Wear damage of Si3N4-graphene nanocomposites at room and elevated temperatures

Mechanical and tribological properties of nanocomposites with silicon nitride matrix with addition of 1 and 3 wt.% of multilayered graphene (MLG) platelets were studied and compared to monolithic Si₃N₄. The wear behavior was observed by means of the ball-on-disk technique with a silicon nitride ball used as the tribological counterpart at temperatures 25 °C, 300 °C, 500 °C, and 700 °C in dry sliding. Addition of such amounts of MLG did not lower the coefficient of friction. Graphene platelets were integrated into the matrix very strongly and they did not participate in lubricating processes. The best performance at room temperature offers material with 3 wt.% graphene, which has the highest wear resistance. At medium temperatures (300 °C and 500 °C) coefficient of friction of monolithic Si₃N₄ and composite with 1%MLG reduced due to oxidation. Wear resistance at high temperatures significantly decreased, at 700 °C differences between the experimental materials disappeared and severe wear regime dominated in all cases.     

Effect of homogenization treatment on the fracture behaviour of silicon nitride/graphene nanoplatelets composites

Si₃N₄ based composites with 7 wt.% of graphene nanoplatelets (GNPs) were prepared using different homogenization methods. Si₃N₄/GNPs powder mixtures were dispersed in isopropanol and homogenized by attritor milling, ball milling or planetary ball milling. The ball milling technique was also used for the homogenization of Si₃N₄/GNPs mixture in dry state. Fractography analysis was carried out in order to assess the individual homogenization treatment. Depending on the homogenization methods, the size of the processing flaws varied from 20 μm up to 400 μm. The agglomeration of the GNPs and the residual porosity were found as the most frequently observed types of the critical flaws. The planetary ball milling with previous ultrasonication of GNPs in isopropanol was found to be the most promising homogenization technique, resulting in the composites with the highest bending strength (average value is 740 MPa) and the lowest average size of the processing flaws (around 20 μm).     

TEM investigations of wear mechanism of Al2O3 and Si3N4 compacts with GLPs additions

Extended lifetime of ceramic cutting plates is ever more desired. One way of approaching it entails sintering precursor materials with graphene-like nanoplatelets (GLPs) acting as solid lubricants. Therefore, Al₂O₃ and Si₃N₄ ceramic powders with addition of GLPs of grade 3 (fine) or grade 4 (coarse) were Spark Plasma Sintered. It is found that the 0.15 wt% GLPs addition of both grades allows to keep hardness practically at the same level as GLPs-free compacts (~16 GPa). Only larger GLPs additions (2 wt%) caused its evident decrease (down to 14−15 GPa). The ball-on-disc test revealed that only Al₂O₃+0.15 wt% GLPs(3) shows a 50% reduction in wear rate. The post mechanical test examination by SEM confirmed that Al₂O₃ compacts with small GLPs showed smooth wear track, as opposed to those having a Si₃N₄ matrix with large meandering cavities. TEM observations revealed that the wear damage caused by the ball was restricted to ~2 µm deep sub-surface areas, while, carbon is found to transfer from the GLPs agglomerates into tribo-film. The present experiments showed, that ceramic sinters with small addition of GLPs platelets could exhibit lower wear than GLPs-free ones and therefore show a potential for application as cutting plates.     

The interfacial and tribological properties of Ni–Cr alloy/ceramic tribo-couples under dry sliding contact

In this paper, the tribological behaviors of Ni–Cr alloy sliding against Si₃N₄ and WC–Co at 20 °C and 600 °C were investigated on a tribometer with a ball-on-disk configuration. The experimental results indicated that Ni–Cr alloy sliding against WC–Co exhibited higher wear resistance than that sliding against Si₃N₄. From the viewpoints of the interfacial interactions between metal and ceramic (chemical reaction, wetting, adhesion, transference), the wear mechanisms were elucidated. The tribological behaviors of Ni–Cr alloy/ceramic tribo-couples were well correlated with the interfacial characteristics, namely the reactive interface and the non-reactive interface. Ni–Cr alloy/Si₃N₄ tribo-couple showed severe adhesive wear as a result of the interfacial reaction between Ni and Si₃N₄, while the non-reactivity of Ni/WC interface is the most important factor corresponding to the moderate adhesive wear in Ni–Cr alloy sliding against WC–Co. Finally, the relations among the interfacial characteristics, wear behavior, and temperature were discussed. The results may provide some experimental evidences on the design and optimization of metal/ceramic tribo-couples.     

Tribological properties of Si3N4–graphene nanocomposites

Mechanical and tribological properties of nanocomposites with silicon nitride matrix with addition of 1 and 3 wt% of various types of graphene platelets were studied. The wear behavior was observed by means of the ball-on-disk technique with a silicon nitride ball used as the tribological counterpart at room temperature in dry sliding. Coefficient of friction and specific wear rates were calculated and related to the damage mechanisms observed in the wear tracks. The measured properties were then assessed with respect to the type and volume fraction of the graphene additives. It is shown that addition of such amounts of carbon phases does not lower the coefficient of friction. Graphene platelets seem to be integrated into the matrix very strongly and they do not participate in lubricating processes. The best performance offers materials with 3 wt% of larger sized graphene, which have the highest wear resistance.     

Robust and wear resistant in-situ carbon nanotube/Si3N4 nanocomposites with a high loading of nanotubes

Highly homogenous carbon nanotube (CNT)/silicon nitride (Si₃N₄) nanocomposites with high CNTs loadings, up to 22 vol.%, are developed through the in-situ synthesis of CNTs on the ceramic powders, and further densification using the spark plasma sintering technique. The CNTs dispersion degree, the composite density, and their properties, especially the tribological ones, are evaluated and compared with those obtained for nanocomposites processed by the ex-situ method based on the mixing of nanotubes and ceramic powders in a solvent media. Fully dense in-situ 12 vol.% CNTs nanocomposites are 87% and 65% more wear resistant than monolithic Si₃N₄ materials and ex-situ nanocomposites, respectively, in the latter case due to the higher nanotubes dispersion and better mechanical properties attained by the in-situ process. These new in-situ CNTs nanocomposites present multifunctionality and are promising for emerging applications, especially for gasoline direct injection systems.     

Preparation and characterization of Si3N4-based composite ceramic tool materials by microwave sintering

Si₃N₄-based composite ceramic tool materials with (W,Ti)C as particle reinforced phase were fabricated by microwave sintering. The effects of the fraction of (W,Ti)C and sintering temperature on the mechanical properties, phase transformation and microstructure of Si₃N₄-based ceramics were investigated. The frictional characteristics of the microwave sintered Si₃N₄-based ceramics were also studied. The results showed that the (W,Ti)C would hinder the densification and phase transformation of Si₃N₄ ceramics, while it enhanced the aspect-ratio of β-Si₃N₄ which promoted the mechanical properties. The Si₃N₄-based composite ceramics reinforced by 15 wt% (W,Ti)C sintered at 1600 °C for 10 min by microwave sintering exhibited the optimum mechanical properties. Its relative density, Vickers hardness and fracture toughness were 95.73 ± 0.21%, 15.92 ± 0.09 GPa and 7.01 ± 0.14 MPa m^1/2, respectively. Compared to the monolithic Si₃N₄ ceramics by microwave sintering, the sintering temperature decreased 100 °C,the Vickers hardness and fracture toughness were enhanced by 6.7% and 8.9%, respectively. The friction coefficient and wear rate of the Si₃N₄/(W,Ti)C sliding against the bearing steel increased initially and then decreased with the increase of the mass fraction of (W,Ti)C., and the friction coefficient and wear rate reached the minimum value while the fraction of (W,Ti)C was 15 wt%.     

Influence of hBN content on mechanical and tribological properties of Si3N4/BN ceramic composites

Silicon nitride materials containing 1–5 wt% of hexagonal boron nitride (micro-sized or nano-sized) were prepared by hot-isostatic pressing at 1700 °C for 3 h. Effect of hBN content on microstructure, mechanical and tribological properties has been investigated. As expected, the increase of hBN content resulted in a sharp decrease of hardness, elastic modulus and bending strength of Si₃N₄/BN composites. In addition, the fracture toughness of Si₃N₄/micro BN composites was enhanced comparing to monolithic Si₃N₄ because of toughening mechanisms in the form of crack deflection, crack branching and pullout of large BN platelets. The friction coefficient was not influenced by BN addition to Si₃N₄/BN ceramics. An improvement of wear resistance (one order of magnitude) was observed when the micro hBN powder was added to Si₃N₄ matrix. Mechanical wear (micro-failure) and humidity-driven tribochemical reaction were found as main wear mechanisms in all studied materials.     

Microstructures and EMI shielding properties of composite ceramics reinforced with carbon nanowires and nanowires-nanotubes hybrid

Carbon/ceramic composites are promising candidates as electromagnetic interference (EMI) shielding materials used at various harsh environments. The aim of present work is to prepare and investigate two kinds of composite ceramics reinforced with carbon nanowires (CNWs) and nanowires-nanotubes (CNWs-CNTs) hybrid, respectively. Results indicate that CNWs is highly curved and multi-defected, and CNWs-CNTs hybrid shows the best crystal structure at an optimal catalyst concentration of 5 wt%. When CNWs accounts for 5.15 wt%, the total shielding effectiveness (SE) of CNWs/Si₃N₄ reaches 25.0 dB with absorbed SE of 21.3 dB, meaning that 99.7% incident signal can be blocked, while it reaches 25.4 dB for CNWs-CNTs/Si₃N₄ as the carbon loading only increasing to 3.91 wt%. By contrast, CNWs/Si₃N₄ exhibits better electromagnetic attenuation capability with stronger absorption, mainly due to the unique microstructure of CNWs. Both of two composite ceramics have great potential to be designed as structural and multi-functional materials.     

Frictional behavior and wear resistance performance of gradient cermet composite tool materials sliding against hard materials

Gradient cermet composites possessing high surface hardness, flexural strength and interface bonding strength were fabricated using vacuum hot-pressing sintering. Ball-on-disk tests were performed to investigate the tribological properties of the gradient cermet composites against 440 C stainless steel, Al₂O₃ and Si₃N₄ balls at different sliding speed and load in comparison with traditional Ti(C,N) cermets. The tribological behavior was characterized in terms of friction coefficient and wear rate. The results showed that friction coefficient was significantly dependent on the sliding speed and load when sliding against Al₂O₃ and Si₃N₄. However, there was no obvious relation between them during sliding against 440 C stainless steel due to the formation of metal adhesive layer. Gradient cermet composites exhibited a higher friction coefficient but lower wear rate than traditional Ti(C,N) cermets. The main wear mechanism of gradient cermet composites was adhesion wear during sliding against 440 C stainless steel, while abrasion wear was the predominant mechanism during sliding against Al₂O₃ and Si₃N₄. It was expected that gradient cermet composites would be excellent candidates for cutting tool materials.     

Structure–property relations of ferroelectric BaTiO3 ceramics containing nano-sized Si3N4 particulates

Barium titanate/silicon nitride (BaTiO₃/xSi₃N₄) powder (when x = 0, 0.1, 0.5, 1 and 3 wt%) were prepared by solid-state mixed-oxide method and sintered at 1400 °C for 2 h. X-ray diffraction result suggested that tetragonality (c/a) of the BaTiO₃/xSi₃N₄ ceramics increased with increasing content of Si₃N₄. Density and grain size of BaTiO₃/xSi₃N₄ ceramic were found to increase for small addition (i.e. 0.1 and 0.5 wt%) of Si₃N₄ mainly due to the presence of liquid phase during sintering. BaTiO₃ ceramics containing such amount of Si₃N₄ also showed improved dielectric and ferroelectric properties.     

Microstructure and fracture toughness of Si3N4 + graphene platelet composites

Silicon nitride + 1 wt% graphene platelet composites were prepared using various graphene platelets (GPLs) as filler. The influence of the addition of GPLs on the microstructure development and on the fracture toughness of Si₃N₄ + GPLs composites was investigated. The GPLs with thickness from 5 nm to 50 nm are relatively homogeneously distributed in the matrix of all composites, however overlapping/bundle formation of GPLs was found, containing 2–4 platelets as well. The single GPLs and overlapped GPLs are located at the boundaries of Si₃N₄, and hinder the grain growth and change the shape of the grains. The fracture toughness was significantly higher for all composites in comparison to the monolithic Si₃N₄ with the highest value of 9.9 MPa m^0.5 for the composite containing the GPLs with smallest dimension. The main toughening mechanisms originated from the presence of graphene platelets, and responsible for the increase in the fracture toughness values are crack deflection, crack branching and crack bridging.     

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.     

Nitrogen-doped-CNTs/Si3N4 nanocomposites with high electrical conductivity

Novel highly electrically conducting nanocomposites consisting of a silicon nitride (Si₃N₄) ceramic matrix containing up to 13.6 vol.% of nitrogen-doped multi-walled carbon nanotubes (CNx) were fabricated. As-synthesized CNx were treated with hydrogen peroxide in order to efficiently detach/isolate the nanotubes from bundles, then they were mixed with the ceramic powders and fully densified using the spark plasma sintering (SPS) technique. Composites containing 13.6 vol.% CNx reached an electrical conductivity of 2174 S m⁻¹ that is the highest value reported hitherto for carbon nanotubes/Si₃N₄ nanocomposites. The nitrogen doping also favored a strong mechanical interlocking between the nanotubes and the Si₃N₄ matrix; when compared to the undoped carbon nanotubes. These novel nanocomposites could be used in devices associated to power generation or telecommunications.     

Wear maps of HIP sintered Si3N4/MLG nanocomposites for unlike paired tribosystems under ball-on-disc dry sliding conditions

Hot isostatically pressed monolithic and multilayer graphene (MLG) reinforced silicon nitride nanocomposites have been investigated by ball-on-disc tests under variable loading conditions. Tests were carried out at room temperature with three different normal loads (10, 40 and 80 N), and six sliding speeds (10, 20, 50, 100, 150 and 200 mm/s) without lubrication using commercial silicon carbide ball counterparts for 54 tribosystems. The aim of the research work was to construct 2D wear transition and 3D wear rate maps of the investigated ceramic composites. The 3D maps visualizing the specific wear rate and the dimensionless wear coefficient as a function of normal load and sliding speed have been completed with morphological analysis of wear tracks and identification of the dominant wear mechanisms. The presented ceramic wear maps provide useful aid for predicting the wear performance of the investigated nanocomposites under various loading conditions.     

Diamond dispersed Si3N4 composites obtained by pulsed electric current sintering

30 vol.% 2 and 30 μm diamond dispersed Si₃N₄ matrix composites were prepared by pulsed electric current sintering (PECS) for 4 min at 100 MPa in the 1550–1750 °C range. The densification behaviour, microstructure, Si₃N₄ phase transformation and stiffness of the composites were assessed, as well as the thermal stability of the dispersed diamond phase. Monolithic Si₃N₄ with 4 wt% Al₂O₃ and 5 wt% Y₂O₃ sintering additives was fully densified at 1550 °C for 4 min and 60 MPa. The densification and α to β-Si₃N₄ transformation were substantially suppressed upon adding 30 vol.% diamond particles. Diamond graphitisation in the Si₃N₄ matrix was closely correlated to the sintering temperature and grit size. The dispersed coarse grained diamonds significantly improved the fracture toughness of the diamond composite, whereas the Vickers hardness was comparable to that of the Si₃N₄ matrix ceramic. The Elastic modulus measurements were found to be an excellent tool to assess diamond graphitisation in a Si₃N₄ matrix.     

Sintering behavior of ZrB2–SiC composites doped with Si3N4: A fractographical approach

ZrB₂–SiC composite ceramics were doped with 0, 1, 3 and 5 wt% Si₃N₄ plus 1.6 wt% carbon (pyrolized phenolic resin) as sintering aids and fabricated by hot pressing process under a relatively low pressure of 10 MPa at 1900 °C for 2 h. For a comparative study, similar ceramic compositions were also prepared by pressureless sintering route in the same processing conditions, with no applied external pressure. The effect of silicon nitride dopant on the microstructural evolution and sintering process of such ceramic composites was investigated by a fractographical approach as well as a thermodynamical analysis. The relative density increased by the addition of Si₃N₄ in hot pressed samples as a fully dense composite was achieved by adding 5 wt% silicon nitride. A reverse trend was observed in pressureless sintered composites and the relative density values decreased by further addition of Si₃N₄, due to the formation of gaseous products which resulted in the entrapment of more porosities in the final structure. The formation of ZrC phases in pressureless sintered samples and layered BN structures in hot pressed ceramics was detected by HRXRD method and discussed by fractographical SEM-EDS as well as thermodynamical analyses.     

Microstructure and tribological properties of cubic boron nitride films on Si3N4 inserts via boron-doped diamond buffer layers

Cubic boron nitride (cBN) coatings were deposited on silicon nitride (Si₃N₄) cutting inserts through conductive boron-doped diamond (BDD) buffer layers in an electron cyclotron resonance microwave plasma chemical vapor deposition (ECR MPCVD) system. The adhesion and crystallinity of cBN coatings were systematically characterized, and the influence of doping level of BDD on the phase composition and microstructure of the cBN coatings were studied. The nano-indentation tests showed that the hardness and elastic modulus of the obtained cBN coatings were 78 GPa and 732 GPa, respectively. The tribological properties of the cBN coatings were evaluated by using a ball-on-disc tribometer with Si₃N₄ as the counterpart. The coefficient of the friction and the wear rate of the cBN coatings were estimated to be about 0.17 and 4.1 × 10^− 7 mm³/N m, respectively, which are remarkably lower than those of titanium aluminum nitride (TiAlN) coatings widely used in machining ferrous metal. The results suggest that cBN/BDD coated Si₃N₄ inserts may have great potentials for advanced materials machining.     

Single-source-precursor synthesis of soft magnetic Fe3Si- and Fe5Si3-containing SiOC ceramic nanocomposites

We present here the single-source-precursor synthesis of Fe₃Si and Fe₅Si₃-containing SiOC ceramic nanocomposites and investigation of their magnetic properties. The materials were prepared upon chemical modification of a hydroxy- and ethoxy-substituted polymethylsilsesquioxane with iron (III) acetylacetonate (Fe(acac)₃) in different amounts (5, 15, 30 and 50 wt%), followed by cross-linking at 180 °C and pyrolysis in argon at temperatures ranging from 1000 °C to 1500 °C. The polymer-to-ceramic transformation of the iron-modified polysilsesquioxane and the evolution at high temperatures of the synthesized SiFeOC-based nanocomposite were studied by means of thermogravimetric analysis (TGA) coupled with evolved gas analysis (EGA) as well as X-ray diffraction (XRD). Upon pyrolysis at 1100 °C, the non-modified polysilsesquioxane converts into an amorphous SiOC ceramic; whereas the iron-modified precursors lead to Fe₃Si/SiOC nanocomposites. Annealing of Fe₃Si/SiOC at temperatures exceeding 1300 °C induced the crystallization of Fe₅Si₃ and β-SiC. The crystallization of the different iron-containing phases at different temperatures is considered to be a consequence of the in situ generation of a Fe–C–Si alloy within the materials during pyrolysis. Depending on the Fe and Si content in the alloy, either Fe₃Si and graphitic carbon (at 1000–1200 °C) or Fe₅Si₃ and β-SiC (at T > 1300 °C) crystallize. All SiFeOC-based ceramic samples were found to exhibit soft magnetic properties. Magnetization versus applied field measurements of the samples show a saturation magnetization up to 26.0 emu/g, depending on the Fe content within the SiFeOC-based samples as well as on the crystalline iron silicide phases formed during pyrolysis.     

In situ synthesis of Si2N2O/Si3N4 composite ceramics using polysilyloxycarbodiimide precursors

In situ synthesis of Si₂N₂O/Si₃N₄ composite ceramics was conducted via thermolysis of novel polysilyloxycarbodiimide ([SiOSi(NCN)₃]_n) precursors between 1000 and 1500 °C in nitrogen atmosphere. The relative structures of Si₂N₂O/Si₃N₄ composite ceramics were explained by the structural evolution observed by electron energy-loss spectroscopy but also by Fourier transform infrared and ²⁹Si-NMR spectrometry. An amorphous single-phase Si₂N₂O ceramic with porous structure with pore size of 10–20 μm in diameter was obtained via a pyrolyzed process at 1000 °C. After heat-treatment at 1400 °C, a composite ceramic was obtained composed of 53.2 wt.% Si₂N₂O and 46.8 wt.% Si₃N₄ phases. The amount of Si₂N₂O phase in the composite ceramic decreased further after heat-treatment at 1500 °C and a crystalline product containing 12.8 wt.% Si₂N₂O and 87.2 wt.% Si₃N₄ phases was obtained. In addition, it is interesting that residual carbon in the ceramic composite nearly disappeared and no SiC phase was observed in the final Si₂N₂O/Si₃N₄ composite.