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.     

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.     

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。     

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.     

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%.     

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.     

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.     

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.     

Performance of single Si3N4 and mixed Si3N4+PCBN wiper cutting tools applied to high speed face milling of cast iron

In this work two face milling cutter systems were used in high speed cutting of gray cast iron under cutting condition encountered in the shop floor. The first system, called ‘A’, has 24 Si₃N₄ ceramic inserts all with square wiper edges. The second system, called ‘B’, is a mixed tool material system, having 24 wiper inserts, 20 of them are Si₃N₄ intercalated by four PCBN inserts. Cutting speed (v_c), depth of cut (doc) and feed rate per tooth (f_z) were kept constant. Surface roughness (R_a and R_t) and waviness (W_t), tool life (based on flank wear, VB_Bmax) and burr formation (length of the burr, h) were the parameters considered to compare the two systems. System ‘B’ presented better performance according to all parameters, although only end of life criterion based on R_t parameter has been reached.     

A comparative study of reactive direct current magnetron sputtered CrAlN and CrN coatings

Approximately 1.5 μm thick CrN and CrAlN coatings were deposited on silicon and mild steel substrates by reactive direct current (DC) magnetron sputtering. The structural and mechanical properties of the coatings were characterized using X-ray diffraction (XRD) and nanoindentation techniques, respectively. The bonding structure of the coatings was characterized by X-ray photoelectron spectroscopy (XPS). The surface morphology of the coatings was studied using scanning electron microscopy (SEM) and atomic force microscopy (AFM). The XRD data showed that the CrN and CrAlN coatings exhibited B1 NaCl structure. Nanoindentation measurements showed that as-deposited CrN and CrAlN coatings exhibited a hardness of 18 and 33 GPa, respectively. Results of the surface analysis of the as-deposited coatings using SEM and AFM showed a more compact and dense microstructure for CrAlN coatings. The thermal stability of the coatings was studied by heating the coatings in air from 400 to 900 °C. The structural changes as a result of heating were studied using micro-Raman spectroscopy. The Raman data revealed that CrN coatings got oxidized at 600 °C, whereas in the case of CrAlN coatings, no detectable oxides were formed even at 800 °C. After annealing up to 700 °C, the CrN coatings displayed a hardness of only about 7.5 GPa as compared to CrAlN coatings, which exhibited hardness as high as 22.5 GPa. The potentiodynamic polarization measurements in 3.5% NaCl solution indicated that the CrAlN coatings exhibited superior corrosion resistance as compared to CrN coatings.     

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.     

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.     

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。     

Influence of the N2 partial pressure on the mechanical properties and tribological behavior of zirconium nitride deposited by reactive magnetron sputtering

Zirconium nitride was deposited by reactive unbalanced magnetron sputtering at different N₂ partial pressures, on an AISI 316L stainless steel substrate. The mechanical properties of the coatings were evaluated by means of nanoindentation tests employing a Berkovich indenter and loads which varied between 120-9000 µN. The sliding wear behavior of the substrate-coating systems was studied under a normal load of 2 N using a ball-on-disc tribometer, with an AISI 52100 ball (6 mm diameter) as counterpart. It has been found that N₂ partial pressure has a significant effect both on the hardness and corresponding Young's modulus of the coatings. As the N₂ partial pressure increases from 1 × 10^− 4 Torr to 10 × 10^− 4 Torr, the hardness and Young's modulus of the coatings decrease from 26 to 20 GPa and 360 to 280 GPa, respectively. The nanoindentation tests revealed the presence of a third oxide layer (10 nm thick, approximately) on the surface of the coating. Scanning electron microscopy (SEM) analysis performed on the worn triboelements indicated that both abrasive and adhesive wear mechanisms could take place in addition to the substrate plastic deformation. The deposition conditions and coating mechanical integrity determine the predominant wear mechanism.     

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.     

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.     

TiO2-g-C3N4 composite materials for photocatalytic H2 evolution under visible light irradiation

In this investigation, we report the preparation of TiO₂-g-C₃N₄ composite materials with varying the wt.% of g-C₃N₄, the characterization of these materials by various techniques and photocatalytic hydrogen production under visible light irradiation in the presence of methanol. The X-ray powder diffraction (XRD) shows that the composite materials are consist of anatase TiO₂ and g-C₃N₄. Fourier transform infrared (FT-IR) spectra show that the absorbance band intensity of composite materials was stronger than that of C₃N₄. The UV-vis absorption spectra show that the absorption edge of the composite materials shifts to the lower energy region comparing to pure anatase and to longer wavelengths with increasing the amount of C₃N₄. The significant photoluminescence quenching was observed in TiO₂-C₃N₄ composite materials, indicating the charge transfer from C₃N₄ to TiO₂. The visible light induced H₂ evolution rate was remarkably enhanced by coupling TiO₂ with C₃N₄.     

Mechanical properties and oxidation resistance of CrAlN/BN nanocomposite coatings prepared by reactive dc and rf cosputtering

CrAlN/BN nanocomposite coatings were deposited through reactive cosputtering, i.e., pulsed dc and rf sputtering, of CrAl and h-BN targets, respectively. X-ray diffraction (XRD) and selected area electron-diffraction (SAED) analysis indicated that the CrAlN/BN coating consists of very fine grains of B1 structured CrAlN phase. With an increasing BN volume fraction of over 8 vol.%, the nanocrystalline nature of the grains is revealed through a dispersion of fine grains in the CrAlN/BN coating. A cross-sectional observation using a transmission electron microscope (TEM) clarified that the coating demonstrating the highest level of hardness has a fiber-like structure consisting of grains that are ~ 20 nm in width and ~ 50 nm in length. X-ray photoelectron spectroscopy (XPS) analysis revealed that the coating consists mainly of CrAlN and h-BN phase. The indentation hardness (H_IT) and effective Young's modulus (E*) of the coatings increased with the BN phase ratio, reaching a maximum value of ~ 46 and ~ 440 GPa at ~ 7 vol.% of BN phase; it then decreased moderately to ~ 40 and ~ 350 GPa at 18 vol.% of BN, respectively. Furthermore, CrAlN/BN coatings showed superior oxidation resistance compared with CrAlN coatings. After annealing at 800 °C in air for 1 h, the indentation hardness of CrAlN coatings decreased to 50% of the as-deposited hardness; in contrast, the hardness of CrAlN/BN nanocomposite coatings either stayed the same or increased, attaining a value of about 46 GPa. After annealing at 900 °C for 1 h, the hardness of all the coatings decreased to about 40%.     

The oxidation of cobalt based alloys containing partially dissolved particles of Si3N4 at 1000°C

The isothermal oxidation behavior of Co-Cr and Co-Cr-Si alloys with and without 5, 10, and 15 vol.% dispersions of unstable Si₃N₄ particles was studied in 1 atm of oxygen at 1000°C. The dispersion of Si₃N₄ which dissolved partially in the matrix, greatly reduced the oxidation rate of Co-Cr alloys. Silicon nitride was found to promote the formation of continuous Cr₂O₃ layers at low chromium concentrations. Furthermore, the unstable Si₃N₄ was more effective in reducing the oxidation rate than an alloy containing an equivalent amount of silicon. Additions of 15vol.% Si₃N₄ tended to increase the oxidation rate by forming nonprotective SiO₂ particles which disrupted the protective Cr₂O₃ scale. The mechanism of oxidation was altered due to the Si₃N₄ additions. Marker experiments indicated oxygen diffusion inward via the CoO lattice, rather than a combination of both oxygen and metal ion motion which is encountered in Co-Cr alloys.     

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.