Effects of Sn addition on the glass forming ability and crystallization behavior in Ni-Zr-Ti-Si alloys

The effect of Sn substitution for Si on the glass forming ability (GFA) and crystallization behavior has been studied in Ni₅₉Zr₂₀Ti₁₆Si_5 − xSn_x (x=0, 3, 5) alloys. A bulk amorphous Ni₅₉Zr₂₀Ti₁₆Si₂Sn₃ alloy with diameter up to 3 mm can be fabricated by injection casting. Partial substitution of Si by Sn in Ni₅₉Zr₂₀Ti₆Si_5 − xSn_x alloys improves the glass forming ability. The improved GFA of the Ni₅₉Zr₂₀Ti₁₆Si₂Sn₃ alloy is can be explained based on the lowering of liquidus temperature. The crystallization sequence becomes completely different with addition of Sn. The amorphous Ni₅₉Zr₂₀Ti₁₆Si₅ alloy crystallizes via precipitation of only a cubic NiTi phase in the first crystallization step, whereas the amorphous Ni₅₉Zr₂₀Ti₁₆Si₂Sn₃ alloy crystallizes via simultaneous precipitation of orthorhombic Ni₁₀(Zr,Ti)₇ and cubic NiTi phases. Addition of Sn in the Ni₅₉Zr₂₀Ti₁₆Si₅ alloy suppresses the formation of the primary cubic NiTi phase. The bulk amorphous Ni₅₉Zr₂₀Ti₁₆Si₂Sn₃ alloy exhibits high compressive fracture strength of about 2.7 GPa with a plastic strain of about 2%.     

Effects of Nb on the formation of icosahedral quasicrystalline phase in Ti-rich Ti-Zr-Ni-Cu-Be glassy forming alloys

As-cast (Ti₄₀Zr₂₅Ni₈Cu₉Be₁₈)_100−xNb_x (0 ? x ? 5) (Ф3) glassy forming alloys were investigated in order to clarify the role of Nb on the formation of icosahedral quasicrystalline phase (I-phase) in Ti-rich Ti-Zr-Ni-Cu-Be glassy system. It is found that an I-phase is formed in Ti-Zr-Ni-Cu-Be glassy alloy by addition of Nb element; however, the nucleation rate of I-phase increases, whereas the grain growth rate decreases with increasing Nb content. Moreover, with increasing Nb content, the thermal stability against crystallization increases, while the temperature range of stability of the I-phase decreases.     

The effect of Sn addition on the glass-forming ability of Cu-Ti-Zr-Ni-Si metallic glass alloys

The effect of Sn substitution for Ni on the glass-forming ability was studied in Cu₄₇Ti₃₃Zr₁₁Ni_8−xSn_xSi₁ (x=0,2,4,6,8) alloys by using thermal analysis and X-ray diffractometry. With increasing x from 0 to 8, the glass transition temperature, T_g, of melt-spun Cu₄₇Ti₃₃Zr₁₁Ni_8−xSn_xSi₁ alloys increased gradually from 720 to 737 K. On the other hand, the crystallization temperature, T_x, increased from 757 K at x=0 to 765 K at x=2, being nearly same with further increase of x. Partial substitution of Ni by Sn in Cu₄₇Ti₃₃Zr₁₁Ni₈Si₁ promotes the glass formation. Both amorphous Cu₄₇Ti₃₃Zr₁₁Ni_8−xSn_xSi₁ alloys prepared by melt spinning and injection casting showed similar crystallization process during continuous heating in DSC. Temperature range of undercooled liquid region exhibits good correlation with the critical diameter for the formation of an amorphous phase in injection casting.     

Far-infrared transmission and bonding arrangement in Ge10Se90−xTex semiconducting glassy alloys

The far-infrared spectra of Ge₁₀Se_90−xTe_x where x = 0, 10, 20, 30, 40, 50 glassy alloys were measured in the wavenumber region 50-650 cm⁻¹ at room temperature. The results were explained in terms of the vibrations of the isolated molecular units. The addition of Te in Ge₁₀Se₉₀ has shown the appearance of GeTe₂ and GeTe₄ molecular units and vibrations of Se-Te bond as Se_8−xTe_x mixed rings. The assignment of various absorption bands has been made on the basis of absorption spectra of pure Se, binary Ge-Se, Ge-Te, Se-Te and ternary Ge-Se-Te glassy alloys. The far-infrared transmission spectrum has been found to shift a little towards lower wavenumber side with the addition of Te content to Ge₁₀Se₉₀. The addition of Te to Ge-Se system replacing Se has found to reduce the Se-Se bonds and Ge-Se bonds and leads to the formation of Se-Te, Ge-Te and Te-Te bonds.     

Structure and dynamics of liquid Al1−xSix alloys by ab initio molecular dynamics simulations

First-principles molecular dynamics (MD) simulations are performed to study the structure and dynamics of liquid Al_1−xSi_x (x = 0.0, 0.12, 0.2, 0.4, 0.6, 0.8) at the temperature of 1573 K. The composition dependence of static structure factors, pair correlation functions, and diffusion constants are investigated. We found that the structure of the liquid Al_1−xSi_x alloys is strongly dependent on the composition. From our simulation and analysis, we can see that although liquid Al_1−xSi_x is metallic, there are some degrees of covalent tetrahedral short-range order in the liquid. The degree of tetrahedral short-range order increases linearly as the Si concentration in the liquid increased. The diffusion coefficients of both Al and Si atoms in liquid Al_1−xSi_x alloys at 1573 K are not very sensitive to the composition.     

Potentiodynamic polarization studies on amorphous Zr46.75Ti8.25Cu7.5Ni10Be27.5, Zr65Cu17.5Ni10Al7.5, Zr67Ni33 and Ti60Ni40 in aqueous HNO3 solutions

Potentiodynamic polarization studies were carried out on virgin specimens of Zr-based bulk amorphous alloys Zr_46.75Ti_8.25Cu_7.5Ni₁₀Be_27.5 and Zr₆₅Cu_17.5Ni₁₀Al_7.5, and conventional-type binary amorphous alloys Zr₆₇Ni₃₃ and Ti₆₀Ni₄₀ in solutions of 0.2 M, 0.5 M and 1.0 M HNO₃ at room temperature. The values of the corrosion current density (I_corr) for the bulk amorphous alloy Zr_46.75Ti_8.25Cu_7.5Ni₁₀Be_27.5 were found to be comparable with those of Zr₆₅Cu_17.5Ni₁₀Al_7.5 in 0.2 M and 0.5 M HNO₃, but the value of I_corr for the former was almost three times more than that of the latter in 1.0 M HNO₃. In the case of conventional binary amorphous alloys, Ti₆₀Ni₄₀ showed lower value of I_corr as compared to Zr₆₇Ni₃₃ in 0.5 M and 1.0 M HNO₃ and a comparable value of I_corr in 0.2 M HNO₃. In general, the binary Ti₆₀Ni₄₀ displayed the best corrosion resistance among all the alloys in all the cases and the corrosion current density (I_corr) for all the alloys was found to increase with the increasing concentration of nitric acid. It is noticed that the bulk amorphous alloys do not possess superior corrosion resistance as compared to conventional binary amorphous alloys in aqueous HNO₃ solutions. The observed differences in their corrosion behavior are attributed to different alloy constituents and composition of the alloys investigated.     

Effect of carbon on the microstructural evolution of Zr66.7−xNi33.3Cx (x = 0, 1, 3) alloys during mechanical alloying

In the present paper, the effect of carbon on the microstructural evolution of Zr_66.7−xNi_33.3C_x (x = 0, 1, 3) alloys during mechanical alloying has been investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results show that these three alloys undergo similar amorphization and crystallization processes, and the final milling product is a metastable fcc-Zr_66.7−xNi_33.3C_x phase. The carbon addition can shorten the milling time for the complete amorphization reaction and enhance the stability of the formed amorphous alloy, which can suppress the mechanically induced amorphous-crystalline phase transformation with further increasing milling time.     

Glass formation ability and mechanical properties of Ti40Cu40Zr10Ni10 alloy

Melt-spun ribbon and bulk samples in cylindrical rod form with diameter ranging from 2 mm to 4 mm of Ti₄₀Cu₄₀Zr₁₀Ni₁₀ alloy were prepared by melt-spinning technique and copper mould casting method, respectively. The microstructure, thermal stability and mechanical properties of the bulk samples were investigated. A completely glassy single phase is formed in the 2 mm rod sample. Increasing the diameter of the rod samples resulted in the formation of CuTi crystalline phase in the 3 mm and 4 mm rod samples. The 2 mm single glassy rod sample exhibited a large supercooled liquid region ΔT_x = 58 K and γ = T_x/(T_g + T_l) is 0.390, which indicated that the alloy possessed a good glass-forming ability. The bulk samples also exhibited good mechanical properties. The 2 mm rod sample showed the highest yield strength of about 2086 MPa. The 3 mm rod sample not only showed high yield strength of about 2000 MPa, but also enhanced plastic strain of about 0.71%.     

Structural and optical properties of Zn(Mg,Cd)O alloy films grown by remote-plasma-enhanced MOCVD

We report the structural and optical properties of wurtzite-structure Zn(Mg,Cd)O ternary alloys. Wurtzite (0 0 0 1) Zn_1−xCd_xO and Mg_yZn_1−yO films were grown on (11–20) sapphire substrates using remote-plasma-enhanced metalorganic chemical vapor deposition. The large bowing parameters of Zn_1−xCd_xO and Mg_yZn_1−yO ternary alloys are 3.0 and 3.5, respectively, which reflects the large difference of each binary’s electronegativity. We have analyzed the broadening of photoluminescence (PL) in Zn(Mg,Cd)O alloys on alloy content by taking into account the statistical alloy fluctuation and the localization of the exciton, and have clarified that the localization of the exciton strongly affects to PL full-width at half-maximum (FWHM) in Zn(Mg,Cd)O alloys. The alloy broadenings in steady-state PL of Zn(Mg,Cd)O alloys are in good agreement with the calculated tendency by the theoretical model based on the statistical alloy fluctuation, while PL FWHM of Zn_1−xCd_xO is three times larger than the calculated results. Moreover, as another way to confirm alloy broadening, we also have done time-resolved PL measurements and derived the localized depth of the exciton in ZnO-based system, indicating a good agreement with the tendency of PL FWHM broadening.     

The presence of a thermally reversing window in Al-Te-Si glasses revealed by alternating differential scanning calorimetry and electrical switching studies

Alternating differential scanning calorimetric (ADSC) studies and electrical switching experiments have been undertaken on Al₁₅Te_85−xSi_x (2 ? x ? 12) system of glasses. These glasses are found to exhibit two crystallization reactions (T_c1 and T_c2), for compositions with x < 8. Above x = 8, a single-stage crystallization is seen. Further, a trough is seen in the composition dependence of non-reversing enthalpy (ΔH^NR), based on which it is proposed that there is a thermally reversing window in Al₁₅Te_85−xSi_x glasses, in the composition range 4 ? x ? 8. Electrical switching studies indicate that Al₁₅Te_85−xSi_x glasses exhibit a threshold type electrical switching at ON state currents less than 2 mA. Further, the switching voltages are found to increase with the increase in silicon content. It is interesting to note that the start (x = 4) and the end (x = 8) of the thermally reversing window are exemplified by a kink and a saturation in the composition dependence of switching voltages, respectively.     

Crystallisation of a simulated borosilicate high-level waste glass produced on a full-scale vitrification line

A simulated (inactive) borosilicate high-level waste (HLW) glass was produced on a full-scale vitrification line with composition simulating vitrified oxide fuel (UO₂) reprocessing waste. As-cast samples were compositionally homogeneous (Type I microstructure) and/or compositionally inhomogeneous displaying compositional ‘banding’ and frequently containing ‘reprecipitated calcine’ (Type II microstructure). Crystal phases identified in as-cast samples were: tetragonal RuO₂, cubic Pd-Te alloy, cubic (Cr,Fe,Ni,Ru)₃O₄, trigonal Na₃Li(MoO₄)₂·6H₂O, ostensibly cubic Zr_{1 − x − y}Ce_xGd_yO_2 − 0.5y and a lanthanoid (Nd,Gd,La,Ce) silicate. Zr_{1 − x − y}Ce_xGd_yO_2 − 0.5y and lanthanoid (Nd,Gd,La,Ce) silicate were found exclusively in the Type II microstructure as component crystal phases of ‘reprecipitated calcine’. Heat treated samples (simulating the retarded cooling experienced by actual (active) borosilicate HLW glasses after pouring) displayed extensive crystallisation and cracking (Type A microstructure) and/or ‘banded’ crystallisation (Type B microstructure) depending on their parent (as-cast) microstructure (Type I and/or Type II respectively). Crystal phases identified in heat treated samples were: tetragonal SiO₂ (α-cristobalite), tetragonal (Na,Sr,Nd,La)MoO₄, cubic Ce_{1 − x − y}Zr_xGd_yO_2 − 0.5y, a Ni-rich phase, a lanthanoid (Nd,Gd,La,Ce) silicate and orthorhombic LiNaZrSi₆O₁₅ (zektzerite). α-cristobalite was found exclusively in the Type A microstructure, while lanthanoid (Nd,Gd,La,Ce) silicate and zektzerite were only found in the Type B microstructure. Potential host phases for HLW radionuclides are: Pd-Te alloy (¹⁰⁷Pd and ⁷⁹Se), (Cr,Fe,Ni,Ru)₃O₄ (⁶³Ni), Zr_{1 − x − y}Ce_xGd_yO_2 − 0.5y (⁹³Zr, Pu and U), both lanthanoid (Nd,Gd,La,Ce) silicates (Am and Cm), (Na,Sr,Nd,La)MoO₄ (⁹⁰Sr, Am and Cm), Ce_{1 − x − y}Zr_xGd_yO_2 − 0.5y (⁹³Zr, Pu and U), the Ni-rich phase (⁶³Ni) and zektzerite (⁹³Zr, ¹²⁶Sn and U). Cracking in samples was attributed to thermal expansion mismatch between the borosilicate HLW glass matrix and RuO₂, cristobalite (both α and β), (Na,Sr,Nd,La)MoO₄ and zektzerite on cooling. There was also a contribution from the cristobalite α-β phase transition.     

Boron content dependance of magnetoimpedance in Fe91−xZr5BxNb4 alloys

A systematic investigation of the influence of B content on the magnetoimpedance (MI) effect in melt-spun Fe_91−xZr₅B_xNb₄ (FZBN, 0 ? x ? 30) ribbons has been performed within a frequency range, f ∼ 310-1110 kHz and under a varying dc magnetic field (H_dc) up to 70 Oe. The MI effect is not observed in the sample with x ? 5 but within the range 8 ? x ? 30. A distinct MI effect has been observed with a maximum change of 180% at around 1.1 MHz in the sample with x = 20, coincident with a saturation magnetic field of 66 Oe and a field sensitivity of about 7%/Oe. Magnetic measurements reveal that the MI effect and B content dependence of the effect are closely related to coercivity of the FZBN alloy series, except for the sample with 20 at.%. The drastic MI ratio observed in the sample with x = 20 is ascribed to its special microstructure. The mechanism of the MI effect in FZBN alloys and of the significant MI value appearing at a B content of x = 20 is discussed in this paper.     

Structure and properties of Ni60(Nb100−xTax)34Sn6 bulk metallic glass alloys

Refractory bulk metallic glasses and bulk metallic glass composites are formed in quaternary Ni-Nb-Ta-Sn alloy system. Alloys of composition Ni₆₀(Nb_100−xTa_x)₃₄Sn₆ (x = 20, 40, 60, 80) alloys were prepared by injection-casting the molten alloys into copper molds. Glassy alloys are formed in the thickness of half mm strips. With thicker strips (e.g., 1 mm), Nb₂O₅ and Ni₃Sn phases and the amorphous phase form an in situ composite. Glass transition temperatures, crystallization temperatures, and ΔT_x, defined as T_x1 − T_g (T_x1: first crystallization temperature, T_g: glass transition temperature) of the alloys increase dramatically with increasing Ta contents. These refractory bulk amorphous alloys exhibit high Young’s modulus (155-170 GPa), shear modulus (56-63 GPa), and estimated yield strength (3-3.6 GPa).     

Effect of Ti addition on the crystallization behavior and glass-forming ability of Zr-Al-Cu alloys

The crystallization behavior of melt-spun (Zr₆₅Al_7.5Cu_27.5)_100−xTi_x (x = 0-15; in at.%) metallic glasses has been investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM) and differential scanning calorimetry (DSC). The DSC traces showed an altered crystallization mode in the vicinity of 3 at.% Ti addition. A metastable icosahedral quasicrystal precipitated at the first crystallization stage of the Ti-bearing metallic glasses, which subsequently transformed to the stable Zr₂Cu-type phase in the followed exothermic reaction. The glass-forming abilities (GFAs) of these metallic glasses were assessed by the recognized GFA indicators T_rg, ΔT_x and γ. BMGs were easily made in the compositions containing 3-7 at.% Ti by means of copper mold casting. The validity of these parameters was clarified using the critical BMG forming diameter evidence.     

Low-temperature RPCVD of Si,SiGe alloy,and Si1−yCy films on Si substrates using trisilane (Silcore)

Si homo-epitaxial growth by low-temperature reduced pressure chemical vapor deposition (RPCVD) using trisilane (Si₃H₈) has been investigated. The CVD growth of Si films from trisilane and silane on Si substrates are compared at temperatures between 500 and 950 °C. It is demonstrated that trisilane efficiency increases versus silane's one as the surface temperature decreases. Si epilayers from trisilane, with low surface roughness, are achieved at 600 and 550 °C with a growth rate equal to 12.4 and 4.3 nm min⁻¹, respectively. It is also shown that Si_1−xGe_x layers can be deposited using trisilane chemistry.     

Devitrification of Ni-based glassy alloys containing noble metals in relation with the supercooled liquid region

The formation of the supercooled liquid region and devitrification behavior of Ni-based glassy alloys were studied by using X-ray diffraction, transmission electron microscopy, differential scanning calorimetry and isothermal calorimetry. oC68 Ni₁₀Zr₇-type phase is primarily formed in the studied alloys in the initial stage of the devitrification process by nucleation and three-dimensional diffusion controlled growth. The replacement of Cu by Ni in Cu₅₅Zr₃₀Ti₁₀Pd₅ glassy alloy induces precipitation of oC68 Ni₁₀Zr₇ phase directly from the glassy phase. The reasons for such a behavior are discussed taking into account mixing enthalpy in a liquid state and the interval of the supercooled liquid region.     

Effect of microalloying of Nb on corrosion resistance and thermal stability of ZrCu-based bulk metallic glasses

Bulk metallic glasses (BMGs) of Zr_46−xNb_xCu_37.6Ag_8.4Al₈ with x = 0, 0.5, 1, 2 and 4 at.% were prepared by copper mould casting. The corrosion resistance of the ZrCu-based BMGs with different Nb contents was carefully examined by weight loss measurements and potentiodynamic polarization tests in 3 mass% NaCl, 1 N HCl and 1 N H₂SO₄ solutions, respectively. Nb addition improves the newly developed BMGs’ corrosion resistance in chloride-containing solutions and the alloys all exhibit excellent corrosion resistance in 1 N H₂SO₄. The corrosion behavior of the alloy containing 0 and 4 at.% Nb in phosphate-buffered solution was examined by electrochemical polarization tests. The influence of Nb addition on glass forming ability (GFA), thermal stability and mechanical property was investigated by X-ray diffraction, differential scanning calorimetry and compression tests, respectively. It is found that the addition of Nb can deteriorate the GFA and thermal stability of the base system, but little effect is observed on the mechanical properties, e.g., yielding strength and plasticity, of the ZrCu-based BMG alloys.     

Crystallization kinetics of Fe73.5−xMnxCu1Nb3Si13.5B9 (x = 0, 1, 3, 5, 7) amorphous alloys

In this study, we have investigated the effect of substituting Mn for Fe on the crystallization kinetics of amorphous Fe_73.5−xMn_xCu₁Nb₃Si_13.5B₉ (x = 1, 3, 5, 7) alloys. The samples were annealed at 550 °C and 600 °C for 1 h under an argon atmosphere. The X-ray diffraction analyses showed only a crystalline peak belonging to the α-Fe(Si) phase, with the grain size ranging from 12.2 nm for x = 0 to 16.7 nm for x = 7. The activation energies of the alloys were calculated using Kissinger, Ozawa and Augis-Bennett models based on differential thermal analysis data. The Avrami exponent n was calculated from the Johnson-Mehl-Avrami equation. The activation energy increased up to x = 3, then decreased with increasing Mn content. The values of the Avrami exponent showed that the crystallization is typical diffusion-controlled three-dimensional growth at a constant nucleation rate.     

Lightweight Ti–Zr–Be–Al bulk metallic glasses with improved glass-forming ability and compressive plasticity

A series of lightweight Ti–Zr–Be–Al bulk metallic glasses (BMGs) have been developed through the addition of Al to Ti–Zr–Be ternary glassy alloy. By replacing Be with Al, the critical size of the glassy rod has been increased from 5 mm for Ti₄₁Zr₂₅Be₃₄ alloy to 7 mm for Ti₄₁Zr₂₅Be₂₉Al₅ alloy, while the yield strength of Ti₄₁Zr₂₅Be_34 ? xAl_x (x = 2–10) has been greatly enhanced, resulting in a significant increase of the specific strength which is defined as yield strength/density. Among these newly developed Ti–Zr–Be–Al BMGs, Ti₄₁Zr₂₅Be₂₆Al₈ glassy alloy exhibits a high specific strength of 4.33 × 10⁵ Nm/kg and a very large compressive plastic strain of 47.0%, which are much larger than those (3.69 × 10⁵ Nm/kg and 2.9%, respectively) for Ti₄₁Zr₂₅Be₃₄ glassy alloy. The present results show that Al is an effective alloying element for improving the glass-forming ability (GFA) and mechanical properties of Ti-Zr-Be glassy alloy.     

A new composition zone of bulk metallic glass formation in the Cu-Zr-Ti ternary system and its correlation with the eutectic reaction

A new composition region of bulk metallic glass formation, around Cu₅₂Zr₄₀Ti₈, was discovered in the Cu-Zr-Ti ternary system, for which monolithic bulk metallic glass rods of 4 mm in diameter can be fabricated using copper mold casting. The solidification of the Cu₅₂Zr₄₀Ti₈ deeply-undercooled liquid mainly undergoes a univariant eutectic reaction, (L → Cu₁₀Zr₇ + CuZr), even though this composition was predicted to be a ternary eutectic point (L → Cu₁₀Zr₇ + CuZr + Cu₂ZrTi) by CALPHAD calculations. With respect to the deep-eutectic reaction of (L → Cu₁₀Zr₇ + CuZr) in the Cu-Zr binary alloys, alloying of Ti has a significant effect on further stabilizing the liquid, as indicated as a drop of the univariant eutectic groove, limiting the coupled growth of two crystalline phases, hence increasing the glass-forming ability.