NMR T1 relaxation time measurements and calculations with translational and rotational components for liquid electrolytes containing LiBF4 and propylene carbonate.

Longitudinal relaxation (T1) measurements of (19)F, (7)Li, and (1)H in propylene carbonate/LiBF4 liquid electrolytes are reported. Comparison of T1 values with those for the transverse relaxation time (T2) confirm that the measurements are in the high temperature (low correlation time) limit of the T1 minimum. Using data from pulsed field gradient measurements of self-diffusion coefficients and measurements of solution viscosity measured elsewhere, it is concluded that although in general there are contributions to T1 from both translational and rotational motions. For the lithium ions, this is mainly translational, and for the fluorine ions mainly rotational.

A comparison of the wear and physical properties of silane cross-linked polyethylene and ultra-high molecular weight polyethylene.

Cross-linked polyethylenes are being introduced widely in acetabular cups in hip prostheses as a strategy to reduce the incidence of wear debris-induced osteolysis. It will be many years before substantial clinical data can be collected on the wear of these new materials. Silane cross-linked polyethylene (XLPE) was introduced into clinical practice in a limited series of acetabular cups in 1986 articulating against 22.225-mm alumina ceramic femoral heads and showed reduced wear rates compared with conventionally sterilized (gamma irradiation in air) ultra-high molecular weight polyethylene (UHMWPE). We compared the wear of XLPE manufactured in 1986 with the wear of UHMWPE manufactured in 1986 in nonirradiated and irradiated forms. In the nonirradiated forms, the wear of XLPE was 3 times less than UHWMPE when articulating against smooth counterfaces. The nonirradiated materials did not show signs of oxidation. In the irradiated forms, only UHMWPE showed high levels of oxidation, and this caused a substantial increase in wear. Antioxidants added to XLPE during processing gave resistance to oxidative degradation. When sliding against scratched counterfaces, the wear of UHMWPE increased by a factor of 2 to 3 times. Against the same scratched counterfaces, the wear of XLPE increased dramatically by 30 to 200 times. This difference may be attributed to the reduction in toughness of XLPE. Clinically, XLPE has been articulated against damage-resistant ceramic heads, and this probably has been an important factor in contributing to reduced wear. New cross-linked polyethylenes differ considerably from XLPE. This study indicates that it is prudent to examine the wear of new polyethylenes under a range of conditions that may occur in vivo.

A depth profile of oxidation and gel fraction in gamma-irradiated silane crosslinked and ultra high molecular weight polyethylenes.

The depth profile of oxidation index and gel fraction has been measured for two silane crosslinked poly(ethylene) (SXLPE) acetabular cups (one gamma irradiated in air, and one non-irradiated, both with a shelf-life of 13 years) and for two UHMWPE components (one gamma irradiated in air and one non-irradiated, with shelf-lives of 13 and 7 years, respectively). Only the irradiated UHMWPE exhibited any variation in these properties with depth. The oxidation profile (maximum 1 mm below surface) has been explained to result from reduced levels of diffused oxygen with depth, giving rise to a balance of alkyl and peroxyl radicals (and hence maximum carbonyl production) just below the surface. The gel fraction profile (maximum 4 mm below surface) is also attributed to the lower levels of diffused oxygen with depth, causing crosslinking to dominate in the bulk and chain scission to dominate at the surface. The resistance to oxidative degradation in the non-irradiated SXLPE was attributed to the use of antioxidants in the polymer processing.