A decade of silicone hydrogel development:surface properties, mechanical properties, and ocular compatibility

Since the initial launch of silicone hydrogel lenses, there has been a considerable broadening in the range of available commercial material properties. The very mobile silicon–oxygen bonds convey distinctive surface and mechanical properties on silicone hydrogels, in which advantages of enhanced oxygen permeability, reduced protein deposition, and modest frictional interaction are balanced by increased lipid and elastic response. There are now some 15 silicone hydrogel material variants available to practitioners; arguably, the changes that have taken place have been strongly influenced by feedback based on clinical experience. Water content is one of the most influential properties, and the decade has seen a progressive rise from lotrafilcon-A (24%) to efrofilcon-A (74%). Moduli have decreased over the same period from 1.4 to 0.3 MPa, but not solely as a result of changes in water content. Surface properties do not correlate directly with water content, and ingenious approaches have been used to achieve desirable improvements (e.g., greater lubricity and lower contact angle hysteresis). This is demonstrated by comparing the hysteresis value of the earliest (lotrafilcon-A, >40°) and most recent (delefilcon-A, <10°) coated silicone hydrogels. Although wettability is important, it is not of itself a good predictor of ocular response because this involves a much wider range of physicochemical and biochemical factors. The interference of the lens with ocular dynamics is complex leading separately to tissue–material interactions involving anterior and posterior lens surfaces. The biochemical consequences of these interactions may hold the key to a greater understanding of ocular incompatibility and end of day discomfort.

Microsegregation in nodular cast iron and its effect on mechanical properties

A review of the literature pertaining to the mechanical properties, solidification and segregation effects in nodular cast iron has been made. A series of investigations concerning the influence of microsegregation on mechanical properties of :pearlitic, ferritic and austenitic nodular cast iron have then been reported. The influence of section size on the tensile and impact properties of cornmercial purity and refined ferritic nodular cast iron has been studied. It has been shown. that an increase in section caused a decrease in impact transition temperature of the commercial purity material without greatly affecting the impact transition temperature of the purer material. This effect has been related to increased amounts of segregation effects such as cell boundary carbides in heavier sections of the commercial purity material. Microsegregation studies on the materials used in this thesis have been carried out using an electron probe microanalyser. This technique has shown that concentrations of chromium and manganese and depletions of nickel and silicon occurred at eutectic cell boundaries in nodular cast iron and were often associated with brittle carbides in these areas. These effects have been shown to be more prevalent in heavier sections. The nature of segregation during the solidification of nodular cast iron has been studied by quenching samples of nodular iron during the solidification process. Micro-analysis of such samples has shown that segregation of manganese and chromium occurs by a gradual build-up of these elements at the solid/liquid interface. The microstructures of the quenched specimens revealed carbide filaments connecting graphite nodules and areas of quenched liquid. These filaments have been used as evidence for a revised hypothesis for the solidification of nodular cast iron by a liquid diffusion mechanism. A similar series of experiments has been carried out on two high nickel austenitic irons containing 0.5 per cent manganese and 4 per cent manganese respectively. In both these materials a decrease in elongation was experienced with increasing section. This effect was more drastic in the 4 per cent manganese material which also contained much greater amounts of cell boundary carbide in heavy sections. Micro-analysis of samples of the 4 per cent manganese material quenched during solidification revealed that manganese concentrated in the liquid and that nickel concentrated in the solid during solidification. No segregation of silicon occurred in this material. Carbide filaments appeared in the microstructures of these specimens. A discussion of all the above effects in terms of current concepts is included.

The relationship between mechanical properties, preffered orientation and press forming behaviour of copper and 70/30 brass

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An examination of the production, heat treatment and mechanical properties of a new wrought magnesium alloy containing 6% Zn. and 1.2% Mn.

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Three-dimensional finite element analysis of the effects of anisotropy on bone mechanical properties measured by nanoindentation

A three-dimensional finite element analysis (FEA) model with elastic-plastic anisotropy was built to investigate the effects of anisotropy on nanoindentation measurements for cortical bone. The FEA model has demonstrated a capability to capture the cortical bone material response under the indentation process. By comparison with the contact area obtained from monitoring the contact profile in FEA simulations, the Oliver-Pharr method was found to underpredict or overpredict the contact area due to the effects of anisotropy. The amount of error (less than 10% for cortical bone) depended on the indentation orientation. The indentation modulus results obtained from FEA simulations at different surface orientations showed a trend similar to experimental results and were also similar to moduli calculated from a mathematical model. The Oliver-Pharr method has been shown to be useful for providing first-order approximations in the analysis of anisotropic mechanical properties of cortical bone, although the indentation modulus is influenced by anisotropy.

Exploring thermal and mechanical properties of selected transition elements under extreme conditions: Experiments at high pressures and high temperatures

Transition metals (Ti, Zr, Hf, Mo, W, V, Nb, Ta, Pd, Pt, Cu, Ag, and Au) are essential building units of many materials and have important industrial applications. Therefore, it is important to understand their thermal and physical behavior when they are subjected to extreme conditions of pressure and temperature. This dissertation presents: • An improved experimental technique to use lasers for the measurement of thermal conductivity of materials under conditions of very high pressure (P, up to 50 GPa) and temperature (T up to 2500 K). • An experimental study of the phase relationship and physical properties of selected transition metals, which revealed new and unexpected physical effects of thermal conductivity in Zr, and Hf under high P-T. • New phase diagrams created for Hf, Ti and Zr from experimental data. • P-T dependence of the lattice parameters in α-hafnium. Contrary to prior reports, the α-ω phase transition in hafnium has a negative dT/dP slope. • New data on thermodynamic and physical properties of several transition metals and their respective high P-T phase diagrams. • First complete thermodynamic database for solid phases of 13 common transition metals was created. This database has: All the thermochemical data on these elements in their standard state (mostly available and compiled); All the equations of state (EoS) formulated from pressure-volume-temperature data (measured as a part of this study and from literature); Complete thermodynamic data for selected elements from standard to extreme conditions. The thermodynamic database provided by this study can be used with available thermodynamic software to calculate all thermophysical properties and phase diagrams at high P-T conditions. For readers who do not have access to this software, tabulated values of all thermodynamic and volume data for the 13 metals at high P-T are included in the APPENDIX. In the APPENDIX, a description of several other high-pressure studies of selected oxide systems is also included. Thermophysical properties (Cp, H, S, G) of the high P-T ω-phase of Ti, Zr and Hf were determined during the optimization of the EoS parameters and are presented in this study for the first time. These results should have important implications in understanding hexagonal-close-packed to simple-hexagonal phase transitions in transition metals and other materials.

Mechanical properties and cellular response of novel electrospun nanofibers for ligament tissue engineering: Effects of orientation and geometry

Electrospun nanofibers are a promising material for ligamentous tissue engineering, however weak mechanical properties of fibers to date have limited their clinical usage. The goal of this work was to modify electrospun nanofibers to create a robust structure that mimics the complex hierarchy of native tendons and ligaments. The scaffolds that were fabricated in this study consisted of either random or aligned nanofibers in flat sheets or rolled nanofiber bundles that mimic the size scale of fascicle units in primarily tensile load bearing soft musculoskeletal tissues. Altering nanofiber orientation and geometry significantly affected mechanical properties; most notably aligned nanofiber sheets had the greatest modulus; 125% higher than that of random nanofiber sheets; and 45% higher than aligned nanofiber bundles. Modifying aligned nanofiber sheets to form aligned nanofiber bundles also resulted in approximately 107% higher yield stresses and 140% higher yield strains. The mechanical properties of aligned nanofiber bundles were in the range of the mechanical properties of the native ACL: modulus=158±32MPa, yield stress=57±23MPa and yield strain=0.38±0.08. Adipose derived stem cells cultured on all surfaces remained viable and proliferated extensively over a 7 day culture period and cells elongated on nanofiber bundles. The results of the study suggest that aligned nanofiber bundles may be useful for ligament and tendon tissue engineering based on their mechanical properties and ability to support cell adhesion, proliferation, and elongation.

Evaluation of mechanical properties and water vapor permeability in Chitosan biofilms using Sorbitol and Glycerol

Chitosan biofilms were prepared with and without plasticizer (glycerol and sorbitol). The physical and mechanical properties of chitosan biofilms with and without plasticizer were evaluated. Chitosan was obtained from shrimp wastes and characterized. The film forming solution (FFS) was obtained through chitosan dissolution and drying. The solution had its pH adjusted to 6.0 and oven dried (40 8C, 24 h) with forced air circulation. Chitosan biofilms without plasticizer showed a tensile strength about 36% higher than biofilms produced with plasticizer. On the other hand, biofilms with plasticizer presented superior values of elongation. The permeability of the water vapor and color presented significant difference (p<0.05) between all biofilms. Chitosan/plasticizer biofilms showed higher values of water vapor permeability in relation to chitosan biofilms without plasticizer.