Deposition and characterization of CrN/Si3N4 and CrAlN/Si3N4 nanocomposite coatings prepared using reactive DC unbalanced magnetron sputtering

Nanocomposite coatings of CrN/Si₃N₄ and CrAlN/Si₃N₄ with varying silicon contents were synthesized using a reactive direct current (DC) unbalanced magnetron sputtering system. The Cr and CrAl targets were sputtered using a DC power supply and the Si target was sputtered using an asymmetric bipolar-pulsed DC power supply, in Ar + N₂ plasma. The coatings were approximately 1.5 μm thick and were characterized using X-ray diffraction (XRD), nanoindentation, X-ray photoelectron spectroscopy and atomic force microscopy. Both the CrN/Si₃N₄ and CrAlN/Si₃N₄ nanocomposite coatings exhibited cubic B1 NaCl structure in the XRD data, at low silicon contents (< 9 at.%). A maximum hardness and elastic modulus of 29 and 305 GPa, respectively were obtained from the nanoindentation data for CrN/Si₃N₄ nanocomposite coatings, at a silicon content of 7.5 at.%. (cf., 24 and 285 GPa, respectively for CrN). The hardness and elastic modulus decreased significantly with further increase in silicon content. CrAlN/Si₃N₄ nanocomposite coatings exhibited a hardness and elastic modulus of 32 and 305 GPa, respectively at a silicon content of 7.5 at.% (cf., 31 and 298 GPa, respectively for CrAlN). The thermal stability of the coatings was studied by heating the coatings in air for 30 min in the temperature range of 400-900 °C. The microstructural changes as a result of heating were studied using micro-Raman spectroscopy. The Raman data of the heat-treated coatings in air indicated that CrN/Si₃N₄ and CrAlN/Si₃N₄ nanocomposite coatings, with a silicon content of approximately 7.5 at.% were thermally stable up to 700 and 900 °C, respectively.     

Structure and mechanical properties of TiAlSiN/Si3N4 multilayer coatings

TiAlSiN/Si₃N₄ multilayer coatings which have different separate layer thicknesses of TiAlSiN or Si₃N₄ were deposited onto glass sheets, single-crystal silicon wafers and polished WC-Co substrates by reactive magnetron co-sputtering. The morphology, crystalline structure and thickness of the as-prepared multilayer coatings were characterized by TEM, SEM, XRD and film thickness measuring instrument. The mechanical properties of the coatings were evaluated by a nanoindenter. The effects of monolayer thickness on the microstructure and properties of TiAlSiN/Si₃N₄ multilayer coatings were explored. The coatings showed the highest hardness when the thickness of Si₃N₄ and TiAlSiN monolayers was 0.33 nm and 5.8 nm, respectively. The oxidation characteristics of the coatings were studied at temperatures ranging from 700 °C to 900 °C for oxidation time up to 20 h in air. It was found that the coatings displayed good oxidation resistance.     

Thermal shock behavior of Si3N4-TiN nano-composites

Si₃N₄-TiN nano-composites were fabricated by hot press sintering nano-sized Si₃N₄ and TiN powders. The microstructure, mechanical properties and thermal shock behavior of Si₃N₄-TiN nano-composites were investigated. The addition of proper amount TiN particles can significantly increase the flexural strength and the fracture toughness. Si₃N₄-TiN nano-composites showed both higher critical temperature difference and higher residual strength compared with those of monolithic silicon nitride nano-ceramic when the amount of TiN is less than 15 wt.%. But a further increase in the amount of TiN leaded to a decrease in the thermal shock resistance.     

Influence of normal load and sliding speed on the tribological property of amorphous carbon nitride coatings sliding against Si3N4 balls in water

Amorphous carbon nitride (a-CN_x) coatings were deposited on Si₃N₄ disks by an ion beam assisted deposition system. The composition, structure and hardness of the a-CN_x coatings were characterized by Auger electronic spectroscopy, Raman spectroscopy and nano-indentation tester, respectively. The influences of normal load and sliding speed on the friction coefficients and the specific wear rates for the a-CN_x/Si₃N₄ tribo-pairs were investigated and analyzed synthetically by ball-on-disk tribometer. The worn surfaces were observed by optical microscope. The results showed that the a-CN_x coatings contained 12 at.% nitrogen, and their structure was a mixture of sp²and sp³ bonds. The a-CN_x coatings’ nanohardness was 29 GPa. The influence of sliding speed on the friction coefficients and the specific wear rate of the CN_x coatings was more obvious than that of normal load. The friction coefficients and the specific wear rate of the CN_x coatings decreased as the sliding speed increased. At a sliding speed higher than 0.1 m/s, the friction coefficients were less than 0.04. The specific wear rates of the a-CN_x coatings were higher than those of Si₃N₄ balls at a sliding speed below 0.1 m/s, while the specific wear rates of the a-CN_x coatings and the Si₃N₄ balls all fluctuated around a lower level of 10^− 8 mm³/Nm as the sliding speed increased beyond 0.2 m/s. To describe the wear behavior of a-CN_x coatings sliding against Si₃N₄ balls in water with normal loads of 3-15 N and sliding speeds of 0.05-0.5 m/s, the wear-mechanism map for the a-CN_x/Si₃N₄ tribo-pairs in water was developed.     

Effects of pelletization of reactants and diluents on the combustion synthesis of Si3N4 powder

Reactants were pelletized, and then combustion synthesis of Si₃N₄ powder was achieved under the N₂ pressure of 3.0 MPa. Effects of the pelletization of reactants and Si₃N₄ diluents on the combustion process parameters and the characteristics of products were studied. The combustion mode of single reactant pellet was preliminarily discussed. The results indicated that the combustion reaction of single pellet was layer-by-layer from the surface to the core, which led to two peaks on the combustion temperature variation waves. With increasing the diluents content, the morphologies of Si₃N₄ particles changed from short rods into equiaxed grains, and residual Si in the final products obviously decreased. Single phase β-Si₃N₄ powder mainly contained equiaxed grains was prepared when 58 wt.% diluents was added.     

纳米Si3N4 对TC4钛合金微弧氧化层微观结构和性能的影响

在基电解液中加入氮化硅纳米颗粒,对TC4钛合金进行微弧氧化（MAO）处理,研究了Si₃N₄浓度对微弧氧化层表面形貌、耐蚀性和耐磨性的影响。添加Si₃N₄的MAO层呈现多孔结构,当Si₃N₄浓度为1 g/L时,涂层厚度最大,且经过7 d的酸腐蚀试验,该涂层的耐蚀性良好,腐蚀速率最低,约为0.057 mg·cm^-2·d^-1。随着Si₃N₄的加入,MAO涂层的抗菌性能先升高后降低。当Si₃N₄的添加量为1 g/L时,该MAO层的抗菌性能最好。Si₃N₄的加入能明显提高涂层在模拟海水中的耐磨性。当Si₃N₄的添加量为3和4 g/L时,所得涂层的摩擦系数低且稳定,且添加3 g/L Si₃N₄制备来的MAO涂层表现出优异的耐磨性。     

采用Ag-Cu-Ti+Mo复合钎料钎焊Si3N4陶瓷

采用Ag-Cu-Ti+Mo复合钎料连接Si3N4陶瓷,利用SEM,TEM,Nanoindentation研究了钎料内钼颗粒含量对接头组织和力学性能的影响.结果表明,在Si3N4/钎料界面处形成了一层致密的反应层,该反应层由TiN和Ti5Si3组成.接头的中间部分由银基固溶体、铜基固溶体、钼颗粒和Ti-Cu金属间化合物组成.借助于纳米压痕技术测定了接头内Ti-Cu化合物以及钎料金属的弹性模量和硬度值.随着钎料内钼颗粒含量的提高,母材/钎料界面反应层厚度逐渐降低;钎料金属中Ti-Cu化合物数量增多;此外,银和铜基固溶体组织逐渐变得细小.当添加5%Mo时,得到最高的接头强度429.4 MPa,该强度相比合金钎料提高了114.7%.     

Mechanical properties improvement related to the isothermal holding time in Si3N4 ceramics sintered with an alternative additive

In the present work, the influence of the isothermal holding time on the physical (relative density and mass loss), chemical (α–β transformation and intergranular phase crystallization) and mechanical (hardness and fracture toughness) properties of Si₃N₄ ceramics with Al₂O₃ and CTR₂O₃ as additives has been studied. CTR₂O₃ is a natural rare earth oxide mixture, produced at DEMAR-FAENQUIL from the mineral xenotime, consisting mainly of Y₂O₃, Yb₂O₃, Er₂O₃ and Dy₂O₃. The increase in hardness and fracture toughness with increasing duration of isothermal sintering is discussed in regard of densification, α–β Si₃N₄ phase transformation and microstructure. The microstructural variations were decisive for the increase of fracture toughness, because larger grains (>4 μm) with higher aspect ratios (>6) developed during increased sinter periods, enhancing crack deflection and crack-bridging mechanism. In this way longer isothermal holding times contribute to the improvement of the physical and mechanical properties of silicon nitride based ceramics.     

采用Ti/Ag-Cu/Cu中间层钎焊连接Si3N4陶瓷和TiAl合金的界面结构及性能

采用Ti/Ag-Cu/Cu中间层实现了Si₃N₄陶瓷与TiAl合金的钎焊连接,获得了良好的接头.利用SEM,EDS等微观手段,分析了接头界面结构和元素分布情况.结果表明,Si₃N₄陶瓷/Ti/Ag-Cu/Cu/TiAl典型界面微观结构可能为:Si₃N₄/TiN/Ti-Si/Cu-Ti+Ag（s,s）+Cu（s,s）/AlCuTi/TiAl.在连接温度1 133 K、保温时间30 min、接头压力0.040 MPa时,接头四点弯曲强度达到最大值170 MPa.     

Synthesis and crystal structure of Ba3Si4C2

SiC powder prepared by the Na flux method at 1023 K for 24 h and Ba were used as starting materials for synthesis of tribarium tetrasilicide acetylenide, Ba₃Si₄C₂. Single crystals of the compound were obtained by heating the starting materials with Na at 1123 K for 1 h and by cooling to 573 K at a cooling rate of −5.5 K/h. The single crystal X-ray diffraction peaks were indexed with tetragonal cell dimensions of a = 8.7693(4) and c = 12.3885(6) Å, space group I4/mcm (No.140). Ba₃Si₄C₂ has the Ba₃Ge₄C₂ type structure which can be described as a cluster-replacement derivative of perovskite (CaTiO₃), and contains isolated anion groups of slightly compressed [Si₄]⁴⁻ tetrahedra and [C₂]²⁻ dumbbells. The electrical conductivity measured for a not well-sintered polycrystalline sample was 2.6 × 10⁻²–7 × 10⁻³ S cm⁻¹ in the temperature range of 370–600 K and slightly increased with increasing temperature. The Seebeck coefficient showed negative values of around −200 to −300 μV K⁻¹.     

Densification, microstructure, and fracture behavior of TiC/Si3N4 composites by spark plasma sintering

TiC/Si₃N₄ composites were prepared using the β-Si₃N₄ powder synthesized by self-propagating high-temperature synthesis (SHS) and 35 wt.% TiC by spark plasma sintering. Y₂O₃ and Al₂O₃ were added as sintering additives. The almost full sintered density and the highest fracture toughness (8.48 MPa·m^½) values of Si₃N₄-based ceramics could be achieved at 1550°C. No interfacial interactions were noticeable between TiC and Si₃N₄. The toughening mechanisms in TiC/Si₃N₄ composites were attributed to crack deflection, microcrack toughening, and crack impedance by the periodic compressive stress in the Si₃N₄ matrix. However, increasing microcracks easily led to excessive connection of microcracks, which would not be beneficial to the strength.     

Influence of the pulse shape on the EDM performance of Si3N4-TiN ceramic composite

This paper describes the influence of the EDM discharge pulse shape on the machining performances and material removal mechanisms of Si₃N₄-TiN. Dramatic differences of material removal, ranging from classical melting to chemical decomposition, are observed by applying different pulse shapes such as the iso-energetic or relaxation type discharge pulses. It not just leads to the change of surface texture and machining performances, but also has influences on the ceramic properties. An EDM strategy is developed for the production of ceramic components in Si₃N₄-TiN and validated through the fabrication of a high temperature mesoscopic gas turbine.     

Microstructure evolution of the Si3N4/Si3N4 joints brazed using Au-Ni-V filler alloys with different V content

Au-Ni-V filler alloys with different vanadium contents were designed to braze Si₃N₄ ceramic at 1373 K for 30 min, and the microstructures of brazing seams were investigated by SEM and TEM. When the Au-Ni-V filler alloy contains 5 at.% V, round-like Ni[Si, V, Au] precipitates form in the Au[Ni] solid solution matrix and a VN reaction layer with 0.5 μm thickness appears on Si₃N₄ interface. When the V content increases to 10 at.%, a new polygonal Ni₂SiV₃ phase occurs in the seam, and the Ni[Si, V, Au] precipitate coarsens and VN layer thickens. With increase of V contents to 15 and 20 at.%, laminar Ni[Au] and polygonal Ni₃V precipitates form. With 25 at.% V content in the filler alloy, the Ni₂SiV₃ and Ni₃V precipitates distribute homogenously in the brazing seam. These microstructure evolutions were attributed to the reaction between Si₃N₄ and vanadium, which forms VN reaction layer and releases Si into the molten alloy.     

Preparation and characteristic of spherical Li3V2(PO4)3

Spherical Li₃V₂(PO₄)₃ was synthesized by using N₂H₄ as reducer. The products were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that single-phase, spherical and well-dispersed Li₃V₂(PO₄)₃ has been successfully synthesized in our experimental process. Electrochemical behaviors have been characterized by charge/discharge measurements. The initial discharge capacities of Li₃V₂(PO₄)₃ were 123 mAh g⁻¹ in the voltage range of 3.0–4.3 V and 132 mAh g⁻¹ in the voltage range of 3.0–4.8 V.     

A new apparatus for finishing large size/large batch silicon nitride (Si3N4) balls for hybrid bearing applications by magnetic float polishing (MFP)

A new apparatus was designed and built for the finishing of large size/large batch silicon nitride (Si₃N₄) balls by magnetic float polishing (MFP) technology for hybrid bearing applications. The polishing chamber is so designed that during polishing it can self-align with the upper part of the polishing chamber connected to the spindle. In situ machining of the upper part of the chamber is performed on the machine tool in which the apparatus is located, in order to achieve high accuracy and geometric alignment of the system. The finishing methodology consists of mechanical polishing followed by chemo-mechanical polishing. Boron carbide (B₄C), silicon carbide (SiC), and cerium oxide (CeO₂) are the three abrasives used in this investigation. Three stages are involved in polishing, namely, 1. a roughing stage to remove maximum material without imparting any damage to the surface, 2. an intermediate stage of semi-finishing to control the size and improve sphericity, and 3. a final finishing stage to obtain best surface finish and sphericity while maintaining the final diameter. Taguchi method was applied for the roughing stage to optimize the polishing conditions for the best material removal rate. Level average response analysis has indicated that a load of 1.5 N/ball, an abrasive concentration of 20%, and a speed of 400 rpm would give a high material removal rate using B₄C (500 grit) abrasive. A groove is formed on the bevel of the upper part of the chamber which plays different roles, some beneficial and other not so beneficial, in each stage. In the roughing stage, it is preferable, though not essential, to machine the groove after each run to maintain high material removal rates. It is, however, necessary to remove the groove formed at the end of the roughing stage. In the intermediate or semifinishing stage, sphericity can be significantly improved by not machining the groove. Thus groove, in this case, facilitates in the improvement of sphericity. Before the beginning of the final finishing stage, machining the groove is necessary for rapid improvement in the surface finish. A batch of 46, 3/4 in. Si₃N₄ balls was finished to a final diameter of 0.7500 in. with an average sphericity of 0.25 μm (best value of 0.15 μm) and an average surface finish, Ra of 8 nm (best value of 6.7 nm) with an actual polishing time of <30 h. This technology is easy to implement in industry and does not entile high capital investment.     

Strengthening of transparent spinel/Si3N4 nanocomposites

In response to a need for improving the mechanical properties of optically transparent ceramics, the nanocomposites approach is used to strengthen transparent magnesium-aluminate spinel with Si₃N₄ nanodispersoids. The as-processed nanocomposites are found to be >70% transparent in the critical infrared wavelength range of 3-4.5 μm. Mie scattering combined with absorption by the Si₃N₄ nanodispersoids explains quantitatively the IR transmission behavior of these nanocomposites. The nanocomposites are also found to be transparent in the visible region. Upon heat treatment (1000 °C for 4 h in air), the optical properties of the nanocomposites remain unchanged. However, the heat treatment results in a 29% increase in the average strength, accompanied by almost doubling of the Weibull modulus, and an 85% increase in the indentation toughness. The improvements in mechanical properties after the heat treatment in these nanocomposites are explained qualitatively, based on generally accepted arguments involving surface-oxidation-induced surface compression and flaw-healing. While further work is needed to fully understand and exploit these effects, this first report on transparent nanocomposites could have broad implications for the creation of mechanically robust, transparent ceramics of the future.     

NiMoO4/g-C3N4的制备及电化学性能研究

超级电容器具有比电容高、循环寿命长和绿色无污染的特点,其优异的电化学性能备受关注。本文水热合成了NiMoO₄/g-C₃N₄复合粉体,并将粉体涂覆在泡沫镍上制备了NiMoO₄/g-C₃N₄电极材料。结果表明,NiMoO₄/g-C₃N₄粉体形貌主要为NiMoO₄纳米棒和团状g-C₃N₄,且NiMoO₄纳米棒生长在g-C₃N₄纳米片上。在NiMoO₄中加入30at%的g-C₃N₄能降低电容体系的等效串联电阻和扩散阻抗,有利于氧化还原反应的进行。相比于其他g-C₃N₄含量的电极材料,g-C₃N₄含量为30at%的NiMoO₄/g-C₃N₄电极材料具有更高的比电容(584.3F/g)和更好的倍率特性。     

Conductivity of a new pyrophosphate Sn0.9Sc0.1(P2O7)1−δ prepared by an aqueous solution method

New pyrophosphate Sn_0.9Sc_0.1(P₂O₇)_1−δ was prepared by an aqueous solution method. The structure and conductivity of Sn_0.9Sc_0.1(P₂O₇)_1−δ have been investigated. XRD analysis indicates that Sn_0.9Sc_0.1(P₂O₇)_1−δ exhibits a 3 × 3 × 3 super structure. It was found that Sn_0.9Sc_0.1(P₂O₇)_1−δ prepared by an aqueous method is not conductive. The total conductivity of Sn_0.9Sc_0.1(P₂O₇)_1−δ in open air is 2.35 × 10⁻⁶ and 2.82 × 10⁻⁹ S/cm at 900 and 400 °C respectively. In wet air, the total conductivity is about two orders of magnitude higher (8.1 × 10⁻⁷ S/cm at 400 °C) than in open air indicating some proton conduction. SnP₂O₇ and Sn_0.92In_0.08(P₂O₇)_1−δ prepared by an acidic method were reported fairly conductive but prepared by similar solution methods are not conductive. Therefore, the conductivity of SnP₂O₇-based materials might be related to the synthetic history. The possible conduction mechanism of SnP₂O₇-based materials has been discussed in detail.     

Preparation of Sr2Si5N8:Eu for white light-emitting diodes by multi-step heat treatment

In order to enhance luminescence properties of Eu²⁺-doped ternary nitride phosphor for white light-emitting diodes (LEDs), Sr₂Si₅N₈:Eu²⁺ phosphors with different Eu²⁺ concentrations were synthesized using a multi-step heat treatment. Impurities and luminescence properties of prepared Sr₂Si₅N₈:Eu²⁺ phosphors were investigated using X-ray diffraction (XRD) and photoluminescence spectroscopy. Excitation spectra of Sr₂Si₅N₈:Eu²⁺ phosphor showed broad excitation bands by both UV and blue light. Emission peak positions in spectra were red-shifted from 613 to 671 nm as Eu²⁺ ion concentrations increased. Phosphors following a multi-step heat treatment showed excellent luminescence properties. These included high emission intensity and very low thermal quenching compared to measurements using a commercially available YAG:Ce³⁺ phosphor.     

Local electric field investigation of Si2N2O and its electronic structure, elastic and optical properties

This paper demonstrates that the Clausius-Mosotti equation cannot be used for Si₂N₂O since the Lorenz approximation is invalid therein. Therefore a modified definition for the Lorenz electric field is suggested which can be derived from the optical dielectric constant calculated using the plane-wave pseudopotential method. In addition, other parameters of Si₂N₂O such as the energy band gap, density of states, elastic and optical properties are also given in this paper. Based on the new expression for local electric field, the modified Clausius-Mosotti equation is suggested, and then the dielectric constant of Si₂N₂O is discussed by using the additivity rule. It is found that the result of the phenomenological analysis of the dielectric constant is basically consistent with the experimental data and the first principles results, which explain the experimental observation that the dielectric constant of Si₂N₂O is enhanced with the increase of Li content. Also, the modified Clausius-Mosotti equation and the additivity rule are suggested to be used in predicting the dielectric behaviors of the new and complex compounds.