Effects of ZnO addition on thermal properties, degradation and biocompatibility of P45Mg24Ca16Na(15−x)Znx glasses

Four phosphate-based glass formulations in the system P45Mg24Ca16Na(15-x)Znx, referred to as P45Znx (x = 0, 5, 10 and 15 mol%), were prepared using a melt quenching process. The effect of ZnO addition on density, molar volume, thermal properties and degradation rates were studied. An increase in the glass transition, crystallisation, melting and liquidus temperatures were seen when replacing Na2O with ZnO. The molar volume of the bulk glasses was seen to decrease with increasing ZnO content. The dissolution rate of the zinc-free glass was 2.48 × 10-8 kg m-2 s-1 and addition of 5 mol% ZnO resulted in a reduction of the dissolution rate to 1.68 × 10-8 kg m-2 s-1. However, further addition of ZnO from 5 mol% to 15 mol% increased the dissolution rate of the glass system. The glasses were deliberately crystallised and XRD studies identified the Z n2P2O7 phase for glass code P45Zn5, and Zn(PO3)2 phase for P45Zn10 and P45Zn15 glasses. Cyto-compatibility studies were conducted using MG63 cells for 14 days. An overall increase in the metabolic activity and DNA concentration of cells was seen from day 1 to day 14 for all glass formulations investigated. However, increasing ZnO content from 0 to 15 mol% seemed to have a negative effect on the cellular activity. Interestingly, a remarkably higher ALP activity was seen at day 14 for glass codes P45Zn5 and P45Zn10 in comparison with the TCP control and the P45Zn0 glass

Effects of modifier additions on the thermal properties, chemical durability, oxidation state and structure of iron phosphate glasses

Modified iron phosphate glasses have been prepared with nominal molar compositions [(1�x)�(0.6P2O5– 0.4Fe2O3)]�xRySO4, where x = 0–0.5 in increments of 0.1 and R = Li, Na, K, Mg, Ca, Ba, or Pb and y = 1 or 2. In most cases the vast majority or all of the sulfate volatalizes and quarternary P2O5–Fe2O3–FeO–RyOz glasses or partially crystalline materials are formed. Here we have characterized the structure, thermal properties, chemical durability and redox state of these materials. Raman spectroscopy indicates that increasing modifier oxide additions result in depolymerization of the phosphate network such that the average value of i, the number of bridging oxygens per –(PO4)– tetrahedron, and expressed as Qi, decreases. Differences have been observed between the structural effects of different modifier types but these are secondary to the amount of modifier added. Alkali additions have little effect on density; slightly increasing Tg and Td; increasing a and Tliq; and promoting bulk crystallization at temperatures of 600–700 �C. Additions of divalent cations increase density, a, Tg, Td, Tliq and promote bulk crystallization at temperatures of 700–800 �C. Overall the addition of divalent cations has a less deleterious effect on glass stability than alkali additions. 57Fe Mössbauer spectroscopy confirms that iron is present as Fe2+ and Fe3+ ions which primarily occupy distorted octahedral sites. This is consistent with accepted structural models for iron phosphate glasses. The iron redox ratio, Fe2+/RFe, has a value of 0.13–0.29 for the glasses studied. The base glass exhibits a very low aqueous leach rate when measured by Product Consistency Test B, a standard durability test for nuclear waste glasses. The addition of high quantities of alkali oxide (30–40 mol% R2O) to the base glass increases leach rates, but only to levels comparable with those measured for a commercial soda-lime-silica glass and for a surrogate nuclear waste-loaded borosilicate glass. Divalent cation additions decrease aqueous leach rates and large additions (30–50 mol% RO) provide exceptionally low leach rates that are 2–3 orders of magnitude lower than have been measured for the surrogate waste-loaded borosilicate glass. The P2O5–Fe2O3–FeO–BaO glasses reported here show particular promise as they are ultra-durable, thermally stable, low-melting glasses with a large glass-forming compositional range

Structural and thermochemical properties of sodium magnesium phosphate glasses

Ternary phosphate based glasses with the general formula (50−x/2)Na2O–xMgO–(50−x/2)P2O5 (0 ⩽ x ⩽ 42.8 mol%), where the O/P ratio was varied from 3 to 3.75, have been prepared using a conventional melt quenching technique. Samples were investigated by means of density measurements, Fourier-transformed infrared (FTIR), Raman and 31P solid state magic angle spinning nuclear magnetic resonance (MAS-NMR) spectroscopies, differential scanning calorimetry (DSC), inductively coupled plasma atomic emission spectroscopy (ICP/AES) analysis and calorimetric dissolution.The depolymerization of metaphosphate chains are described by the decrease of Q2 tetrahedral sites allowing the formation of pyrophosphate groups (Q1) revealed by spectroscopic investigations. As a result, the increase of density and glass transition temperature when x rises. Calorimetric study shows that the dissolution phenomenon is endothermic for a lower MgO content and becomes exothermic when magnesium oxide is gradually incorporated, suggesting the disruption of phosphate chains with increasing O/P ratio