A kinetic and mechanistic study into the transformation of calcium sulfate hemihydrate to dihydrate.

The conversion of CaSO4·0.5H2O to CaSO4·2H2O is of great importance industrially, being the reaction behind plasterboard production and the setting of medical plasters. A detailed kinetic and mechanistic study of this process was conducted using time-resolved synchrotron X-ray diffraction in this work. The CaSO4·2H2O product is very similar regardless of whether the α- or ß-form of CaSO4·0.5H2O is used as the starting material, but the reaction process is very different. The induction time is usually shorter for α-CaSO4·0.5H2O than ß-CaSO4·0.5H2O, and a greater conversion percentage is observed with the former (although in neither case does the reaction proceed to 100% completion). The temperature of the system, widely used in industry as an indirect measure of the extent of the hydration process, is found to be a poor proxy for this, with the maximum temperature reached well before the reaction is complete. The Avrami-Erofe'ev and Gualtieri models could both be fitted to the experimental data, with the fits being substantially closer in the case of α-CaSO4·0.5H2O. The rate of reaction in the Avrami model tends to increase with the amount of gypsum seeds added to accelerate the process, and the importance of nucleation declines. The Gualtieri analysis suggested that the rate of nucleation increases substantially with the amount of seeds added, while there are less distinct changes in the rate of crystal growth. At low seed concentrations (<0.5% w/w) the rate of crystal growth is greater than the rate of nucleation, but at concentrations above 0.5% w/w nucleation is faster. These findings represent the first synchrotron study of the conversion of CaSO4·0.5H2O to CaSO4·2H2O, and will be of importance to gypsum producers globally.

Electrosprayed Particles Loaded with Kartogenin as a Potential Osteochondral Repair Implant.

The restoration of cartilage damage is a slow and not always successful process. Kartogenin (KGN) has significant potential in this space-it is able to induce the chondrogenic differentiation of stem cells and protect articular chondrocytes. In this work, a series of poly(lactic-co-glycolic acid) (PLGA)-based particles loaded with KGN were successfully electrosprayed. In this family of materials, PLGA was blended with a hydrophilic polymer (either polyethyleneglycol (PEG) or polyvinylpyrrolidone (PVP)) to control the release rate. Spherical particles with sizes in the range of 2.4-4.1 µm were fabricated. They were found to comprise amorphous solid dispersions, with high entrapment efficiencies of >93%. The various blends of polymers had a range of release profiles. The PLGA-KGN particles displayed the slowest release rate, and blending with PVP or PEG led to faster release profiles, with most systems giving a high burst release in the first 24 h. The range of release profiles observed offers the potential to provide a precisely tailored profile via preparing physical mixtures of the materials. The formulations are highly cytocompatible with primary human osteoblasts.

Nanomagnetite- and Nanotitania-Incorporated Polyacrylonitrile Nanofibers for Simultaneous Cd(II)- and As(V)-Ion Removal Applications.

This work reports the fabrication of nanomagnetite- and nanotitania-incorporated polyacrylonitrile nanofibers (MTPANs) by an electrospinning process, which has the potential to be used as a membrane material for the selective removal of Cd(II) and As(V) in water. The fiber morphology was characterized by scanning electron microscopy (SEM). The incorporation of nanomagnetite and nanotitania in the composite fiber matrix was confirmed by energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), and Fourier transform infrared (FT-IR) spectroscopy. The fibers doped with nanomagnetite and nanotitania (MPAN and TPAN fibers, respectively), as well as MTPAN and neat polycrylonitrile (PAN) fibers, after thermally stabilizing at 275 °C in air, were assessed for their comparative As(V)- and Cd(II)-ion removal capacities. The isotherm studies indicated that the highest adsorption of Cd(II) was shown by MTPAN, following the Langmuir model with a q m of 51.5 mg/m2. On the other hand, MPAN showed the highest As(V)adsorption capacity, following the Freundlich model with a K F of 0.49. The mechanism of adsorption of both Cd(II) and As(V) by fibers was found to be electrostatically driven, which was confirmed by correlating the point of zero charges (PZC) exhibited by fibers with the pH of maximum ion adsorptions. The As(V) adsorption on MPAN occurs by an inner-sphere mechanism, whereas Cd(II) adsorption on MTPAN is via both surface complexation and an As(V)-assisted inner-sphere mechanism. Even though the presence of coexistent cations, Ca(II) and Mg(II), has been shown to affect the Cd(II) removal by MTPAN, the MTPAN structure shows >50% removal efficiency even for minute concentrations (0.5 ppm) of Cd(II) in the presence of high common ion concentrations (10 ppm). Therefore, the novel polyacrylonitrile-based nanofiber material has the potential to be used in polymeric filter materials used in water purification to remove As(V) and Cd(II) simultaneously.