Mechanical properties of oxynitride glasses

Oxynitride glasses combine a high refractoriness, with Tg typically >850°C, and remarkable mechanical properties in comparison with their parent oxide glasses. Their Young's modulus and fracture toughness reach 170 GPa and 1.4 MPa m^.5, respectively. Most reports show good linear relationships between glass property values and nitrogen content. There is a clear linear dependence of Young's modulus and microhardness on fractional glass compactness (atomic packing density). They also have a better resistance to surface damage induced by indentation or scratch loading. The improvements stem from the increase of the atomic network cross-linking—because of three-fold coordinated nitrogen—and of the atomic packing density, despite nitrogen being lighter than oxygen and the Si–N bond being weaker than the Si–O bond. For constant cation composition, viscosity increases by ∼3 orders of magnitude as ∼17 eq.% oxygen is replaced by nitrogen. For rare earth oxynitride glasses with constant N content, viscosity, Young's modulus, Tg, and other properties increase with increasing cation field strength (decreasing ionic radius). Research continues to find lighter, stiffer materials, including glasses, with superior mechanical properties. With higher elastic moduli, hardness, fracture toughness, strength, surface damage resistance, increased high temperature properties, oxynitride glasses offer advantages over their oxide counterparts.     

Grain boundary glasses in silicon nitride: A review of chemistry,properties and crystallisation

Silicon nitride for engineering applications is densified by liquid phase sintering using oxide additives such as yttria and alumina. The oxynitride liquid remains as an intergranular glass. This paper provides a review of microstructural development in silicon nitride, grain boundary oxynitride glasses and effects of chemistry on properties. Nitrogen increases T_g, viscosities, elastic moduli and microhardness. These property changes are compared with known effects of grain boundary glass chemistry in silicon nitride ceramics where significant improvements in fracture resistance of silicon nitride can be achieved by tailoring the intergranular glass chemistry.Crystallisation of the grain boundary Y–Si–Al–O–N glass phase can improve properties. Nucleation and crystallisation of a Y–Si–Al–O–N glass, similar to that found in grain boundaries of silicon nitride densified with yttria and alumina, can be optimised to form different Y-disilicate polymorphs at different temperatures. One solution to provide a single disilicate phase over a range of temperatures is discussed.     

Origins of colour in Yb–Si–Al–O–N glasses

Previous work has shown that some RE-Si–Al–O–N glasses are coloured. In particular, oxynitride glasses containing Ytterbium were observed to display a wide range of colours depending on their composition. The reasons for this were not immediately evident. As Ytterbium and Europium have been reported to display valency variations in silicate glasses and α-sialons, the current study prepared a range of Yb–Si–Al–O–N glasses, characterised them by means of X-ray photoelectron, Raman, FTIR and UV–vis spectroscopy as well as thermal analysis and X-ray diffraction. The correlation between the structural features of the glasses with the changes in colour occurring when varying the Yb:Al ratio were investigated. Ytterbium garnet was found to be the source of colour change in the Yb–Si–Al–O–N in the compositions studied.     

The influence of the mixed alkaline earth effect on the structure and properties of (Ca,Mg)–Si–Al–O–N glasses

Alkaline earth oxynitride glasses of (Ca, Mg)–Si–Al–O–N with different CaO/(CaO + MgO) molar ratios (0, 0.25, 0.5, 0.75, and 1) were successfully prepared using the sol-gel method, and their structural compositions were characterised by Raman and FT-IR techniques. The glass dynamic properties of thermal expansion coefficient, glass transition temperature (T_g), and static properties of density, molar volume, Vickers hardness and compressive strength were systematically measured and analysed. The results showed that the static properties exhibited an overall regular change as the CaO/(CaO + MgO) ratio gradually increased, while the dynamic properties had an obvious mixed alkaline earth effect, which represented the appearance of an extreme value point in CaO/(CaO + MgO) mole ratios of 0.25 and 0.75, respectively. The typical thermal expansion coefficient and T_g of mixed alkaline earth oxynitride glasses deviated far from the linear connection between single alkaline earth oxynitride glasses. Raman spectra and infrared spectra revealed that the ratio value of the Q³/(Q²+Q⁴) decreased (Qⁿ: n = no. of bridging anions joining SiO₄ tetrahedra) in the mixed alkaline earth oxynitride glasses with increasing the amount of Ca, confirming that Ca decreased the crosslinking between individual tetrahedra via the transformation of Q³ species into Q² and Q⁴ species.     

Remote hydrogen microwave plasma chemical vapor deposition of silicon carbonitride films from a (dimethylamino)dimethylsilane precursor: Compositional and structural dependencies of film properties

The physical, optical, and mechanical properties of amorphous hydrogenated silicon carbonitride (a-Si:C:N:H) films produced by the remote hydrogen plasma chemical vapor deposition (RP-CVD) from (dimethylamino)dimethylsilane have been investigated in relation to their chemical composition and structure. The films deposited at different substrate temperature (30–400 °C) were characterized in terms of their density, refractive index, adhesion to a substrate, hardness, elastic modulus, friction coefficient, and resistance to wear predicted from the “plasticity index” values. The correlations between the film compositional parameters, expressed by the atomic concentration ratios N/Si and C/Si, as well as structural parameters described by the relative integrated intensities of the absorption IR bands from the Si–N, Si–C, and C–N bonds, and the XPS Si2p band from the Si–C bonds (controlled by substrate temperature) were investigated. On the basis of the results of these studies, reasonable compositional and structural dependencies of film properties have been determined.     

Oxynitride Glasses

Oxynitride glasses are grain boundary phases within silicon nitride ceramics. The desire to understand their nature led to various investigations on oxynitride glass formation, structure, properties, and crystallization. This paper provides a review of oxynitride glasses and outlines the effect of glass chemistry, including nitrogen contents and cation ratios, on properties such as glass transition temperature, Young's modulus, and viscosity and relates this to structural features within the glass. A short outline of crystallization of oxynitride glasses to form glass–ceramics is presented.     

Composition–structure–property relationships of transparent Ca–Al–Si–O–N oxynitride glasses: The roles of nitrogen and aluminum

We explore the formation and composition–structure–property correlations of transparent Ca–Al–Si–O–N glasses, which were prepared by a standard melt-quenching technique using AlN as the nitrogen source and incorporating up to 8 at.% of N. Their measured physical properties of density, molar volume, compactness, refractive index, and hardness—along with the Young, shear, and bulk elastic moduli—depended roughly linearly on the N content. These effects are attributed primarily to the improved glass-network cross-linking from N compared to O, rather than the formation of higher-coordination AlO₅ and AlO₆ groups, where ²⁷Al magic-angle-spinning nuclear magnetic resonance experimentation revealed that aluminum is predominately present in tetrahedral coordination as AlO₄ units. Yet, several physical properties, such as the refractive index along with the bulk, shear, and Young's elastic moduli, increase concomitantly with the Al content of the glass. We discuss the incompletely understood mechanical–property boosting role of Al as observed both herein and in previous reports on oxynitride glasses, moreover suggesting glass-composition domains that are likely to offer optimal mechanical properties.     

Dissolution,bioactivity behavior,and cytotoxicity of rare earth-containing bioactive glasses (RE = Gd,Yb)

Rare earth-containing bioactive glasses (RE-BGs) have been poorly explored in the biomaterials field, although RE has optical, nuclear, and magnetic properties that could be used in different biomedical applications. In order to verify whether these glasses can be promising as biomaterials, we studied the dissolution, bioactivity, and cytotoxicity of RE-BGs based on the SiO₂–Na₂O–CaO–P₂O₅–RE₂O₃ (RE = Gd, Yb) system. The glasses were obtained by melting-quenching and their particle size was determined by laser diffraction. Their dissolution behavior was studied in Tris-HCl, while bioactivity was performed in simulated body fluid solution under physiological conditions during several periods. The cytotoxicity test was performed using glass-derived conditioned medium and mesenchymal stem cell derived from deciduous teeth. The dissolution results showed that the glasses dissolved under two different kinetics, which are lower for rare earth-containing glasses, due to the more covalent character of Si–O–RE bonds. The bioactivity results evidenced that all glasses showed bioactivity after 24 hours. However, gadolinium and ytterbium promoted a more calcium phosphate deposition, which contrasts with the slower dissolution kinetics of rare earth-containing glasses. All the glasses were considered biocompatible, showing cell viability higher than 80%. The overall results showed that RE-BGs are promising materials for applications that require bioactivity and/or biocompatibility.     

Synthesis of bulk silicon oxynitride glass through nitridation of SiO2 aerogels and determination of Tg

The development of transparent glass for use in high-temperature applications is continuing. In this study, we synthesized bulk silicon oxynitride glasses (a-Si(O,N)_x) through the nitridation of SiO₂ aerogels containing methyl (CH₃-) groups and evaluated their bulk properties, including their glass transition temperature (T_g). Tetramethyl orthosilicate and methyltrimethoxysilane were added into the precursor gels, and those gels were subjected to a supercritical CO₂ drying process. The presence of CH₃-group in the gel avoided cracking during ammonolysis at 750°C–1400°C, and the transparency of the gel was remained even after ammonolysis at 1300°C. The ammonolysis successfully introduced nitrogen into the gels even at relatively low temperatures, for example, 750°C, and the highest nitrogen content (11.7 mass%) was achieved in the gel after ammonolysis at 1300°C. As the nitrogen-related signals in electron spectroscopy indicated presence of nitride ions (N³⁻) after ammonolysis and the infrared absorption signals attributed to Si–N bonds were enhanced with the increase of nitrogen concentration, we successfully obtained oxynitride glasses. Those oxynitride glasses showed increase of T_g with their nitrogen concentration.     

Compositional Effects on the Properties of Si-Al-RE-Based Oxynitride Glasses (RE = La, Nd, Gd, Y, or Lu)

A series of silicon-aluminum oxynitride-glass compositions containing selected rare-earth (RE) additions were prepared to examine the effects of specific RE, as well as Si:Al:RE and N:O ratio, on properties. The properties that were characterized included density, thermal expansion coefficient (α), glass-transition temperature ( T _g), hardness ( H ), and Young's modulus ( E ). The compositions (in equivalent percent) selected included: 55 Si-20 RE-25 Al oxide and 80 O-20 N oxynitride, and 45 Si-30 RE-25 Al oxide and 70 O-30 N glasses. The results show that the density increased significantly with an increase in the RE atomic mass and slightly with an increase in N:O ratio. For each of the fixed Si-Al-RE-O-N compositions, the E , H , and T _g values were each increased by substituting smaller RE ions, whereas the α value was decreased. For each specific cation composition and RE, increasing the N:O ratio systematically led to a decrease in the α values but an increase in the E , H , and T _g values. The observed response in the glass properties to changes in composition appears to reflect modifications in the bonding within the glass network.     

Effect of TiO2 addition on thermal and mechanical properties of Y-Si-Al-O-N glasses

Y-Si-Al-O-N glasses are intergranular phases in silicon nitride based ceramics in which the composition and volume fraction of oxynitride glass phases determine the sintering/shrinkage behaviour. Several investigations on oxynitride glass formation and properties have shown that addition of nitrogen increases glass transition and softening temperatures, viscosity, elastic modulus and hardness. In the present study, effect of TiO₂ addition on thermal and mechanical properties of Y-Si-Al-O-N glasses is investigated since the most typical Si₃N₄ ceramics for bearing applications are fabricated using a Si₃N₄-Y₂O₃-Al₂O₃-TiO₂-AlN system. Addition of TiO₂ is effective in preparing Y-Si-Al-O-N glasses with lower glass transition temperatures and with higher hardness.     

Viscosity of high-nitrogen content Ca–Si–O–N glasses

The viscosity of three high-nitrogen content Ca–Si–O–N glasses, with 30–58 e/o N and 36–39 e/o Ca, was determined by micro-indentation. The measurements were made using an automated set-up, designed and built in-house, capable of measurements up to 1200 °C with applied loads of 0.01–15 N. The viscosity increases significantly with the nitrogen content and reaches viscosity values close to reported values for rare-earth silica oxynitride glasses. The glass transition temperatures range between 878 and 995 °C and are in very good agreement with values measured by differential thermal analysis. The apparent viscosity activation energies are very high, ranging from 855 to 2170 kJ/mol. The glasses can accordingly be classified as being both very refractory and very fragile. Implications of the viscosity values and mechanical properties of the glasses for their structures are discussed.     

The preparation and properties of zirconia-doped Y–Si–Al–O–N oxynitride glasses and glass-ceramics

Two series (N-9 and N-18 series) of zirconia-doped Y–Si–Al–O–N oxynitride glasses and glass-ceramics were designed. Nominal compositions of the glass samples in equivalent percent (eq%) are xZr: (24–0.25x)Y: (15–0.25x)Al: (61–0.5x)Si: 91O: 9 N and xZr: (24–0.25x)Y: (15–0.25x)Al: (61–0.5x)Si: 82O: 18 N (x=0, 2, 4, 6), respectively. The obtained samples were characterized by differential thermal analysis (DTA), X-ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). Densities, Vickers hardness, fracture toughness, glass transition temperature, and thermal expansion coefficient data were established for each sample. Effect of Zr and N content on glass network structure, thermal and mechanical properties was investigated. It was found that the addition of zirconia is effective in preparing Y–Si–Al–O–N oxynitride glasses with lower glass transition temperature and higher hardness.     

Comparison of the Properties of Oxycarbide and Oxynitride Glasses

Oxycarbide glasses in the Mg-Al-Si-O-C system and oxynitride glasses in the Mg-Al-Si-O-N system were synthesized by conventional melting techniques, chemically analyzed, and evaluated for selected mechanical properties as a function of carbon or nitrogen content. Both glass systems exhibited increases in density, Young's elastic modulus, microhardness, and fracture toughness with increasing anionic substitutions. Carbon substitutions were found to be more effective than nitrogen additions for improving glass properties.     

Revealing structural role of ZrO2 in silicate glasses from macroscale property by rigid-unit packing fraction method

The structural role of an oxide as a former and modifier can have significant effects on the chemical durability and mechanical properties of the glass. Some oxides with high-field strength cations, for example, MgO and ZrO₂, are often labeled as a third group—intermediate, due to their either undetermined or dual structural roles dependent on the glass compositions. Based on our recent modification of the Makishima–Mackenzie (MM) model using the rigid-unit Packing Fraction (RUPF), we analyzed a series of novel zirconia-containing bioactive glasses. The RUPF-based MM-model provides better prediction of the elastic moduli of these new glasses in comparison to experimental measurements. At the same time, the structural role of zirconia can be determined by comparison with calculations by assuming various structural roles and those from experiments. We reveal that ZrO₂ acts as the network former in phosphosilicate glasses, which leading to significant increase in packing fraction and consequent increase in Young's modulus. The recent experimental and atomistic simulation results support the glass former role of zirconia in silicate glasses. This method is general and applicable to other oxides in glasses.     

Novel Na–Li–SiAlPON glasses prepared by melt synthesis using AlN

Amorphous alumino–silicophosphate materials containing up to 1.70 wt.% nitrogen have been successfully prepared by aluminium nitride solution in Na–Li–Si–Al–P–O melts at 850 °C thus preventing phosphorus volatilisation. Although the solubility limit for nitrogen in these glasses was limited to 8.31 wt.%, the presence of nitrogen in the materials greatly increases their glass transition temperatures, suppresses the devitrification and has a significant effect on their melting behaviour. Comparative analysis of Raman spectra for the oxide and oxynitride glasses shows the substitution of P–O–P linkages by PN–P linkages while tri-coordinated nitrogen bridges were not detected. The attendant increase in network connectivity arising from such a substitution is responsible for the increase in glass transition temperature when nitrogen substitutes for oxygen.     

The influence of the pyrolysis process on mechanical parameters and tightness of the black glasses layers on titanium substrates

Black glasses are amorphous materials in which structure Si–O bonds coexist with Si–C bonds. The substitution of divalent oxygen ions by tetravalent carbon ions causes the change of properties, especially mechanical ones. The materials were obtained from the sol-gel synthesized ladder-like polysilsesquioxane organosilicon precursors. After deposition on titanium substrates and ceramization, continuous and hermetic layers were obtained. Adhesion, Young's modulus, hardness, roughness and corrosion resistance were examined as the most relevant mechanical properties of the obtained layers. Nanoindentation, surface mapping, electrochemical, SEM and confocal microscope measurements results are discussed in relation to the pyrolysis temperature of the black glasses layers.     

Structural characterisation of Er–Si–Al–O–N glasses by Raman spectroscopy

Er–Si–Al–O–N glasses have been prepared with cation ratio Er:Si:Al = 3.45:3:2 containing various amounts of nitrogen (N = 0, 5, 8, 15 and 22 equiv.%). Glass properties such as microhardness, glass transition temperature and dilatometric softening temperature were measured and it was found that these properties increased linearly with increasing nitrogen content. Glasses were then characterised using Raman spectroscopy in order to obtain information about the structure of these glasses. Deconvolution of peaks in the Raman spectra of Er–Si–Al–O–N glasses revealed that, as nitrogen content increases then the proportion of Q³ species decreases and there is a corresponding increase in the proportion of Q⁴ species (Qⁿ: n = no. of bridging anions joining SiO₄ tetrahedra), confirming that nitrogen increases the crosslinking between individual tetrahedra via the transformation of Q³ oxide species into Q⁴ oxynitride species.     

Structure of Phosphorus Oxynitride Glasses

The structures of phosphourus oxynitride glasses have been determined using a combination of solid-state ³¹P, ¹⁵N, and ²³Na nuclear magnetic resonance and Raman spectroscopies. Raman spectra of model phosphazene compounds with different types of P–N bonding have been used to confirm spectral assignments. Results indicate that nitrogen replaces oxygen in the phosphrus atoms (via one double bond and one single bond) and as nitrogen bonded to three phosphorus atoms via three single bonds. The observed structural features are consistent with data which show that nitrogen influences the chemical durability, thermal expansion, and other properties of phosphate glasses by cross-linking ploymeric phosphate chain to gether in the glass network.     

Structure-property relations in crack-resistant alkaline-earth aluminoborosilicate glasses studied by solid state NMR

The effect of the average ionic potential ξ = Ze/r of the network modifier cations on crack initiation resistance (CR) and Young's modulus E has been measured for a series of alkaline-earth aluminoborosilicate glasses with the compositions 60SiO₂–10Al₂O₃–10B₂O₃–(20−x)M₍₂₎O–xM’O (0 ≤ x ≤ 20; M, M’ = Mg, Ca, Sr, Ba, Na). Systematic trends indicating an increase of CR with increasing ionic potential, ξ, have been correlated with structural properties deduced from the NMR interaction parameters in ²⁹Si, ²⁷Al, ²³Na, and ¹¹B solid state NMR. ²⁷Al NMR spectra indicate that the aluminum atoms in these glasses are essentially all four-coordinated, however, the average quadrupolar coupling constant <C_Q> extracted from lineshape analysis increases linearly with increasing average ion potential computed from the cation composition. A similar linear correlation is observed for the average ²⁹Si chemical shift, whereas the fraction of four-coordinate boron decreases linearly with increasing ξ. Altogether the results indicate that in pure alkaline-earth boroaluminosilicate glasses the crack resistance/E-modulus trade-off can be tailored by the alkaline-earth oxide inventory. In contrast, the situation looks more complicated in glasses containing both Na₂O and the alkaline-earth oxides MgO, CaO, SrO, and BaO. For 60SiO₂–10Al₂O₃–10B₂O₃–10MgO–10Na₂O glass, the NMR parameters, interpreted in the context of their correlations with ionic potentials, are consistent with a partial network former role of the MgO component, enhancing crack resistance. Altogether the presence of MgO in aluminoborosilicate glasses helps overcome the trade-off issue between high crack resistance and high elasticity modulus present in borosilicate glasses, thereby offering additional opportunities for the design of glasses that are both very rigid and very crack resistant.