Carbon fiber reinforced ceramic matrix composites with an oxidation resistant boron nitride interface coating

Toughening a ceramic in a ceramic matrix composite (CMC) depends on an ability of the composite to tolerate an accumulation of matrix cracks. When the reinforcement phase is carbon fiber, these cracks leave the fiber susceptible to destructive oxidation by ingress of air during high temperature exposure. Generally, a graphitic carbon interface coating is applied to carbon fibers because it provides for a weak bond between fiber and matrix that is required to promote toughening. This investigation seeks to utilize a BN coating instead of a C coating in order to promote oxidation resistance. Like graphitic carbon, BN is soft and easily cleavable. Preliminary observations that C/BN/SiC CMC's using Toray T300 carbon fibers were highly brittle and of low strength lead to a requirement of heat treating the fibers prior to the CVD of BN for toughened composites to be fabricated. It is likely heat treating removed reactive functionalities from the fiber surface to yield a weakly adhered and compliant interface.     

An algorithm for the generation of silicon nitride structures

Silicon nitride is used for demanding tasks due to its high stiffness, strength and, especially, its high fracture toughness. Examples include cutting tools, forming rolls and ball bearings. The microstructure is characterized by elongated β-Si₃N₄ grains of different size and shape, which lead to the increased fracture toughness. Consequently, the paper will present an algorithm for the generation of three-dimensional and periodic silicon nitride-like microstructures, which will be used for micromechanical finite element simulations. The structure generation algorithm enhances the sequential adsorption technique with growth of particles and steric hindrance, which are motivated by experimental results. Results of the structure generator, such as the pseudo-time evolution and its statistical geometric distributions are presented and compared to literature data. With the finite element simulations, using a periodic unit cell, a validation of the model with literature values for Young's modulus and Poisson's ratio was possible.     

Mechanical properties and electrical conductivity in a carbon nanotube reinforced silicon nitride composite

The influence of carbon nanotubes (CNTs) addition on basic mechanical, thermal and electrical properties of the multiwall carbon nanotube (MWCNT) reinforced silicon nitride composites has been investigated. Silicon nitride based composites with different amounts (1 or 3 wt%) of carbon nanotubes have been prepared by hot isostatic pressing. The fracture toughness was measured by indentation fracture and indentation strength methods and the thermal shock resistance by indentation method. The hardness values decreased from 16.2 to 10.1 GPa and the fracture toughness slightly decreased by CNTs addition from 6.3 to 5.9 MPa m^1/2. The addition of 1 wt% CNTs enhanced the thermal shock resistance of the composite, however by the increased CNTs addition to 3 wt% the thermal shock resistance decreased. The electrical conductivity was significantly improved by CNTs addition (2 S/m in 3% Si₃N₄/CNT nanocomposite).     

Fabrication of non-oxide ceramic powders by carbothermal-reduction from industrial minerals

The most promising method for obtaining a large variety of non-oxide products having important technical uses is carbothermal-reduction reaction (CRR). By using this procedure, SiC and ZrC/SiC powders are obtained from diatomaceous earth and zircon powder. In this way the synthesized powders are obtained at a relatively low temperature due to good homogenization. Starting C/ZrSiO₄ admixtures having different molar ratios (3:1, 4:1, 5:1 and 7:1) and C/SiO₂ having ratios 1:1, 3:1, 4:1, and 7:1 were heated at temperatures between 1300 and 1600 °C in a controlled Ar flow atmosphere. The phase evolution was a function of the raw materials molar ratios and sintering temperature. The optimal parameters for the synthesis of SiC and ZrC/SiC powders were obtained. The results obtained by EDS analysis are in good agreement with those obtained by XRD analysis for the synthesized carbide powders.     

Determination of structural and mechanical properties of multilayer graphene added silicon nitride-based composites

Silicon nitride based nanocomposites have been prepared with different amount (1 and 3 wt%) of multilayer graphene (MLG) as well as exfoliated graphite nanoplatelets (xGnP) and nano graphene platelets (Angstron) in comparison. The microstructure and mechanical properties of the graphene reinforced silicon nitride based composite materials have been investigated. Homogeneous distribution of the MLG additives have been observed on the fracture surface of the sintered material. The scanning electron microscopy examinations showed that graphene platelets are inducing porosity in matrix. The bending strength and elastic modulus of MLG/Si₃N₄ composites showed enhanced values compared to the other graphene added silicon nitride ceramic composites. These observations may be explained by the different type and quality of the starting materials and by the dispersion grade of graphene platelets having direct impact to the resulting density of the sintered samples.     

Enhanced thermoelectric properties of carbon fiber reinforced cement composites

Thermoelectric properties of carbon fiber reinforced cement composites (CFRCs) have attracted relevant interest in recent years, due to their fascinating ability for harvesting ambient energy in urban areas and roads, and to the widespread use of cement-based materials in modern society. The enhanced effect of the thin pyrolytic carbon layer (formed at the carbon fiber/cement interface) on transport and thermoelectric properties of CFRCs has been studied. It has been demonstrated that it can enhance the electrical conduction and Seebeck coefficient of CFRCs greatly, resulting in higher power factor 2.08 µW m⁻¹ K⁻² and higher thermoelectric figure of merit 3.11×10⁻³, compared to those reported in the literature and comparable to oxide thermoelectric materials. All CFRCs with pyrolytic carbon layer, exhibit typical semiconductor behavior with activation energy of electrical conduction of 0.228-0.407 eV together with a high Seebeck coefficient. The calculation through Mott’s formula indicates the charge carrier density of CFRCs (10¹⁴–10¹⁶ cm⁻³) to be much smaller than that of typical thermoelectric materials and to increase with the carbon layer thickness. CFRCs thermal conductivity is dominated by phonon thermal conductivity, which is kept at a low level by high density of micro/nano-sized defects in the cement matrix that scatter phonons and shorten their mean free path. The appropriate carrier density and mobility induced by the amorphous structure of pyrolytic carbon is primarily responsible for the high thermoelectric figure of merit.     

HfB2-CNTs composites with enhanced mechanical properties prepared by spark plasma sintering

HfB₂-x vol%CNTs (x=0, 5, 10, and 15) composites are prepared by spark plasma sintering. The influence of CNTs content and sintering temperature on densification, microstructure and mechanical properties is studied. Compared with pure HfB₂ ceramic, the sinterability of HfB₂-CNTs composites is remarkably improved by the addition of CNTs. Appropriate addition of CNTs (10 vol%) and sintering temperature (1800 °C) can achieve the highest mechanical properties: the hardness, flexural strength and fracture toughness are measured to be 21.8±0.5 GPa, 894±60 MPa, and 7.8±0.2 MPa m^1/2, respectively. This is contributed to the optimal combination of the relative density, grain size and the dispersion of CNTs. The crack deflection, CNTs debonding and pull-out are observed and supposed to exhaust more fracture energy during the fracture process.     

Indentation fracture resistance test round robin on silicon nitride ceramics

Reproducibility of indentation fracture resistance of three commercial silicon nitrides including bearing balls was evaluated by an international round robin with six laboratories. The between-laboratory standard deviations for indentations at 196 N on the perfectly mirror-finished surfaces were in the range of 0.2–0.5 MPa m^1/2, demonstrating an excellent precession of the test results. The scatter in the fracture resistance increased as the indentation load decreased from 196 to 98 N. The errors in measuring crack lengths deduced from the deviation of each laboratory's readings from author's reading for the same indentations tended to increase with a decrease in the magnification of the lab's microscope, which suggested that finding exact crack tips with lower magnification was difficult especially for those samples with insufficiently mirror-finished surfaces indented at 98 N. Observation of indentations at the load of 196 N with powerful optics was advised to ensure the validity of the indentation technique which is used as the quality assessment of Si₃N₄ bearing balls.     

Technological properties of celsian reinforced glass matrix composites

Monoclinic celsian derived from an innovative route, i.e. cation exchanged zeolites heat-treated at low temperature, was added at different contents (10, 20, 30 wt%) to a glass matrix, in order to improve its mechanical and electrical performances. The effect of the celsian reinforcement was evaluated by testing several properties of the composite materials, such as the elastic modulus, abrasion resistance, flexural strength and electrical insulation. The results so far obtained suggest that the addition of the monoclinic celsian to the glass matrix may produce low-cost particulate composites with interesting technological properties.     

Silicon nitride based nanocomposites produced by two different sintering methods

This research explores the use of a variety of carbon nanostructures as reinforcing agents for Si₃N₄ matrix composites. We have chosen highly promising families of carbon materials: multiwall, singlewall carbon nanotubes (MWCNTs, SWCNTs), graphene, carbon black nanograins and graphite micrograins for use as fillers. These materials were dispersed with a concentration of 3 wt% in silicon nitride matrices. A high efficiency attritor mill has also been used for effective dispersion of second phases in the matrix. In the present work the development of sintering processes (hot isostatic pressing (HIP) and spark plasma sintering (SPS)) has been performed to consolidate and tailor the microstructure of Carbon nanotube (CNT)-reinforced silicon nitride-based ceramic composites. The silicon nitride nanocomposite systems retained the mechanical robustness of the original systems. Elastic modulus measurements and micro-indentation investigations of the hardness and fracture toughness have been performed as well as scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray diffraction in order to characterize the composites produced by the two sintering methods.     

Processing of micro-components made of sintered reaction-bonded silicon nitride (SRBSN). Part 1: Factors influencing the reaction-bonding process

In order to establish a process for the manufacturing of injection moulded micro-components of sintered reaction-bonded silicon nitride (SRBSN) several process parameters were investigated with regard to their influence on the reaction-bonding step. One question to be answered was how the sintering aids affect the nitridation behaviour of a silicon green body. For the processing of micro-components it was of special interest to study, how a decreasing sample size and wall thickness would influence the rate of Si₃N₄ formation. By varying the added amounts of the sintering aids, it was found that increasing the Y₂O₃ and MgO contents both improved the nitridation rate, whereas an increase of Al₂O₃ content resulted in reduced nitridation rates. Within the investigated range of sample dimensions (0.2–4.0 g) the unexpected observation was made, that with decreasing sample weight the nitridation rate also decreased. This was explained by the exothermic nature of the reaction between Si and N₂ and the fact that small samples with a large surface-to-volume ratio attain thermal equilibrium with their environment better than large samples which may be subject to local overheating.     

Relationship between fracture toughness determined by surface crack in flexure and fracture resistance measured by indentation fracture for silicon nitride ceramics with various microstructures

The reliability of the Vickers indentation fracture (IF) method for various types of silicon nitride (Si₃N₄) ceramics was assessed by comparing the fracture resistance, K_R obtained from the IF test with the fracture toughness, K_Ic from the surface crack in flexure (SCF) technique in the same crack depth region. The K_R of a fine-grained and equiaxed Si₃N₄ matched with the K_Ic from the SCF test when Miyoshi's equation was used, while the K_Ic of a bearing-grade Si₃N₄ was found to lie between K_R values calculated with Niihara's equation (higher side) and Miyoshi's equations (lower side). In the case of coarse Si₃N₄ with elongated grains, the K_R determined using Niihara's equation gave the best fit with K_Ic. The inconsistent outcomes were explained by the probable mechanisms, indicating that the K_R from the IF test cannot be correlated directly with the K_Ic unless the effective crack length for the IF test was clarified.     

Porous Si3N4 ceramics prepared via slip casting of Si and reaction bonded silicon nitride

Slip casting process combined with reaction bonded silicon nitride (RBSN) was used to prepare porous Si₃N₄ ceramic with near-net and complex shape. A butyl stearate (BS) coated process was introduced to restrain the hydrolysis of Si, and ammonium polyacrylate (NH₄PAA) was used to enhance the dispersion of coated Si. The measured oxygen content showed that the hydrolysis of Si was strongly prohibited by BS coating, and relatively low viscosity was obtained with the addition of 0.25-1.5 wt% NH₄PAA to the 60 wt% solid load slurry. 40-60 wt% solid load slurries were used for slip casting in the experiment. After vacuum degassing, slip casting, debindering and nitridation, a density of 1.57-1.92 g/cm³ (porosity 50.9-40%) and a flexural strength of 47-108 MPa were obtained. The samples without vacuum degassing showed a large number of nanowires grown in the large pores.     

Enhanced thermoelectric effect of carbon fiber reinforced cement composites by metallic oxide/cement interface

Thermoelectric power of carbon fiber reinforced cement composites was firstly enhanced efficiently by metallic oxide microparticles in the cement matrix. The absolute Seebeck coefficient of these composites increased steadily with increasing metallic oxide content and achieved 4–5 folds of the original one. The largest absolute thermoelectric power of +100.28 µV/°C was obtained for the composite with 5.0 wt% Bi₂O₃ microparticles. The carrier scattering of the interface between oxide microparticles and cement matrix is probably attributed to the Seebeck effect enhancement.     

Mechanical and electrical properties of carbon nanofibers reinforced aluminum nitride composites prepared by plasma activated sintering

High density carbon nanofibers (CNFs) reinforced aluminum nitride (AlN) composites were successfully fabricated by plasma activated sintering (PAS) method. The effects of CNFs on the microstructure, mechanical and electrical properties of the AlN composites were investigated. The experimental results showed that the grain growth of AlN was significantly inhibited by the CNFs. With 2 wt.% CNFs added into the composites, the fracture toughness and flexural strength were increased, respectively to 5.03 MPa m^1/2 and 354 MPa, which were 20.9% and 13.4% higher than those of monolithic AlN. The main toughening mechanisms were CNFs pullout and bridging, and the main reason for the improvements in strength should be the fine-grain-size effect caused by the CNFs. The DC conductivity of the composites was effectively enhanced through the addition of CNFs, and showed a typical percolation behavior with a very low percolation threshold at the CNFs content of about 0.93 wt.% (1.51 vol.%).     

Structure and properties of short fibre reinforced silica matrix composite foams

Glass (GFC) and silica (SFC) fibre reinforced silica matrix composite foams with 84–90% porosity content have been developed through slurry-based processing, involving random dispersion of 10 wt.% fibres with aspect ratios of >1000 in hydrophobized silica-based suspensions, and direct foaming for air entrapment. Fibre entanglement has not been found either in the suspensions or in the sintered composite foams. Microstructural and mercury porosimetry studies of the composite foams have shown a trimodal size distribution with small (4–8 μm), medium (40–200 μm), and large (1 mm or more) pores. The pores appear spherical and interconnected, with the fibres embedded in cell-walls or struts. The dynamic Young's modulus of the silica-coated GFCs is found to be 3.5 and 5.2 times that of the coated and uncoated monolithic silica foams, respectively, confirming that both fibre-reinforcement and the presence of surface coating are beneficial for increase in stiffness of the composite foams.     

Influence of surface defects on the biaxial strength of a silicon nitride ceramic - Increase of strength by crack healing

Failure of brittle materials starts in general from defects which exist in the volume or on the surface of the specimens. Surface flaws, which are more dangerous than volume flaws, can be introduced by machining. They decrease the strength of specimens and components.For this investigation silicon nitride specimens were produced using different machining conditions. About half of them were strength tested by use of the biaxial ball-on-three balls (B3B) test. It has been shown that better (more gentle) machining increases the strength but may also cause an increased scatter of strength data.The remaining specimens were heat treated (annealed) at 1000 °C in air and afterwards also strength tested using the B3B test. Compared to the non heat treated specimens a significant increase in strength could be proven, which was - depending on the machining conditions - between almost 300 MPa and more than 500 MPa. The scatter of strength data was largely decreased.The improvement was caused by the formation of a thin (0.5-2 μm) glassy layer which filled surface cracks and surface related pores during annealing.     

Low temperature densification of silicon nitride using Li2O-based surface coatings

For better control of the mechanical properties of Si₃N₄ ceramics, it is necessary to generate homogeneous microstructures, and for this purpose, chemical heterogeneities must be minimised, by careful control of powder processing and the subsequent consolidation steps. Coating of the starting silicon nitride powder is a convenient way of incorporating a liquid forming sintering aid more homogeneously than can be achieved by current commercial methods such as ball-milling.Thin layers of oxides, corresponding to additions of up to 5 w/o Li₂O have been deposited on the surface of grains of a commercial silicon nitride powder using alcoholic solutions containing appropriate amounts of the metal alkoxide. The resulting powders have been densified by pressurelesss sintering techniques, and their sintering characteristics identified in comparison with equivalent materials produced by adding the oxide in particulate form. In every case, a better sintering performance was observed at lower temperatures for the oxide-coated materials, with fully dense pressureless-sintered materials being obtained at temperatures as low as 1250 °C. An added observation was that for the coated samples, the final microstructure was more uniform, and showed an absence of large pores.     

Oxidation behaviors and shear properties of z-pinned joint made of two-dimensional carbon fiber reinforced silicon carbide composite

Chemical vapor infiltration has been introduced for preparing z-pinned joint, which is made of two-dimensional carbon fiber reinforced silicon carbide composite. The effects of oxidation on the shear properties of the joint were investigated. The results showed that the joint strength increases with the increase of oxidation temperature, which is consistent with the oxidation consumption of the carbon phases. An exponential relationship is presented between the weight loss and the joint strength. In contrast, linear relationships are presented between the weight loss and the mechanical properties of the composite. The exponential relationship results from the coupled shear and bending stress states of the pin, according to the failure mechanisms of the joint. It is observed that in-plane and intra-layer cracks are formed under the shear stress. And these cracks are bridged by the fibers under the bending stress. Accordingly, the fiber bridging mechanism contributes to the joint strength before and after oxidation. For the conditions of this study, the joint strength can be roughly estimated as the plus of the in-plane shear strength and the tensile matrix cracking stress.     

In situ preparation of Si3N4–TiN composite by pyrolysis of polytitanosilazane (PTSZ)

Si₃N₄–TiN composite powders were obtained by in situ pyrolysis of polytitanosilazane. Dense Si₃N₄–TiN composites were prepared by hot-pressing at 1800 °C under 20 MPa for 2 h without sintering additive. Crystallization of amorphous PTSZ powders occurred between 1400 and 1500 °C with major phases, α-Si₃N₄, β-Si₃N₄, and small amount of phase TiN. Mechanical properties and microstructure of Si₃N₄–TiN composites were characterized. The results showed that the mechanical strength was 620 MPa, the fracture toughness was 7.8 MPa m^1/2 and the Vickers hardness was 8.5 GPa. SEM analysis indicated that Si₃N₄–TiN composite possessed excellent fracture toughness because TiN grains produced by in situ pyrolysis were well dispersed in Si₃N₄ matrix.