Citric Acid as a Set Retarder for Calcium Aluminate Phosphate Cements

Citric acid added as set retarder significantly contributed to enhancing the setting temperature and to extending the thickening time of a calcium aluminate phosphate (CaP) geothermal cement slurry consisting of calcium aluminate cement (CAC) as the base reactant and sodium polyphosphate (NaP) solution as the acid reactant. The set-retarding activity of citric acid was due to the uptake of Ca2' ions from the CAC by carboxylic acid groups within the citric acid. This uptake led to the precipitation of a Ca-complexed carboxylate compound as a set-retarding barrier layer on the CAC grains' surfaces. However, this barrier layer was vulnerable to disintegration by the attack of free Ca2' ions from CAC, and also to degradation at elevated temperature, thereby promoting the generation of exothermic energy from acid-base reactions between the CAC and NaP after the barrier was broken. The exothermic reaction energy that was promoted in this way minimized the loss in strength of the citric acid-retarded cement. The phase composition assembled in both retarded and non-retarded cements after autoclaving at 180°C encompassed three reaction products, hydroxyapatite (HOAp), hydrogrossular and boehmite, which are responsible for strengthening the autoclaved cement. The first two reaction products were susceptible to reactions with sulhric acid and sodium sulfate to form crystalline bassanite scale as the corrosion product. The boehmite phase possessed a great resistance to acid and sulfate. Although the bassanite scales clinging to the cement's surfaces were the major factor governing the loss in weight, they served in protecting the cement from hrther acidand sulfate-corrosion until their spallation eventually occured. Nevertheless, the repetitive processes of HOAp and hydorgrossular -+ bassanite -+ spallation played an important role in extending the usehl lifetime of CaP cement in a low pH environment at 180OC.