in etch pit morphology, step anisotropy, and step activation energies from the present study with those of studies far-from-equilibrium can be explained by increased influence of the backward reaction, or growth, near-equilibrium. We propose that the backward reaction occurs preferentially at the acute–acute kink sites. The kinetics and effective activation energies of near-equilibrium calcite dissolution presented in this work provide accurate experimental data under likely CO2 sequestration conditions, and thus are crucial to the development of robust geochemical models that predict the long-term performance of mineral-trapped CO2. [Copyright &y& Elsevier]