Papers by Author: Stuart Hampshire

Abstract: Oxynitride glasses are effectively alumino-silicate glasses in which nitrogen substitutes for oxygen in the glass network, resulting in increases in glass transition and softening temperatures, viscosities (by two to three orders of magnitude), elastic moduli and microhardness. Calcium alumino-silicate glasses containing fluorine are known to have useful characteristics as potential bioactive materials. Therefore, the combination of both nitrogen and fluorine additions to these glasses may give useful bioglasses with enhanced mechanical stability. This paper gives a review of oxynitride glasses and reports glass formation and evaluation of glass properties in the Ca-Si-Al-O-N-F system. Within the previously defined glass forming region in the Ca-Si-Al-O-N system, homogeneous, dense glasses are formed. However, addition of fluorine affects glass formation and reactivity of the glass melts and can lead to fluorine loss as SiF4, but also nitrogen loss, and cause bubble formation. At high fluorine and high Ca contents under conditions when Ca- F bonding is favoured, CaF2 crystals precipitate in the glass. It was found that fluorine expands the glass forming region of Ca-Sialon system and facilitates the solution of nitrogen into the melt.

Abstract: Five-component B-phase may be readily formed through the nucleation and crystallisation heat treatment of nitrogen-rich parent glasses with composition (e/o) 35R:45Si:20Al:83O:17N. This paper is focussed on the B-phase structure where R stands for ytterbium, erbium or yttrium. Fine probe EDX analysis in the TEM has shown that the lenticular B-phase crystals take up a substantial range of composition and that the element R is always clearly anti-correlated with silicon. A larger R3+ cation radius moves the B-phase composition range to lower R contents, and as a consequence of the anti-correlation with silicon, the silicon solid solution range goes to higher values. The EDX results lend support to a B-phase structure consisting of two-dimensional network of randomly linked (Si,Al)(O,N)4 tetrahedra between layers of R3+ cations. It is suggested that, in addition to the random substitution of silicon by aluminium in the (Si,Al)(O,N)4 tetrahedra, a locally increased density in the bi-dimensional network of randomly oriented tetrahedra is associated with an increased density of vacancies in the R3+ cation lattice.

Abstract: Oxynitirde glasses are found at triple point junctions and as intergranular films in silicon nitride based ceramics. The glass chemistry, particularly the content of modifyer,usually Y or a rare earth (RE) ion, and the volume fractions of these oxynitride glass phases within the ceramic control the properties of silicon nitride, in particular, creep at high temperature. It is known that, as nitrogen substitutes for oxygen in silicate and aluminosilicate glass networks, increases are observed in glass transition and softening temperatures, viscosities (by two to three orders of magnitude), elastic moduli and microhardness. If changes are made to the RE:Si:Al ratios or different rare earth cation are substituted, properties such as viscosity can be increased by a further two to three orders of magnitude. These effects have implications for the high temperature properties of silicon nitride based ceramics, especially creep resistance. This paper provides an overview of oxynitride glasses and outlines the effect of composition on properties such as glass transition temperature and viscosity and discusses the effects on high temperature behaviour of silicon nitride ceramics.

Abstract: In this work partially and fully densified silicon nitride based composites have been prepared using carbon black and graphite additions. Alumina and yttria sintering additives were also added to silicon nitride starting powders. Sinter-HIP and pressure-less sintering (PLS) have been employed for composite processing. The effects of carbon nano- and micro-grains on the microstructure, bending strength and hardness have been investigated. Higher strengths could be achieved by HIP, whereas more homogeneous properties can be assured by PLS.

Abstract: Y-SiAlON glasses of composition 36.5 Y: 42.3 Si: 21.2 Al with different amounts of N (0, 5, 8, 15 and 22 in e/o) were produced by melting appropriate mixtures of powders under flowing nitrogen at 1715°C. This composition is known to give B-phase (Y2SiAlO5N) on crystallisation at temperatures below 1050°C. In this work, the effect of nitrogen in the starting glass composition on the crystalline phases formed is discussed. High temperature in-situ XRD analysis was performed on powdered glass samples up to 1150°C by using a Philips X’pert PRO MPD (Multi Purpose Diffractometer) with a HTK1200 Oven Camera (Anton Paar, Austria). As expected, the results show that different nitrogen contents affect the crystalline phases formed. In all glasses, yttrium apatite silicate forms first, followed by crystallisation of B-phase. The phase transformation from B-phase to Iw-phase (Y3Si2Al[O,N10] i.e. 10 e/o N) takes place at relatively low temperatures (1050°C) for the lower nitrogen containing samples (5 and 8 e/o), whereas, the transformation does not take place for the glasses with higher nitrogen contents even at the maximum temperature studied (1150°C). This work also confirms that there is a correlation between the temperature where the first crystals appear and the amount of nitrogen in the starting glass.

Abstract: M-Si-Al-O-N glasses (where M = Y or rare earth cation) are intergranular phases in silicon nitride based ceramics in which the composition and volume fraction of these oxynitride glass phases determine the properties of the material, in particular, high temperature mechanical behaviour. Investigations on oxynitride glass formation and properties have shown that nitrogen increases the glass transition and softening temperatures, viscosity, elastic modulus and hardness. By changing the cation ratios or the type of rare earth cation incorporated, properties such as viscosity can be increased further. This paper provides an overview of oxynitride glasses and outlines the effect of composition on properties such as glass transition temperature and viscosity. These effects have important implications for silicon nitride based ceramics where amorphous intergranular films control high temperature properties such as creep resistance.