Abstract:The aims of this study were to investigate the feasibility of generating 3D structures directly in rapid-hardening Portland cement (RHPC) using 3D Printing (3DP) technology. 3DP is a Additive Layer Manufacturing (ALM) process that generates parts directly from CAD in a layer-wise manner. 3D structures were successfully printed using a polyvinylalcohol: RHPC ratio of 3:97 w/w, with print resolutions of better than 1mm. The test components demonstrated the manufacture of features, including off-axis holes, overhangs / undercuts etc that would not be manufacturable using simple mould tools. Samples hardened by 1 day postbuild immersion in water at RT offered Modulus of Rupture (MOR) values of up to 0.8±0.1MPa, and, after 26 days immersion in water at RT, offered MOR values of 2.2±0.2MPa, similar to bassanite-based materials more typically used in 3DP (1-3 MPa). Post-curing by water immersion restructured the structure, removing the layering typical of ALM processes, and infilling porosity.

This paper reports the effect of curing on the susceptibility of cementitious composites to carbonation using supercritical carbon dioxide. Samples made using a compression moulding technique were cured in water before and/or after carbonation and the effect on porosity, microstructure, solid phase assemblage and flexural strength was determined. In terms of development of mechanical strength, no benefit was gained from any period of pre-or post-carbonation curing regime. Yet samples cured prior to carbonation underwent minimal chemical reaction between supercritical carbon dioxide and calcium hydroxide, unhydrated cement or C-S-H. Thus there was no correlation between chemical degree of reaction and strength development. The effects responsible for the marked strength gain in supercritically carbonated samples must involve subtle changes in the microstructure of the C-S-H gel, not simple pore filling by calcium carbonate as is often postulated.

This work combined compression moulding with subsequent super-critical carbonation treatment (100 bar, 60°C, 24 h) to fabricate cement and/or lime based ceramic composites with various aggregates. Composites were examined using mechanical testing, XRD, He pycnometry and thin-section petrography. Composites with lime-only binders were significantly weaker than those with cement-lime binders regardless of the degree of carbonation. Flexural strengths in excess of 10 MPa were routinely achieved in large (>100 mm) specimens. Aggregate type (calcareous vs siliceous) had a significant effect on the microstructure and properties of the composites. Calcareous aggregates appear to augment the strength enhancement effected during super-critical carbonation by encouraging preferential precipitation of calcite at the binder-aggregate interface.

Structural ceramics were manufactured from industrial byproducts and lime by a compression moulding/vacuum dewatering technique. Treatment of these ceramics with supercritical carbon dioxide was found to both significantly increase their flexural strength and activate cementation in the industrial byproducts at least as efficiently as heat curing. Flexural strengths of up to 10 MPa were achieved. Strength improvements were associated with decreased porosity and conversion of calcium hydroxide to calcium carbonate. Life cycle assessment of proposed products made from such materials indicated that the total reduction in embodied carbon dioxide achieved, as a result of combining use of byproducts with recombination of carbon dioxide, was up to 70%.