Bulk metallic glass formation in Cu–Zr–Ti ternary system

The formation of bulk metallic glasses (BMG) in the Cu-rich Cu–Zr–Ti ternary system is studied by using the ‘e/a-variant line criterion’. Three such lines, (Cu₉Zr₄)_1−xTi_x, (Cu_61.8Zr_38.2)_1−xTi_x and (Cu₅₆Zr₄₄)_1−xTi_x, are defined in the Cu–Zr–Ti system by linking three binary compositions Cu₉Zr₄, Cu_61.8Zr_38.2 and Cu₅₆Zr₄₄ to the third element Ti. The binary compositions Cu₉Zr₄, Cu_61.8Zr_38.2 and Cu₅₆Zr₄₄ correspond to specific Cu–Zr binary clusters. BMGs are obtained by copper mould suction casting method with Ti contents of 7.5–15 at.%, 7.5–12.5 at.% and 5–12 at.%, respectively along the (Cu₉Zr₄)_1−x Ti_x, (Cu_61.8Zr_38.2)_1−xTi_x and (Cu₅₆Zr₄₄)_1−xTi_x lines. The BMGs on each composition line manifest decreased thermal stabilities and glass forming abilities (GFAs) with increasing Ti contents. The maximum GFA appears at Cu₆₄Zr_28.5Ti_7.5, with characteristic thermal parameters of T_g = 736 K, T_x = 769 K, T_g/T_l = 0.627 and γ = 0.403, which are all superior to those reported for the known Cu₆₀Zr₃₀Ti₁₀ BMG.     

Amorphous and quasicrystalline Ti–Ni–Zr powders synthesized by mechanical alloying

The formation of amorphous and quasicrystalline phases in the Ti₄₅Zr₃₈Ni₁₇ system both directly by mechanical alloying and after subsequent annealing was studied. The presence of amorphous, icosahedral quasicrystalline and the Ti₂Ni-type with a fcc structure phases together with the initial metallic components was found in as-milled samples by X-ray diffraction. An increase of the milling time results in an increase of the amorphous phase content. Icosahedral quasicrystalline phases of Ti–Ni–Zr system were produced by mechanical alloying and subsequent annealing. Differential scanning calorimetry studies up to 520 °C showed an extended exothermal effect starting from 300 °C, which corresponds to the crystallization of the as-milled samples. The shape and size of the particles of the alloys were investigated by scanning electron microscopy and argon adsorption. The Specific area surface of the as-milled sample was rather small, in agreement with scanning electron microscopy data. The kinetics of the hydrogenation of the amorphous alloy Ti₄₅Zr₃₈Ni₁₇ at different temperatures was studied.     

Structural properties of Cr2O3–Fe2O3–P2O5 glasses,Part I

The structural properties of xCr₂O₃–(40 − x)Fe₂O₃–60P₂O₅, 0 ⩽ x ⩽ 10 (mol%) glasses have been investigated by Raman and Mössbauer spectroscopies, X-ray diffraction (XRD) and differential scanning calorimetry (DSC). The Raman spectra show that the addition of up to 5.3 mol% Cr₂O₃ does not produce any changes in the glass structure, which consists predominantly of pyrophosphate, Q¹, units. This is in accordance with O/P ≈ 3.5 for these glasses. The increase in glass density and T_g that occurs with increasing Cr₂O₃ suggests the strengthening of glass network. The Mössbauer spectra indicate that the Fe²⁺/Fe_tot ratio increases from 0.13 to 0.28 with increasing Cr₂O₃ content up to 5.3 mol%, which can be related to an increase in the melting temperature from 1423 to 1473 K. After annealing, the 10Cr₂O₃–30Fe₂O₃–60P₂O₅ (mol%) sample was partially crystallized and contained crystalline β-CrPO₄ and Fe₃(P₂O₇)₂. The SEM and AFM micrographs of the partially crystallized sample revealed randomly distributed crystals embedded in a homogeneous glass matrix. EDS analysis indicated that the glass matrix was rich in Fe₂O₃ (39.6 mol%) and P₂O₅ (54.9 mol%), but contained only 5.5 mol% of Cr₂O₃. These results suggest that the maximum solubility of chromium in these iron phosphate melts is 5.5 mol% Cr₂O₃.     

Local structure and medium range ordering of tetrahedrally coordinated Fe3+ ions in alkali–alkaline earth–silica glasses

Tetrahedral iron (III) environments in alkali–alkaline earth–silica glasses have been studied as functions of alkali and alkaline earth cation type and Fe₂O₃ content using photoluminescence and optical absorption spectroscopies. The luminescence band centered at 13 000–15,500 cm⁻¹ is attributed to the ⁴T₁(G) → ⁶A₁(S) transition of tetrahedral Fe³⁺ ions. This band has Gaussian linewidths of 1500–3000 cm⁻¹ but linewidths exhibit no clear compositional dependency. Ligand field strength, 10Dq, and the Racah parameters B and C are consistent with tetrahedral Fe³⁺ and here for the first time their linear variation with the alkali/alkaline earth ratio of ionic radii, cation field strengths or individual oxide basicities is demonstrated. This is attributed to the effects of near-neighbor cations on length and covalency of Fe³⁺–O bonds and on host glass structure. Alkali cations stabilize Fe³⁺ ions in tetrahedral coordination; stabilization increases linearly with increasing alkali ionic radius and therefore with decreasing alkali field strength. The role of alkaline earth cations in Fe³⁺ stabilization in these glasses is not clear, although their effect is the inverse of that of the alkalis. The structural behavior of Fe³⁺ is defined as selective, reflecting its strong local ordering effects.     

Fe3+ doped SiO2 nanostructured gel-glasses: Structural,optical and magnetic properties

Transparent crack-free and bubble-free Fe³⁺ doped SiO₂ nanostructured gel-glasses were obtained by the sol–gel process. The process involves the hydrolysis and condensation of an appropriate molar ratio of tetraethoxysilane (TEOS), absolute ethanol, nitric acid and ferric nitrate, followed by stepwise annealing at temperatures ranging from 110 °C to 1000 °C. The structural variation of the gel-glasses and their influence on physical properties during annealing has been studied. It has been observed that monolithicity and chemical environment around Fe³⁺ in the gel-glasses are strongly dependent on the annealing temperatures. The colour of gel-glass samples is different for different annealing temperatures, mainly due to the different co-ordination state of Fe³⁺ and the generation of Fe₂O₃ colloids of size 20–60 nm in the silica matrix. The annealing process facilitates the tuning of the UV–visible transmission cut-off edge in high optical quality Fe³⁺ doped silica gel-glasses. A marked difference in the magnetic properties of these glasses is also observed with annealing temperatures.     

Change in environmental structure around Al in Zr60Ni25Al15 metallic glass upon crystallization studied by nuclear magnetic resonance

In order to investigate the structural evolution around Al, pulse NMR experiments were carried out on ²⁷Al in the Zr₆₀Ni₂₅Al₁₅ metallic glass and the related crystalline compound, Zr₆NiAl₂. Different chemical shift peaks were observed around 2750 and 3000 ppm in the as-quenched Zr₆₀Ni₂₅Al₁₅ and crystalline compound, Zr₆NiAl₂, respectively. Considering that the capped triangular prism of Zr₉Al₃ is formed around Al in the Zr₆NiAl₂ crystal, chemical correlation pairs of Al–Zr and/or Al–Al are fairly faint while that of Al–Ni may be dominant instead in the as-quenched state. These results suggest an inhomogenous chemical bonding nature in the Zr₆₀Ni₂₅Al₁₅ metallic glass. The resonant peaks around 3000 ppm, which were distinctive in the Zr₆NiAl₂ crystal, appeared and became stronger upon crystallization through the relaxed state. Thus, drastic change in the local atomic configuration around Al was confirmed so as to form the unlike chemical correlation pairs of Al–Zr upon crystallization. The high glass-forming ability of the Zr₆₀Ni₂₅Al₁₅ metallic glass should be attributed to the difficulties of significant atomic redistribution of the constituents around Al.     

Structural and magnetic investigations of Fe2O3–TeO2 glasses

A series of tellurite glasses containing Fe₂O₃ with the nominal composition x(Fe₂O₃)–(1−x)(TeO₂), where x = 0.05, 0.10, 0.15, and 0.20, have been synthesized and investigated using X-ray photoelectron spectroscopy (XPS) and magnetization techniques. The Te 3d core level spectra for all glass samples show symmetrical peaks at essentially the same binding energies as measured for TeO₂ indicating that the chemical environment of the Te atoms in these glasses does not vary significantly with the addition of Fe₂O₃. Furthermore, the full-width at half-maximum (FWHM) of each peak does not vary with increasing Fe₂O₃ content which suggests that the Te ions exist in a single configuration, namely TeO₄ trigonal bipyramid (tbp). The O 1s spectra are narrow and symmetric for all compositions such that oxygen atoms in the Te–O–Te, Fe–O–Fe and Te–O–Fe configurations must have similar binding energies. The analysis of the Fe 3p spectra indicates the presence of Fe³⁺ ions only, which is consistent with the valence state of the Fe ions determined from magnetic susceptibility measurements.     

Low temperature dielectric dispersion and electrical conductivity studies on Fe2O3 mixed lithium yttrium silicate glasses

Lithium yttrium silicate glasses mixed with different concentrations of Fe₂O₃ of the composition (40 ? x) Li₂O–10Y₂O₃–50SiO₂: x Fe₂O₃, with x = 0.3, 0.5, 0.8, 1.0, 1.2 and 1.5 (all in mol%) were synthesized. Electrical and dielectric properties including dielectric constant, ε′(ω), loss, tan δ, ac conductivity, σ_ac, impedance spectra as well as electric moduli, M(ω), over a wide continuous frequency range of 40 Hz to 10⁶ Hz and in the low temperature range 100 to 360 K were measured as a function of the concentration of Fe₂O₃. The dc conductivity is also evaluated in the temperature range 100 … 360 K. The temperature and frequency dispersions of dielectric constant as well as dielectric loss have been analyzed using space charge polarization model. The ac and dc conductivities have exhibited increasing trend with increasing Fe₂O₃ content beyond 0.5 mol%, whereas the activation energy for the conductivity demonstrated decreasing tendency in this dopant concentration range. Both quantum mechanical tunneling (QMT) and correlated barrier hopping models (CBH) were used for clarification of ac conductivity origin and the corresponding analysis has indicated that CBH model is more appropriate for this glass system. For the better understanding of relaxation dynamics of the electrical properties we have drawn the scaling plots for ac conductivity and also electric moduli. The plots indicated that the relaxation dynamics is independent on temperature but depends on concentration of Fe₂O₃. The dc conductivity is analyzed using small polaron hoping model. The increase of conductivity with the concentration of Fe₂O₃ beyond 0.5 mol% is explained in terms of variations in the redox ratio of iron ions in the glass network. The results were further analyzed quantitatively with the support of experimental data from IR, optical absorption and ESR spectral studies. The overall analysis has indicated that Li₂O–Y₂O₃–SiO₂ glasses containing more than 0.5 mol% of Fe₂O₃ are more suitable for achieving good electrical conductivity in these glasses.     

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.     

Mixed transition-ion effect in the glass system: Fe2O3-MnO-TeO2

In earlier studies on phosphate and tellurite glasses containing vanadium and iron oxides, non-linear variation of physical properties as functions of the ratios of the transition ions (V/V + Fe) were observed. The most striking effect was observed with electrical conductivity, where a 3 orders of magnitude reduction in conductivity was observed at a V/V + Fe ratio of ~ 0.4. The effect was termed Mixed Transition-ion Effect or MTE. In phosphate glasses, however, MTE was not observed when one of the transition ions was manganese. It was concluded that Mn does not contribute to conduction in these glasses. In the present study, we demonstrate a mixed transition ion effect in tellurite glasses containing MnO and Fe₂O₃ (xFe₂O₃(0.2 ? x) MnO0.8TeO₂ with x varying from 0 to 0.2). A maximum in the property at an intermediate composition (x = 8.5 mol%), was observed in DC resistivity, activation energy, molar volume etc. Mossbauer and optical absorption (UV–VIS–NIR) measurements were performed on these glasses and the transport mechanism has been identified to be hopping of small polarons between Fe^3 + (Mn^3 +) and Fe^2 + (Mn^2 +) sites.     

Structural relaxation and glass transition behavior of novel (Ti33Zr33Hf33)50(Ni50Cu50)40Al10 alloy developed by equiatomic substitution

A series of glass forming alloys (Ti₃₃Zr₃₃Hf₃₃)_100−x−y(Ni₅₀Cu₅₀)_xAl_y (x = 20–70 at.% and y = 0–30 at.%) have been developed by equiatomic substitution of similar elements. Of these alloys (Ti₃₃Zr₃₃Hf₃₃)₅₀(Ni₅₀Cu₅₀)₄₀Al₁₀ was chosen in this study to investigate the structural relaxation and glass transition behavior. The as-quenched (Ti₃₃Zr₃₃Hf₃₃)₅₀(Ni₅₀Cu₅₀)₄₀Al₁₀ alloy was fully amorphous and had a wide supercooled liquid region ΔT = T_x(503 °C) − T_g(433 °C) = 70 °C, where T_g and T_x are the glass transition and crystallization temperatures, respectively. Low temperature pre-heat treatments of the (Ti₃₃Zr₃₃Hf₃₃)₅₀(Ni₅₀Cu₅₀)₄₀Al₁₀ alloy for 10 min at 310 °C, 370 °C and 390 °C caused structural relaxation accompanied by the formation of very fine scale lattice ordering. After these heat treatments, the glass transition became hard to observe in the (Ti₃₃Zr₃₃Hf₃₃)₅₀(Ni₅₀Cu₅₀)₄₀Al₁₀ alloy. Increasing the pre-heat treatment temperatures and holding times caused the glass transition to become more clearly detectable with increasing endothermic heat release.     

Thermal and optical properties of CuO–BaO–B2O3–P2O5 glasses

CuO-doped barium borophosphate glasses in a series of xCuO–(45 − x)BaO–10B₂O₃–45P₂O₅ in molar ratio with x = 0–15 mol% were prepared by a melt-quenching technique. All the glasses had excellent thermal stability against crystallization. Glass transition temperature, thermal expansion coefficient and molar volume decrease with increasing CuO concentration. The linear relationship between the absorption coefficient and CuO concentration exists for a peak wavelength in the transitions of ²A_1g → ²B_1g, ²B_2g → ²B_1g, ²E_g → ²B_1g. The relationship between the properties and glass structure evaluated by Raman spectroscopy is discussed.     

Bulk glass formability for Cu–Hf–Zr–Ag and Cu–Zr–Ag–Si alloys

The effects of the gradual substitution of Zr by Hf on glass formability and thermal stability in the Cu₄₅Zr_45?xHf_xAg₁₀ alloys and the effects of small additions of Si on glass formability in the Cu₄₅Zr₄₅Ag₁₀ alloy are reported and discussed. The samples were prepared as ribbons of thickness in the range 25–200 μm by melt spinning and as conical bulk shapes, with a length of 50 mm and cone base diameters in the range 2–10 mm, by suction die casting. The alloy Cu₄₅Zr₄₅Ag₁₀ had a critical cylindrical rod diameter for glass formation, d_c, of 3.5 mm but substitution of 1.5 and 3.5 at.% Zr by Hf resulted in substantial increases to 5.5 and 4.5 mm, respectively. However, for x in the range 5–40 at.%, d_c was reduced to <1 mm_. The small addition of Si proved to be beneficial to the glass forming ability (GFA), increasing d_c up to 5.5 mm for 0.5 at.% Si. Thus the chemical and atomic size similarities of Hf and Zr do not guarantee that bulk glass formation will be maintained on substituting large proportions of Zr by Hf though small substitutions of Hf and of minor additions of Si were beneficial to the GFA. These effects are discussed in terms of the possible influence of the alloying additions on the liquid structure and on the number density of heterogeneous nucleants.     

Nd5Fe64B23Mo4Y4 bulk nanocomposite permanent magnets produced by crystallizing amorphous precursors

The glass forming ability and magnetic properties of Nd₅Fe_68 ? xB₂₃Mo₄Y_x (x = 0, 2, 4, 6) alloys prepared by copper mold casting technique have been studied. Amorphous rods with a diameter of 2 mm were obtained in the Nd₅Fe₆₄B₂₃Mo₄Y₄ alloy. After annealing for 10 min at 1013 K, the Nd₅Fe₆₄B₂₃Mo₄Y₄ alloy showed optimal hard magnetic properties with the coercivity of 764.2 kA/m, remanence of 0.6 T and maximum energy product of 57.3 kJ/m³, respectively. The enhanced magnetic properties can be ascribed to the strong exchange coupling among the magnetically soft α-Fe (25–30 nm), Fe₃B (30–35 nm) and hard Nd₂Fe₁₄B (40–50 nm) grains present in the magnet microstructure. Large size bulk nanocomposite magnets with sound magnetic properties make the Nd–Fe–B–Mo–Y alloy system a promising candidate for industrial applications.     

Dielectric behavior and impedance spectroscopy of bismuth iron phosphate glasses

The electrical and dielectrical properties of Bi₂O₃–Fe₂O₃–P₂O₅ glasses were measured by impedance spectroscopy in the frequency range from 0.01 Hz to 4 MHz and over the temperature range from 303 to 473 K. It was shown that the dc conductivity strongly depends on the Fe₂O₃ content and Fe(II)/Fe_tot ratio. With increasing Fe(II) ion content from 17% to 34% in the bismuth-free 39.4Fe₂O₃–59.6P₂O₅ and 9.8Bi₂O₃–31.7Fe₂O₃–58.5P₂O₅ glasses, the dc conductivity increases. On the other hand, the decrease in dc conductivity for the glasses with 18.9 mol% Bi₂O₃ is attributed to the decrease in Fe₂O₃ content from 31.7 to 23.5 mol%, which indicates that the conductivity for these glasses depends on Fe₂O₃ content. The conductivity for these glasses is independent of the Bi₂O₃ content and arises mainly from polaron hopping between Fe(II) and Fe(III) ions suggesting an electronic conduction. The evolution of the complex permittivity as a function of frequency and temperature was investigated. At low frequency the dispersion was investigated in terms of dielectric loss. The thermal activated relaxation mechanism dominates the observed relaxation behavior. The relationship between relaxation parameters and electrical conductivity indicates the electronic conductivity controlled by polaron hopping between iron ions. The Raman spectra show that the addition of up to 18.9 mol% of Bi₂O₃ does not produce any changes in the glass structure which consists predominantly of pyrophosphate units.     

Electronic conductivity in zinc iron phosphate glasses

The electrical properties of (40−x)ZnO–xFe₂O₃–60P₂O₅ (x = 10, 20, 30 mol%) glasses were measured by impedance spectroscopy in the frequency from 0.01 Hz to 4 MHz and the temperature range from 303 to 473 K. It was shown that the dc conductivity strongly depends on the Fe₂O₃ content and Fe(II)/Fe_tot ratio. The increase in dc conductivity for these glasses is attributed to the increase in Fe₂O₃ content from 10 to 30 mol%. With increasing Fe(II) ion content from 6% to 17% the dc conductivity increases. This indicated that the conductivity arises mainly from polaron hopping between Fe(II) and Fe(III) ions suggesting an electron conduction in these glasses. By applying scaling on conductivity data measured at different temperatures, single master curve was obtained for each glass. On the other hand, deviation from the master curve at high frequencies was observed for glasses with different compositions. This deviation originates from a various mobility of charge carriers in different glass structures. Raman spectra showed the change of structure, from metaphosphate to pyrophosphate, with increasing Fe₂O₃ content from 10 to 30 mol%.     

Studies of lead–iron phosphate glasses by Raman,Mössbauer and impedance spectroscopy

The effect of Fe₂O₃ content on electrical conductivity and glass stability against crystallization in the system PbO–Fe₂O₃–P₂O₅ has been investigated using Raman, XRD, Mössbauer and impedance spectroscopy. Glasses of the molar composition (43.3 − x)PbO–(13.7 + x)Fe₂O₃–43P₂O₅ (0 ⩽ x ⩽ 30), were prepared by quenching melts in the air. With increasing Fe₂O₃ content and molar O/P ratio there is corresponding reduction in the length of phosphate units and an increase in the Fe(II) ion concentration, which causes a higher tendency for crystallization. Raman spectra of the glasses show that the interaction between Fe sites, which is essential for electron hopping, strongly depends on the cross-linking of the glass network. The electronic conduction of these glasses depends not only on the Fe(II)/Fe_tot ratio, but also on easy pathways for electron hopping in a non-disrupted pyrophosphate network. The Raman spectra of crystallized glasses indicate a much lower degree of cross-linking since more non-bridging oxygen atoms are present in the network. Despite the significant increase in the Fe₂O₃ content and Fe(II) ion concentration, there is a considerable weakening in the interactions between Fe sites in crystalline glasses. The impedance spectra reveal a decrease in conductivity, caused by poorly defined conduction pathways, which are result of the disruption and inhomogeneity of the crystalline phases that are formed during melting.     

The formation and crystallization of amorphous Al65Fe20Zr15

Amorphous Al₆₅Fe₂₀Zr₁₅ alloy has been prepared by mechanical alloying. The as-milled powders were analyzed by XRD and DTA. The fully amorphous alloy was identified by the hallo rings of XRD pattern. The effective activation energy of crystallization was estimated with modified Kissinger’s plot and it is 321.0 kJ/mol evaluated from the peak temperature of crystallization. The product phases of crystallization composed of Al₃Zr, Al₈₂Fe₁₈, AlFeZr and an unidentified phase. The crystallization kinetics was also discussed by using the isochronal DTA scans and the values of corresponding kinetic parameters were determined.     

Precipitation of zinc ferrite nanoparticles in the Fe2O3–ZnO–SiO2 glass system

Glass materials in the ZnO–Fe₂O₃–SiO₂ system, containing zinc ferrite nanoparticles, were prepared by the sol–gel method and characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), Mössbauer spectroscopy, AC- and DC-magnetization techniques. The gel samples, dried at 130 °C, were further heat treated in air at 500 and 800 °C. At 500 °C zinc ferrite and hematite nanoparticles, with an average size of approximately 24 nm, were precipitated in the brown and opaque 10ZnO–10Fe₂O₃–80SiO₂ and in the ruby colored transparent 5ZnO–5Fe₂O₃–90SiO₂ and 2.5ZnO–2.5Fe₂O₃–95SiO₂ glass matrices. In the 5ZnO–5Fe₂O₃–90SiO₂ sample the nanoparticles exhibited ferro or ferrimagnetic interactions combined with superparamagnetism with a blocking temperature of approximately 14 K. Heating at 800 °C seems to cause partial dissolution of the zinc ferrite and hematite particles in all the investigated compositions. Accordingly at 800 °C the 5ZnO–5Fe₂O₃–90SiO₂ glass shows a paramagnetic behavior down to 2 K.     

Phase separation and crystallization in a melt-spun Ti45Zr35Ni17Cu3 alloy

Structure and crystallization behavior of amorphous and quasicrystalline Ti₄₅Zr₃₅Ni₁₇Cu₃ alloy have been studied. DSC trace of the amorphous alloy obtained during continuous heating to 1300 K shows distinctly an exothermic peak and two endothermic peaks. The amorphous alloy has different structures depending on annealing temperature. The first exothermic reaction at low temperature region from 400 K to 900 K is due to the precipitation of an icosahedral quasicrystalline phase, and the second endothermic reaction at higher temperature region from 950 K to 990 K results from the transformation of the I-phase to C14 Laves and α-(Ti, Zr) phases.