Maßgeschneiderte Schicht-Interfacesysteme mittels ionenstrahlgestützter Beschichtung

Custom-Tailored Coating-Interface Systems by Means of lon Beam Assisted Deposition A coated sample represents in its most simple form a threefold junction consisting of substrate interface and top layer. In many cases the top layer consists again of several sublayers or the interface contains a modified substrate surface and an interconnection between top layer and interface. An ideal coating technique is evaporation under simultaneous ion bombardment with an ion source it is possible because of several free parameters to come close to an ideal system. For the coating Al/Al₂O₃ on steel it is shown that the width of a composition gradient between the sublayers Al and Al₂O₃ can be optimized with respect to excellent corrosion resistance. The example Cr_xN coating on steel or corrosion and wear resistence demonstrate the ability to optimize the corrosion and wear resistence by modifying the microstructure via variation of the parameters ion energy, ion impact angle, ion to atom ratio and process temperature. Finally, TiN layers on steel were chosen to show that the ion beam parameters influence the porosity and the crystal structure of the coatings. This fact can be used to optimize the corrosion protection or wear reduction obtained by the coating. Especially the multilayer Ti/TiO₂/TiN exhibits very interesting properties.     

Ti-Al球磨粉反应等离子喷涂涂层的组织与性能

为制备Ti-Al金属间化合物复合涂层并研究其性能,以机械球磨的Ti-Al混合粉在Q235钢表面进行反应等离子喷涂实验,分别采用X射线衍射、扫描电子显微镜对涂层的成分、显微组织进行了分析,并测试了涂层的结合强度、显微硬度和耐腐蚀性能.结果表明:涂层由Al3Ti、TiN、Al2O3、少量TiAl与Ti3Al、以及残留的Al和Ti组成;球磨可促进喷涂时的反应,但喷涂时Al和Ti仍未完全反应,且在空气环境中喷涂容易氧化和氮化;涂层与基体之间是镶嵌式的机械结合,结合强度平均为30.24 MPa;涂层表面的显微硬度平均为206.1 HV,涂层的耐腐蚀性优于基体.总体上看,当球磨时间较长、电流较大、喷涂距离较大、气流量较小时,喷涂时的反应较充分,且涂层比较均匀、致密,其强度、硬度以及耐腐蚀性能较高.     

Effects of temperature on the tribological behavior of Al0.25CoCrFeNi high-entropy alloy

The tribological behavior of Al_0.25CoCrFeNi high-entropy alloy (HEA) sliding against Si₃N₄ ball was investigated from room temperature to 600 ℃. The microstructure of the alloys was characterized by simple FCC phase with 260 HV. Below 300 ℃, with increasing temperature, the wear rate increased due to high temperature softening. The wear rate remained stabilized above 300 ℃ due to the anti-wear effect of the oxidation film on the contact interface. The dominant wear mechanism of HEA changed from abrasive wear at room temperature to delamination wear at 200 ℃, then delamination wear and oxidative wear at 300 ℃ and became oxidative above 300 ℃. Moreover, the adhesive wear existed concomitantly below 300 ℃.     

Balancing Scattering Channels: A Panoscopic Approach toward Zero Temperature Coefficient of Resistance Using High‐Entropy Alloys

Designing alloys with an accurate temperature‐independent electrical response over a wide temperature range, specifically a low temperature coefficient of resistance (TCR), remains a big challenge from a material design point of view. More than a century after their discovery, Constantan (Cu–Ni) and Manganin (Cu–Mn–Ni) alloys remain the top choice for strain gauge applications and high‐quality resistors up to 473–573 K. Here, an average TCR is demonstrated that is up to ≈800 times smaller in the temperature range 5–300 K and >800 times smaller than for any of these standard materials over a wide temperature range (5 K < T < 1200 K). This is achieved for selected compositions of Al_xCoCrFeNi high‐entropy alloys (HEAs), for which a strong correlation of the ultralow TCR is established with the underlying microstructure and its local composition. The exceptionally low electron–phonon coupling expected in these HEAs is crucial for developing novel devices, e.g., hot‐electron detectors, high‐Q resonant antennas, and materials in gravitational wave detectors.     

Role of Al additions in wear control of nanocrystalline Mo(Si1−xAlx)2 coatings prepared by double cathode glow discharge technique

Abstract

Four kinds of nanocrystalline Mo(Si_1?xAl_x)₂ coatings with differing Al contents are prepared onto a Ti–6Al–4V substrates by a double cathode glow discharge apparatus. The microstructural features of the deposited coatings were characterised by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. These coatings are composed of the equiaxed C40–MoSi₂ grains with the average grain size of ～5 nm. Nano-indentation measurements indicated that the hardness H, elastic modulus E and the H/E or H³/E² ratio of the nanocrystalline Mo(Si_1?xAl_x)₂ coatings slightly increase with the increase in Al content. The tribological behaviour of the nanocrystalline Mo(Si_1?xAl_x)₂ coating sliding against a ZrO₂ ceramic ball at room temperature has been compared using a ball-on-disc type tribometer under unlubricated conditions. Experimental results showed that the specific wear rates of the nanocrystalline Mo(Si_1?xAl_x)₂ coatings decrease with increasing Al content and are dramatically reduced by more than 1–2 orders of magnitude over the uncoated Ti–6A1–4V. The enhancement of wear resistance of the nanocrystalline Mo(Si_1?xAl_x)₂ coatings by Al additions is correlated with the increased mechanical properties and the forming oxide layer by tribochemical reactions.     

Impact of Al and Cr alloying in TiN-based PVD coatings on cutting performance during machining of hard to cut materials

The microstructure and electronic structure of nanodispersed (Al₆₇Ti₃₃N) and (Ti₁₀Al₇₀Cr₂₀N) PVD coatings were investigated by high-resolution transmission electron microscopy (HRTEM) and electron spectroscopy techniques: X-ray photoelectron spectroscopy (XPS) and high-resolution electron energy loss spectroscopy (HREELS). The grain size measured by HRTEM was 5-20 nm for Al₆₇Ti₃₃N and TiAlCrN type coatings, correspondingly. The spinodal decomposition of Al supersaturated nitrides under its deposition was found. Chromium increases the metastable solubility of h-AlN in c-Ti_1 − xAl_xN. The lifetime of the cutting tools with Al-rich coatings has been evaluated under ball nose end milling of hardened tool steel H13 (HRC 50-52) and aerospace materials. TiAlCrN coatings are preferable for steel machining, and AlTiN coatings are better for aerospace material processing. It was found that AlTiN coating has lower hardness but higher plasticity and improved impact fatigue fracture resistance. The TiAlCrN coating has much better hot hardness and oxidation stability at high temperatures, but it is stiffer than AlTiN.     

Influence of Al content on thermal stability of nanocrystalline AlxCoCrFeNi high entropy alloys at low and intermediate temperatures

Thermal stability of mechanically alloyed nanocrystalline Al_xCoCrFeNi (x = 0, 0.3, 0.6, 1 mol) high entropy alloys (HEAs) has been investigated for the low and intermediate temperature range of 673–1073 K. Single phase FCC structure is observed in the as milled CoCrFeNi. A mixture of FCC and BCC phases is exhibited by × = 0.3, 0.6 and 1, alloys where the volume fraction of BCC increases with increasing Al content. Phase evolution in heat-treated Al_xCoCrFeNi HEAs proceeds via increasing BCC fraction at 673 K, followed by subsequent reduction at elevated temperatures. For each alloy, the major phase observed in as milled condition and it is retained even after prolonged exposure at the 1073 K. Al favors the formation of the BCC phase due to its high affinity to form ordered B2 structures with constituent elements Co, Fe and Ni. Thermal exposure of Al_xCoCrFeNi HEAs also leads to the formation of Cr₇C₃, owing to the higher negative free energy of carbide formation for Cr among other constituents. Transmission electron microscopy (TEM) investigations substantiated that nanostructure of milled powder is maintained even after the heat treatment. Grain growth factor for quinary HEAs is relatively lower than quaternary CoCrFeNi owing to their slower rates of diffusion.     

Chemical constitution and microstructure of TiC x coatings chemically vapour deposited on Fe-C substrates; effects of iron and chromium

TiC _x coatings were chemically vapour deposited in an industrial reactor on Fe-C substrates with carbon contents between 0.06 and 1.20 wt % C. Electron probe microanalyses showed that significant amounts of chromium and iron were present in the coatings and that chromium was also present in the substrate region adjacent to the coatings. By comparing calculated and measured lattice parameters (corrected for the internal stresses present) it became evident that the chromium was in solid solution in TiC _x , whereas the iron was not. This was confirmed by micro Auger electron spectroscopy and X-ray diffraction phase analyses. The carbon to metal ratio,x, of the TiC _x coatings decreased with increasing distance to the coating/substrate interface. The effect of iron on the X-ray diffraction line broadening and hardness of the coatings was large (in contrast with the effect of chromium) and increased with increasing distance to the coating/substrate interface because of a decreasing iron particle size. The TiC _x crystallite size was small and constant throughout the thickness of the coatings. The chromium present in the substrate region adjacent to the TiC _x coatings influenced the microstructure of the substrate by formation of iron, chromium-carbides and reduced the growth rate of the coatings.     

Einfluss einer PVD‐Al‐Zwischenschicht auf die Eigenschaften eines thermisch gespritzten Wärmedämmschichtsystems nach Temperaturwechselbelastung

Thermal barrier coatings (TBC) generally consist of a metallic bond coat (BC) and a ceramic top coat (TC). Co–Ni–Cr–Al–Y metallic super alloys and Yttria stabilised zirconia (YSZ) have been widely used as bond coat and top coat for thermal barrier coatings systems, respectively. As a result of long‐term exposure of thermal barrier coatings systems to oxygen‐containing atmospheres at high temperatures, a diffusion of oxygen through the porous ceramic layer occurs and consequently an oxidation zone is formed in the interface between ceramic top coat and metallic bond coat. Alloying components of the BC layer create a so‐called thermally grown oxides layer (TGO). One included oxide type is α‐Al₂O₃. α‐Al₂O₃ lowers oxygen diffusion and thus slows down the oxidation process of the bond coat and consequently affects the service life of the coating system positively. The distribution of the alloying elements in the bond coat layer, however, generally causes the formation of mixed oxide phases. The different oxide phases have different growth rates, which cause local stresses, micro‐cracking and, finally, delamination and failure of the ceramic top coat layer. In the present study, a thin Al inter‐layer was deposited by DC‐Magnetron Sputtering on top of the Co–Ni–Cr–Al–Y metallic bond coat, followed by thermal spraying of yttria‐stabilised zirconia (YSZ) as a top coat layer. The deposited Al inter‐layer is meant to transform under operating conditions into a closed layer with high share of α‐Al₂O₃ that slows down the growth rate of the resulting thermally grown oxides layer. Surface morphology and microstructure characteristics as well as thermal cycling behaviour were investigated to study the effect of the intermediate Al layer on the oxidation of the bond coat compared to standard system. The system with Al inter‐layer shows a smaller thermally grown oxides layer thickness compared to standard system after thermal cycling under same conditions.     

Corrosion and erosion behavior of iron aluminide (FeAl(Cr)) coating deposited by detonation spray technique

The electrochemical corrosion and erosion behavior of FeAlCr coating was reported in this article. The FeAlCr coatings were deposited by detonation spray coating system (DSC) by utilizing the gas atomized powder with a nominal composition of Fe-12Al-5Cr at two different pulse frequencies on mild steel (MS) substrate. Feedstock and coatings were characterized using XRD, SEM and elemental mapping. Nanoindentation tests using a Berkovich indenter indicate a hardness of 5.5 GPa and 4.9 GPa for the coatings deposited at 3 Hz and 6 Hz respectively as compared to 1.5 GPa of the substrate. Electrochemical corrosion tests were performed on coated samples in 3.5 wt% NaCl and 2 N H₂SO₄ media and are compared with the bulk MS substrate. Detonation pulse frequency significantly influenced the coating microstructure and corrosion performance. The coating deposited at a frequency of 6 Hz exhibited higher resistance against electrochemical corrosion in 3.5 wt% NaCl medium than the coating that was deposited at 3 Hz frequency. Solid particle erosion tests performed at room temperature (25 °C) and an impingement angle of 90° (normal incidence) using Al₂O₃ as the erodent medium demonstrate a higher erosion loss of the coatings than the bulk MS. On the contrary, at a temperature of 400 °C, the coatings exhibited notably better erosion resistance than the MS substrate, illustrating the potential of FeAlCr coatings for high temperature wear-corrosion resistant applications.     

Verschleißfeste Beschichtungen von Aluminium‐Stahl‐Hybridstrukturen mittels thermischer Spritztechnik

Spraying of wear‐resistant coatings of aluminium‐steel‐hybrid‐structures By means of high velocity oxy fuel flame spraying of aluminium‐hybrid‐structures consisting of a Al Zn 5,5 Mg Cu 1,5 (ENAW7075) and a NiCrBSi‐coating as well as a Cr₃C₂ 25NiCr‐ coating are manufactured. The hybrid composite structures are analysed and compared with each other regarding to hardness, surface roughness, wear‐resistance and coating density.     

Elektronenstrahlbehandlung von PVD‐Hartstoffschichten

Electron beam treatment of PVD – hard coatings Coatings of the type CrN_x, (Ti, Cr)N, (Ti, Al)N, Ti(C, N) and Ti(B,N) were deposited on the quenched and tempered steel C45 to investigate the effect of electron beam treatment on the structure and the properties of hard coated steels. A controlled energy input by electron beams was used to investigate the thermal behaviour of hard coatings with fixing the transformation levels by self‐quenching. Simultaneously a different case hardening of the substrate was caused providing a different effect of supporting the hard layer. There are big differences in the thermal stability of the investigated coatings. The surface hardness, adhesion and wear resistance of the composit hard coating/steel was improved in dependence on the energy input. The use of electron beam technologies enables the generation of support layers which locally increase the working behaviour of hard coated steel.     

Microstructure of high velocity oxy-fuel sprayed Ti2AlC coatings

The microstructure formation and phase transformations in Ti₂AlC-rich coatings deposited by High Velocity Oxy-fuel spraying of Maxthal 211^? powders is presented. High resolution electron microscopy analysis, using both scanning and transmission electron microscopy with energy dispersive spectrometry and energy filtering, combined with X-ray diffraction reveals that the coatings consist of Ti₂AlC grains surrounded by regions of very small TiC grains embedded in Ti _x Al _y . The composition of the Ti _x Al _y depends on its surrounding and varies with size and distribution of the adjacent TiC grains. Impact of spray parameters on coating microstructure is also discussed. Two spray parameters were varied; powder size distribution and flame power. They were found to greatly affect the coating microstructure. Increasing powder size and decreasing flame power increase the amount of Ti₂AlC, but produces thinner coatings with lower cohesion. Larger powder size will also decrease oxygen incorporation.     

Effect of heat treatment on the microstructure and property of cold-sprayed nanostructured FeAl/Al2O3 intermetallic composite coating

It is difficult to deposit dense intermetallic compound coatings by cold spraying directly using compound feedstock powders due to their intrinsic low temperature brittleness. A method to prepare intermetallic compound coatings in-situ employing cold spraying was developed using a metastable alloy powder assisted with post heat treatment. In this study, a nanostructured Fe(Al)/Al₂O₃ composite alloy coating was prepared by cold spraying of ball-milled powder. The cold-sprayed Fe(Al)/Al₂O₃ composite alloy coating was evolved in-situ to FeAl/Al₂O₃ intermetallic composite coating through a post heat treatment. The effect of heat treatment on the phase formation, microstructure and microhardness of cold-sprayed Fe(Al)/Al₂O₃ composite coating was investigated. The results showed that annealing at a temperature of 600 °C results in the complete transformation of the Fe(Al) solid solution to a FeAl intermetallic compound. Annealing temperature significantly influenced the microstructure and microhardness of the cold-sprayed FeAl/Al₂O₃ coating. On raising the temperature to over 950 °C, diffusion occurred not only in the coating but also at the interface between the coating and substrate. The microhardness of the FeAl/Al₂O₃ coating was maintained at about 600HV_0.1 at an annealing temperature below 500 °C, and gradually decreased to 400HV_0.1 at 1100 °C.     

Interfacial microstructures and properties of aluminum alloys/galvanized low-carbon steel under high-pressure torsion

A new composite processing technology characterized by hot-dip Zn–Al alloy process was developed to achieve a sound metallurgical bonding between Al–7 wt% Si alloy (or pure Al) castings and low-carbon steel inserts, and the variations of microstructure and property of the bonding zone were investigated under high-pressure torsion (HPT). During hot-dipping in a Zn–2.2 wt% Al alloy bath, a thick Al₅Fe₂Zn_x phase layer was formed on the steel surface and retarded the formation of Fe–Zn compound layers, resulting in the formation of a dispersed Al₃FeZn_x phase in zinc coating. During the composite casting process, complex interface reactions were observed for the Al–Fe–Si–Zn (or Al–Fe–Zn) phases formation in the interfacial bonding zone of Al–Si alloy (or Al)/galvanized steel reaction couple. In addition, the results show that the HPT process generates a number of cracks in the Al–Fe phase layers (consisting of Al₅Fe₂ and Al₃Fe phases) of the Al/aluminized steel interface. Unexpectedly, the Al/galvanized steel interface zone shows a good plastic property. Beside the Al/galvanized steel interface zone, the microhardnesses of both the interface zone and substrates increased after the HPT process.     

(Cr1‐x,Alx)N ein Review über ein vielseitig einsetzbares Schichtsystem

(Cr_1‐x,Al_x)N a review about a multi‐purpose coating system Nitride based coatings claimed a big market share for PVD‐coatings. Especially in the field for high temperature die casting and cutting operations chromium based coatings are well used. These coatings are also used in low temperature processes for the coating of machine parts. In the beginning of the nineties first examinations are done on the ternary system Chromium‐Aluminium‐Nitride. This system shows an excellent corrosion behaviour against many different liquids, but gains also a high hardness for a good wear behaviour. By changing the AlN to CrN content and the coating design CrAlN opens up a wide range for different coating applications. A major step for machine parts was the reducing of coating process temperature beneath 200 °C. This was only possible by using pulsed power supplies. CrAlN shows a very good performance on the fast growing market of coated machine parts e.g. on spindle bearings.     

A study on sliding and erosive wear behaviour of atmospheric plasma sprayed conventional and nanostructured alumina coatings

Alumina coatings on stainless steel substrate (SS304) were deposited by using atmospheric plasma spray technique with a feed stock of manually granulated and sieved nano Al₂O₃ powder. The hardness, sliding, and erosive wear of the nanostructured alumina coatings (NC) were investigated and compared with that of conventional alumina coatings (CC). Pin-on disc type sliding wear test on the alumina coatings (NC and CC) was performed with load varying from 30 N to 80 N at a sliding speed of 0.5 m/s. Pot type slurry erosion test of the coatings was conducted for different concentrations of Al₂O₃ and a mixture of Al₂O₃ and SiO₂ slurry. The microstructural features of both NC and CC of alumina were characterized by using FE-SEM/EDS and SEM analysis to substantiate the failure of coatings due to wear. Wear and erosion resistance of nano alumina coating is better than the conventional alumina coating as observed in the present work. The bimodal structure of NC contributes for the enhanced wear resistance. The high fracture toughness of NC is due to suppression of cracks by partially melted particles in the coatings.     

Untersuchung der Haftmechanismen kaltgasgespritzter Al‐Schichten auf Al2O3

The metallization of ceramics by means of cold gas spraying has been in the focus of numerous publications in the recent past. However, the bonding mechanisms of metallic coatings on non‐ductile substrates are still not fully understood. Former investigations of titanium coatings on corundum revealed that a combination of recrystallisation induced by adiabatic shear processes and heteroepitaxial growth might be responsible for the high adhesions strengths of coatings applied on smooth ceramic surfaces. In the present work, it is intended to examine the interface area of cold gas sprayed aluminum on alumina substrates. Besides a variation of powder fraction and substrate temperature, it is investigated if a downstream heat treatment has an influence on tensile strength and hardness of the coatings. The splat formation of single particles is investigated by means of scanning electron microscopy, while a high resolution transmission electron microscope is used to examine the Al/Al₂O₃ interface. First results suggest that mechanical clamping is the primary bonding mechanism on polycrystalline coatings with a sub‐micrometer‐scaled surface roughness, while heteroepitaxial growth is the main bonding mechanism for Al coatings on single‐crystalline, atomically smooth sapphire (α‐Al₂O₃) substrates. Heteroepitaxy is promoted by deformation‐induced recrystallisation of the cold gas‐sprayed aluminum.     

Effect of nano-CeO2 on microstructure properties of TiC/TiN+TiCN-reinforced composite coating

TiC/TiN+TiCN-reinforced composite coatings were fabricated on Ti–6Al–4V alloy by laser cladding, which improved surface performance of the substrate. Nano-CeO₂ was able to suppress crystallization and growth of crystals in the laser-cladded coating to a certain extent. With the addition of proper content of nano-CeO₂, this coating exhibited fine microstructure. In this study, Al₃Ti+TiC/TiN+nano-CeO₂ laser-cladded coatings have been studied by means of X-ray diffraction and scanning electron microscope. X-ray diffraction results indicated that Al₃Ti+TiC/TiN+nano-CeO₂ laser-cladded coating consisted of Ti₃Al, TiC, TiN, Ti₂Al₂₀Ce, TiC_0·3N_0·7, Ce(CN)₃ and CeO₂, this phase constituent was beneficial in increasing microhardness and wear resistance of Ti–6Al–6V alloy.     

Wetting of grain boundaries in Al by the solid Al<Subscript>3</Subscript>Mg<Subscript>2</Subscript> phase

The microstructure of binary Al_100−x –Mg _x (x = 10, 15, 18 and 25 wt%) alloys after long anneals (600–4000 h) was studied between 210 and 440 °C. The transition from incomplete to complete wetting of Al/Al grain boundaries (GBs) by the second solid phase Al₃Mg₂ has been observed. The portion of completely wetted GBs increases with increasing temperature beginning from T _wsmin = 220 °C. Above T _wsmax = 410 °C all Al/Al GBs are completely wetted by the Al₃Mg₂ phase.