Relation between microstructure and hardness of nano-composite CrN/Si3N4 coatings obtained using CrSi single target magnetron system

Sintered targets with mixed Cr and Si (10, 20, 30, 35 and 40 at. %) elemental powders were sputtered in mixture of argon and nitrogen on silicon substrates kept either at ambient temperature or at 600 °C. The microstructure was characterized using transmission electron microscopy, while mechanical properties were estimated based on hardness measurements. Observations showed that magnetron sputtering of targets with high silicon content on substrates at ambient temperature resulted in the formation of gradient nano-composites that are partly amorphous and partly crystalline. The amorphous phase dominated in the zone close to the substrate, while the nano-crystalline character was more pronounced nearer to the coating surface. The volume of crystalline phase in the coatings was decreasing with increasing silicon content to such an extent that those obtained from CrSi40 target were fully amorphous. The coatings deposited on substrates resistively heated up to 600 °C showed fine columnar microstructure with diameter decreasing with increasing silicon content, which changed to nano-composite and eventually fully amorphous for those obtained using CrSi35 and CrSi40 targets. The Elemental mapping by electron energy filtered imaging helped prove that in the nano-composite coatings the CrN–type crystalline phase and the amorphous phase are enriched respectively in chromium and silicon. The hardness of the coatings deposited at ambient temperature and characterized by mixed crystalline and amorphous microstructure was close to 20 GPa, except those containing layers enriched in chromium and silicon, which fall down to 15 GPa or even 10 GPa. The hardness of crystalline coatings deposited at 600 °C was increasing from 20 to 30–35 GPa with decreasing average column diameter from ∼40 to ∼35 and ∼25 nm (obtained from CrSi10, CrSi20 and CrSi30 targets). The higher silicon content in the coatings caused both further diminishing of the average crystallite size below 10 nm and simultaneous formation of an amorphous phase. The hardness of the coatings with such nano-composite microstructure was however decreased to ∼25 GPa. Finally, the hardness of fully amorphous coatings obtained from CrSi40 target under the same deposition conditions was at the level of 10 GPa. Our experiments proved that it is possible to obtain extremely fine columnar (Cr,Si)N coatings twice as hard as pure CrN, although a basic one target magnetron system and oxygen-contaminated CrSi targets were only used.     

Structure and Properties of Electroless Ni Deposits

The changes in structure and the hardness of two electroless deposited Ni-P alloy coatings (with P content of 1.5 and 9.5 wt pct) with heat treatment have been studied by XRD and TEM. The deposits containing 1.5 wt pct P can be represented as an fcc NiP supersaturated solid solution of 5~10 nm microcrystallites. whereas the deposits containing 9.5 wt pct P are amorphous. The heat treatment process induces crystallization of amorphous Ni to Ni phosphides and fcc Ni.Both of the deposits reach maximum hardness after annealing at 400℃ for 1 h. All coated steel specimens are inferior in fatigue strength to uncoated steel specimens mainly due to the poor fatigue resistance of the coating itself     

Structure and mechanical properties of Ti-Al-Si-N protective coatings deposited from separated plasma of a vacuum arc

Protective coatings of the Ti-Al-Si-N system have been deposited from vacuum arc by sputtering a cathode of composition 78Ti-16Al-6Si in nitrogen. The coatings of the Ti-Al-Si-N system have been studied using X-ray diffraction analysis to examine phase compositions and substructure, atomic force microscopy to analyze the topography, X-ray fluorescence to define the chemical composition, and nanoindentation to measure hardness and elastic modulus. It has been found that as the nitrogen pressure in the deposition chamber increases, in the Ti-Al-Si-N system the transition from nanocrystalline (to 0.04 Pa) to nanocomposite (0.04–0.66 Pa) and X-ray amorphous (0.66–1.1 Pa) coatings takes place, and at a pressure of 2.7 Pa, the amount of the crystalline phase abruptly increases again. The highest mechanical characteristics and thermal stability have been shown by a coating having the nanocrystalline structure and nanocomposite coatings with a low content of amorphous phase, whose hardness attains 47 GPa.     

Hardness and the nature of microplasticity of hydroxyapatite

The hardness of thin (1.0–4.0 μm) hydroxyapatite (HA) coatings with different structures (nanocrystalline, amorphous-crystalline, and amorphous) grown on Ti and Si by rf magnetron sputtering has been studied using nanoindentation. In all of the coatings, deformation was observed to have an elastoplastic nature. The hardness of the nanocrystalline coatings corresponds to medium hardness values of HA microcrystals. The structure of the nanocrystalline coatings has been studied by high-resolution transmission electron microscopy in the indent zone and away from it. Comparison of the hardness values of coatings with different structures and analysis of the intragranular structure leads us to assume a nondislocation mechanism of plastic deformation. Its nature is interpreted in terms of a cluster representation of the structure of HA and amorphous calcium phosphates and cluster-boundary sliding in the course of deformation.     

Study of (Zr,Ti)CN, (Zr,Hf)CN and (Zr,Nb)CN films prepared by reactive magnetron sputtering

(Zr,Ti)CN, (Zr,Hf)CN and (Zr,Nb)CN coatings, in which Ti, Hf and Nb were added to ZrCN base compound, have been prepared by reactive magnetron sputtering. The coatings, with two different non-metal/metal ratios, were comparatively investigated in terms of elemental and phase composition, texture, surface morphology, hardness and friction performance. It has been shown that the films exhibit nanocomposite structures, consisting of a mixture of crystalline metal carbonitride and amorphous carbon. As compared with ternary ZrCN coatings, the quaternary coatings were found to exhibit superior mechanical and friction characteristics. In general, the films with higher non-metal content revealed finer morphologies, higher hardness and lower friction coefficient. Depending on the coating type and non-metal/metal ratio, the hardness values ranged from about 21 to 29 GPa, being higher than those of ZrCN reference films. The coefficients of friction varied from 0.2 to 0.5, the lowest values being obtained for the coatings with the highest non-metal content.     

Hard plasmachemical a-SiCN coatings

The amorphous SiCN coatings have been plasmachemically (PECVD) deposited onto silicon substrates using the heksamethyldisylazan as the basic precursor. The effect of the deposition temperature on the structure, chemical composition, and mechanical properties of the coatings has been studied. It has been found that at temperatures below 400°C the deposition of hydrogenated amorphous SiCN (a-SiCN:H) coatings, whose hardness does not exceed 23 GPa, takes place. At the further increase of the temperature the distribution of the Si–C, Si–N, and C–N strong bonds in coatings does not practically change, while the number of C–H, Si–H and N–H weak hydrogen bonds decreases. As a result of such a redistribution of chemical bonds, at the temperature 600–700°C a-SiCN coatings are deposited with hardness up to 32 GPa. The annealing in vacuum at 1200°C is shown not to noticeably affect the structure, hardness, and elastic modulus of a-SiCN coatings.     

Mikrostruktur und Eigenschaften lichtbogengespritzter Schichten auf Eisenbasis

Microstructure and properties of Fe‐based wire arc sprayed coatings Innovative iron based feedstocks for wire arc spraying are a promising alternative for conventional carbide reinforced feedstocks for wear applications. Recently the main area of research is focused on improving the properties of deposited functional coatings by varying the wire composition. The influence on the crystalline structure and the dimension of the hard phases in the resulting microstructure is of particular interest in this context. The objective of the investigation is to produce coatings with an amorphous phase, submicron and nanocrystalline structure. The forming of the amorphous phase is influenced by high cooling rates of the molten and partly molten particles impinging on the substrate. Thus, the achieved coatings are characterized by high hardness as well as high corrosion and wear resistance. The present paper introduces iron based coatings produced by wire arc spraying. Due to the application of cored wires with a modified alloy composition the forming of an amorphous phase as well as a submicron‐ and nanocrystalline structure is promoted. The filling of the cored wires are based on FeB with a eutectic composition and is varied by adding Cr₃C₂, FeSi, FeCrC and AlMg. The adding of further elements like Cr, C, Si, Al and Mg should improve the forming of the amorphous phase. The deposited coatings are analyzed regarding to the resulting coating properties and phase composition in connection with the composition of the cored wires. XRD‐analysis’ proved that the Fe‐based coatings contain an amorphous phase.     

Amorphous transition metal carbides

Titanium carbide films were deposited by chemical vapor deposition from tris(2,2'-bipyridine)titanium. Other films of titanium carbide and niobium carbide were obtained by electron beam vaporization of the corresponding crystalline compound. X-ray and electron diffraction studies showed that the structure of the deposits ranged from microcrystalline to amorphous. The coatings were analyzed by secondary ion mass spectroscopy, Auger electron spectroscopy and electron spectroscopy for chemical analysis. The results of these studies lead to an understanding of the formation and nature of the films. The objective is to modify the mechanical properties of brittle transition metal carbides.     

X-ray diffraction studies on the relative proportion and decomposition of amorphous phase in electroless NiB deposits

Electroless nickel-boron deposits with 2.34, 3.85 and 4.32 wt.% boron were produced on mild steel substrates. The deposits had a structure consisting of a mixture of microcrystalline nickel and amorphous NiB phases in the as deposited condition. From the ratios of the integrated intensities of the X-ray diffraction profiles of amorphous and crystalline phases, the relative proportion of the two phases was estimated. The quantity of amorphous phase increased with increasing boron content. The amorphous phase decomposed in one single step as Ni+Ni₃B at around 523K. There are indications that boron might be diffusing out of the crystalline phase into the amorphous phase just prior to the decomposition of the amorphous phase.     

Electrodeposition of Ni-W Amorphous Alloy andNi-W-SiC Composite Deposits

Ni-W alloy shows not only higher hardness,betterwear and corrosion resistan.e[1-3], but also enhancedhigh temperature oxidation resistance, easier moldreleasel4]. Therefore, it is used widely in casting andforging molds, axle bearing and bar injecting plasticsin industries, and it is also a substitute for Ti partsimplallted in the bodiesIS].Easy atom diffusion in crystal and some characteristics of Ni-W alloys will be changed when amorphousNi-W alloys are heated. The hardness of all kinds o…     

高速电弧喷涂FeAlNbB非晶纳米晶涂层的组织与性能

为了提高钢铁材料的耐磨性和硬度,利用高速电弧喷涂技术在45钢基体上制备了FeAlNbB非晶纳米晶涂层.采用扫描电镜(SEM)、能谱分析仪(EDAX),透射电镜(TEM)和X射线衍射仪等设备对涂层的组织结构和相组成进行了分析,研究了非晶纳米晶的形成机制.实验结果表明:FeAlNbB非晶纳米晶涂层是非晶相、α-Fe、FeAl纳米晶和Fe3Al微晶共存的多相组织,涂层中非晶相含量约36.2%,纳米晶尺寸约14.1 nm;涂层组织均匀,结构致密,平均孔隙率约2.3%;非晶纳米晶涂层具有较高的硬度,其耐磨性是相同实验条件下制备的3Cr13涂层的2.2倍.     

Influence of multi-interfacial structure on mechanical and tribological properties of TiSiN/Ag multilayer coatings

The TiSiN/Ag multilayer coatings with bilayer periods of ~50, 65, 80, 115, 150, and 410 nm have been deposited on Ti6Al4 V alloy by arc ion plating. In order to improve the adhesion of the TiSiN/Ag multilayer coatings, TiN buffer layer was first deposited on titanium alloy. The multi-interfacial TiSiN/Ag layers possess alternating TiSiN and Ag layers. The TiSiN layers display a typical nanocrystalline/amorphous microstructure, with nanocrystalline TiN and amorphous Si₃N₄. TiN nanocrystallites embed in amorphous Si₃N₄ matrix exhibiting a fine-grained crystalline structure. The Ag layers exhibit ductile nanocrystalline metallic silver. The coatings appear to be a strong TiN (200)-preferred orientation for fiber texture growth. Moreover, the grain size of TiN decreases with the decrease of the bilayer periods. Evidence concluded from transmission electron microscopy revealed that multi-interfacial structures effectively limit continuous growth of single (200)-preferred orientation coarse columnar TiN crystals. The hardness of the coatings increases with the decreasing bilayer periods. Multi-interface can act as a lubricant, effectively hinder the cracks propagation and prevent aggressive seawater from permeating to substrate through the micro-pores to some extent, reducing the friction coefficient and wear rates. It was found that the TiSiN/Ag multilayer coating with a bilayer period of 50 nm shows an excellent wear resistance due to the fine grain size, high hardness, and silver-lubricated transfer films formed during wear tests.     

电沉积法制备钴与镧、铈的非晶态合金及其晶化动力学研究

稀土元素(La,Ce)的标准还原电位较负,在水溶液中很难电沉积出来,通过选用适合的络合剂和工艺条件制备出Co-La,Co-La-P,Co-Ce,Co-Ce-P以及Co-P合金,并具有非晶态的结构.本文对这几种非晶态合金进行了晶化动力学研究,用差示扫描量热法(DSC)测定了它们的晶化活化能以及所遵守的动力学方程.     

超音速电弧与普通电弧喷涂FeCrNiB涂层的耐磨损性能

为了提高电弧喷涂涂层的结合强度及耐磨损性能,采用超音速电弧喷涂技术和普通电弧喷涂技术在Q235钢表面分别制备了Fe17Cr5NiB涂层,通过扫描电镜(SEM)、X射线衍射仪(XRD)、显微硬度计、摩擦磨损试验机等手段对比分析了2种涂层的微观结构及性能。结果表明:超音速电弧涂层具有更加致密的结构,其平均孔隙率为0.95%,远低于普通电弧涂层;超音速电弧涂层与基体呈紧密结合,其结合强度为60 MPa,而普通电弧涂层与基体之间呈明显的分层状态,其结合强度仅为28 MPa;超音速电弧涂层具有良好的非晶态结构及致密性,使其具有远高于普通电弧涂层的硬度以及耐磨损性能,显微硬度高出普通电弧涂层32.27%,耐磨损性能是普通电弧涂层的2倍以上(是基体的14倍以上)。     

Nanocomposite Hard Coatings: Deposition Issues and Validation of their Mechanical Properties

The limitations of conventional coatings due to inferior hardness or poor oxidation stability can be overcome by nanocomposite hard coatings such as nc‐TiN/a‐SiN_x, which consists of nanocrystalline TiN and a non‐crystalline tissue phase of SiN_x which are mutually immiscible. The properties of nanocomposite coatings, especially their increased hardness, can be explained by their nanostructure, which leads to a maximum hardness at typically 80 atomic percent of the crystalline phase. We show that enhanced hardness can only be attained when the silicon nitride phase is sufficiently nitrided. The accurate and reliable measurement of the hardness and elastic modulus requires the use of appropriate nanoindentation equipment and a careful tip correction with periodical validation. It is shown that for a correct hardness determination of a few microns thick nanocomposite coatings, an indentation depth of 100 nm is sufficient. The maximum hardness of our nc‐TiN/a‐SiN_x coatings deposited by a hybrid UBM/arc‐PVD process is about 40 GPa. This value represents a global hardness value, due to the nanocomposite structure there may be a local hardness variation of about ±10 %.     

Electro-spark deposition of Fe-based amorphous alloy coatings

A simple and effective surface coating technique, electro-spark deposition (ESD), has been used to produce amorphous alloy coatings. Fe-Cr-Mo-Gd-C-B amorphous alloy rods produced by copper mould casting were used as electrode to produce coatings onto 304 stainless steel substrate. Classical X-ray diffraction (XRD), glancing angle XRD (GAXRD), and scanning electron microscopy (SEM) with energy dispersive X-ray (EDX) analysis indicate that the coatings have an average thickness of ∼ 30 μm, show an amorphous structure, and are metallurgically bonded to the substrate. Microhardness tests showed that the coating layer has a high hardness of 1542 kg/mm², implying a much improved wear resistance on surface of stainless steels.     

SiCp/Al复合材料表面电镀Ni-P合金的工艺研究

在高体积分数SiCp/Al复合材料表面镀覆一层Ni-P合金可有效改善其可焊性.为在体积分数60%的SiCp/Al复合材料表面电镀一层Ni-P合金,采用正交试验对电镀工艺参数进行了优化,研究了电镀前预处理工艺,并考察了预处理对电镀层的影响.由正交试验获得了最佳硬度和最佳表面质量的工艺参数;采用SEM、EDS、X射线衍射仪和显微硬度计等对镀层进行表征.研究结果表明:P含量通过影响Ni-P的晶体结构,进而影响其性能,随着P含量(9.38%~15.4%)的增加,Ni-P的非晶态结构越明显,硬度在P含量11.4%时达到最大值723.3 HV;与SiCp/Al表面SiC相上的沉积相比,电沉积Ni-P在Al相上的初始沉积迅速,且长大速度快,导致镀层微观表面凹凸不平.经165℃活化热处理及化学镀18 min后,再电镀40 min,获得的镀层微观表面平整、厚12.90~14.79μm.说明经过优化工艺参数和预处理,可制备表面平整且结合良好的Ni-P电镀层.     

Mechanical properties and scratch resistance of filtered-arc-deposited titanium oxide thin films on glass

The mechanical properties and the scratch resistance of titanium oxide (TiO₂) thin films on a glass substrate have been investigated. Three films, with crystalline (rutile and anatase) and amorphous structures, were deposited by the filtered cathodic vacuum arc deposition technique on glass, and characterized by means of nanoindentation and scratch tests. The different damage modes (arc-like, longitudinal and channel cracks in the crystalline films; Hertzian cracks in the amorphous film) were assessed by means of optical and focused ion beam microscopy. In all cases, the deposition of the TiO₂ film improved the contact-mechanical properties of uncoated glass. Crystalline films were found to possess a better combination of mechanical properties (i.e. elastic modulus up to 221 GPa, hardness up to 21 GPa, and fracture strength up to 3.6 GPa) than the amorphous film. However, under cyclic sliding contact above the critical fracture load, the amorphous film was found to withstand a higher number of cycles. The results are expected to provide useful insight for the design of optical coatings with improved contact-damage resistance.     

Characterization and adhesion study of thin alumina coatings sputtered on PET

Thin amorphous alumina coatings have been deposited on polyethylene terephthalate (PET) by rf magnetron sputtering in a pure argon plasma. Their microstructure, composition, stresses and adhesion to the PET films have been studied. SEM microstructure study showed a good agreement with Thornton's structure zone model, i.e. a progression from a dense structure to a columnar structure was observed as the pressure was increased. The composition of deposits, determined by RBS, showed that oxygen-rich alumina was obtained when high plasma pressures (more than 1 Pa) were used. FTIR spectra of alumina indicate that the excess oxygen was essentially due to the presence of hydroxyl groups in the coatings. The stress evolution in alumina deposits, determined by the bending beam method, was correlated with the microstructural change. Adhesion of alumina on PET has been studied by a peel test. Best results were obtained when sputtering parameters combined moderate power (1 W cm⁻²) and pressure of about 1 Pa. XPS analysis of the alumina/PET interface showed that bonding between the ceramic and the polymer occurred primarily via Al-O-C bonds.     

Mechanical properties and deformation behaviour of some zirconium-nickel amorphous alloys

A series of zirconium-nickel alloys have been melt-spun under identical conditions to produce partly crystalline and fully amorphous ribbons. The mechanical properties: hardness and fracture strength of these ribbons have been determined. The deformation and fracture behaviour in bending and tension have been studied and the effect of the crystalline particles on the deformation and fracture processes has been examined. The structure of the deformation defects has also been investigated.