Microstructure,chemical reaction and mechanical properties of TiC/Si3N4 and TiN-coated TiC/Si3N4 composites

Silicon nitride containing various compositions of as-received TiC and TiN-coated TiC, were hot pressed at 1800 °C for 1 h in a nitrogen atmosphere. In TiN-coated TiC/Si₃N₄ composites, TiC reacted first with the TiN coating to form a titanium carbonitride interlayer at 1450 °C, which essentially reduced further reactions between TiC and Si₃N₄ and enhanced densification. TiN-coated TiC/Si₃N₄ composites exhibited better densification, hardness, flexural strength and fracture toughness than those of as-received TiC/Si₃N₄. The toughening mechanisms for as-received TiC/Si₃N₄ and TiN-coated TiC/Si₃N₄ composite were attributed to crack deflection, load transfer and crack impedence by the compressive thermal residual stress.     

Hardness and fracture toughness of thermoelectric La<Subscript>3−<Emphasis Type="Italic">x</Emphasis></Subscript>Te<Subscript>4</Subscript>

Lanthanum telluride (La_3?x Te₄) is a state-of-the-art n-type high temperature thermoelectric material that behaves as a weak and brittle ceramic. Vickers microindentation hardness testing was explored as a rapid analysis technique to characterize the mechanical properties of this material. An indentation size effect was observed with hardness values ranging from 439 ± 31 kgf/mm² (0.01 kgf/10 s contact time) to 335 ± 6 kgf/mm² (0.5 kgf/10 s contact time). The Vickers indentation fracture toughness, K _VIF, based on measurements of crack lengths emanating from the corners of the Vickers indents was 0.70 ± 0.06 MPa m^1/2.     

Fabrication of a polymer composite with high thermal conductivity based on sintered silicon nitride foam

A novel route was developed to fabricate Si₃N₄/epoxy composite. In this route, the Si₃N₄ particles were constructed into the foamed shape by using protein foaming method, firstly. Then the Si₃N₄ foams were sintered to bond these Si₃N₄ particles together. Finally, the Si₃N₄/epoxy composite was fabricated by infiltrating the epoxy resin solution into the sintered Si₃N₄ foams. This route was proved to be an efficient way in enhancing the thermal conductivity of epoxy matrix at a low loading fraction. For example, the thermal conductivity of the as-prepared Si₃N₄/epoxy composite with a loading fraction of 22.2 vol% was up to 3.89 W m⁻¹ K⁻¹, which was about 17 times higher than that of neat epoxy.     

Slow growth of microcracks in hydroxyapatite during aging

Hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂ or HA) is a brittle material that is subject to environmentally assisted slow crack growth. While most slow crack growth studies are carried out after aging, this study examines the slow growth of radial cracks induced by Vickers indentation in dense HA (94 % of theoretical density) during aging in ambient air, where the observed crack growth is consistent with a process in which residual stress drives crack growth. For indentation loads of 0.98, 1.96, 2.94, and 4.91 N, the average radial crack length increased exponentially with time for indentation loads of 0.98, 1.96, 2.94, and 4.91 N, with crack lengths saturating within 1 h following indentation. However, no radial crack growth was observed for 9.81 N loads. The load dependence of radial crack growth is proposed to be linked to the partitioning of residual strain energy by the lateral crack growth, which has not been reported in the literature.     

A novel fiber-reinforced polyethylene composite with added silicon nitride particles for enhanced thermal conductivity

A novel thermally conductive plastic composite was prepared from a mixture of silicon nitride (Si₃N₄) filler particles and an ultrahigh molecular weight polyethylene–linear low density polyethylene blend. The effects of Si₃N₄ particle sizes, concentration, and dispersion on the thermal conductivity and relevant dielectric properties were investigated. With proper fabrication the Si₃N₄ particles could form a continuously connected dispersion that acted as the dominant thermally conductive pathway through the plastic matrix. By adding 0–20% Si₃N₄ filler particles, the composite thermal conductivity was increased from 0.2 to ～1.0 W m^?1 K^?1. Also, the composite thermal conductivity was further enhanced to 1.8 W m^?1 K^?1 by decreasing the Si₃N₄ particle sizes from 35, 3 and 0.2 μm, and using coupling agent, for the composites with higher filler content. Alumina short fibers were then added to improve the overall composite toughness and strength. Optimum thermal, dielectric and mechanical properties were obtained for a fiber-reinforced polyethylene composite with 20% total alumina–Si₃N₄ (0.2 μm size) filler particles.     

Dynamic fatigue behaviour of a steatite ceramic

Dynamic fatigue of a low dielectric loss steatite was investigated. To this end, the values of n and B, the so‐called subcritical crack growth (SCG) parameters were experimentally determined. The steatite exhibited the expected dynamic fatigue behaviour, so that the stress corrosion susceptibility parameter, n, of 24 was obtained. In addition, the material/environment parameter B, which is a constant for a given test environment, was also attained. These parameters are instrumental in predicting the lifetime of components under stress. When the applied load is such that the resulting strength equals half of the inert strength (σ_i), defined as the strength of a sample tested in an inert environment or at a fast stress rate, i.e. where no subcritical crack growth occurs, the time to failure (t_f) of the material was found to be ～140 h. Measurement of the fracture toughness of steatite is also of upmost importance and so it was determined using three test methods. A value of K_Ic = 1.91 ± 0.29 MPa m^1/2 was attained by the indentation fracture method through measurement of the cracks emanating from the Vickers indentation. This value is in good agreement with those determined using the K_Isc (surface crack in flexure) test method (2.21 ± 0.07 MPa m^1/2) and fractography analysis test method (2.00 ± 0.44 MPa m^1/2). Differences in test procedure and analysis causing the values from each test method to be different are discussed.     

Carbon fibre-reinforced silicon nitride composite

The processing of silicon nitride reinforced with carbon fibre was studied. The problems of physical and chemical incompatibility between carbon fibre and the silicon nitride matrix were solved by addition of a small amount of zirconia to the matrix and by low-temperature hot-pressing. The composite material possesses a much higher toughness than hot-pressed silicon nitride. Its work of fracture increased from 19.3 J m^–2 for unreinforced Si₃N₄, to 4770 J m^–2; its fracture toughness,K _lc , increased from 3.7 MN m^–3/2 for unreinforced material, to 15.6 MN m^–3/2. The strength remains about the same as unreinforced Si₃N₄ and the thermal expansion coefficient is only 2.51×10^–6 ° C^–1 (RT to 1000° C). It is anticipated that this composite may be promising because of its mechanical and good thermal shock-resistance properties.     

Evaluation of elastic/mechanical properties of some glasses and nanocrystallized glass by cube resonance and nanoindentation methods

Elastic and mechanical properties of 10La₂O₃·30Bi₂O₃·60B₂O₃ (LaBiB) glass, 15K₂O·15Nb₂O₅·68TeO₂·2MoO₃ (KNbTeMo) glass and a transparent KNbTeMo nanocrystallized (particle size: ∼40 nm) glass were examined using cube resonance and nanoindentation methods. The values of Poisson’s ratio, Young’s modulus (E), Debye temperature (θ_D), fractal bond connectivity, Martens hardness, indentation hardness, indentation Young’s modulus, elastic recovery, Vickers hardness, fracture toughness (K_c) and brittleness for the samples were evaluated, and the relation with the structure and nanocrystallization were clarified. LaBiB glass containing high oxygen-coordinated La³⁺ ions and two-dimensional BO₃ structural units shows excellent properties of E=90.6 GPa, θ_D=404 K and K_c=0.72 MPa m^1/2 and a high resistance against deformation during Vickers indentation. KNbTeMo glass with the three-dimensional network structure and consisting of weak Te-O bonds has small values of E=51.4 GPa and K_c=0.29 MPa m^1/2. It was demonstrated that the elastic and mechanical properties of KNbTeMo precursor glass are largely improved by nanocrystallization, e.g., E=69.7 GPa and K_c=0.32 MPa m^1/2. The nanocrystallization also induces a high resistance against deformation during Vickers indentation.     

Interface fracture analysis of joints with a ductile interlayer

Plane strain problem of an interface crack with two interface shear yield zones and one crack-face contact zone is studied. The plastic yielding of the interlayer is stimulated by the interface shear yield zones and contact zone is included near one tip of the interface crack. An interesting and important phenomenon found in this analysis is that for such an interface crack the applied compressive normal stress can increase the stress intensity factor K ₁ at one of the two crack tips, the size of the crack-face contact zone, and the maximum value of the crack opening, in a combined normal and shear stress field. Examples are given for two pairs of materials used in ceramic-metal brazed joints, Si₃N₄/Ni and Si₃N₄/Incoloy 909.     

Microwave sintering of Si3N4 with LiYO2 and ZrO2 as sintering additives

Phase transformation, microstructure development and mechanical properties of 2.45 GHz microwave-sintered silicon nitride (Si₃N₄) with lithium yttrium oxide (LiYO₂) and zirconia (ZrO₂) sintering additives were investigated. It was found that α to β phase transformation completed at a lower temperature of 1500 °C. Scanning electron microscopy (SEM) micrographs revealed a bimodal microstructure with a large number of elongated β-Si₃N₄ grains in addition to smaller grains. Surface residual porosity was observed in all sintered samples due to selective localized over heating of grain-boundary glassy phase. The high aspect-ratio of β-Si₃N₄ grains exhibited significant crack deflection, debonding and pull-out. It was observed that Vickers hardness and indentation fracture toughness increased with increasing sintering temperature.     

Enhanced thermal conductivity of Cu matrix composites reinforced with Ag-coated β-Si3N4 whiskers

Cu matrix composites reinforced with 10 vol.% Ag-coated β-Si₃N₄ whiskers (ASCMMCs) were prepared by powder metallurgy method. With the aim of improving the thermal conductivity of the composites, a quite thin Ag layer was deposited on the surface of β-Si₃N₄ whiskers. The results indicated that thermal conductivity of ASCMMCs with 0.30 vol.% Ag (0.30ASCMMCs) reached up to 273 W m⁻¹ K⁻¹ at 25 °C, which was 98 W m⁻¹ K⁻¹ higher than that of Cu matrix composites reinforced with uncoated β-Si₃N₄ whiskers (USCMMCs). The Ag coating could promote the densification of composites, reduce the aggregation of β-Si₃N₄ whiskers and enhance the Cu/Si₃N₄ interfacial bonding, therefore it could efficiently enhance the thermal conductivity of Cu matrix composites reinforced with β-Si₃N₄ whiskers (SCMMCs).     

Characterization of silicon nitride single crystals and polycrystalline reaction sintered silicon nitride by microhardness measurements

Identification of - and -phases of Si₃N₄ single crystals grown from Si melt could be made with the help of Vickers microhardness measurements. The effect of chemical additives, e.g. metallic Fe and BaF₂, on the microhardness of Si₃N₄ was also determined. Different constants involved in the empirical Meyer relationship between load and indentation diameters could be correlated with the porosity and microhardness of Si₃N₄ single crystals and polycrystalline, reaction sintered Si₃N₄.     

Indentation-induced subsurface tunneling cracks as a means for evaluating fracture toughness of brittle coatings

When a plate glued to a compliant substrate is subject to indentation, cracks may initiate from its subsurface due to flexure. Upon increasing the load, the damage develops into a set of tunnel radial cracks which propagate stably under a diminishing stress field. This phenomenon is utilized here to extract fracture toughness K _C for brittle materials in the form of thin plates or films. Experiments show that the SIF at the tip of the subsurface radial cracks is well approximated as K ~ P/c ^3/2, where P is the indentation load and c the mean length of the crack fragments. Using a transparent substrate, c can be easily determined after unloading, from which K _C is found. This simple and economic concept is applied to a wide variety of thin ceramic coatings, yielding toughness data consistent with literature values. Because the tip of the tunneling cracks are well removed from the contact site, the method circumvents certain complications encountered in common top-surface radial cracking techniques such as the effect of plastic deformation, residual stresses and crack extension after unloading. Although the present tests are limited to coating thicknesses >150 μm, it is believed that thinner coatings may be studied as well provided that the indenter radius is kept sufficiently small to insure that subsurface radial cracking dominates over all other failure modes.     

Microstructure and properties of the Si3N4/silica aerogel composites fabricated by the sol–gel method via ambient pressure drying

Si₃N₄ particle reinforced silica aerogel composites have been fabricated by the sol–gel method via ambient pressure drying. The microstructure and mechanical, thermal insulation and dielectric properties of the composites were investigated. The effect of the Si₃N₄ content on the microstructure and properties were also clarified. The results indicate that the obtained mesoporous composites exhibit low thermal conductivity (0.024–0.072 Wm^− 1 K^− 1), low dielectric constant (1.55–1.85) and low loss tangent (0.005–0.007). As the Si₃N₄ content increased from 5 to 20 vol.%, the compressive strength and the flexural strength of the composites increased from 3.21 to 12.05 MPa and from 0.36 to 2.45 MPa, respectively. The obtained composites exhibit considerable promise in wave transparency and thermal insulation functional integration applications.     

Corrosion and strength degradation of Si3N4 and sialons in K2CO3 and K2SO4 melts

Si₃N₄-based ceramics, such as hot isostatically pressed Si₃N₄, hot-pressed Si₃N₄, hot-pressed sialons containing 0, 30, 60 and 100% a phase, were corroded by K₂SO₄ and K₂CO₃ melts at 1150 to 1300 and 925 to 1150° C, respectively. The surface chemical reaction-controlled shrinking core model adequately described the relationship between the weight loss of the specimen and time for the corrosion reactions in both K₂SO₄ and K₂CO₃ melts, and the apparent activation energies were 380 to 608 and 157 to 344 kJ mol^?1, respectively. The corrosion rate in K₂CO₃ melt decreased with increasing content of aluminium and yttrium ions in the specimens, but no systematic relation was observed for the reaction in K₂SO₄ melts. The fracture strength of the specimens corroded by K₂SO₄ and K₂CO₃ melts degraded to 2/3 to 2/5 of the original values up to a 2% weight loss, and then was almost constant up to 30% weight loss.     

Production and characteristics of glass-ceramics derived from manganese crust tailings

Glass-ceramics have been produced via vitrification from manganese crust tailings with over 23% reduction in tailings volume. The crystalline behaviour of parent glass and glass-ceramics were investigated using DTA, TGA, XRD, and SEM/EDS. XRD analysis revealed that the major crystalline phase was iron manganese oxide. The Vickers microhardness (H _v) was 9.74 MPa, the indentation strength (K _c) was 1.88 Mpa m^1/2, and elastic modulus (E) was 140 MPa. The properties of the glass-ceramic compared well with known research and industrial glass-ceramic materials. Results suggest that manganese crust tailings have potential to be vitrified into useful, marketable glass-ceramic materials.     

Fracture toughness of ceramics and semi-brittle alloys using a miniaturized disk-bend test

∞ is the crack resistance at ”infinite” crack length. It is convincingly shown that this so-called R-curve equation correctly predicts K_∞, which is comparable to the conventionally measured Mode I plain-strain fracture toughness, K_Ic, of the same material. The fundamental constants in the fracture-mechanics-based equations are discussed, emphasizing the aspects pertinent to the small specimens used in the MDBT. Results are presented on 8 materials: ZnS, glass-ceramic, Si₃N₄, Ti₅Si₃, SiC, Ni₃Ge, NiAl and Ti-46.5A1-2.1Cr-3.0Nb-0.2W. All are brittle except for the latter two, which undergo slight plastic deformation before fracturing. The resulting values of K_∞ are in excellent agreement with published values derived from conventional measurements, providing considerable confidence in the method. where Q is a constant and K_∞ is the crack resistance at ”infinite” crack length. It is convincingly shown that this so-called R-curve equation correctly predicts K_∞, which is comparable to the conventionally measured Mode I plain-strain fracture toughness, K_Ic, of the same material. The fundamental constants in the fracture-mechanics-based equations are discussed, emphasizing the aspects pertinent to the small specimens used in the MDBT. Results are presented on 8 materials: ZnS, glass-ceramic, Si₃N₄, Ti₅Si₃, SiC, Ni₃Ge, NiAl and Ti-46.5A1-2.1Cr-3.0Nb-0.2W. All are brittle except for the latter two, which undergo slight plastic deformation before fracturing. The resulting values of K_∞ are in excellent agreement with published values derived from conventional measurements, providing considerable confidence in the method. Received: 13 October 1999 / Reviewed and accepted: 9 November 1999     

Microstructure and fracture-mechanical properties of carbon derived Si3N4 + SiC nanomaterials

The microstructure and basic mechanical properties, as hardness, fracture toughness, fracture strength and subcritical crack growth at room temperature were investigated and creep behavior at high temperatures was established. The presence of SiC particles refined the microstructure of Si₃N₄ grains in the Si₃N₄ + SiC nanocomposite. Higher hardness values resulted from introducing SiC nanoparticles into the material. A lower fracture toughness of the nanocomposite is associated with its finer microstructure; crack bridging mechanisms are not so effective as in the case of monolithic Si₃N₄. The strength value of the monolithic Si₃N₄ is higher than the characteristic strength of nanocomposites. Fractographic analysis of the fracture surface revealed that a failure started principally from an internal flaw in the form of cluster of free carbon, and on large SiC grains which degraded strength of the nanocomposite. The creep resistance of nanocomposite is significantly higher when compared to the creep resistance of the monolithic material. Nanocomposite exhibited no creep deformation, creep cracks have not been detected even at a test at 1400 °C and a long loading time, therefore the creep is probably controlled mainly by diffusion. The intergranular SiC nanoparticles hinder the Si₃N₄ grain growth, interlock the neighboring Si₃N₄ grains and change the volume fraction, geometry and chemical composition of the grain boundary phase.     

Mechanical and dielectric properties of porous Si3N4–SiO2 composite ceramics

In order to prepare a structural/functional material with not only higher mechanical properties but also lower dielectric constant and dielectric loss, a novel process combining oxidation-bonding with sol–gel infiltration-sintering was developed to fabricate a porous Si₃N₄–SiO₂ composite ceramic. By choosing 1250 °C as the oxidation-bonding temperature, the crystallization of oxidation-derived silica was prevented. Sol–gel infiltration and sintering process resulted in an increase of density and the formation of well-distributed micro-pores with both uniform pore size and smooth pore wall, which made the porous Si₃N₄–SiO₂ composite ceramic show both good mechanical and dielectric properties. The ceramic with a porosity of 23.9% attained a flexural strength of 120 MPa, a Vickers hardness of 4.1 GPa, a fracture toughness of 1.4 MPa m^1/2, and a dielectric constant of 3.80 with a dielectric loss of 3.11 × 10⁻³ at a resonant frequency of 14 GHz.     

Microstructure and property enhancement of silicon nitride-barium aluminum silicate composites with β-Si3N4 seed addition

Si₃N₄-barium aluminum silicate (BAS) self-reinforced composites have been prepared by pressureless sintering at 1800 °C for 2 h. The β-Si₃N₄ seeds incorporated in the starting α-Si₃N₄ powders encouraged the α- to β-Si₃N₄ phase transformation, and the final bimodal microstructure with large grains, consequently, led to the improvement of the fracture toughness, from 7.74 to 8.34 MPa m^1/2. The almost-complete crystallized BAS benefited the high-temperature mechanical properties. The residual stress, crack deflection, grain bridging, and pullout were considered as the major toughening mechanisms in this composite.