Synthesis, thermal stability and properties of [(Fe1−xCox)72Mo4B24]94Dy6 bulk metallic glasses

A series of [(Fe_1−xCo_x)₇₂Mo₄B₂₄]₉₄Dy₆ (x = 0.1, 0.2, 0.3, 0.4 and 0.5 at.%) bulk metallic glasses (BMGs) in rod geometries with critical diameter up to 3 mm were fabricated by copper mold casting method. This alloy system exhibited good thermal stability with high glass transition temperature (T_g) 860 K and crystallization temperature (T_x) 945 K. The addition of Co was found to be effective in adjusting the alloy composition deeper to eutectic, leading to lower liquidus temperature (T_l). The [(Fe_0.8Co_0.2)₇₂Mo₄B₂₄]₉₄Dy₆ alloy showed the largest supercooled liquid region (ΔT_x = T_x − T_g = 92 K), reduced glass transition temperature (T_rg = T_g/T_l = 0.622) and gamma parameter (γ = T_x/(T_g + T_l) = 0.424) among the present system. Maximum compressive fracture strength of 3540 MPa and micro-Vickers hardness of 1185 kg/mm² was achieved, resulting from the strong bonding structure among the alloy constituents. The alloy system possessed soft magnetic properties with high saturation magnetization of 56.61-61.78 A m²/kg and coercivity in the range of 222-264.2 A/m, which might be suitable for application in power electronics devices.     

Microstructure, mechanical, EPR and optical properties of lithium disilicate glasses and glass-ceramics doped with Mn ions

The microstructure, mechanical, EPR and optical properties of transparent MnO₂ doped lithium disilicate (LDS) glass-ceramics prepared by melt quenching and controlled crystallization, have been studied. The microstructure of the glass-ceramics has been characterized using FE-SEM, TEM, FT-IR and XRD techniques. FE-SEM micrographs show elongated, highly interlocked, dense (∼80 vol.%) nanocrystals of LDS with an average size ∼100 nm. XRD and FT-IR studies reveal that the only crystalline phase formed after heat-treatment at 700 °C for 1 h is LDS. A good combination of average microhardness ∼5.6 GPa, high fracture toughness ∼2.8 MPa m^1/2, 3-point flexural strength ∼250 MPa and moderate elastic modulus 65 GPa has been obtained. The EPR spectra of both LDS glasses and glass-ceramics exhibit resonance signals with effective g values at g = 4.73, g = 4.10, g = 3.3, and g = 1.98. The resonance signal at g = 1.98 is found to be more intense than the other signals and exhibits hyperfine structure at lower concentration of manganese. From the observed spectrum, the spin-Hamiltonian parameters have been evaluated. In glass samples the optical absorption spectrum exhibits a broad band around ∼20,320 cm⁻¹ which has been assigned to the transition ⁶A_1g(S) → ⁴A_1g(G) ⁴E_g(G)-of Mn²⁺ ions. The cerammed samples upon 394 nm excitation emit a green luminescence (565 nm, ⁴T_1g → ⁶A_1g(G) transition of Mn²⁺ ions), and a weak red emission (710 nm). From the ultraviolet absorption edges, the optical bandgap energies (E_opt) were evaluated and are discussed.     

Subsurface microstructural changes in a cast heat resisting alloy caused by high temperature corrosion

A cast HP ModNb alloy (Fe-25Cr-35Ni-1Nb, wt.%) was oxidised and carburised in CO-CO₂ corresponding to a_C = 0.1 and p_O2 = 3 × 10⁻¹⁶ atm at 1080 °C. Formation of an external, chromium-rich oxide scale led to depletion of this metal in a deep alloy subsurface zone. Within that zone, secondary chromium-rich carbides dissolved, primary carbides oxidised, solute silicon and aluminium internally oxidised, and extensive porosity developed. Pore volumes correspond to the difference between metal loss by scaling and metal displacement by internal oxidation, assuming the scale-metal interface to be fixed. The pores are concluded to be Kirkendall voids.     

Anisotropy compensation and high low-field magnetostriction of epoxy/Tb1−xHox(Fe0.8Co0.2)2 composites (0.60 ≤ x ≤ 1.0)

The anisotropy compensation and magnetostrictive properties of Tb_1−xHo_x(Fe_0.8Co_0.2)₂ (0.60 ≤ x ≤ 1.0) alloys have been investigated. The easy magnetization direction (EMD) at room temperature rotates from the 〈1 1 1〉 axis (x ≤ 0.75) to the 〈1 0 0〉 axis (x ≥ 0.90) through an intermediate state 〈1 1 0〉, subjected to the anisotropy compensation between Tb³⁺ and Ho³⁺ ions. Composition anisotropy compensation is realized near x = 0.75. The Tb_0.25Ho_0.75(Fe_0.8Co_0.2)₂ alloy has a minimum anisotropy and a large spontaneous magnetostriction coefficient λ₁₁₁ (≈740 ppm) at room temperature. The strong 〈1 1 1〉-oriented 1-3 epoxy-bonded composite has been fabricated by curing under a moderate magnetic field. A high low-field magnetostriction of about 400 ppm at 3 kOe is obtained for the 1-3 epoxy/Tb_0.25Ho_0.75(Fe_0.8Co_0.2)₂ composite with 40-vol% alloy particles, which can be attributed to the low magnetic anisotropy, EMD lying along 〈1 1 1〉 direction, the strong 〈1 1 1〉-textured orientation and the chain structure.     

Magnetic properties and large magnetocaloric effect in Gd-Ni amorphous ribbons for magnetic refrigeration applications in intermediate temperature range

Amorphous Gd_68−xNi_32+x (x = −3, 0, 3) ribbons were prepared by melt-spinning method. The crystallization onset temperatures T_x1 for Gd_68−xNi_32+x amorphous ribbons with x = −3, 0, and 3 are 561, 568, and 562 K, respectively. All the samples undergo the second-order magnetic transition at temperatures between ∼122 (x = −3 and 3) and 124 K (x = 0). The Curie temperature T_C does not change with the composition significantly. The maximum isothermal magnetic entropy changes (−ΔS_M)_max of Gd₇₁Ni₂₉, Gd₆₈Ni₃₂, and Gd₆₅Ni₃₅ amorphous ribbons for a magnetic field change of 0-5 T were 9.0, 8.0, and 6.9 J kg⁻¹ K⁻¹, respectively. Large values of the refrigerant capacity (RC) were obtained in these ribbons. For example, Gd₇₁Ni₂₉ amorphous ribbon has a maximum RC value of 724 J kg⁻¹. Large magnetic entropy change and RC values together with high stability enable the Gd₇₁Ni₂₉ amorphous alloy a competitive candidate among the magnetic refrigeration materials working at temperatures near 120 K.     

Luminescent properties of UV excitable blue emitting phosphors MSr4(BO3)3:Ce (M = Li and Na)

A series of Ce³⁺ doped novel borate phosphors MSr₄(BO₃)₃ (M = Li or Na) were successfully synthesized by traditional solid-state reaction. The crystal structures and the phase purities of samples were characterized by powder X-ray diffraction. The optimal concentrations of dopant Ce³⁺ ions in compound MSr₄(BO₃)₃ (M = Li or Na) were determined through the measurements of photoluminescence spectra of phosphors. Ce³⁺ doped phosphors MSr₄(BO₃)₃ (M = Li or Na) show strong broad band absorption in UV spectral region and bright blue emission under the excitation of 345 nm light. In addition, the temperature dependences of emission spectra of M_1+xSr_4−2xCe_x(BO₃)₃ (M = Li or Na) phosphors with optimal composition x = 0.05 for Li and x = 0.09 for Na excited under 355 nm pulse laser were also investigated. The experimental results indicate that the M_1+xSr_4−2xCe_x(BO₃)₃ (M = Li or Na) phosphors are promising blue emitting phosphors pumped by UV light.     

Structure and electrical conduction behavior of LiZnVO4 ceramic prepared by solution-based chemical route

In the present work, an evaluation of the structural and electrical properties of a compound (LiZnVO₄) has been undertaken. This compound was prepared by solution-based chemical route. The electrical properties were measured using a.c. impedance spectroscopy method in the frequency range of 10³-10⁶ Hz at various temperatures from 28 to 300 °C. X-ray diffraction study indicates a rhombohedral unit cell structure with lattice parameters a = 14.1934 Å, b = 14.1934 Å, c = 9.4926 Å, V = 1656.12 (Å)³, α = 90°, β = 90° and γ = 120°. A field emission scanning electron micrograph reveals a polycrystalline texture of the compound with grains of unequal sizes ∼0.2-2.0 μm. The electrical conduction in the material is a thermally activated process due to the bulk effect. Frequency dependence of a.c. conductivity obeys Jonscher's universal law (σ_ac = σ_dc + Aωⁿ).     

Passivity breakdown on AISI Type 403 stainless steel in chloride-containing borate buffer solution

Passivity breakdown on AISI Type 403 stainless steel (SS), a commonly employed blade alloy in low pressure steam turbines, has been studied and the data are interpreted in terms of the point defect model (PDM). The near normal distribution in breakdown potential measured in deaerated borate buffer solution (pH = 8.1 ± 0.1) with different chloride concentrations is in satisfactory agreement with the quantitative characterization of the breakdown potential distribution using the PDM. The linear dependence of breakdown potential on the square root of potential scan rate (υ^1/2), as predicted by the PDM, yields an estimate of the critical areal concentration of condensed vacancies at the metal/film interface (ξ < 7.0 × 10¹⁴ cm⁻²) that leads to passivity breakdown. This is in excellent agreement with that calculated from the unit cell dimensions of the substrate Fe-Cr alloy (ξ ≈ 10¹⁵ cm⁻²) and the barrier layer oxide (Cr₂O₃) (ξ ≈ 10¹⁴ cm⁻²) for vacancy condensation on the alloy lattice or on the cation sublattice, respectively, of the film. These provide convincing evidences for the validity of the PDM for modeling passivity breakdown on Type 403 SS.     

PEO coatings obtained on an Mg-Mn type alloy under unipolar and bipolar modes in silicate-containing electrolytes

Protective surface layers with high corrosion resistance (R_p = 3.3·105 ohm cm²) and significant microhardness (H = 4.8 GPa), as compared to the substrate material, were obtained on MA8 magnesium alloy by bipolar Plasma Electrolytic Oxidation (PEO) in a silicate-fluoride electrolyte. The phase and elemental composition and morphology of the coatings were investigated. It was found that the application of the bipolar PEO mode enables one to synthesise on the alloy's surface a high-temperature phase of magnesium silicate, forsterite (Mg₂SiO₄) having good anticorrosion and mechanical properties.     

W-type hexaferrite nanoparticles: A consideration for microwave attenuation at wide frequency band of 0.5-10 GHz

The static and dynamic magnetic properties of W-type hexaferrites are tuned to meet the requirements of wide band frequencies for attenuation of electromagnetic interference and microwave absorptions purposes. For this purpose, the W-type hexaferrite of entirely new composition of BaCoZnFe_16−2yAl_yCe_yO₂₇ (y = 0, 0.2, 0.4, 0.6, 0.8 and 1.0) has been synthesized by the chemical co-precipitation. The material is characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM) and vibrating sample magnetometer (VSM). The complex permittivity (?_r = ?′ − j?″) and permeability (μ_r = μ′ − jμ″) spectra are determined using Vector Network Analyzer (VNA) in a range from 0.5 GHz to 10 GHz. During this study, it is noticeable that the Al³⁺ and Ce³⁺ ions have considerable effect on the shape of the nanoparticles. Samples having Al-Ce contents y = 0.2 and y = 0.4 showed large values for magnetization (70.5 emu/g) and remanent magnetization (32.9 emu/g). In addition, more than 99% absorption (>−20 dB) is noted for this sample composition. Based on these results it is concluded that the microwave absorption characteristics of these compounds can be tuned for the required frequency by varying the thickness of the absorber. Due to this reason, potential employment of the synthesized nanoparticles for absorption of electromagnetic radiations at wide frequency band of 0.5-10 GHz has been proposed.     

Effect of ZrO2 addition on the microstructure and electromagnetic properties of YIG

In this work, we reported the microstructure and electromagnetic properties of a series of zirconium substituted yttrium iron garnet ferrites (YCaZrIG) with iron deficiency composition of Y_3−xCa_xZr_xFe_4.93−xO₁₂ (x = 0.1, 0.2, 0.3, and 0.4, with electrostatic balance by Ca²⁺ substituted for Y³⁺ ions) prepared by a solid-reaction method. The addition of ZrO₂ shows no obvious influence on the phase, density and dielectric constant of YIG ferrites. When Zr addition x ≤ 0.3, the substitution of Zr⁴⁺ for Fe³⁺ decreases the amount of Fe ions, increases the lattice parameter and enhances the grain growth of garnet phase. The solubility of zirconium in YCaZrIG ferrite was found to be approximately 0.3, above which excess ZrO₂ would lead to the precipitation of a second phase inside the YCaZrIG ferrite. This would inhibit the grain growth of garnet phase and cause an increase in the dielectric loss and coercivity. The observed reduce for saturation magnetization when x = 0.4 is possibly due to antiparallel alignment of magnetic moment of Fe³⁺ in the d site caused by the decrease of a-d exchange interaction. Additionally, we got the optimum electromagnetic properties in the samples with x = 0.3: ?_r = 14.1, tan δ_e = 2.5 × 10⁻⁴, H_c = 47 A/m, 4πM_s = 1936 × 10⁻⁴T, ΔH = 7.1 KA/m.     

Synthesis, crystal structures, and optical properties of NaCdPnS3 (Pn = As, Sb)

Two compounds NaCdPnS₃ (Pn = As (1), Sb (2)) were synthesized as transparent yellow and red platelets by reacting cadmium powder with the molten mixtures of Na₂S/As₂S₃/S and Na₂S/Sb/S at 500 °C. Both compounds are plagued with crystal twinning and acceptable crystal structure refinement could only be obtained by identifying the type of the twinning laws. NaCdAsS₃ (1) crystallizes in the monoclinic space group P2₁/n (no. 14) with a = 5.6561(8), b = 16.5487(15), c = 5.6954(8) Å, β = 90.315(11)°, and Z = 4. NaCdSbS₃ (2) crystallizes in the monoclinic space group C2/c (no. 15) with a = 8.1329(6), b = 8.1296(4), c = 17.2600(13) Å, β = 103.499(6)°, and Z = 8. The structures of both compounds feature a ²_∞[CdPnS₃]⁻ layer composed of [CdS₄] tetrahedra and [AsS₃] or [SbS₃] pyramidal units. Between the ²_∞[CdPnS₃]⁻ (Pn = As, Sb) layers the Na⁺ cations reside in a distorted octahedral environment of S atoms. Compound 1 is characterized with UV/Vis diffuse reflectance spectroscopy and IR and Raman spectra.     

Surface characterisation of DC plasma electrolytic oxidation treated 6082 aluminium alloy: Effect of current density and electrolyte concentration

Plasma electrolytic oxidation (PEO) is a specialised but well-developed process which has found applications in aerospace, oil/gas, textile, chemical, electrical and biomedical sectors. A novel range of coatings having technologically attractive physical and chemical properties (e.g. wear- and corrosion-resistance) can be produced by suitable control of the electrolyte as well as electrical parameters of the PEO process. Oxide ceramic films, 3 to 40 μm thick, were produced on 6082 aluminium alloy by DC PEO using 5 to 20 A/dm² current density in KOH electrolyte with varied concentration (0.5 to 2.0 g/l). Phase analysis (composition and crystallite size) was carried out using X-ray diffraction and TEM techniques. Residual stresses associated with the crystalline coating phase (α-Al₂O₃) were evaluated using the X-ray diffraction Sin²ψ method. Nanoindentation studies were conducted to evaluate the hardness and elastic modulus. SEM, SPM and TEM techniques were utilised to study surface as well as cross-sectional morphology and nano features of the PEO coatings. Correlations between internal stress and coating thickness, surface morphology and phase composition are discussed. It was found that, depending on the current density and electrolyte concentration used, internal direct and shear stresses in DC PEO alumina coatings ranged from − 302 ± 19 MPa to − 714 ± 22 MPa and − 25 ± 12 MPa to − 345 ± 27 MPa, respectively. Regimes of PEO treatment favourable for the production of thicker coatings with minimal stress level, dense morphology and relatively high content of α-Al₂O₃ phase are identified.     

Microstructure and adhesion of Cr3C2-NiCr vacuum plasma sprayed coatings

Vacuum plasma spraying (VPS) was used to spray a Cr₃C₂-NiCr coating of ∼ 150, 300 and 450 μm in thickness onto a plain carbon steel substrate, employing a commercially available Cr20Ni9.5C powder. The splat microstructures observed in the coating were found to consist of a NiCr matrix with a predominant Cr₃C₂ phase, besides Cr₇C₃ and Cr₂O₃. The adhesion of the coating to the substrate was evaluated by means of interfacial indentation techniques. It has been found that the interfacial toughness value changes from 7.6 to 10.1 MPa m^1/2 when the thickness increases from 150 to 450 μm. Also, it has been found that the parameter Kca_o, determined by linear regression from the Kca versus 1 / e² curve by means of the interfacial indentation model advanced by Chicot et al., has a value of ∼ 9.8 MPa m^1/2.     

Synthesis, crystal and band structures, and optical properties of a new framework mercury pnictides: [Hg4As2](InBr3.5As0.5) with tridymite topology

A new framework compound, [Hg₄As₂](InBr_3.5As_0.5) (1), has been prepared by the solid-state reaction of Hg₂Br₂ with elemental In and As at 450 °C. Compound 1 crystallizes in the space group P₆₃/mmc of the Hexagonal system with two formula units in a cell: a = b = 7.7408(6) Å, c = 12.5350(19) Å, V = 650.47(12) Å³. The crystal structure of 1 features a novel 3D framework, [Hg₄As₂]²⁺ with tridymite topology. The optical properties were investigated in terms of the diffuse reflectance and infrared spectra. The electronic band structure along with density of states (DOS) calculated by DFT method indicates that the present compound is semiconductor, and the optical absorption is mainly originated from the charge transitions from Br-4p and As-4p states to Hg-6s and In-5p states.     

Negative magnetization, magnetic anisotropy and magnetic ordering studies on Al-substituted copper ferrite

Detailed magnetic properties of Al³⁺-modified CuFe₂O₄ spinel ferrite system: CuAl_xFe_2−xO₄; x = 0.0, 0.2, 0.4 and 0.6, have been studied by means of X-ray powder diffraction, field cooled (FC) and zero field cooled magnetization (ZFC) (H = 10 mTesla, T = 4-325 K), magnetic hysteresis (H_max = 2 Tesla, T = 10 and 300 K) and low field (40 A/m) ac susceptibility (T = 300-750 K) measurements. The system exhibits canted spin structure. It has been shown that the observed features of the FC-ZFC magnetization and ac susceptibility curves arise due to the low magneto crystalline anisotropy, not due to the cluster spin-glass-like magnetic ordering. The interesting features like low temperature cusp in the ZFC magnetization for all the compositions and negative magnetization for x = 0.6 composition have been observed. An attempt has been made to explain the negative magnetization within the framework of available models.     

Studies on the power factor of (Ba,Sr)Co2+xRu4−xO11 compounds

We have prepared polycrystalline single-phase ACo_2+xRu_4−xO₁₁ (A = Sr, Ba; 0 ≤ x ≤ 0.5) using the ceramic method and we have studied their structure, electrical resistivity and Seebeck coefficient, in order to estimate their power factor (P.F.). These layered compounds show values of electrical resistivity of the order of 10⁻⁵ Ωm and their Seebeck coefficients are positive and range from 1 μV K⁻¹ (T = 100 K) to 20 μV K⁻¹ (T = 450 K). The maximum power factor at room temperature is displayed by BaCo₂Ru₄O₁₁ (P.F.: 0.20 μW K⁻² cm⁻¹), value that is comparable to that shown by compounds such as SrRuO₃ and Sr₆Co₅O₁₅.     

Crystal structures and magnetic properties of iron (III)-based phosphates: Na4NiFe(PO4)3 and Na2Ni2Fe(PO4)3

Crystal structures from two new phosphates Na₄NiFe(PO₄)₃ (I) and Na₂Ni₂Fe(PO₄)₃ (II) have been determined by single crystal X-ray diffraction analysis. Compound (I) crystallizes in a rhombohedral system (S. G: R-3c, Z = 6, a = 8.7350(9) Å, c = 21.643(4) Å, R₁ = 0.041, wR₂=0.120). Compound (II) crystallizes in a monoclinic system (S. G: C2/c, Z = 4, a = 11.729(7) Å, b = 12.433(5) Å, c = 6.431(2) Å, β = 113.66(4)°, R₁ = 0.043, wR₂=0.111). The three-dimensional structure of (I) is closely related to the Nasicon structural type, consisting of corner sharing [(Ni/Fe)O₆] octahedra and [PO₄] tetrahedra forming [NiFe(PO₄)₃]⁴⁺ units which align in chains along the c-axis. The Na⁺ cations fill up trigonal antiprismatic sites within these chains. The crystal structure of (II) belongs to the alluaudite type. Its open framework results from [Ni₂O₁₀] units of edge-sharing [NiO₆] octahedra, which alternate with [FeO₆] octahedra that form infinite chains. Coordination of these chains yields two distinct tunnels in which site Na⁺.The magnetization data of compound (I) reveal antiferromagnetic (AFM) interactions by the onset of deviations from a Curie-Weiss behaviour at low temperature as confirmed by Mössbauer measurements performed at 4.2 K. The corresponding temperature dependence of the reciprocal susceptibility χ⁻¹ follows a typical Curie-Weiss behaviour for T > 105 K. A canted AFM state is proposed for compound (II) below 46 K with a field-induced magnetic transition at H ≈ 19 kOe, revealed in the hysteresis loop measured at 5 K. This transition is most probably associated with a spin-flop transition.     

Influence of cluster composition on NLO properties of neutral cubane-like heterothiometallic clusters

A series of new candidates as nonlinear optical materials, tetra-nuclear heterobimetallic clusters [MOS₃M₃′Y(PPh₃)₃] (M = Mo, M′ = Ag, Y = Br 1; M = W, M′ = Ag, Y = I 2; M = Mo, M′ = Cu, Y = I 3; M = W, M′ = Cu, Y = I 4), have been synthesized by newly developed ligand-redistribution reaction for third-order nonlinear optical (NLO) studies. Single-crystal X-ray diffraction shows that clusters [MoX(μ₃-S)₃(μ₃-Br)(AgPPh₃)₃] 1 and [WX(μ₃-S)₃(μ₃-I)(CuPPh₃)₃] 4 (X = O_0.5S_0.51, O 4) adopt an isomorphous neutral cubane-like skeleton. Their optical nonlinearities were measured by Z-scan technique with an 8 ns pulsed laser at 532 nm. These clusters were found to exhibit effective nonlinear absorption, self-focusing effects and large optical limiting capabilities. The effective NLO susceptibilities χ⁽³⁾ and the corresponding second-order hyperpolarizabilities γ of these clusters are also reported. The influence of cluster composition on NLO properties has been discussed accordingly.