ESCA studies of Ni-Cr alloys

ESCA examination on Ni-Cr alloys has shown that a thin passive film was formed after 24 h immersion in 0.1 M NaCl. The film contained only chromium oxide in the form of Cr₂O₃. Electrochemical techniques according to ASTM G59 and ASTM G5 were used for the determination of the relative corrosion rate of the alloys. Both Ni-10 wt. % Cr and Ni-20 wt. % Cr alloys showed a slightly higher corrosion rate than the Ni-40 wt. % Cr alloy.The present ESCA study of the Ni-Cr system is part of our programme which involves an examination of the four binary alloy systems Fe-Si, Cr-Co, Ni-Cr, and Mo-Ni [1]. The aim is to correlate the structure and composition of the passive films formed in 0.1 M NaCl to the corrosion behaviour in the same solution.     

ESCA studies of Cr-Co alloys

ESCA examination of films formed on Cr-Co alloys after immersion in 0.1M NaCl for 24 h has shown that the thickness of passive films decreased with an increase in chromium content. Surface films consisted of chromium and cobalt oxides as Cr₂O₃ and CoO. The amount of CoO in the surface film of the alloy was decreased with an increase in chromium but Cr₂O₃ was found at a greater depth in the passive film at any composition. Cr₂O₃ was a major component of the surface film when the chromium content in the alloy was 10% or higher. Electrochemical techniques according to ASTM G59 and ASTM G5 were used for the determination of the relative corrosion rate. Both Co-10 wt.% Cr and Co-30 wt.% Cr alloys investigated showed a lower corrosion rate than the Co-5 wt.% Cr alloy. Corrosion rate measured could be correlated to the surface film composition and structure as determined by ESCA.     

ESCA studies of Si-Fe alloys

ESCA examination of films formed on Si-Fe alloys after immersion in 0.1 M NaCl for 24 h has hown that the thickness of passive films decreased with an increase in silicon content. A thick passive film containing oxidized silicon and oxidized iron was formed on Fe-20 wt% Si and the oxidized iron was about three times higher than the oxidized silicon in the passive film. However, an obvious reduction in the oxidized iron in the film on Fe-30 wt % Si was observed. Oxidized iron was detected up to a depth of 1.0 nm and at a depth greater than 1.0 nm from the surface, the film was exclusively in oxidized silicon. The film was exclusively silicon oxide when the silicon content was increased to 50 wt %. Electrochemical techniques according to ASTM G59 and ASTM G5 were used for the determination of the relative corrosion rate. Fe-50 wt % Si was found to have a corrosion rate smaller than those lower silicon alloys. This relates to the surface film composition and structure as determined by ESCA.     

Characterisation of Interfaces Between Liquid Tin and Alumina in the Presence of Titanium Alloy Additions

Neutron reflection spectroscopy has been used to characterise the composition of interfaces between liquid Sn-Ti alloys and Al₂O₃. The reflectivity profiles for both 1% and 3% Ti alloys are consistent with the presence of a layer approximately 2 nm thick at the liquid/solid interface, showing extensive segregation of Ti. The composition of this layer is not pure Ti but shows a greater Ti content than any known Ti oxide composition. In all interfaces exposed to liquid metals at elevated temperature (including pure Sn) there is a layer of thickness 20–100 nm on the alumina surface with slightly lower neutron scattering length density than pure alumina. This is interpreted as evidence for surface roughening of the Al₂O₃ surface during exposure to the liquid metal.     

Reaction products and oxide thickness formed by Ti out-diffusion and oxidization in poly-Pt/Ti/SiO2/Si with oxide films deposited

In the paper, we present experimental results to enhance the understanding of Ti out-diffusion and oxidization in commercial poly-Pt/Ti/SiO₂/Si wafers with perovskite oxide films deposited when heat-treated in flowing oxygen ambient. It indicates that when heat-treated at 550 and 600 °C, PtTi₃+PtTi and PtTi are the reaction products from interfacial interaction, respectively; while heat-treated at 650 °C and above, the products become three layers of titanium oxides instead of the alloys. Confirmed to be rutile TiO₂, the first two layers spaced by 65 nm encapsulate the Pt surface by the first layer with 60 nm thick forming at its surface and by the next layer with 35 nm thick inserting its original layer. In addition, the next layer is formed as a barrier to block up continuous diffusion paths of Ti, and thus results in the last layer of TiO_2−x formed by the residual Ti oxidizing.     

Characterization of sp carbon produced by plasma deposition on gamma-TiAl alloys

Surfaces of two gamma-TiAl alloys, Ti-47%Al-2%Nb-2%Cr (MJ12) and Ti-47%Al-2%Nb-2%Mn + 0.8%TiB₂ (MJ47), were modified by acetylene plasma deposition at −3 kV bias voltage for 0.5-4 h. By using GIXRD and SAED, C (n-diamond), TiC, Al, AlTi, AlTi₂, AlTi₃, Al_0.64Ti_0.36 and Al₂Ti were detected on both alloys. Additional TiB₂ was detected on MJ47. XPS and Raman analyses revealed the presence of sp³ and sp² carbon deposited on the alloy surfaces with their binding energies of 283.9-284.8 eV for MJ12 and 283.9-285.0 eV for MJ47. Both sp³ and sp² contents were increased with the increase in the exposure times. The increasing rate of the first was less than that of the second, due to the stress developed in the films. Moiré fringe and crystallographic planes were detected using TEM. Knoop hardness of the deposited alloys, influenced by sp³ carbon, was increased with the increase in the exposure time. Those of MJ12 and MJ47 with 4 h deposition are 1.88 and 1.57 times of the corresponding untreated alloys, respectively.     

Investigation on ultrasonic cavitation erosion of TiMo and TiNb alloys in sulfuric acid solution

Two kinds of Ti-alloys, i.e., TiMo and TiNb alloys are manufactured in this paper, and their ultrasonic cavitation erosion behaviors in 0.1 M H₂SO₄ solution are evaluated by the mean depth erosion (MDE), SEM and white light photograph. The results show that MDE of TiMo and TiNb alloys obviously increase with increasing the cavitation erosion time, however, they evidently decrease with the increment of Mo or Nb content at each fixed cavitation erosion time, and even some large blank areas (uneroded areas) still exist on the sample surface after ultrasonic cavitation erosion for 2 h in the case of Ti10Mo and Ti20Nb samples, implying the enhanced anti-cavitation erosion property of Ti-alloy by adding Mo or Nb element. The MDE of Ti10Mo or Ti20Nb sample is lower than that of TC4 sample in the case of each cavitation erosion time, indicating the better cavitation erosion resistance of of Ti10Mo or Ti20Nb sample. The influences of Mo and Nb on the passivity of TiMo and TiNb alloys during the ultrasonic cavitation erosion are detected by potentiodynamic curves. The results display that Ti, TC4, TixMo (x = 1, 5, 10) and TixNb (x = 5, 10, 20) samples are all almost in the passive state within the potential region from 0V_SCE to 1.5V_SCE during ultrasonic cavitation erosion, and the passive current density evidently decreases with increasing Mo or Nb content, indicating the enhanced passive characteristic by adding Mo or Nb alloys during the ultrasonic cavitation erosion.     

Effects of niobium on thermal stability and corrosion behavior of glassy Cu-Zr-Al-Nb alloys

The corrosion behavior of Cu_95−xZr_xAl₅ (x=40, 42.5 and 45 at.%) in 1 N HCl, 3 mass% NaCl and 1 N H₂SO₄ solutions was studied. As Zr content increases, the corrosion resistance is slightly enhanced. In order to improve the corrosion resistance of the Cu-Zr-Al glassy alloy, Nb was selected to substitute Cu. Although the supercooled liquid region ΔT_x of the Cu-Zr-Al glassy alloys decreases with increasing Nb content, the alloys still retain high glass-forming ability and bulk glassy samples with 1.5 mm diameter can be obtained when up to 5 at.% Nb was added. It is found that the addition of Nb results in improvement of the corrosion resistance of the glassy Cu-Zr-Al alloys.     

Titanium metallization of alumina ceramics by molten salt reaction

In this work, we reported a novel method that is flexible to metallize alumina ceramics with complex surface. Through Ti²⁺ disproportionation occurred in molten NaCl-KCl-K₂TiF₆ bath, the dense Ti layer was deposited on Al₂O₃ ceramics surface with strong adhesion. The effects of reaction temperature, time and initial K₂TiF₆ concentration on deposition rate were investigated. As-prepared coatings compose of bilayer structure of reactive Ti₂O phase, namely, the outer layer with coarse grains and the inner layer with fine grains. The wettability of eutectic Ag72Cu28 and Pb37Sn63 alloys with metallized Al₂O₃ ceramics was measured by using sessile drop method and compared with that of original ceramics. The results show that the metallized Al₂O₃ surface could be reactively wetted well with Ag72Cu28 and Pb37Sn63 alloys. The contact angles lowered to 35° and 8°, respectively, when temperature rose to 900 °C, showing significant enhancement of wettability after Ti metallization by molten salt reaction.     

Electrochemical and surface behavior of hydyroxyapatite/Ti film on nanotubular Ti-35Nb-xZr alloys

In this paper, we investigated the electrochemical and surface behavior of hydroxyapatite (HA)/Ti films on the nanotubular Ti-35Nb-xZr alloy. The Ti-35Nb-xZr ternary alloys with 3-10 wt.% Zr content were made by an arc melting method. The nanotubular oxide layers were developed on the Ti-35Nb-xZr alloys by an anodic oxidation method in 1 M H₃PO₄ electrolyte containing 0.8 wt% NaF at room temperature. The HA/Ti composite films on the nanotubular oxide surfaces were deposited by a magnetron sputtering method. Their surface characteristics were analyzed by field-emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDS) and an X-ray diffractometer (XRD). The corrosion behavior of the specimens was examined through potentiodynamic and AC impedance tests in 0.9% NaCl solution. From the results, the Ti-35Nb-xZr alloys showed a solely β phase microstructure that resulted from the addition of Zr. The nanotubular structure formed with a diameter of about 200 nm, and the HA/Ti thin film was deposited on the nanotubular structure. The HA/Ti thin film-coated nanotubular Ti-35Nb-xZr alloys showed good corrosion resistance in 0.9% NaCl solution.     

Thickness dependence on thermal stability of sputtered Ag nanolayer on Ti/Si(1 0 0)

Thermal stability of Ag layer on Ti coated Si substrate for different thicknesses of the Ag layer have been studied. To do this, after sputter-deposition of a 10 nm Ti buffer layer on the Si(1 0 0) substrate, an Ag layer with different thicknesses (150-5 nm) was sputtered on the buffer layer. Post annealing process of the samples was performed in an N₂ ambient at a flow rate of 200 ml/min in a temperature range from 500 to 700 °C for 30 min. The electrical property of the heat-treated multilayer with the different thicknesses of Ag layer was examined by four-point-probe sheet resistance measurement at the room temperature. Phase formation and crystallographic orientation of the silver layers were studied by θ-2θ X-ray diffraction analysis. The surface topography and morphology of the heat-treated films were determined by atomic force microscopy, and also, scanning electron microscopy. Four-point- probe electrical measurement showed no considerable variation of sheet resistance by reducing the thickness of the annealed Ag films down to 25 nm. Surface roughness of the Ag films with (1 1 1) preferred crystallographic orientation was much smaller than the film thickness, which is a necessary condition for nanometric contact layers. Therefore, we have shown that the Ag layers with suitable nano-thicknesses sputtered on 10 nm Ti buffer layer were thermally stable up to 700 °C.     

Effect of thermal annealing on microstructural properties of Ti/Ge2Sb2Te5/Ti thin films deposited on SiO2/Si substrates by a sputtering method

Ti/Ge₂Sb₂Te₅/Ti thin films deposited by a sputtering method on SiO₂/Si substrates were annealed at 400 °C in N₂ atmosphere and characterized by using transmission electron microscopy (TEM) and Auger electron spectroscopy (AES) in order to investigate the inter-diffusion of the Ti/Ge₂Sb₂Te₅/Ti system due to annealing. The TEM and AES results showed that the interface between the Ti and the Ge₂Sb₂Te₅ layers was unstable and Ti atoms were incorporated into the Ge₂Sb₂Te₅ thin film upon annealing. The Te and Sb atoms of the Ge₂Sb₂Te₅ layer diffused into the Ti layer. The intermixing layers between the Ge₂Sb₂Te₅ layer and two Ti layers were formed. These results indicate that the microstructural properties of the Ti/Ge₂Sb₂Te₅/Ti systems can be degraded by the postgrowth thermal annealing.     

Synthesis and structures of Al–Ti nanoparticles by hydrogen plasma-metal reaction

Three kinds of Al–Ti nanoparticles (7.7, 27.8, and 42.6 at.% Ti) have been prepared from Al–65, Al–85, and Al–88 at.% Ti master alloys by hydrogen plasma-metal reaction, with average particle sizes of 30, 25, and 80 nm, respectively. The higher evaporation rate of Al than Ti resulted in the low Ti contents in the nanoparticles than those in the master alloys. Microscopy observation revealed that the primary nanoparticles are spherical in shape, and occur as chain aggregates of several individual nanoparticles due to the faster collision rate than the coalescence rate. All the Al–Ti nanoparticles contain amorphous alumina layers of about 2–3 nm in thickness surrounding the crystalline core. AlTi intermetallic nanoparticles were successfully produced for Al–27.8 at.% Ti, with a single crystal of AlTi in one chain aggregate. The composite nanoparticles of Al together with some Al₃Ti phases are prepared for Al–7.7 at.% Ti, with each phase in the individual particle of one chain aggregate. The composite nanoparticles of AlTi with some AlTi₃ were produced for Al–42.6 at.% Ti, with each phase in the individual particle of one chain aggregate. The formation mechanism of Al–Ti nanoparticles was interpreted in terms of phase transition and the effect of hydrogen.     

Measurements of degree of sensitization (DoS) in aluminum alloys using EMAT ultrasound

Sensitization in 5XXX aluminum alloys is an insidious problem characterized by the gradual formation and growth of beta phase (Mg₂Al₃) at grain boundaries, which increases the susceptibility of alloys to intergranular corrosion (IGC) and intergranular stress-corrosion cracking (IGSCC). The degree of sensitization (DoS) is currently quantified by the ASTM G67 Nitric Acid Mass Loss Test, which is destructive and time consuming. A fast, reliable, and non-destructive method for rapid detection and the assessment of the condition of DoS in AA5XXX aluminum alloys in the field is highly desirable. In this paper, we describe a non-destructive method for measurements of DoS in aluminum alloys with an electromagnetic acoustic transducer (EMAT). AA5083 aluminum alloy samples were sensitized at 100 °C with processing times varying from 7 days to 30 days. The DoS of sensitized samples was first quantified with the ASTM 67 test in the laboratory. Both ultrasonic velocity and attenuation in sensitized specimens were then measured using EMAT and the results were correlated with the DoS data. We found that the longitudinal wave velocity was almost a constant, independent of the sensitization, which suggests that the longitudinal wave can be used to determine the sample thickness. The shear wave velocity and especially the shear wave attenuation are sensitive to DoS. Relationships between DoS and the shear velocity, as well as the shear attenuation have been established. Finally, we performed the data mining to evaluate and improve the accuracy in the measurements of DoS in aluminum alloys with EMAT.     

Effect of Ti doping on Ta2O5 stacks with Ru and Al gates

The Ti-doped Ta₂O₅ thin films (<10 nm) obtained by rf sputtering are studied with respect to their composition, dielectric and electrical properties. The incorporation of Ti is performed by two methods - a surface doping, where a thin Ti layer is deposited on the top of Ta₂O₅ and a bulk doping where the Ti layer is sandwiched between two layers of Ta₂O₅. The effect of the process parameters (the method and level of doping) on the elemental distribution in-depth of the films is investigated by the time of flight secondary ion mass spectroscopy (ToF-SIMS). The Ti and Ta₂O₅ are intermixed throughout the whole thickness but the layers are very inhomogeneous. Two sub-layers exist in all the samples — a near interfacial region which is a mixture of Ta-, Ti-, Si-oxides as well as TaSiO, and an upper Ti-doped Ta₂O₅ sub-layer. For both methods of doping, Ti tends to pile-up at the Si interface. The electrical characterisation is performed on capacitors with Al- and Ru-gate electrodes. The two types of MIS structures exhibit distinctly different electrical behavior: the Ru gate provides higher dielectric permittivity while the stacks with Al electrode are better in terms of leakage currents. The specific metal-dielectric reactions and metal-induced electrically active defects for each metal electrode/high-k dielectric stack define its particular electrical behavior. It is demonstrated that the Ti doping of Ta₂O₅ is a way of remarkable improvement of leakage characteristics (the current reduction with more than four orders of magnitude as compared with undoped Ta₂O₅) of Ru-gated capacitors which originates from Ti induced suppression of the oxygen vacancy related defects.     

Effects of TiN coating on the corrosion of nanostructured Ti-30Ta-xZr alloys for dental implants

Electrochemical characteristics of a titanium nitride (TiN)-coated/nanotube-formed Ti-Ta-Zr alloy for biomaterials have been researched by using the magnetic sputter and electrochemical methods. Ti-30Ta-xZr (x = 3, 7 and 15 wt%) alloys were prepared by arc melting and heat treated for 24 h at 1000 °C in an argon atmosphere and then water quenching. The formation of oxide nanotubes was achieved by anodizing a Ti-30Ta-xZr alloy in H₃PO₄ electrolytes containing small amounts of fluoride ions at room temperature. Anodization was carried out using a scanning potentiostat, and all experiments were conducted at room temperature. The microstructure and morphology of nanotube arrays were characterized by optical microscopy (OM), field emission scanning electron microscopy (FE-SEM) and X-ray diffraction (XRD). The TiN coatings were obtained by the radio-frequency (RF) magnetron sputtering technique. The depositions were performed from pure Ti targets on Ti-30Ta-xZr alloys substrates. The corrosion properties of the specimens were examined using potentiodynamic test in a 0.9% NaCl solution by using potentiostat. The microstructures of Ti-30Ta-xZr alloys were changed from an equiaxed to a needle-like structure with increasing Zr content. The interspace between the nanotubes was approximately 20, 80 and 200 nm for Zr contents of 3, 7 and 15 wt%, respectively. The corrosion resistance of the TiN-coated on the anodized Ti-30Ta-xZr alloys was higher than that of the untreated Ti alloys, indicating a better protective effect.     

Large area excimer laser induced deposition of titanium from titanium tetrachloride

Large area excimer laser induced deposition of titanium on fused silica from TiCl₄ is studied with an emphasis on process modeling. We show that several TiCl₄ monolayers can be adsorbed if the surface is adequately prepared and that the Ti thin film growth occurs through the photodecomposition of this adsorbed TiCl₄ layer. We propose two growth regimes. During an initiation phase, up to 3 nm in thickness, the adsorbed layer is photochemically decomposed giving a growth rate of 0.015 nm/pulse. In a second phase, the deposition rate increases to between 2 and 7 nm/pulse due to the laser heating of the preceding photochemically deposited titanium film. Between consecutive pulses, TiCl₄ molecules primarily from the adsorbed layer diffuse to the reaction zone leading to a new adsorbed layer ready to be transformed to solid titanium.     

Phase transition and pitting corrosion behaviour for Mo—implanted aluminium

Molybdenum ions are implanted into aluminium with high ion flux and high dose at elevated temperatures of 200℃, 400℃ and 500℃. Due to the high temperature and high flux of vacancies and interstitial atoms, the atom diffusion and chemical effects are enhanced during the ion implantation. The effects increase with increasing ion flux and dose, so that new phase formation and phase transition emerge noticeably. X-ray diffraction analysis shows that when the aluminium is implanted with Mo ions at a low ion flux (25μA/cm²), the Al₅Mo alloy is formed. The atomic ratio of Mo/Al of the Al₅Mo phase is close to 20%. When the aluminium is implanted with Mo ions at a high ion flux (50μA/cm²), the phase transition from Al₅Mo to Al₁₂Mo appears, and the latter is dominant, which is determined to be the final phase. The ratio of Mo/Al in Al₁₂Mo is 7.7%. Rutherford backscattering spectroscopy indicates also that the Mo/Al atom ratio is ～7% to ～8% in Mo-implanted aluminium. The atomic ratios of the constituents in Al₅Mo and Al₁₂Mo are of stoichiometric composition for these alloys. The thicknesses of the Al₁₂Mo alloy layers for Mo-implanted Al with ion doses of 3×10¹⁷/cm² and 1×10¹⁸/cm² are 550nm and 2000nm, respectively. The pitting corrosion potential V_p increases obviously. It is clear that due to the formation of Al₁₂Mo alloy layer, the pitting corrosion resistance is enhanced.     

Spin‐polarized electron gas in Co2M Si/SrTiO3 (M = Ti,V, Cr,Mn, and Fe) heterostructures

Spin‐polarized density functional theory is used to study the TiO₂ terminated interfaces between the magnetic Heusler alloys Co₂Si (M = Ti, V, Cr, Mn, and Fe) and the non‐polar band insulator SrTiO₃. The structural relaxation at the interface turns out to depend systematically on the lattice mis‐ match. Charge transfer from the Heusler alloys (mainly the M 3d orbitals) to the Ti d_xy orbitals of the TiO₂ interface layer is found to gradually grow from M = Ti to Fe, resulting in an electron gas with increasing density of spin‐polarized charge carriers. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Effect of surface roughness on the development of protective Al2O3 on Fe-10Al (at.%) alloys containing 0-10 at.% Cr

The effect of alloy surface roughness, achieved by different degrees of surface polishing, on the development of protective alumina layer on Fe-10 at.% Al alloys containing 0, 5, and 10 at.% Cr was investigated during oxidation at 1000 °C in 0.1 MPa oxygen. For alloys that are not strong Al₂O₃ formers (Fe-10Al and Fe-5Cr-10Al), the rougher surfaces increased Fe incorporation into the overall surface layer. On the Fe-10Al, more iron oxides were formed in a uniform layer of mixed aluminum- and iron-oxides since the layer was thicker. On the Fe-5Cr-10Al, more iron-rich nodules developed on an otherwise thin Al₂O₃ surface layer. These nodules nucleated preferentially along surface scratch marks but not on alloy grain boundaries. For the strong Al₂O₃-forming Fe-10Cr-10Al alloy, protective alumina surface layers were observed regardless of the surface roughness. These results indicate that the formation of a protective Al₂O₃ layer on Fe-Cr-Al surfaces is not dictated by Al diffusion to the surface. More cold-worked surfaces caused an enhanced Fe diffusion, hence produced more Fe-rich oxides during the early stage of oxidation.