Abstract

Porous tablets of crystalline calcium carbonate were formed upon sintering of a precursor powder of amorphous calcium carbonate (ACC) under compressive stress (20 MPa) at relatively low temperatures (120–400 °C), induced by pulsed direct currents. Infrared spectroscopy ascertained the amorphous nature of the precursor powders. At temperatures of 120–350 °C and rates of temperature increase of 20–100 °C min−1, the nanoparticles of ACC transformed into crystallites of mainly aragonite, which is generally difficult to achieve using wet-chemicals under kinetic control. The amorphous precursor particles (∼10 nm) transformed into crystallites (∼30–50 nm) during sintering. Consistently, the specific surface areas of 140–160 m2 g−1 for the precursor particles were reduced to 10–20 m2 g−1 for the porous tablets. The porous network within the tablets consisted of fused aragonite and vaterite particles in a ratio of ∼80 : 20. The fraction of aragonite to vaterite was invariant to the temperature and rate of temperature change used. The particle size increased only to a small amount on an increased rate of temperature change. At temperatures above 400 °C, porous tablets of calcite formed. The later transformation was under thermodynamic control, and led to a minor reduction of the specific surface area. The size of the crystallites remained small and the transformation to calcite appeared to be a solid-state transformation. Porous, template- and binder-free tablets of calcium carbonate could find applications in for example, biology or water treatment.

Highlights

  • Porous calcium carbonates are used as fillers in paper,[1] and are studied for applications in tooth paste[2] and as a substrate for the controlled delivery of drugs.[3]

  • Porous powders are seldom useful in practical applications as such, and they often need to be assembled into macroscopic shapes designed for a particular application

  • We extended the protocol of Gebauer et al.[23] to be able to synthesize large enough quantities of amorphous calcium carbonate (ACC)

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Summary

Introduction

Sintering commercial powders of calcium carbonate at high temperatures.[10] These membranes had large pores (.500 nm) and porosities of 30–40%. We show that nanoparticles of ACC obtained in this manner can be used as precursors to monolithic tablets of porous and crystalline calcium carbonate by using compressive stress (20 MPa) and a moderate temperature (120 uC–400 uC), induced by pulsed direct currents in a sintering device. An equimolar amount of sodium carbonate was dissolved in 50 ml of water (0.5–2.5 mmol; Sigma Aldrich, CAS number: 497-19-8) This aqueous solution was quickly added to the ethanol-rich solution described above. Powders of ACC were subjected to a compressive stress of 20 MPa and pulsed direct currents that rapidly raised the temperature using a sintering device (Dr Sinter 2050, Sumitomo Coal Mining Co., Tokyo, Japan). Specific surface areas were evaluated in the model of Brunauer, Emmett and Teller (BET) using the adsorbed amount of N2 at relative pressures of 0.06–0.3

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