Phase equilibria of the Cu-Ni-Si system at 700 °C

The phase equilibria at the isothermal section of the Cu-Ni-Si system at 700 °C were experimentally investigated. Thirty Cu-Ni-Si alloys were prepared by arc melting and annealed at 700 °C for 30 or 80 days, and examined with optical microscopy, X-ray diffraction, scanning electron microscopy with energy dispersive X-ray spectroscopy and electron probe microanalysis. Twelve three-phase regions were determined. The existence of the ternary compound τ₁-Cu_56.8-63Ni_10.4-16.1Si_26.6-27.3 reported in literature was confirmed and a new compound τ₂-Cu_45.8Ni₂₅Si_29.2 with nearly no homogeneity range was observed. The θ-Ni₂Si compound, which exists above 820 °C in the binary Ni-Si system, was found to be stable at 700 °C and the composition range of Cu is 12.7-20.6 at.% Cu. The ternary solubilities of binary compounds were measured and noticeably the Cu₅₆Si₁₁ compound can dissolve Ni up to 21.9 at.%.     

Structure and oxidation behavior of Si-Y co-deposition coatings on an Nb silicide based ultrahigh temperature alloy prepared by pack cementation technique

In order to improve the oxidation resistance of silicide coatings on Nb silicide based alloys, Y-modified silicide coatings were prepared by co-depositing Si and Y at 1050, 1150 and 1250 °C for 5-20 h, respectively. It has been found that the coatings prepared by co-depositing Si and Y at 1050 and 1150 °C for 5-20 h as well as at 1250 °C for 5 h were composed of a thick (Nb,X)Si₂ (X represents Ti, Cr and Hf elements) outer layer and a thin (Nb,X)₅Si₃ inner layer, while the coatings prepared by co-depositing Si and Y at 1250 °C for 10-20 h possessed a thin outer layer composed of (Ti,Nb)₅Si₃ and Ti-based solid solution, a thick (Nb,X)Si₂ intermediate layer and a thin (Nb,X)₅Si₃ inner layer. EDS analyses revealed that the content of Y in the (Nb,X)Si₂ layers of all the coatings was about 0.34-0.58 at.% while that in the outer layers of the coatings prepared by co-depositing Si and Y at 1250 °C for 10-20 h was about 1.39-1.88 at.%. The specimens treated by co-depositing Si and Y at 1250 °C for 10 h were selected for oxidation test. The oxidation behavior of the coating specimens at 1250 °C indicated that the Si-Y co-deposition coating had better oxidation resistance than the simple siliconized coating because the oxidation rate constant of the Si-Y co-deposition coating was lower than that of the simple siliconized coating by about 31%. The scale developing on the Si-Y co-deposition coating consisted of a thicker outer layer composed of SiO₂ and TiO₂ and a thinner SiO₂ inner layer.     

High temperature tribological characterisation of TiAlSiN coatings produced by cathodic arc evaporation

This study reports on the wear properties at medium-high temperatures of TiAlSiN films deposited by cathodic arc evaporation on hot work steel substrates. The chemical composition and microstructure of the coatings were characterised by glow discharge optical emission spectroscopy, scanning electron microscopy and X-ray diffraction. The mechanical properties, i.e. hardness and elastic modulus were evaluated by nanoindentation, and the adhesion of the coatings was tested by scratch tests. Coatings with stoichiometries of Ti_0.31Al_0.1Si_0.06N_0.53 and Ti_0.23Al_0.12Si_0.09N_0.55 exhibit microstructures consisting of solid solutions of (Ti,Al,Si)N, where Al and Si replace Ti atoms. These films show high hardness and good adhesion strength to the hot work steels. Conversely, coatings with a stoichiometry of Ti_0.09Al_0.34Si_0.02N_0.55 show a wurtzite-like microstructure, low hardness and poor adhesion strength.The wear rates of the coatings were investigated by ball-on-disc experiments at room temperature, 200 °C, 400 °C and 600 °C, using alumina balls as counter surfaces. At room temperature, the films show wear rates of the same order of magnitude of TiN and TiAlN coatings. On the other hand, the wear rates of solid solution (Ti,Al,Si)N coatings measured at 200, and 400 °C are one order of magnitude smaller than those measured at room temperature due to the formation of oxide-containing tribofilms on the wear tracks. At 600 °C the wear rates increase but still keep smaller than those measured at room temperature, although this effect can be influenced by the softening of the steel substrates by over-tempering. EDS analyses revealed that, between 200 °C and 400 °C, the oxidation of the coating occurs only at the contact zone between the film and the counterpart body due to the sliding process.     

On the stability of the Higher Manganese Silicides

We investigated in this work the stability of the Higher Manganese Silicides (HMS). Several alloys in the composition range 62-66 at.% Si were prepared from their constitutive elements by arc-melting. The prepared alloys were then analysed by in situ X-ray diffraction measurements and Electron Probe Micro-Analyser (EPMA). The whole results allow us to suggest that whatever the composition is, only Mn₂₇Si₄₇ is stable for the temperatures 500 °C and 800 °C. At higher temperatures, the studied samples undergo two phase transformations which consecutively lead to the formation of Mn₁₅Si₂₆ and Mn₁₁Si₁₉. Mn₄Si₇ was never evidenced in the present work. It is shown for the first time in this work that Mn₂₇Si₄₇ is the only HMS stable phase at room temperature.     

Synthesis of Ti3SiC2 by infiltration of molten Si

High-purity Ti₃SiC₂ compounds have been fabricated by infiltration of molten Si into a precursor, a partially sintered TiC_x (x = 0.67) preform. The Si source and the TiC_x preform were placed side by side on carbon cloth, and the system was heated to 1550 °C. Molten Si infiltrated the preform through the carbon cloth, and a direct reaction between TiC_x and molten Si immediately occurred at the reaction temperature to yield pure Ti₃SiC₂. We could observe phase formation and the microstructure of the bulk products with time, which were investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM) equipped with energy-dispersive spectroscopy (EDS). Pure Ti₃SiC₂ compounds were formed on the exterior of the TiC_x preform at 1550 °C when the sintered TiC_x:Si ingot molar ratio was 3:1.4. At 1550 °C, no other minor phases were detected for any of the sintering time ranges.     

Experimental phase diagram of the Ti-Si-Sn ternary system at 473 K

The phase diagram of the ternary system Ti-Si-Sn system at 473 K was investigated by means of powder X-ray diffraction (XRD), differential thermal analysis (DTA) and scanning electron microscope (SEM) with energy dispersive analysis (EDX). The isothermal section consists of 14 single phase regions, 26 binary phase regions and 13 ternary phase regions. The 10 binary compounds, namely Ti₃Si, Ti₅Si₃, Ti₅Si₄, TiSi, TiSi₂, Ti₃Sn, Ti₂Sn, Ti₅Sn₃, Ti₆Sn₅, Ti₂Sn₃, have been confirmed at 473 K. Moreover, a ternary phase with the crystal structure of tetragonal W₅Si₃ structure type and I4/mcm space group is confirmed in the Ti-Si-Sn system. The combined results of both EDX and XRD show that the composition of this ternary phase is 60.25-61.03 at.% Ti, 15.01-21.77 at.% Si and balance Sn.     

Effect of Mg, Si and Cu content on the microstructure of dilute 6000 series aluminium alloys

The effect of Mg, Si and Cu content on the microstructural development during ageing treatment of dilute 6000 series alloys have been investigated using transmission electron microscopy (TEM). Four dilute alloys were used in this study. These alloys were subjected to quenching and artificial ageing at 100 °C, 185 °C and 300 °C. The microstructural developments of the precipitates formed were monitored by TEM. The ageing temperature of 100 °C was found to be too low to form precipitates. It was found that needle or rod-shaped precipitates were formed in the alloys after ageing at 185 and 300 °C. Prolong ageing up to 1000 h at 300 °C resulted in the formation of Mg₂Si precipitate that coexists with the type of AlFeSi and Si precipitates. The results show a correlation between the Mg₂Si, Si and Cu content on the microstructure of the four dilute alloys after ageing treatment.     

Microstructure and martensitic transformation of cast TiNiSi shape memory alloys

The martensitic transformation behavior, second phases and hardness of Ti₅₁Ni_49−xSi_x shape memory alloys (SMAs) with x = 0, 1 and 2 at.% are investigated. The transformation temperature of one stage martensitic reaction B2 ↔ B19′ is associated with the forward (M_s) and reverse (A_s) martensitic transformations, respectively. All experimental DSC results such as martensitic transformation peaks (M*) and reverse martensitic transformation peaks (A*) are increased and became sharper with increasing Si-content. The microstructure investigation of the studied SMAs (Ti₅₁Ni_49−xSi_x) showed that there are two types of precipitated second phase particles. The first one is Ti₂Ni which mainly located at grain boundaries and intermetallic compound of Ti₂(Ni + Si) phase distributed inside the matrix. The volume fraction of these two phases is increased with Si content. Additionally, a small amount of Si remained in solid solution of the matrix of Ti₅₁Ni_49−xSi_x SMAs. Moreover, hardness of Ti₅₁Ni_49−xSi_x SMAs is increased as the Si-content increases.     

High-temperature SO2-gas corrosion of TiN–Ti5Si3 composites prepared by polymer pyrolysis

By pyrolyzing a mixture of Si-containing pre-ceramic polymers and TiH₂ powders in a N₂ atmosphere, a TiN–Ti₅Si₃ composite was synthesized. The composite was then corroded between 700 °C and 1000 °C for 20 h in an Ar–0.2% SO₂ atmosphere. TiN was mainly oxidized to rutile TiO₂. Ti₅Si₃ was oxidized to TiO₂ supersaturated with Si ions, and sulfidized to Ti₂S supersaturated with Si ions. At initial stage of corrosion, oxidation dominated sulfidation. As corrosion proceeded, sulfidation progressively occurred underneath the oxide scale based on the decreased oxygen potential and increased sulfur potential near the scale/matrix interface.     

Preparation of Ti+Ti6Si2B powders by high-energy ball milling and subsequent heat treatment

The present work reports on the preparation of two-phase Ti_SS+Ti₆Si₂B alloys by high-energy milling and subsequent heat treatment. The milled and heat-treated products were characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), and microanalysis via WDS. Results indicated the dissolution of silicon and boron atoms into the Ti lattice to form supersaturated solid solutions during the ball milling of Ti–10Si–5B and Ti–20Si–10B powders. TiB₂ precipitates were formed during ball milling, and the metastable structures were decomposed due to the released heat from its exothermic formation. After heat treatment at 1100 °C for 4 h, the equilibrium microstructures of the Ti–10Si–5B and Ti–20Si–10B alloys indicated the majority presence of the Ti and Ti₆Si₂B phases. TiB precipitates were found in Ti–10Si–5B and Ti–20Si–10B powders after heat treatment at 1200 °C for 16 h, indicating that the composition was moved from two-phase Ti+Ti₆Si₂B region to the three-phase Ti+Ti₆Si₂B+TiB field.     

Structure, morphology and electrical properties of sputtered Zr-Si-N thin films: From solid solution to nanocomposite

DC reactive magnetron co-sputtering was used for the deposition of Zr-Si-N thin films. Si content (C_Si) was varied by changing the power applied on the Si target, whereas that on Zr target was kept constant. Three series of samples have been deposited at various substrate temperatures: room temperature, 240 °C and 440 °C. The evolution of morphology, crystalline structure, grain size and lattice constant has been investigated by X-ray diffraction analyses. Nanohardness, stress and resistivity measurements provide complementary information, which validate the proposed 3-step model for the film formation of the Zr-Si-N system deposited by reactive magnetron co-sputtering. For low Si content the Si atoms substitute the Zr atoms in the ZrN lattice. Above the solubility limit, a nanocomposite film containing ZrN:Si nanocrystallites and amorphous SiN_y is formed. Further increase of Si content results in a reduction of grain size (D), while the thickness of the SiN_y layer at the crystallite surface remains constant. The increasing amount of the SiN_y amorphous phase in the films is realized by increasing the surface to volume ratio of the crystallites. In this concentration range, the size of the crystallites in the Zr-Si-N films decreases according to the relationship C_Si ∼ 1 / D. With increasing substrate temperature, the solubility limit of Si in ZrN decreases whereas the films' global nitruration (C_N / (C_Si + C_Zr)) increases. The concentration dependence of the electrical resistivity is interpreted in terms of the variation of the SiN_y layer thickness.     

Phase transformation behavior and shape memory characteristics of Ti−Ni−Si alloys

Transformation behavior, microstructures and shape memory characteristics of Ti−(50−X)Ni−XSi (X=2, 4, 6 at.%) and (50−X)Ti−Ni−XSi (X=2, 5, 7, 10 at.%) alloys were investigated by means of scanning electron microscopy, transmission electron microscopy, X-ray diffraction, differential scanning calorimetry, electrical resistivity measurements and constant load thermal cycling tests. Ti₅Si₃, Ni₁₆Ti₆Si₇ and Ni₄Ti₄Si₇ were formed in Ti−(50−X)Ni−XSi alloys, while Ti₅Si₄, Ni₃Si, Ni₃Ti₂ and Ni₃Ti₂Si were found in (50−X)Ti−Ni−XSi alloys. The total amount of silicides increased with increasing Si content, irrespective of Si content. The B2→B19 transformation occurred in Ti−(50−X)Ni−XSi alloys, and their transformation temperatures appeared to be almost constant. Transformation elongation associated with the B2→B19 transformation decreased with increasing Si content. In contrast to Ti−(50−X)Ni−XSi alloys, a transformation accompanied with structural change did not occur in (50−X)Ti−Ni−XSi alloys.     

High-temperature oxidation of Ti3Al−Nb alloys

Titanium aluminide (Ti₃Al–Nb) has potential for high-temperature applications because of its low density and high-temperature strength. This research is aimed at improving the high-temperature oxidation resistance of a Ti₃Al–Nb alloy by modification of its composition. The oxidation rates of Ti₃Al–Nb alloys were measured from 600 to 900°C in air. The oxide layer was examined by X-ray diffraction, scanning electron microscopy, and electron probe microanalysis. The experimental results reveal that alloys with added Nb tend to form denser oxide layers and that oxidation rate can be reduced by increasing Nb content (up to 11 at.% in this study), which is in good agreement with other investigators. The only exception is a Ti₆₅Al₂₅Nb₁₀ alloy, which shows better oxidation resistance than the commercial Ti₆₅Al₂₄Nb₁₁ alloy. The oxidation resistance of Ti₆₅Al₂₅Nb₁₀ alloy can also be improved slightly by the addition of small amounts of Si or Cr. An increase in the oxidation resistance of Ti₆₅Al₂₅Nb₁₀ alloy containing Y was observed at 900°C but not at 800°C or below. The parabolic oxidation rate equation is adequate to describe the high-temperature oxidation reaction of the Ti₃Al–Nb alloys in the atmosphere.     

Oxidation Resistance of Ti5Si3 and Ti5Si3Zx at 1000°C (Z = C,N, or O)

The oxidation behavior of Ti₅Si_3+y (y=0 or 0.2) and Ti₅Si₃Z_x (Z=C, N or O, x=0.25 or 0.5) was studied at 1000°C in air or argon–oxygen mixtures for up to 500 h. Ti₅Si₃ has poor oxidation resistance in air because of the formation of an oxide scale rich in rutile and subscale formation of TiN, TiSi, TiSi₂ and Si. In contrast, Ti₅Si_3.2 has excellent oxidation resistance because of the formation of a silica scale. Samples with interstitial oxygen or nitrogen show only slight improvements in the early stages of oxidation, compared to Ti₅Si₃, which is in stark contrast to previous research. However, samples with interstitial carbon displayed excellent oxidation resistance at 1000°C, consistent with previous research.     

Ru incorporation on marked enhancement of diffusion resistance of multi-component alloy barrier layers

In this study, amorphous AlCrTaTiZr quinary alloy and 20 at.% Ru-incorporated AlCrTaTiZrRu senary alloy films were developed as diffusion barrier layers to inhibit Cu diffusion in interconnect structures. Under annealing at 700 °C, the interdiffusion of Cu and Si through the AlCrTaTiZr quinary alloy layer of 50 nm thick occurred, and compounds including Cu₃Si consequently formed. In comparison, at 800 °C, the interdiffusion was still effectively retarded by the Ru-incorporated AlCrTaTiZrRu senary alloy layer of only 5 nm thick without obvious formation of silicides. It suggests the high diffusion resistance of the Ru-incorporated barrier layer possibly attributed to the large lattice distortions caused by the addition of extra-large-sized Ru atoms.     

Corrosion behavior of Ni-based amorphous alloys and their crystalline counterparts

In this paper, we report the corrosion behavior of Ni₅₉Zr₂₀Ti₁₆Si₂Sn₃ and Ni₅₃Nb₂₀Ti₁₀Zr₈Co₆Cu₃ (at.%) amorphous alloys with glass forming ability (GFA) of ∼3 mm, and their crystalline counterparts in severe corrosive environment of 1 M HCl aqueous solution. From the results of polarization curves and X-ray photoelectron spectroscopy (XPS), it was found that the corrosion behavior in Ni-based amorphous alloys is very sensitive to the compositions and the structural homogeneity is favorable for their corrosion-resistance in 1 M HCl aqueous solution.     

Characterization of Sn and Si nanocrystals embedded in SiO2 matrix fabricated by magnetron co-sputtering

Sn and Si nanocrystals were prepared by depositing Sn-Si-rich SiO₂ films using a co-sputtering process and a subsequent annealing. The microstructure and optical properties of Sn and Si nanocrystals were characterized by scanning electron microscopy (SEM), Raman spectra, X-ray diffraction and photoluminescence spectra. The crystallization of Sn has started at the annealing temperature of 400 °C, and was accomplished at 700 °C. However, the phase of amorphous Si starts to transform into nanocrystal Si when the annealing temperature is higher than 700 °C. These results illustrate that Sn existence as an element may played an important role in lowering the crystallization temperature of Si, and the crystallization rate of Si will be enhanced when Sn atom serves as the nucleation centre. Because quantum confinement effects are expected at relatively large radius for nanocrystal Sn, the redshift of high-energy PL peak may result from quantum confinement effects of nanocrystal Sn. However, the low-energy PL peak may be attributed to defects.     

Hydrogen and Zr-based metallic glasses: Gas/solid absorption process and structure evolution

The absorption of hydrogen by means of gas-solid reaction and its consequence on the structure have been studied for fully amorphous alloys as well as quasicrystals/glassy composite alloys based on the composition Zr₅₉Ti₃Cu₂₀Al₁₀Ni₈. The process of hydrogen absorption has been performed and monitored under 20 bar of H₂ using high pressure-differential scanning calorimetry (HP-DSC). The structure evolution of the samples has been followed by X-ray diffractometry (XRD). Results show that the nature of the surface oxide layer strongly affects the process of hydrogen absorption, especially its starting temperature. The structure evolves nevertheless along the same basic sequence, regardless of the sample: (i) the alloys keep a global amorphous structure up to roughly H/M = 0.8 and T = 350 °C; (ii) then ZrH₂ and at higher temperature Cu₂AlZr are formed. The stability of the glass is weakened and the formation of quasicrystals is inhibited under 20 bar of H₂. An heterogeneous distribution of hydrogen atoms inside the amorphous matrix has been inferred from the results.     

Fabrication and oxidation behavior of Cr2AlC coating on Ti6242 alloy

An ∼ 5 µm Cr₂AlC coating was synthesized on near-α titanium alloy Ti6242 using an industrially sized magnetron sputtering coater. Isothermal oxidation at 700 °C and 800 °C, and cyclic oxidation at 700 °C of the bare alloys and coated specimens were investigated in air. The results indicated that the Ti6242 alloy faced serious oxidation problems at 700 °C and 800 °C. Repeated formation and spallation of the multilayered oxide scale on the Ti6242 alloy occurred during oxidation testing. The coated specimens exhibited much better oxidation behaviour as compared to the bare alloy. A continuous Al-rich oxide scale formed on the coating surface during the initial oxidation stages. The oxide scale and coating itself acted as diffusion barriers blocking the further ingress of oxygen and protected the substrate alloy from oxidation. The oxidation mechanisms of the bare alloy and the coated specimens were investigated based on the experimental results.     

Phase transformations in face centered cubic (Al0.32Cr0.68)2O3 thin films

Face centered cubic (Al_0.32Cr_0.68)₂O₃ thin films have been annealed in the temperature range of 500–1000 °C during 2–8 h. The fcc structure of the film remains intact when annealed at temperatures up to 700 °C for 8 h. X-ray diffraction and transmission electron microscopy show the onset of phase transformation to corundum phase alloys in the sample annealed at 900 °C for 2 h, where annealing at 1000 °C for 2 h results in complete phase transformation to α-(Al_0.32Cr_0.68)₂O₃. In-plane and out-of-plane line scans performed in EDX TEM and θ/2θ XRD patterns did not show any phase separation into α-Cr₂O₃ and Al₂O₃ prior and after the annealing. The apparent activation energy of this process is 380–480 kJ/mol as determined by the Johnson–Mehl–Avrami model.