Ultrasonic reactivation of phosphonate poisoned calcite during crystal growth

The effect of ultrasonic irradiation (42,150 Hz, 17 W dm−3/7.1 W cm−2) on the growth of calcite in the presence of the inhibitor nitrilotris(methylene phosphonic acid) (NTMP) was investigated at constant composition conditions. In seeded growth experiments, it was found that the inhibiting effect of NTMP on crystal growth could be seriously mitigated under influence of ultrasonic irradiation. An approximately twofold increase in volumetric growth rate was achieved during ultrasonic irradiation, and recovery of the growth rate following inhibition was strongly enhanced compared to growth experiments without ultrasonic irradiation. The results could be explained in part by the physical effect of ultrasound that causes breakage and attrition of poisoned crystals, which resulted in an increase in fresh surface area. Mass spectroscopy analysis of sonicated NTMP solutions revealed that there is also a chemical effect of ultrasound that plays an important role. Several breakdown products were identified, which showed that ultrasound caused the progressive loss of phosphonate groups from NTMP, probably by means of physicochemically generated free radicals and/or pyrolysis in the hot bubble–bulk interface.

► Ultrasonic reactivation of phosphonate poisoned calcite crystals was investigated.
► The inhibiting effect of phosphonate NTMP is strongly mitigated by ultrasound.
► Crystal breakage/attrition and NTMP degradation were identified as primary mechanisms.