Preparation and characterization of TiO2/ZnO composite coating on carbon steel surface and its anticorrosive behavior in seawater

The TiO₂/ZnO composite coatings with various atomic ratios of Ti to Zn were prepared on carbon steel surface via sol–gel process followed by thermal treatment at different temperature. The as-prepared coatings were characterized through X-ray diffraction method, scanning electron microscopy, energy dispersive X-ray spectroscopy, and their anticorrosive behaviors in sterilized seawater were electrochemically assessed. The obtained coatings were quite thin even for the 8-layer samples. The thermal treatment at 500 °C led to severe oxidation of the steel substrate. The incorporation of ZnO avoided crack formation and refined the particles of the composite coatings. The electrochemical measurements of both the potentiodynamic polarization curves and electrochemical impedance spectroscopy revealed a substantial protection of the coatings for the substrate. In particular, the 8-layer TiO₂/ZnO composite coatings with atomic molar ratios of Ti to Zn of 1/1 and 1/3 after thermal treatment at 500 °C showed better anticorrosive performances than others.     

Effect of negative bias voltage on mechanical and electrochemical nature in Ti–W–N coatings

Mechanical and electrochemical surface properties of Si (100) and AISI D3 steel substrates-coated Ti–W–N, deposited by r.f. magnetron sputtering process from a binary (50% Ti, 50% W) target in an Ar/N₂ (90%/10%) mixture, have been studied using nanoindentation, Tafel polarization curves and electrochemical impedance spectroscopy (EIS). The crystallinity of the coatings was analyzed via X-ray diffraction (XRD) and the presence of TiN(111), TiN(200), WN₂(107), and W₂N(220) phases were determined. Depth sensing nanoindentation measurements were used to investigate the elasto-plastic behavior of Ti–W–N coatings. Each group of samples was deposited under the same experimental conditions (power supply, Ar/N₂ gas mixture and substrate temperature), except the d.c. negative bias voltage that varied (0, ?50, and ?100 V) in order to study its effect on the mechanical and electrochemical properties of AISI D3 steel coated with Ti–W–N coatings. The measurements showed that the hardness and elastic modulus increase from 19 to 30 GPa and from 320 to 390 GPa, respectively, as a function of the increasing negative bias voltage. Coating track and coating-substrate debonding have been observed with atomic force microscopy (Asylum Research MFP-3D^®) on the indentation sites. Finally, the corrosion resistance of Ti–W–N coatings in 3.5 wt% NaCl solution was obtained from electrochemical measurements in relation to the increase of the negative bias voltage. The obtained results have shown that at the higher negative bias voltage (?100 V), the steel coated with Ti–W–N coatings presented the lower corrosion resistance. The corrosion resistance of Ti–W–N in 3.5 wt% NaCl solution was studied in relation to the increase of the bias voltage.     

Microstructure and properties of Ti(C,N) coatings produced by moderate temperature chemical vapour deposition

In this work, Ti(C,N) coatings produced by moderate temperature chemical vapour deposition (MTCVD) were investigated and compared with Ti(C,N) coatings produced by conventional CVD. Detailed characterisation of the microstructure was made using transmission electron microscopy in combination with electron diffraction and electron energy-loss spectroscopy. The mechanical properties of different Ti(C,N) coatings were also dealt with. The deposited Ti(C,N) coatings had a twinned columnar microstructure with strong [112] texture. Large {001} crystal faces result in a rough and facetted surface. MTCVD coated tools have higher transverse rupture strength values than CVD coated ones, due to reduced decarburisation of the cemented carbide substrates and lower residual tensile stresses. Reduced decarburisation and the absence of the reversible η-phase reaction lead to improved edge strength.     

Performance evaluation of TiAlCrYN nanocomposite coatings deposited using four-cathode reactive unbalanced pulsed direct current magnetron sputtering system

Approximately 1.5-2.5 μm thick nanocomposite coatings of TiAlCrYN were deposited using a four-cathode reactive unbalanced pulsed direct current magnetron sputtering system from the sputtering of Ti, Al, Cr, and Y targets in Ar + N₂ plasma. The TiAlCrYN nanocomposite coatings were deposited on various substrates such as high speed steel (HSS) drill bits, mild steel and silicon. TiAlCrYN coatings with almost similar mechanical properties but with different Ti, Al, Cr and Y contents were prepared to study their thermal stability and machining performance. The structural and mechanical properties of the coatings were characterized using X-ray diffraction and nanoindentation technique, respectively. The elemental composition, bonding structure, surface morphology and cross-sectional data were studied using energy-dispersive X-ray analysis, X-ray photoelectron spectroscopy and field-emission scanning electron microscopy, respectively. Nanoscratch tests were performed to determine the adhesive strength of the coatings. The corrosion behavior of TiAlCrYN nanocomposite coatings on mild steel substrate was studied using potentiodynamic polarization in a 3.5% NaCl solution. Micro-Raman spectroscopy was used to characterize the structural changes as a result of heating of the nanocomposite coatings in air (600-1000 °C). TiAlCrYN coatings prepared at 17 at.% Ti, 13 at.% Al, 21 at.% Cr and 1 at.% Y exhibited thermal stability as high as 900 °C in air (denoted as Sample 3). For the performance evaluation, the TiAlCrYN coated HSS drill bits were tested under accelerated machining conditions. With a drill speed of 800 rpm and a feed rate of 0.08 mm/rev the TiAlCrYN coated HSS drill bits (Sample 3) averaged 657 holes, while drilling a 12 mm thick 304 stainless steel plate under dry conditions, before failure. Whereas, the uncoated drill bits failed after drilling 50 holes under the same machining conditions. Results indicated that for the HSS drill bits coated with TiAlCrYN, the tool life increased by a factor of more than 12.     

Control of hydrogen cracking in the welded steel using microstructural traps

Hydrogen diffusion into steel can embrittle the material in H₂S environments, but this effect can be offset by suitable hydrogen trapping sites in the microstructure. Fine Ti(C,N) inclusions have been studied as the trapping sites in high strength low alloy (API X-70) welds, with Ti additions ranging from 0.004 to 0.16?wt.%. The trapping sites were investigated by electron microscopy and thermal desorption spectroscopy. Manganese sulphide particles were the main initiation sites for hydrogen induced cracking as expected. The optimum Ti addition was around 0.02% with no evidence of cracking in the weld. The estimated values of trapping activation energy for dislocations, microvoids, MnS and Ti(C, N) were approximately 25.9, 34.6, 65.1 and 87.6?kJ?mol^?1, respectively.     

Corrosion behaviour of decorative and wear resistant coatings on steel deposited by reactive magnetron sputtering - Tests and improvements

Depositions of decorative and wear resistant single layer coatings like TiN, Ti(B,N), CrN, NbN, NbON, (Ti,Mg)N and multilayer coatings like Cr/CrN, Nb/NbN, CrN/NbN and NbN/Nb-C:H were performed using reactive magnetron sputtering. The corrosion behaviour of the coated high speed steel substrates was studied in sodium chloride containing media by open-circuit-potential measurements, potentiodynamic corrosion tests and salt spray tests. Up to now, the best improvements with respect to the corrosion resistance in salt spray tests could be obtained for the system (Ti,Mg)N/high speed steel.     

Korrosionsuntersuchungen an mittels PVD mit Zn und Zn/Mn beschichteten Stählen

Corrosion Studies of Steels Coated by means of PVD with Zn and Zn/Mn Alternative methods for hot dip‐ or electrogalvanic deposition of zinc coatings on steel are gas phase depositions (PVD). They posess high flexibility with respect to alloy composition, and are environmentally harmless. However, a PVD‐coated steel must have at least the same corrosion resistance than steels with “classical” surface finishing. Therefore, the corrosion behaviour of Zn‐coatings and Zn/Mn/system‐coatings deposited by electron beam evaporation without and with ion beam assistance (IBAD) on low alloy steel, was determined by means of salt spray test and electrochemical potential/time measurements. At first the influence of chemical and irradiation pre‐treatment and ion bombardment during deposition on the corrosion resistance of the coatings was investigated. Than the effect of the Zn‐layer thickness was determined in comparison with an 8μm thick electrogalvanized reference coating. Finally Zn/Mn‐alloys, Zn/Mn‐multilayers and Zn‐coatings with Mn‐ or Zn/Mn‐surface layers (top layers) were investigated. By means of optimised pre‐treatment and ion bombardment conditions one obtains, considering the layer thickness, PVD‐Zn coatings with corrosion resistance comparable with the reference layer. The best Mn‐containing coatings are Zn‐coatings with Mn‐toplayer. They surpass the corrosion resistance of the reference layer considerably. Additionally it could be shown that in tendency the potential/time measurements agree very well with the results of the salt spray test.     

A study of the nanostructure and hardness of electron beam evaporated TiAlBN Coatings

TiAlBN coatings have been deposited by electron beam (EB) evaporation from a single TiAlBN material source onto AISI 316 stainless steel substrates at a temperature of 450 °C and substrate bias of − 100 V. The stoichiometry and nanostructure have been studied by X-ray photoelectron spectroscopy, X-ray diffraction and transmission electron microscopy. The hardness and elastic modulus were determined by nanoindentation. Five coatings have been deposited, three from hot-pressed TiAlBN material and two from hot isostatically pressed (HIPped) material. The coatings deposited from the hot-pressed material exhibited a nanocomposite nc-(Ti,Al)N/a-BN/a-(Ti,Al)B₂ structure, the relative phase fraction being consistent with that predicted by the equilibrium Ti-B-N phase diagram. Nanoindentation hardness values were in the range of 22 to 32 GPa. Using the HIPped material, coating (Ti,Al)B_0.29N_0.46 was found to have a phase composition of 72-79 mol.% nc-(Ti,Al)(N,B)_1 − x+ 21-28 mol.% amorphous titanium boride and a hardness of 32 GPa. The second coating, (Ti,Al)B_0.66N_0.25, was X-ray amorphous with a nitride+boride multiphase composition and a hardness of 26 GPa. The nanostructure and structure-property relationships of all coatings are discussed in detail. Comparisons are made between the single-EB coatings deposited in this work and previously deposited twin-EB coatings. Twin-EB deposition gives rise to lower adatom mobilities, leading to (111) (Ti,Al)N preferential orientation, smaller grain sizes, less dense coatings and lower hardnesses.     

Laser cladding composite coatings by Ni–Cr–Ti–B4C with different process parameters

To investigate the effect of laser process parameters on microstructure and properties of composite coating, the composite coatings were manufactured by laser cladding Ni–Cr–Ti–B₄C mixed powder on Q235 mild steel with different process parameters. The coatings are bonded with the substrate by remarkable metallurgical binding without cracks and pores. The composite coatings are consisted of in situ synthesized solid solution Ni–Cr–Fe, intermetallic compound (IMC) Ni₃Ti, Cr₂Ti, and ceramic reinforcements TiB₂, TiC. Results of scanning electron microscopy (SEM) revealed that the ceramic reinforcements became coarser with higher specific energy (E_s). There were independent ceramics TiB₂, TiC, eutectic ceramic TiB₂–TiC in coatings, and eutectic alloy–ceramic was detected. Compared with the substrate, the microhardness of coatings was increased significantly, and the maximum microhardness of coatings was approximately five times as high as the substrate. The wear resistance of coatings was improved dramatically than the substrate. Compared to the coatings with lower E_s, higher E_s led to lower microhardness and worse wear resistance ascribing to more Fe diffused into the coating from the substrate.     

Titanium oxy-nitride films deposited on stainless steel by an ion beam assisted deposition technique

Surfaces of stainless steel SUS304 were coated with titanium oxy-nitride (TiON) films at temperatures of 400–770°C using an ion-beam assisted deposition technique constructed from an electron beam evaporator for Ti evaporation and a microwave ion source for ionizing nitrogen gas. The N ions were accelerated at energies of 0.5–2.0 keV. Most of the deposited TiON films consisted of (60–80)% TiN and (40–20)% TiO₂, and the fraction of TiO₂ increased with increasing substrate temperature. Hardness of the TiNO films varied in the range from 160 GPa to 260 GPa with increasing substrate temperature. The titanium oxy-nitride film could be deposited on stainless steel without a significant deterioration surface layer at 600°C. However, when TiNO films were deposited at temperatures higher than 700°C, the thickness of the TiNO films were significantly thinner and a thick layer containing nitride such as Cr₂N, CrFe, Fe₂N and Fe₄N was formed in a near surface region of stainless steel because more nitrogen diffused into stainless steel.     

Effects of O addition on the thermal behaviour of hard W-N sputtered coatings

The structural thermal behaviour of three W-O-N sputtered coatings with similar metalloid to metal ratio (∼2.1) was investigated up to 900 °C after annealing in a vacuum tube furnace as well as in-situ HT-XRD under a controlled atmosphere of Ar-5%H₂. The as-deposited microstructure of the coatings consisting in a nanocomposite of low-order W-O and W-N phases evaluated differently as a function of the oxygen content. The W-O-N film containing more than 27 at.% O delaminated severely from the steel substrates for temperatures as low as 500 °C. In opposite, for the coatings with less O content, the low range order of the as-deposited structure was maintained up to 800 °C and with further annealing crystallized into a mixture of WO₂ and W₂N. The thermal behaviour of the oxynitride films overcame that observed for oxygen-free nitride ones. This is due to the greater N content retaining during annealing treatment, in opposite to the W-N films which give rise to the single metallic α-W phase. The structural and compositional evolution supported the hardness behaviour obtained by the thermal treatment in protective ambiance.     

Substrate dependent cracking behavior of CrAlN coatings

The present study investigated the effect of substrate deformation behavior on crack resistance of CrAlN coatings under quasi-static and cyclic loads using nanoindentation. (Cr₄₇Al₅₃)N coatings were deposited on cemented carbide WC-Co and high-speed steel HS652C substrates through physical vapor deposition (PVD) und characterized. In order to study the coating cracking behavior, the coated substrates were subjected to quasi-static nanoindentations with indentation force F_max = 1 N, F_max = 1.5 N and F_max = 2 N. Moreover, the crack resistance under cyclic loading with frequency f = 0.16 Hz was analyzed at F = 1 N and F = 1.5 N after n = 900 cycles. A conical diamond indenter was used for the tests. At the end, the indentation imprints were analyzed by scanning electron microscopy (SEM). The substrate dependency was apparent in cracking behavior of the coating. Albeit the lower indentation depth compared to the variant with HS6-5-2C substrate, the CrAlN coating on WC-Co substrate showed surface cracks under quasi-static and cyclic loading. These cracks on the coated surface were absent in the variant with HS6-5-2C substrate. This could be related to higher resistance of cemented carbide substrates against plastic deformation, prompting earlier crack initiation in CrAlN coating for effective energy dissipation during indentation.     

Filter effects on the wear and corrosion behaviors of arc deposited (Ti,Al)N coatings for application on cold-work tool steel

In this study, (Ti,Al)N coatings were deposited on Japanese Industrial Standard SKD11 modified cold-work tool steel using a cathodic arc deposition system with and without magnetic filter attachment. Coating morphology and properties such as coating structure, adhesion, hardness, abrasion and corrosion behaviors were analyzed to evaluate the effects of magnetic filter on the coatings. The results showed that magnetic filtering slowed down (Ti,Al)N deposition rate, but it improved component homogeneity, roughness and adhesion of the coatings. Although (Ti,Al)N coated specimens produced with or without filter both showed superior abrasion resistance in service, however, filtered (Ti,Al)N coatings yielded better corrosion protection of the steel than unfiltered ones in 3.5 wt.% NaCl aqueous medium.     

Influence of boron doping on mechanical and tribological properties in multilayer CVD-diamond coating systems

Titanium alloy (Ti6Al4V) substrates were deposited with smooth multilayer coatings, by hot filament chemical vapour deposition technique. The effect of boron doping on lattice parameter, residual stresses, hardness and coefficient of friction in multilayer-diamond coating system was studied. The frictional behaviour of the coatings was studied using a ball-on-disc micro-tribometer by sliding the coated samples of titanium alloy (Ti6Al4V) substrates against alumina (Al₂O₃) balls, and increasing normal load from 1 to 10 N. The average friction coefficient decreased from 0.36 to 0.29 for undoped multilayer-diamond coating system and from 0.33 to 0.18 for boron- doped (BD) multilayer-diamond coating system. The average indentation depths for undoped and BD multilayer- diamond coating systems were found to be equal to ～>58 and ～65 nm, respectively, and their hardness values were 60 and 55 GPa, respectively.     

PIIID-formed (Ti,O)/Ti, (Ti,N)/Ti and (Ti,O, N)/Ti coatings on NiTi shape memory alloy for medical applications

(Ti, O)/Ti, (Ti, N)/Ti and (Ti, O, N)/Ti composite coatings were fabricated on NiTi shape memory alloy via plasma immersion ion implantation and deposition (PIIID). Surface morphology of samples was investigated using atomic force microscopy (AFM) and scanning electron microscopy (SEM). Cross-sectional morphology indicated that the PIIID-formed coatings were dense and uniform. X-ray diffraction (XRD) was used to characterize the phase composition of samples. X-ray photoelectron spectroscopy (XPS) results showed that the surface of coated NiTi SMA samples was Ni-free. Nanoindentation measurements and pin-on-disc tests were carried out to evaluate mechanical properties and wear resistance of coated NiTi SMA, respectively. For the in vitro biological assessment of the composite coatings in terms of cell morphology and cell viability, osteoblast-like SaOS-2 cells and breast cancer MCF-7 cells were cultured on NiTi SMA samples, respectively. SaOS-2 cells attached and spread better on coated NiTi SMA. Viability of MCF-7 cells showed that the PIIID-formed composite coatings were noncytotoxic and coated samples were more biocompatible than uncoated samples.     

Investigations on the thermal stability of microstructures generated by different thermal electron beam surface treatments

Surface treatments are frequently used to improve the wear and/or corrosion resistance of metal components. In the case of cast iron, the material-specific graphite limits both its treat-ability and load-bearing behaviour. A promising option for overcoming these limitations is provided by combination processes, in which near-surface graphite is first removed in an initial liquid-phase surface treatment – such as, e. g., remelting, alloying or cladding using electron beam (EB) – before application of thermochemical processes or hard coatings. A prerequisite for this is sufficient thermal resistance of these microstructures. This was investigated by means of annealing tests. The ranges of temperature used for annealing are based on those typically used for hard coating (250 °C–500 °C), nitriding (400 °C–600 °C) and boriding (600 °C–860 °C). The metastable microstructures produced as a result of rapid solidification during the electron beam liquid-phase treatments differ in their alloy content and, therefore, in their microstructural components. Hardness measurements after annealing provided an initial indication of thermal stability. Based on these measurements, interesting treatment conditions were analysed in more detail using scanning electron microscopy and x-ray diffraction. The focus of interest was on the formation of secondary graphite and the dissolution of ledeburitic carbides and other intermetallic phases.     

Hochtemperatureigenschaften von MCrAlY(Ti,Hf) beschichtetem Ventilstahl X 45 CrSi 9 3 bei 600 und 700°C

High temperature properties of MCrAlY(Ti, Hf) coated steel X 45 CrSi 9 3 at 600 and 700°C Within the COST-project 501.2 WP6 several plasmasprayed MCrAlY- and Zirkonia-coatings were tested for application in diesel engines as anti corrosion coatings and as thermal barrier coatings respectively. With coated and uncoated specimens of steel X 45 CrSi 9 3, creep tests up to 1700 h at 600 and 700°C were carried out in air and under streaming hot gas simulating diesel engine exhaust gas. Under the hot gas condition a strong sulphur induced corrosion occurred at the nickel- and ironbase alloys. Silicon containing alloys exhibited the best hot gas corrosion resistance. An additional thermal barrier coating increased the corrosion resistance effectively. In all cases the coated specimens exhibited a higher creep strength in comparison to the uncoated specimens. However, no strength decrease due to the hot gas corrosion was observed.     

Hard coatings on light-metal components under mechanical surface loading

In this work the behaviour of hard coated light-metal components was investigated when they are mechanically loaded. Three lightmetal alloys, Ti-6Al-4V, AlSi7Mg and AlMgSi0.5 and 100Cr6 steel (as a reference material) were coated by two different physical vapour deposition processes: radio frequency magnetron sputtering and electron beam evaporation. The coating materials utilised were CrN and TiN. Standard test methods with different loading conditions were used to evaluate the substrate/coating-combinations: the hardness test (applying a static normal load), the scratch test (applying a combination of a static normal and a static tangential force) and the impact test (applying a dynamic normal load). It was observed that the load support of coated materials depends on the loading conditions. The coated aluminium alloys showed poor load support under all loading test conditions but produced a higher surface hardness than uncoated steel. Coated Ti-6Al-4V showed very good load support properties, similar to coated steel. All coated light-metal substrates demonstrated significant improvement in load support behaviour with an increase in coating thickness. The results of the scratch test, which is commonly used to asses adhesion properties of thin coatings, showed an immediate indenter-breakthrough on the aluminium alloy substrates, but causing no coating delamination. Due to this behaviour, the scratch test is not suitable to evaluate adhesion properties on coated soft light-metals. Yet the impact test allowed assessment of coating delamination on the aluminium alloys, proving its usefulness for adhesion measurement even on soft substrates. The study indicates that substitution of steel with coated lightmetal alloys is a viable proposition for certain applications.     

Thermally grown oxide scales on γ-TiAl coated with thermal protection systems

Abstract

Thermal barrier coatings (TBCs) of yttria partially stabilized zirconia were deposited on gamma TiAl samples using electron-beam physical vapour deposition. The specimens were coated with intermetallic Ti –Al – Cr layers and CrAlYN/CrN nanoscale multilayer coatings. The lifetime of the TBC systems was determined performing cyclic oxidation tests in air at temperatures between 850 and 950–C. The TBC systems with Ti –Al – Cr and CrAlYN/CrN layers did not fail at 850 and 900–C during the maximum exposure time period of 1000 cycles of 1 h dwell time at high temperature. No spallation of the thermal barrier coatings was observed. As revealed by post-oxidation microstructural analysis, the protective coatings were severely degraded when exposed at 900–C, resulting in growth of mixed oxides on the substrate. Underneath the thermal barrier coating an outer oxide scale with a columnar structure was observed, consisting of rutile and α-Al₂O₃. Energy-dispersive X-ray spectroscopy analysis revealed zirconia and chromia being dissolved in the outer oxide scale. The columnar structure and the presence of zirconia indicated an effect of the TBC on the morphology of the outer oxide scale. The zirconia top coat exhibited an excellent adherence to this oxide scale formed on the protective layers when degraded, and at defects like cracks. When thermally cycled at 950–C, the TBC system on specimens coated with Ti –Al – Cr failed by spallation of the thermally grown mixed oxides, whereas the thermal barrier coating was well adherent to the outer oxide scale at this temperature, too.     

Optimization of PVD Parameters for the Deposition of Ultrahard Ti–Si–B–N Coatings

Multicomponent Ti–Si–B–N coatings were deposited on high-speed steel (HSS) substrates by reactive magnetron sputtering using a SHS TiB + 20 wt% Si target. The influences of the substrate temperature, bias voltage, and nitrogen partial pressure on the structure and the elemental compositions of the films were studied. The films were characterized by high-resolution transmission electron microscopy (HRTEM), Auger spectroscopy (AES), and X-ray diffraction (XRD). The results of HRTEM analysis indicated the formation of an ordered–disordered structure with fine crystalline grains of hexagonal Ti(B,N) _x phase and amorphous integrain layers. The stoichiometry of the Ti(B,N) _x phase was strongly affected by PVD process parameters. The films were characterized in terms of their microhardness and wear resistance. The reasons for the high value of microhardness appear to be the result of stoichiometric phase composition, compressive residual stress, and dense and fine microstructure of the Ti–Si–B–N coatings. The tribological wear test results indicated the superior wear-resistant properties of Ti–Si–B–N coatings compared to TiN and Ti(C,N) coatings.