Al2O3/Si3N4 nanocomposite coating on aluminum alloy by the anodizing route: Fabrication,characterization, mechanical properties and electrochemical behavior

An Al₂O₃/Si₃N₄ nanocomposite coating was successfully fabricated on commercial aluminum alloy. Hardness measurements, polarization and electrochemical impedance spectroscopy (EIS) were employed to study the mechanical and corrosion behaviors of the coatings. Field-Emission Scanning Electron Microscopy (FE-SEM) equipped with Energy Dispersive Spectroscopy (EDS) and X-ray diffraction (XRD) were utilized to characterize the surface morphology and phase composition of the coatings. Also, coatings abrasive wear properties were evaluated with a modified ASTM G105 standard. FE-SEM image, EDS and XRD analysis revealed the presence of Si₃N₄ in the coating. Furthermore, the results showed hardness of the coatings to increase from 380±50 HV for the anodized layer to 712±36 HV for the composite coatings that were formed in an electrolyte containing 6 gr/lit Si₃N₄ nanoparticles. Electrochemical measurements indicated that corrosion resistance of the nanocomposite coating significantly increased compared to the anodized coating. In addition, the effect of Si₃N₄ nanoparticles into the nanocomposite coatings on abrasive wear mechanism and mass loss rate of the coatings was investigated.     

A MoSi2-SiOC-Si3N4/SiC anti-oxidation coating for C/C composites prepared at relatively low temperature

In this study, SiC coating for C/C composites was prepared by pack cementation method at 1773 K, and MoSi₂-SiOC-Si₃N₄ as an outer coating was successfully fabricated on the SiC coated samples by slurry method at 1273 K. The microstructure and phase composition of the coatings were analyzed. Results showed that a porous β-SiC inner coating and a crack-free MoSi₂-SiOC-Si₃N₄ coating are formed. Effect of Si₃N₄ content on the oxidation resistance of the coated C/C composites at 1773 K in air was also investigated. The weight loss curves revealed that introducing the appropriate proportion of Si₃N₄ could improve the oxidation resistance of coating. The MoSi₂-SiOC/SiC coated C/C sample had an accelerated weight loss after oxidation in air for 20 h. However, the coating containing 45% Si₃N₄ could protect C/C composition from oxidation for 100 h with a minute weight loss of 0.63%.     

Synthesis and characterization of yttrium and ytterbium silicates from their oxides and an oligosilazane by the PDC route for coating applications to protect Si3N4 in hot gas environments

Environmental barrier coatings are required to protect Si₃N₄ against hot gas corrosion and enable its application in gas turbines, among which yttrium and ytterbium silicate-coatings stand out. Thus, the polymer-derived ceramic route was used to synthesize these silicates for basic investigations regarding their intrinsic properties from a mixture of Y₂O₃ or Yb₂O₃ powders and the oligosilazane Durazane 1800. After pyrolysis above 1200 °C in air, the silicates are predominant phases. The corrosion behaviour of the resulting composites was tested at 1400 °C for 80 h in moist environments. The material containing x₂-Yb₂SiO₅ and Yb₂Si₂O₇ undergoes the lowest corrosion rate (−1.8 μg cm⁻² h⁻¹). Finally, the processing of Y₂O₃/Durazane 1800 as well-adherent, crack-free and thick (40 μm) coatings for Si₃N₄ was achieved after pyrolysis at 1400 °C in air. The coating consisted of an Y₂O₃/Y₂SiO₅ top-layer and an Y₂O₃/Y₂Si₂O₇ interlayer due to the interaction of the coating system with the substrate.     

Damage resistance of SiC and Si3N4 coatings with control of microstructure and thickness

We investigated the contact damage and indentation stress–strain behavior of silicon carbide (SiC) coatings and binary coatings consisting of SiC and silicon nitride (Si₃N₄), synthesized on graphite substrates with porosities of 10 and 13% by a solid–vapor reaction, in order to determine the coatings’ damage resistance. The coating thickness was affected by the porosity of the substrate. The coatings on the substrate with 13% porosity showed a graded interface structure below the top dense layer. The SiC coatings were thicker than the SiC/Si₃N₄ composite coatings. The SiC coatings made the substrates hard, and SiC-coated substrates exhibited higher stress–strain curves than the substrates alone, but the SiC/Si₃N₄ composite coatings appeared unaffected. The coating thickness played an important role in limiting the effect of damage. The hardness values of the SiC coatings were higher than those of the substrates and the SiC/Si₃N₄ coatings. These corresponded well with the indentation stress–strain curves. The values of each coating showed saturated points depending on the applied load. This indicated that the substrate itself influenced the damage resistance of the coatings because of the layered structure of a harder coating with a softer substrate. The coatings enhanced contact damage and transmitted the damage to the substrates at a high load of P = 2000 N. Both coatings showed an extensive subsurface damage, independent of the porosity of the substrate. In cyclic indentation tests, the contact diameters linearly increased with the number of cycles and depended on the porosity of the substrate, showing smaller contact diameters by coating the substrate.     

Chemical synthesis of TiO2 nanoparticles and their inclusion in Ni–P electroless coatings

The work addresses the preparation of Ni3P3TiO₂ nanocomposite coatings on mild steel substrate by the electroless technique. Nanosized TiO₂ particles were first synthesized by the precipitation method and then were codeposited (4 g/l) into the Ni3P matrix using alkaline hypophosphite reduced EL bath. The surface morphology, particle size, elemental composition and phase analysis of as-synthesized TiO₂ nanoparticles and the coatings were characterized by field emission scanning electron microscopy (FESEM), energy-dispersive analysis of X-ray (EDAX) and X-ray diffraction (XRD). Coatings with 20 µm thickness were heat treated at 400 °C for 1 h in argon atmosphere. The morphology, microhardness, wear resistance and friction coefficient characteristics (ball on disc) of electroless Ni3P3TiO₂ nanocomposite coatings were determined and compared with Ni3P coatings. The results show that as-synthesized TiO₂ nanoparticles are spherical in shape with a size of about12 nm. After heat treatment, the microhardness and wear resistance of the coatings are improved significantly. Superior microhardness and wear resistance are observed for Ni3P3TiO₂ nanocomposite coatings over Ni3P coatings.     

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.     

Effect of Ti particle size on mechanical and tribological properties of TiCN coatings prepared by reactive plasma spraying

Titanium carbonitride (TiCN) coatings were successfully fabricated by reactive plasma spraying (RPS) from agglomerated Ti-graphite feedstock. The effect of Ti particle size on the microstructure and phase composition of plasma sprayed TiCN coatings was investigated. The Vickers microhardness of coatings was measured by a Microhardness Test and the corresponding Weibull distribution were also analyzed. In addition, a pin-on-disk tribometer was employed to determine the trobological properties of coatings. Results show that all the coatings consist of TiC_xN_1−x (0 ≤ x ≤1) and minor Ti₂O phases, and the amount of Ti₂O increases with the increase of Ti particle size. The Weibull distribution of Vickers microhardness of all the coatings shows apparent scattering, while the coating sprayed with Ti particle size of 28 µm exhibits a relatively even distribution. Compared with the coating sprayed with Ti particle size of 14 µm or 48 µm, the coating sprayed with Ti particle size of 28 µm exhibits improved mechanical and tribological properties, which are attributed to the high microhardness and strong bonding strength.     

Friction and wear property of a-CNx coatings sliding against ceramic and steel balls in water

The amorphous carbon nitride coatings (a-CN_x) were deposited on Si₃N₄ disks using ion beam assisted deposition (IBAD), and their composition and chemical bonding were determined by X-ray photoelectron spectroscopy (XPS). The a-CN_x coatings' hardness was measured by nano-indentation and the friction and wear property of the a-CN_x coatings sliding against Si₃N₄, SiC, Al₂O_3, SUS440C and SUJ2 balls in water were investigated by using ball-on-disk tribo-meter. The worn surfaces were observed using optical microscopy and analyzed by XPS. The results of XPS analysis showed that the a-CN_x coatings contained 12 at.% nitrogen and the major chemical bonding was sp² C = N and sp³C–N. The nano-hardness of the a-CN_x coatings was 29 GPa, higher than those of balls. Among five kinds of tribo-systems, the lowest friction coefficient was obtained in the range of 0.01 to 0.02 for the tribo-systems with SiC and Si₃N₄ balls, the largest wear rate of the a-CN_x coating of 1.77 × 10^− 7 mm³/Nm was obtained as sliding against Al₂O₃ ball, while the smallest wear rate of a-CN_x coating of 1.44 × 10^− 8 mm³/Nm was gotten as sliding against Si₃N₄ ball. However, SUJ2 ball showed the highest wear rate of 7.0 × 10^− 7 mm³/Nm, whereas Al₂O₃ ball exhibited the lowest wear rate of ball of 3.55 × 10^− 9 mm³/Nm. The XPS analysis on the worn surface for the a-CN_x coatings displayed that the nitrogen concentration decreased and the sp²-bonding-rich structure was formed after sliding tests in water.     

Improved electromagnetic absorbing properties of Si3N4–SiC/SiO2 composite ceramics with multi-shell microstructure

Porous Si₃N₄–SiC composite ceramic was fabricated by infiltrating SiC coating with nano-scale crystals into porous β-Si₃N₄ ceramic via chemical vapor infiltration (CVI). Silica (SiO₂) film was formed on the surface of rod-like Si₃N₄–SiC grains during oxidation at 1100 °C in air. The as-received Si₃N₄–SiC/SiO₂ composite ceramic attains a multi-shell microstructure, and exhibits reduced impedance mismatch, leading to excellent electromagnetic (EM) absorbing properties. The Si₃N₄–SiC/SiO₂ fabricated by oxidation of Si₃N₄–SiC for 10 h in air can achieve a reflection loss of ?30 dB (>99.9% absorption) at 8.7 GHz when the sample thickness is 3.8 mm. When the sample thickness is 3.5 mm, reflection loss of Si₃N₄–SiC/SiO₂ is lower than ?10 dB (>90% absorption) in the frequency range 8.3–12.4 GHz, the effective absorption bandwidth is 4.1 GHz.     

Corrosion behavior of porous silicon nitride ceramics in different atmospheres

The corrosion behavior of silicon nitride (Si₃N₄) ceramics with a porosity of 46% at 1200–1500 °C under different conditions including dry O₂, O₂ containing 20 vol% H₂O and Ar containing 20 vol% H₂O is compared. The results show that porous Si₃N₄ ceramics exhibit good oxidation resistance up to 1200 °C. Their corrosion behavior varies depending on the temperature and atmosphere. Water vapor can obviously affect the morphology of the reaction product and thus accelerate the corrosion rate due to its specific inward diffusion mechanism and devitrified effect at high temperature. In view of the reaction kinetics, it proceeds in a diffusion-controlled manner in dry O₂ while follows the parabolic-linear law at water-containing atmosphere. Furthermore, a new model considering both oxidation and volatilization reactions is established. These provide a baseline for expanding the application fields of non-oxide porous ceramics such as Si₃N₄ and silicon carbide (SiC) etc.     

Synthesis,electromagnetic reflection loss and oxidation resistance of pyrolytic carbon-Si3N4 ceramics with dense Si3N4 coating

Si₃N₄-coated porous pyrolytic carbon-Si₃N₄ ceramics (PyC-Si₃N₄/Si₃N₄) were fabricated by chemical vapour infiltration of PyC into porous Si₃N₄ ceramic and then chemical vapour deposition of Si₃N₄ coating on the surface of the obtained PyC-Si₃N₄. The PyC-Si₃N₄/Si₃N₄ with 3.1 vol.% PyC content possesses electromagnetic reflection loss as low as ?11.5 dB. Due to the excellent sealing effect of dense Si₃N₄ coating, the PyC-Si₃N₄/Si₃N₄ possesses good oxidation resistance, which makes PyC-Si₃N₄/Si₃N₄ a good electromagnetic absorbing material that can be used at temperature as high as 1100 °C.     

Catalytic nitridation preparation of high-performance Si3N4(w)-SiC composite using Fe2O3 nano-particle catalyst: Experimental and DFT studies

The complete conversion from Si into Si₃N₄ was achieved after 2 h nitridation at 1400 °C by using in-situ formed Fe₂O₃ nano-particles (NPs) as a catalyst. Such a synthesis condition was remarkably milder than that (>1450 °C for many hours) required by the conventional Si nitridation method. Density functional theory (DFT) calculations suggest that Fe₂O₃ catalyst accelerates the Si nitridation via weakening the bond strength of absorbed N₂ molecule. Furthermore, Si₃N_4(w)-SiC composites prepared by the present catalytic nitridation method showed excellent high-temperature properties including modulus of rupture (MOR of 29.9 MPa at 1400 °C), thermal shock resistance (residual MOR percentage of 50% at ΔT = 1300 °C), as well as good oxidation resistance and cryolite corrosion resistance against molten cryolite. It can be concluded that, Fe₂O₃ NPs not only greatly accelerated the Si nitridation and Si₃N₄ formation, but also facilitated the epitaxial growth of reinforcement phase of Si₃N₄ whisker in the Si₃N_4(w)-SiC composites.     

Mechanical properties and microstructure of porous BN–SiO2–Si3N4 composite ceramics

Porous silicon nitride (Si₃N₄) ceramics incorporated with hexagonal boron nitride (h-BN) and silica (SiO₂) nanoparticles were fabricated by pressureless-sintering at relatively low temperature, in which stearic acid was used as pore-making agent. Bending strength at room and high temperatures, thermal shock resistance, fracture toughness, elastic modulus, porosity and microstructure were investigated in detail. The mechanical properties and thermal shock resistance behavior of porous Si₃N₄ ceramics were greatly influenced by incorporation of BN and SiO₂ nanoparticles. Porous BN–SiO₂–Si₃N₄ composites were successfully obtained with good critical thermal shock temperature of 800 °C, high bending strength (130 MPa at room temperature and 60 MPa at 1000 °C) and high porosity.     

The preparation of silicon nitride ceramics by gelcasting and pressureless sintering

A new gelling system based on the polymerization of hydantion epoxy resin and 3,3′-Diaminodipropylamine (DPTA) was successfully developed for fabricating silicon nitride (Si₃N₄) ceramics. The effects of pH value, the dispersant content, solid volume fraction and hydantion epoxy resin amount on the rheological properties of the Si₃N₄ slurries were investigated. The relative density of green body obtained from the solid loading of 52 vol% Si₃N₄ slurry reached up to 62.7%. As the concentration of hydantion epoxy resin increased from 5 wt% to 20 wt%, the flexural strength of Si₃N₄ green body enhanced from 5.3 MPa to 31.6 MPa. After pressureless sintering at 1780 °C for 80 min, the sintered samples exhibited the unique interlocking microstructure of elongated β-Si₃N₄ grains, which was beneficial to improve the mechanical properties of Si₃N₄ ceramics. The relative density, flexural strength and fracture toughness of Si₃N₄ ceramics reached 97.8%, 687 MPa and 6.5 MPa m^1/2, respectively.     

Performance of EP/PpPDA and EP/PpPDA/SiO2 nanocomposite on corrosion inhibition of steel in hydrochloric acid solution

Epoxy-poly p-phenylendiamine (EP/PpPDA) and its nanocomposite with SiO₂ nanoparticles (EP/PpPDA/SiO₂) were synthesized and tested as potential corrosion inhibitors of steel in 1 M HCl solution. Performance of EP/PpPDA/SiO₂ and EP/PpPDA coatings on protection of steel against corrosion was investigated using potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), and Atomic force microscopy (AFM) and at various temperatures between 298 and 328 K. Changes in the coating resistance and charge-transfer resistance with temperature were analyzed to determine the activation energies of the processes involved. The determined values of activation energy showed that the EP/PpPDA/SiO₂ coating has better anti-corrosion effect than EP/PpPDA. The thermodynamic functions of dissolution processes were also calculated and discussed. The results from AFM observations indicated that the presence of SiO₂ nanoparticles increased the roughness of Epoxy-poly p-phenylendiamine/SiO₂ nanocomposite (EP/PpPDA/SiO₂). It was finally concluded that the presence of silica nanoparticles enhance the protection properties of EP/PpPDA coating as a novel potential corrosion inhibitor for steel.     

Investigation of corrosion protection properties of an epoxy nanocomposite loaded with polysiloxane surface modified nanosilica particles on the steel substrate

In this study, it has been aimed to investigate the corrosion protection properties of an epoxy/polyamide coating loaded with different concentrations (ranged from 3 to 6% (w/w)) of the polysiloxane surface modified silica nanoparticles (nano-SiO₂). The nanocomposites were applied on the steel substrates. Field emission scanning electron microscope (FE-SEM) and UV–vis techniques were utilized in order to investigate the nanoparticles dispersion in the coating matrix. The effects of addition of nanoparticles on the corrosion resistance of the coating were studied by an electrochemical impedance spectroscopy (EIS) and salt spray test. The coating surface degradation was studied by optical microscope and Fourier transform infrared radiation (FT-IR) spectroscopy. Results obtained from UV–vis and FE-SEM analyses revealed proper and uniform distribution of surface modified nanoparticles in the epoxy coating matrix. It was shown that the coating corrosion protection properties were significantly enhanced in the presence of 5 wt% silica nanoparticles. Less degradation occurred on the surface of the coatings loaded with 5 wt% nanoparticles.     

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.     

Microstructure and mechanical properties of tantalum carbide ceramics: Effects of Si3N4 as sintering aid

Stoichiometric Tantalum carbide (TaC) ceramics were prepared by reaction spark plasma sintering using 0.333–2.50 mol% Si₃N₄ as sintering aid. Effects of the Si₃N₄ addition on densification, microstructure and mechanical properties of the TaC ceramics were investigated. Si₃N₄ reacted with TaC and tantalum oxides such as Ta₂O₅ to form a small concentration of tantalum silicides, SiC and SiO₂, with significant decrease in oxygen content in the consolidated TaC ceramics. Dense TaC ceramics having relative densities >97% could be obtained at 0.667% Si₃N₄ addition and above. Average grain size in the consolidated TaC ceramics decreased from 11 µm at 0.333 mol% Si₃N₄ to 4 µm at 2.50 mol% Si₃N₄ addition. The Young's modulus, Vickers hardness and flexural strength at room temperature of the TaC ceramic with 2.50 mol% Si₃N₄ addition was 508 GPa, 15.5 GPa and 605 MPa, respectively. A slight decrease in bending strength was observed at 1200 °C due to oxidation of the samples.     

Pressureless sinterability of slip cast silicon nitride bodies prepared from coprecipitation-coated powders

The sinterability of compositions from different powder preparation methods (coprecipitation-coating of Si₃N₄ powder or mechanical mixing of Si₃N₄ with Y₂O₃ and Al₂O₃) and compaction routes (dry pressing or slip casting) was compared. Both the coating method and the slip casting process improved silicon nitride sinterability over the mechanical mixing method and dry pressing route. However, the minimisation of powder agglomeration in the green bodies achieved by slip casting is more determinant to the sintering behaviour than the homogeneous distribution of the sintering additives around the Si₃N₄ offered by the coated powder. The coating powder method in combination with the slip casting process is the most favourable processing route, leading to a homogeneous and fully dense microstructure by pressureless sintering at a relatively low temperature of 1750°C. This technique produced materials with hardness of 15·2 GPa, fracture toughness of 7 MPa  m^1/2 and flexural bending strength of 910 MPa.     

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.