Tribological properties and hardness of silicon nitride ceramics after ion implantation and subsequent annealing

Silicon nitride ceramic (β-Si₃N₄) with Y₂O₃ and Al₂O₃ as sintering additives was implanted with Cr or Ti ions to a fluence of 10¹⁷ cm⁻² at energies ranging from 200 keV to 2 MeV. Changes in the phase composition in the near surface layer due to the implantation and subsequent annealing at 1000 and 1200 °C and their correlation with the behaviour of hardness and wear were investigated. Implantation results in amorphization of the near surface layer, which is buried for MeV implantations. For Ti-implanted samples, annealing leads to oxidation, resulting in the formation of γ-YSi₂O₇ and cristobalite besides the β-Si₃N₄. In the case of Cr implantation with MeV energies, the amorphous layer recrystallizes to -Si₃N₄ already at 1000 °C catalyzed by the chromium. This causes a significant suppression of the oxidation. Consequently, the hardness and the tribological behaviour of Ti- and Cr-implanted samples, respectively, are affected differently by the annealing process. For chromium, the improved wear behaviour due to the high-energy implantation remains after annealing while the reduced hardness as result of the amorphized surface is partly recovered. For titanium, the oxide formation leads to a poorer hardness and tribological behaviour.     

Friction characteristic of micro-arc oxidative Al2O3 coatings sliding against Si3N4 balls in various environments

The alumina ceramic coatings were prepared on 2024Al alloy by micro-arc oxidation (MAO) technique. The phase structure of the MAO Al₂O₃ coating was determined using X-ray diffraction. The thickness and micro-hardness of the MAO Al₂O₃ coatings was measured using eddy current thickness equipment and micro-hardness tester. The friction property of MAO Al₂O₃ coatings sliding against Si₃N₄ ceramic balls were investigated in air, water and oil by a ball-on-disk tribo-meter, and the worn surfaces of the MAO Al₂O₃ coatings were observed using scanning electron microscope (SEM). The results showed that the MAO Al₂O₃ coatings mainly contained -Al₂O₃ and γ-Al₂O₃ phase. The micro-hardness of the polished MAO coatings was HV1740 ± 87. With an increase in normal load and sliding speed, the friction coefficient in air increased from 0.74 to 0.87, while decreased from 0.72 to 0.57 in water and 0.24 to 0.11 in oil. This indicates that the fluid lubrication could improve the friction behavior of the MAO Al₂O₃ coatings. The worn surfaces' observation indicated that the wear mechanism of the MAO Al₂O₃ coatings changed from abrasive wear in air to mix wear in water, and became microploughing wear in oil.     

A closed form solution for laser drilling of silicon nitride and alumina ceramics

A closed form solution has been obtained for laser drilling of silicon nitride (Si₃N₄) and alumina ceramics (Al₂O₃). The drilling of workpiece is performed by using a TEM₀₀ 10 ns pulse Nd:YAG laser. It is assumed that the phase transition from solid to vapor occurs without melting. Considering the absorption of plasma plume formed on the surface of the ceramics, the one-dimensional thermal model is developed in order to describe the drilling process. The governing equation of heat-diffusion is solved analytically using a Laplace transformation method. Erosion depth per laser pulse obtained from the closed form solution agrees with the available experimental data.     

激光结构磨削在氮化硅陶瓷中的磨削行为

为提高氮化硅陶瓷的加工精度，用激光辅助复合加工技术在氮化硅表面烧蚀出4种具有相同表面积的结构化图案，然后用金刚石砂轮对氮化硅表面进行磨削，研究图案结构对磨削效果的影响，并分析砂轮转速、进给速率等参数对磨削力的影响。结果表明:激光烧蚀能够在氮化硅表面产生凹槽并降低表面氮化硅的强度，从而有利于磨削液进入并降低磨削力，最高降幅达63%。同时，金刚石砂轮磨损也有效降低。磨削结构化的氮化硅表面时，砂轮转速和进给速率对磨削力的影响规律同磨削普通氮化硅时的规律一致。      

Nucleation and growth of combustion flame deposited diamond on silicon nitride

The effect of substrate temperature (T_s) on the nucleation and growth of diamond on silicon nitride (Si₃N₄) based substrates deposited via the oxy-acetylene combustion flame technique was investigated. The diamond deposits were characterized via scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques. The nucleation density of the resulting deposits, which was of the order 10⁵ nuclei/cm², was used to approximate the activation energy for heterogeneous nucleation of diamond as32 – 40 kcal/mol. An Arrhenius plot of particle growth rate was used to calculate the activation energy for diamond growth as9.4 and 8.3 kcal/mol in the center and outside annulus of the deposit, respectively. These results suggest that the heterogeneous nucleation of diamond is a highly energetic process and may in fact be responsible for the observed low nucleation density of diamond on Si₃N₄. Thermodynamic analysis of gas/substrate reactions under conventional process conditions predicted that SiC formation, which is known to be a necessary precursor to diamond nucleation on Si, is energetically forbidden. Via kinetic and thermodynamic considerations, a patented in situ multistage deposition technique was developed which yielded continuous diamond coatings on Si₃N₄ substrates without extensive substrate preparation.     

钎料中Ti元素含量对Si3N4/Si3N4接头界面结构及性能的影响

在900℃保温10 min的工艺条件下采用Ti含量不同的AgCu+Ti+nano-Si₃N₄复合钎料（AgCu_C）实现了Si₃N₄陶瓷自身的钎焊连接,并对不同Ti元素含量的接头界面组织及性能进行了分析.结果表明,接头典型界面结构为Si₃N₄/TiN+Ti₅Si₃/Ag_（s,s）+Cu_（s,s）+TiN_P+Ti₅Si_3P/TiN+Ti₅Si₃/Si₃N₄.随着复合钎料中Ti元素含量的增加,钎缝中团聚的纳米Si₃N₄颗粒逐渐减少,母材侧的反应层厚度逐渐增加后趋于稳定.当Ti元素含量高于4%时,钎缝中形成了类似于颗粒增强金属基复合材料的界面组织;当Ti元素含量达到10%时,有少量Ti-Cu金属间化合物在钎缝中形成;钎焊接头的抗剪强度随着Ti元素含量的增加而呈现先增加后降低的变化趋势,当Ti元素含量为6%时接头的抗剪强度达到最高值,即75 MPa.     

Friction and wear properties of Fe–Mo intermetallic compounds under oil lubrication

In this study several disc specimens of three different compositions of the Fe–Mo system were prepared by spark plasma sintering and annealing, and their friction and wear properties were investigated. It was found that, when ASTM 52100 steel balls were used as the paired materials, both the Fe–42 at% Mo and Mo disc specimens exhibited lower friction coefficients and lower wear rates than the Fe and cast iron disc specimens. It was also found that the spark plasma-sintered Fe–42 at% Mo disc specimens without any heat treatments exhibited lower friction coefficients than those annealed at 1323 K for 172.8 ks. According to the XPS analysis, iron oxides and iron sulfides were found on the worn surfaces of the Fe disc specimens that were slid against the ASTM 52100 steel balls, while molybdenum oxides such as MoO₂, but not MoS₂, were observed on the worn surfaces of the annealed Fe–42 at% Mo and Mo disc specimens that were slid against the steel balls.     

Properties of copper matrix reinforced with various size and amount of Al2O3 particles

Copper matrix was reinforced with Al₂O₃ particles of different size and amount by internal oxidation and mechanical alloying accomplished using high-energy ball milling in air. The inert gas-atomised prealloyed copper powder containing 1 wt.% Al as well as a mixture of electrolytic copper powder and 3 wt.% commercial Al₂O₃ powder served as starting materials. Milling of Cu-1 wt.% Al prealloyed powder promoted formation of fine dispersed particles (1.9 wt.% Al₂O₃, approximately 100 nm in size) by internal oxidation. During milling of Cu-3 wt.% Al₂O₃ powder mixture the uniform distribution of commercial Al₂O₃ particles has been obtained. Following milling, powders were treated in hydrogen at 400 °C for 1 h in order to eliminate copper oxides formed at the surface during milling. Compaction was executed by hot-pressing. Compacts processed from 5 to 20 h-milled powders were additionally subjected to high-temperature exposure at 800 °C in order to examine their thermal stability and electrical conductivity. Compacts of Cu-1 wt.% Al prealloyed powders with finer Al₂O₃ particles and smaller grain size exhibited higher microhardness than compacts of Cu-3 wt.% Al₂O₃ powder mixture. This indicates that nano-sized Al₂O₃ particles act as a stronger reinforcing parameter of the copper matrix than micro-sized commercial Al₂O₃ particles. Improved thermal stability of Cu-1 wt.% Al compacts compared to Cu-3 wt.% Al₂O₃ compacts implies that nano-sized Al₂O₃ particles act more efficiently as barriers obstructing grain growth than micro-sized particles. Contrary, the lower electrical conductivity of Cu-1 wt.% Al compacts is the result of higher electron scatter caused by nano-sized Al₂O₃ particles.     

Mechanical and tribological properties of TiCxN1−x wear resistant coatings

The aim of this work is to investigate the mechanical and tribological properties of TiC_xN_1−x wear resistant coatings grown on a Ti–0.2 Pd alloy substrate. Films were deposited by dual ion beam sputtering (DIBS) system with different proportions of N₂ and Ar in the assisting beam. The friction tests have been carried out with a pin-on-disc tribometer with different applied loads. The films present high hardness and elastic properties whose values depend upon preparation conditions. The mechanical properties and the tribological behaviour of the coatings seem to depend on their stoichiometry and microstructure. The coating TiC_0.5N_0.5 shows less hardness and better wear resistance than the coating with stoichiometry TiC_0.15N_0.85. The influence of the stoichiometry and the local structure of the films on its mechanical properties have been ruled out.     

钎焊温度对Ti60合金与Si3N4陶瓷接头界面组织及性能的影响

为研究钎焊温度对Ti60/Si₃N₄接头组织与力学性能的影响,采用Ag-28Cu共晶钎料在870~910℃温度区间,保温10 min条件下进行钎焊连接.利用扫描电子显微镜、能谱仪对钎焊接头界面组织进行分析,得到的典型接头界面组织结构为Ti60/Ti-Cu化合物/Ag（s,s）+Cu（s,s）/Ti-Cu化合物/Ti₅Si₃+TiN/Si₃N₄,并对钎焊接头的组织演变过程进行了分析.结果表明,随着钎焊温度的升高,Ti60侧的Ti-Cu化合物反应层与Si₃N₄陶瓷侧的Ti₅Si₃+TiN反应层厚度逐渐增加,Ag（s,s）与Cu（s,s）含量减少,同时,扩散至Si₃N₄陶瓷侧的Ti元素与液相中Cu元素反应生成Ti-Cu化合物并在Ti₅Si₃+TiN反应层中形核.剪切测试表明,在钎焊温度880℃,保温10 min工艺参数条件下获得的接头最大抗剪强度为61.7 MPa.     

Dielectric properties of sintered aluminum nitride

In the present work, the effects of sintering additives on dielectric loss tangent (tan δ) of AlN ceramics were explored. Different amounts of Y₂O₃ and Mg₃N₂ were respectively added as sintering additives to AlN powders, and pressureless-sintering was performed at 1900 °C for 2 h in a nitrogen flow atmosphere. The resulted AlN ceramics became denser due to the addition of Mg₃N₂, and nearly fully dense sample was obtained with a relative density of 0.998. tan δ decreased with increasing Mg₃N₂ amount and it was found to depend on the density of the AlN ceramic. The best tan δ value of 3.9 × 10⁻⁴ was obtained by adding 1 mol% of Y₂O₃ and Mg₃N₂ together.     

Fabrication and wear characteristics of MoSi2 matrix composite reinforced by WSi2 and La2O3

MoSi₂ matrix composites (RWM) reinforced by the addition of both WSi₂ and La₂O₃ were fabricated by mechanical alloying and self-propagating high-temperature synthesis (SHS) technique. This composite was analysed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). It is difficult to synthesize RWM composite by mechanical alloying with Mo–W–Si–La₂O₃ powder mixture, and suitable by self-propagating high-temperature synthesis. The hardness and toughness of MoSi₂ was improved significantly by the addition of both, WSi₂ and La₂O₃ more than by only WSi₂. By adding 0.8 wt.% La₂O₃ and 50 mol.% WSi₂ into the MoSi₂ matrix, this composite has the highest hardness and toughness and exhibits more wear resistance than monolithic MoSi₂ during the sliding wear test under oil lubrication, in this case, the material removal mechanism has been observed to be micro-cutting and micro-fracture.     

Bulk titanium nitride material obtained from SHS starting powder: Densification, mechanical characterization and tribological approach

Powders used for this study were synthesized by the self-propagating high temperature synthesis (SHS) process. This method allows producing titanium nitride powders in an economic and easy way. Densification of these original powders is carried out by the hot pressing process. Sintering is achieved, under a 50 MPa pressure, at different temperatures (1400 °C, 1600 °C and 1800 °C). At 1600 °C properties are optimised and bulk specimen density is superior to 98%. In addition, microhardness reaches the average value of 1790 ± 225 H_V and Young modulus measured is 430 ± 10 GPa. A tribological characterization is then carried out with an adapted four balls machine tribometer. Titanium nitride tribological behavior is compared with the one of other hard materials such as 100C6 steel, titanium carbide and two cemented carbides of different compositions. Parameters such as toughness, hardness and wear volume are correlated in order to understand wear mechanisms origins.     

Wear and Friction Properties of Electrodeposited Ni-Based Coatings Subject to Nano-enhanced Lubricant and Composite Coating

This paper presents research findings on the tribological performance of electrodeposited coatings subject to nano-lubricants with the addition of nano-Al_2O_3 and graphene and Ni/nano-Al_2O_3 composite coatings. Electrodeposited coatings were produced by using a pulse electrodeposition method. Tribological experiments were conducted by using a linear reciprocating ball on flat sliding tribometer. Experimental results confirmed that the wear and friction resistance properties were significantly enhanced by doping of nano-effects in the lubricating oil and composite coating. The addition of Al_2O_3 nanoparticles in the lubricating oil showed the best tribological properties, followed by Ni–Al_2O_3 composite coatings and nano-oil with graphene. The surface morphology and microstructure of electrodeposited coatings were examined by scanning electron microscopy, energy-dispersive spectroscopy and X-ray diffraction. The wear mechanisms of these coatings subjected to tribological testing were investigated by post-test surface analyses. This research provides a novel approach to design durable nano-coatings for tribological applications in various industries such as automotive,aerospace, locomotive and renewable energy technologies.     

Microstructure and properties of CVD γ-Al2O3 coatings

This work deals with the microstructures and wear properties of chemical vapour deposited γ-Al₂O₃. The γ-Al₂O₃ coatings were deposited at 800 °C on TiN and Ti(C,N) pre-coated cemented carbide substrates. The microstructures developed in the γ-Al₂O₃ coatings and the influence of the nucleation surface on the growth of γ-Al₂O₃ were characterised using transmission electron microscopy, electron energy-loss spectroscopy and X-ray diffraction. The γ-Al₂O₃ coatings were fine-grained with a high density of {1 1 1} growth twins and contained some residual sulphur. γ-Al₂O₃ was found to grow epitaxially on the investigated substrates. The mechanical properties were evaluated in metal cutting and were compared with those of κ-Al₂O₃ coated tools. As compared with the κ-Al₂O₃ coatings, the γ-Al₂O₃ coatings exhibited slightly worse adhesion and tendency for edge chipping. However, the γ-Al₂O₃ coatings showed better crater wear resistance on the rake face than κ-Al₂O₃ coatings.     

From diamond to crystalline silicon carbonitride: effect of introduction of nitrogen in CH4/H2 gas mixture using MW-PECVD

Microwave plasma enhanced chemical vapor deposition (MW-PECVD) is considered as one of the most successful growth techniques in recent diamond and crystalline carbon nitride investigations. In this study, we tried to synthesize crystalline carbon nitride film using MW-PECVD by gradually increasing the content of nitrogen into H₂/CH₄ gas mixture. Well-faceted crystalline diamond films could be synthesized with a H₂/CH₄ gas ratio of 198:2. With the gradual increase of nitrogen content up to 3% in the gas mixture diamond film quality deteriorates seriously, and the morphological crystal size and growth rate of diamond coatings decreased significantly. With the nitrogen gas content increased to approximately 6–22%, a lot of separated round diamond or diamond-like carbon particles formed on the surface rather than a continuous film. Only with the nitrogen content increased above 72%, could some tiny crystals with a type of hexagonal facet form on the silicon surface, together with many large, round diamond particles. With the further increase of nitrogen gas content above 90%, many large, well-faceted hexagonal crystals formed on Si surface. However, XRD, energy dispersive X-ray spectrometry, X-ray photoelectron spectroscopy and nano-indentation analysis indicated that these crystals were actually silicon carbonitride (Si–C–N) with a crystalline structure of Si₃N₄ modified with the introduction of carbon atoms, rather than carbonitride as expected and regarded.     

C3N4 as a precursor for the synthesis of NbC, TaC and WC nanoparticles

While there already exit some routes to prepare carbides, highly efficient and facile routes are still desired to meet the increasing demand on carbides. By a facile solid-state reaction process using graphite-like phase of C₃N₄ (g-C₃N₄) as the carbonizing reagent, we synthesized three technologically important carbides including cubic NbC and TaC, and hexagonal WC nanoparticles at relatively low temperature (1150 °C). The products were characterized by power X-ray diffraction (XRD), field-emission scanning electron microscope (FE-SEM), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM) and high-resolution TEM (HRTEM). The results show that g-C₃N₄ is a highly efficient carbonizing reagent and the oxides Nb₂O₅, Ta₂O₅ and WO₃ are completely converted into the corresponding carbides at 1150 °C, which is significantly lower than that reported for the commercial preparation of the carbides, typically >1600 °C. The NbC, TaC and WC nanoparticles are found to have an average particle size of 4, 35 and 60 nm, respectively. An important feature of this solid-state reaction process is that g-C₃N₄ plays double roles as both efficiently reducing and carbonizing reagent.     

Preparation and crystal structure of a new barium silicon nitride, Ba5Si2N6

Single crystals of a new ternary nitride, Ba₅Si₂N₆, were synthesized by slow cooling from 750°C using a starting mixture of Ba, Si, Na and NaN₃, where Na and NaN₃ were a flux and a nitrogen source respectively. It crystallizes with orthorhombic symmetry: space group P2₁2₁2₁ (No. 19), A = 6.159, B = 10.305, C = 15.292 Å, and Z = 4. The crystal structure was determined from single-crystal data and refined to R1 = 0.0495 for all 1637 observed reflections and 89 variables. A pair of SiN₄ tetrahedra contained in the structure forms a nitridometallate anion of [Si₂N₆]¹⁰ by edge sharing.     

Influence of Treatment Sequence on Tribological Performance of Duplex Surface-Treated AISI 1045 Steel

The surface of AISI 1045 steel specimens was modified via two duplex surface treatments of(i) titanium diffusion coating followed by plasma nitriding(Ti–PN) and(ii) plasma nitriding followed by titanium diffusion coating(PN–Ti). A comparative study on the microstructure and wear properties of the fabricated TiN coatings was conducted. A scanning electron microscope equipped with energy-dispersive X-ray spectroscopy, X-ray diffractometer(XRD), and pin-on-disk wear test was utilized to evaluate the microstructures, phases, and wear properties of the coatings. XRD patterns of duplex-treated specimens illustrated that the modified layer consisted of nitride and carbo-nitride phases such as TiN and TiC_(0.7)N_(0.3). The results also showed that Ti–PN treatment led to a low friction coefficient and the lowest wear factors, as compared with the PN–Ti treatment. Oxidation and mild fatigue fracture wear were found to be the main wear mechanism of the Ti–PN coating. The wear mechanism in the PN–Ti specimen involved a higher oxidative wear regime followed by plastic deformation wear regimes.     

The oxidation of micro-crystalline Co–Cr alloys under balanced oxygen pressure of Co2O3/Co powders

Surface micro-crystallizing was applied to Co–5Cr, Co–10Cr and Co–15Cr alloys by electro-spark deposition (ESD) and the oxidation behaviors of both cast and micro-crystalline alloys were investigated at 1000 °C under balanced oxygen pressure of Co₂O₃/Co-mixed powders. Surface and cross-section SEM morphologies, EDS and XRD analysis show that micro-crystallizing promotes both the external oxidation and internal oxidation of Co–5Cr alloy. Micro-crystallizing provides more grain boundaries so that the diffusion is enhanced. The inwards diffusion of O makes internal oxidation zone thicker while the outwards diffusion of Cr makes external oxidation more prominent for the micro-crystalline Co–5Cr alloy. For both the cast and micro-crystalline Co–10Cr and Co–15Cr alloys, 10 wt.% Cr is enough to form complex selective oxides (AO/AB₂O₄/BO) scales and 15 wt.% Cr is still not enough to form a single Cr₂O₃ oxide scale. Micro-crystallizing promotes the outwards diffusion of Cr and selective Cr₂O₃ scales are easier to form so that the external oxides scales of micro-crystalline Co–10Cr and Co–15Cr alloy are much thinner and their Cr/Co ratios are higher. The oxidation model of A–B alloy under oxygen pressure that both A and B can be oxidized is also proposed.