Understanding and controlling precipitation reactions is a major challenge for industrial crystallization. Calcium carbonate is a widely studied system: more than 3000 papers have been devoted to the subject over the past 10 years. The first step of the precipitation of calcium carbonate, from relatively concentrated solutions (0.01 mol/L), involves the formation of an initial gel phase which later transforms into calcite, vaterite, or a mixture of both phases. Our work aimed at controlling this first step. Nanosized seeds (8 nm), formed in situ, were used in order to control the often chaotic nucleation step which normally leads to poor phase selection and broad particle size distributions. Seeding has often been used to avoid spontaneous nucleation in metastable solutions for growth mechanism investigations of single-crystal calcium carbonate. Here the ability of a seeding method to control the precipitation reaction evolution even in the case of high supersaturation is demonstrated. The seeds and the presence of a polymeric additive (poly(acrylic acid)) allow the control of the precipitated polymorph and the specific surface area, while maintaining a narrow particle size distribution in the submicron range. Direct characterization methods did not succeed in identifying these nanoseeds; indirect methods using solubility calculations are used to demonstrate their existence and quantify size and number density of the nanosized seeds.

The synthesis of powders with controlled shape and narrow particle size distributions is still a major challenge for many industries. A continuous Segmented Flow Tubular Reactor (SFTR) has been developed to overcome homogeneity and scale‐up problems encountered when using batch reactors. Supersaturation is created by mixing the co‐reactants in a micromixer inducing precipitation; the suspension is then segmented into identical micro‐volumes by a non‐miscible fluid and sent through a tube. These micro‐volumes are more homogeneous when compared to large batch reactors leading to narrower size distributions, better particle morphology, polymorph selectivity and stoichiometry. All these features have been demonstrated on single tube SFTR for different chemical systems. To increase productivity for commercial application the SFTR is being “scaled‐out” by multiplying the number of tubes running in parallel instead of scaling‐up by increasing their size. The versatility of the multi‐tube unit will allow changes in type of precipitate with a minimum of new investment as new chemistry can be researched, developed and optimised in a single tube SFTR and then transferred to the multi‐tube unit for powder production.

a b s t r a c tThermodynamic solubility calculations are normally only related to thermodynamic equilibria in solution. In this paper, we extend the use of such solubility calculations to help elucidate possible precipitation reaction pathways during the entire reaction. We also estimate the interfacial energy of particles using only solubility data by a modification of Mersmann's approach. We have carried this out by considering precipitation reactions as a succession of small quasi-equilibrium states. Thus possible equilibrium precipitation pathways can be evaluated by calculating the evolution of surface charge, particle size and/ or interfacial energy during the ongoing reaction. The approach includes the use of the Kelvin's law to express the influence of particle size on the solubility constant of precipitates, the use of Nernst's law to calculate surface potentials from solubility calculations and relate this to experimentally measured zeta potentials. Calcium carbonate precipitation and zeta potential measurements of well characterised high purity calcite have been used as a model system to validate the calculated values. The clarification of the change in zeta potential on titration illustrates the power of this approach as a tool for reaction pathway prediction and hence knowledge based tailoring of precipitation reactions.

Our work investigates the precipitation mechanism of a seeded calcium carbonate reaction, by using cryogenic TEM to observe the early stages of the reaction. The early precipitation of a hydrated phase is proposed as an intermediate phase before transformation into calcite. Thermodynamic modeling in conjunction with pH, surface potential measurements, and colloidal stability modeling demonstrate that calcite growth is dominated by agglomeration. This is in agreement with the cryogenic TEM observations, which suggest oriented attachment dominates early aggregation. The final stage of the reaction is described by a ripening mechanism that is significantly inhibited when high concentrations of polyacrylic acid (PAA) are used. The different concentrations of PAA lead to significant differences in the final particle substructure observed using cross section TEM. At low PAA concentrations, single crystal particles result, coherent with the proposed early oriented attachment mechanism and interfacial energy calculations. A core shell model is proposed for high PAA concentrations, whereas internal ripening of nanosized pores has been observed for low PAA concentrations, suggesting trapped solvent during the rapid initial particle formation at the relatively high supersaturations (S ) 30) investigated.

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