Role of Mass Transport in the Deposition, Growth, and Transformation of Calcium Carbonate on Surfaces at High Supersaturation.

We demonstrate how combined in-situ measurements and finite element method modeling can provide new insight into the relative contribution of mass transport to the growth of calcium carbonate on two model surfaces, glass and gold, under high-supersaturation conditions relevant to surface scaling. An impinging jet-radial flow system is used to create a high-supersaturated solution at the inlet of different cells: an optical microscope cell presenting a glass surface for deposition and quartz crystal microbalance (QCM) and in-situ IR spectroscopy cells, both presenting a gold surface. The approach described is quantitative due to the well-defined mass transport, and both time-lapse optical microscopy images and QCM data are analyzed to provide information on the growth kinetics of the calcite crystals. Initially, amorphous calcium carbonate (ACC), formed in solution, dominates the deposition process. At longer times, the growth of calcite is more significant and, on glass, is observed to consume ACC from the surface, leading to surface regions depleted of ACC developing around calcite microcrystals. On Au, the mass increase becomes linear with time in this region. Taken together, these microscopic and macroscopic measurements demonstrate that calcite growth has a significant component of mass transport control at high supersaturation. Finite element method (FEM) simulations of mass-transport-limited crystal growth support the strong mass transport contribution to the growth kinetics and further suggest that the observed growth must be sustained by more than just the Ca2+ and CO3 2- in solution, with dissolution/direct attachment of ACC and/or ion pairs also contributing to the growth process.

Combinatorial localized dissolution analysis: Application to acid-induced dissolution of dental enamel and the effect of surface treatments.

A combination of scanning electrochemical cell microscopy (SECCM) and atomic force microscopy (AFM) is used to quantitatively study the acid-induced dissolution of dental enamel. A micron-scale liquid meniscus formed at the end of a dual barrelled pipette, which constitutes the SECCM probe, is brought into contact with the enamel surface for a defined period. Dissolution occurs at the interface of the meniscus and the enamel surface, under conditions of well-defined mass transport, creating etch pits that are then analysed via AFM. This technique is applied to bovine dental enamel, and the effect of various treatments of the enamel surface on acid dissolution (1mM HNO3) is studied. The treatments investigated are zinc ions, fluoride ions and the two combined. A finite element method (FEM) simulation of SECCM mass transport and interfacial reactivity, allows the intrinsic rate constant for acid-induced dissolution to be quantitatively determined. The dissolution of enamel, in terms of Ca(2+) flux ( [Formula: see text] ), is first order with respect to the interfacial proton concentration and given by the following rate law: [Formula: see text] , with k0=0.099±0.008cms(-1). Treating the enamel with either fluoride or zinc ions slows the dissolution rate, although in this model system the partly protective barrier only extends around 10-20nm into the enamel surface, so that after a period of a few seconds dissolution of modified surfaces tends towards that of native enamel. A combination of both treatments exhibits the greatest protection to the enamel surface, but the effect is again transient.

Hopping intermittent contact-scanning electrochemical microscopy (HIC-SECM) as a new local dissolution kinetic probe: application to salicylic acid dissolution in aqueous solution.

Dissolution kinetics of the (110) face of salicylic acid in aqueous solution is determined by hopping intermittent contact-scanning electrochemical microscopy (HIC-SECM) using a 2.5 µm diameter platinum ultramicroelectrode (UME). The method operates by translating the probe UME towards the surface at a series of positions across the crystal and inducing dissolution via the reduction of protons to hydrogen, which titrates the weak acid and promotes the dissolution reaction, but only when the UME is close to the crystal. Most importantly, as dissolution is only briefly and transiently induced at each location, the initial dissolution kinetics of an as-grown single crystal surface can be measured, rather than a surface which has undergone significant dissolution (pitting), as in other techniques. Mass transport and kinetics in the system are modelled using finite element method simulations which allows dissolution rate constants to be evaluated. It is found that the kinetics of an 'as-grown' crystal are much slower than for a surface that has undergone partial bulk dissolution (mimicking conventional techniques), which can be attributed to a dramatic change in surface morphology as identified by atomic force microscopy (AFM). The 'as-grown' (110) surface presents extended terrace structures to the solution which evidently dissolve slowly, whereas a partially dissolved surface has extensive etch features and step sites which greatly enhance dissolution kinetics. This means that crystals such as salicylic acid will show time-dependent dissolution kinetics (fluxes) that are strongly dependent on crystal history, and this needs to be taken into account to fully understand dissolution.

Measurement of the efficacy of calcium silicate for the protection and repair of dental enamel.

OBJECTIVES: To investigate the formation of hydroxyapatite (HAP) from calcium silicate and the deposition of calcium silicate onto sound and acid eroded enamel surfaces in order to investigate its repair and protective properties. METHODS: Calcium silicate was mixed with phosphate buffer for seven days and the resulting solids analysed for crystalline phases by Raman spectroscopy. Deposition studies were conducted on bovine enamel surfaces. Acid etched regions were produced on the enamel surfaces using scanning electrochemical cell microscopy (SECCM) with acid filled pipettes and varying contact times. Following treatment with calcium silicate, the deposition was visualised with FE-SEM and etch pit volumes were measured by AFM. A second set of bovine enamel specimens were pre-treated with calcium silicate and fluoride, before acid exposure with the SECCM. The volumes of the resultant acid etched pits were measured using AFM and the intrinsic rate constant for calcium loss was calculated. RESULTS: Raman spectroscopy confirmed that HAP was formed from calcium silicate. Deposition studies demonstrated greater delivery of calcium silicate to acid eroded than sound enamel and that the volume of acid etched enamel pits was significantly reduced following one treatment (p<0.05). In the protection study, the intrinsic rate constant for calcium loss from enamel was 0.092 ± 0.008 cm/s. This was significantly reduced, 0.056 ± 0.005 cm/s, for the calcium silicate treatments (p<0.0001). CONCLUSIONS: Calcium silicate can transform into HAP and can be deposited on acid eroded and sound enamel surfaces. Calcium silicate can provide significant protection of sound enamel from acid challenges. CLINICAL SIGNIFICANCE: Calcium silicate is a material that has potential for a new approach to the repair of demineralised enamel and the protection of enamel from acid attacks, leading to significant dental hard tissue benefits.

Dual-barrel conductance micropipet as a new approach to the study of ionic crystal dissolution kinetics.

A new approach to the study of ionic crystal dissolution kinetics is described, based on the use of a dual-barrel theta conductance micropipet. The solution in the pipet is undersaturated with respect to the crystal of interest, and when the meniscus at the end of the micropipet makes contact with a selected region of the crystal surface, dissolution occurs causing the solution composition to change. This is observed, with better than 1 ms time resolution, as a change in the ion conductance current, measured across a potential bias between an electrode in each barrel of the pipet. Key attributes of this new technique are: (i) dissolution can be targeted at a single crystal surface; (ii) multiple measurements can be made quickly and easily by moving the pipet to a new location on the surface; (iii) materials with a wide range of kinetics and solubilities are open to study because the duration of dissolution is controlled by the meniscus contact time; (iv) fast kinetics are readily amenable to study because of the intrinsically high mass transport rates within tapered micropipets; (v) the experimental geometry is well-defined, permitting finite element method modeling to allow quantitative analysis of experimental data. Herein, we study the dissolution of NaCl as an example system, with dissolution induced for just a few milliseconds, and estimate a first-order heterogeneous rate constant of 7.5 (±2.5) × 10(-5) cm s(-1) (equivalent surface dissolution flux ca. 0.5 µmol cm(-2) s(-1) into a completely undersaturated solution). Ionic crystals form a huge class of materials whose dissolution properties are of considerable interest, and we thus anticipate that this new localized microscale surface approach will have considerable applicability in the future.

Holistic approach to dissolution kinetics: linking direction-specific microscopic fluxes, local mass transport effects and global macroscopic rates from gypsum etch pit analysis.

Dissolution processes at single crystal surfaces often involve the initial formation and expansion of localized, characteristic (faceted) etch-pits at defects, in an otherwise comparatively unreactive surface. Using natural gypsum single crystal as an example, a simple but powerful morphological analysis of these characteristic etch pit features is proposed that allows important questions concerning dissolution kinetics to be addressed. Significantly, quantitative mass transport associated with reactive microscale interfaces in quiescent solution (well known in the field of electrochemistry at ultramicroelectrodes) allows the relative importance of diffusion compared to surface kinetics to be assessed. Furthermore, because such mass transport rates are high, much faster surface kinetics can be determined than with existing dissolution methods. For the case of gypsum, surface processes are found to dominate the kinetics at early stages of the dissolution process (small etch pits) on the cleaved (010) surface. However, the contribution from mass transport becomes more important with time due to the increased area of the reactive zones and associated decrease in mass transport rate. Significantly, spatial heterogeneities in both surface kinetics and mass transport effects are identified, and the morphology of the characteristic etch features reveal direction-dependent dissolution kinetics that can be quantified. Effective dissolution velocities normal to the main basal (010) face are determined, along with velocities for the movement of [001] and [100] oriented steps. Inert electrolyte enhances dissolution velocities in all directions (salting in), but a striking new observation is that the effect is direction-dependent. Studies of common ion effects reveal that Ca(2+) has a much greater impact in reducing dissolution rates compared to SO(4)(2-). With this approach, the new microscopic observations can be further analysed to obtain macroscopic dissolution rates, which are found to be wholly consistent with previous bulk measurements. The studies are thus important in bridging the gap between microscopic phenomena and macroscopic measurements.

Quantitative visualization of molecular transport through porous membranes: enhanced resolution and contrast using intermittent contact-scanning electrochemical microscopy.

The use of intermittent contact-scanning electrochemical microscopy (IC-SECM) in diffusion-limited amperometric mode to visualize and quantify mass transport through multiporous membranes is described using dentin as a model example. The IC mode of SECM employs the damping of a vertically modulated ultramicroelectrode (UME) to achieve positioning close to the receptor side of a membrane. In this way the UME can detect electroactive species close to the pore exit. A key aspect of IC-SECM is that in addition to the direct current (dc) from the diffusion-limited detection of the analyte, an alternating current (ac) also develops due to the motion of the probe. It demonstrates that this ac signal enhances the spatial resolution of SECM detection and allows the hydrodynamic flow of species to be detected from individual closely spaced pores. The experimental deductions are supported by three-dimensional finite element modeling which allows IC-SECM current maps to be analyzed to reveal transport rates through individual pores. The method described should be widely applicable to multiporous membrane transport.

Formation and evaluation of electrochemically-active ultra-thin palladium-Nafion nanocomposite films.

A simple method for producing electrochemically-active palladium nanoparticles within ultra-thin Nafion films is described.