Substitution effects of La3+ ions on the structural and magnetic properties of Co2Y hexaferrites synthesized by sol–gel autocombustion method

Y-type hexaferrite Sr₂Co₂La_xFe_12?xO₂₂ (x = 0.0, 0.05, 0.10, 0.15, 0.20) powders have been synthesized using the sol–gel autocombustion method. Differential Scanning Calorimetry, Thermogravimetry, Fourier Transform Infra-Red spectroscopy, X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy and vibrating sample magnetometery were used to investigate the samples. XRD patterns confirm the formation of Y-type hexaferrite phase. SEM patterns show that mostly grains exhibit rod shape and some appear in the form of hexagonal platelet shape. The rod or rice shape hexaferrite may be used in catalysis, information storage, surface enhanced Raman scattering, imaging and sensing. The samples with hexagonal platelet-like shape particles may be suitable as microwave absorbing materials. The energy dispersive X-ray spectroscopy spectrum shows the presence of dissolved reactants Sr, Co, La and Fe. The saturation magnetization (M_s) calculated using the law of approach to saturation decrease with the increasing of lanthanum (La³⁺) contents. The decrease in ‘M_s’ may be because of magnetic dilution and spin canting and hence reduction in the super-exchange interactions. The retentivity (M_r) and coercivity (H_c) enhance with the increase of La³⁺ contents. The enhancement in coercivity from 193 to 598.6 Oe may be because of increase in the porosity of samples with the increase of La³⁺ contents. The coercivity of the synthesized materials is few hundred oersteds (Oe), which may be suitable for security, switching, sensing, high frequency applications and is also favorable for electromagnetic materials.     

Novelty, preparation, characterization and enhancement of magnetic properties of Mn nanoferrites using safety binder (egg white)

Nanocrystalline MnFe₂O₄ ferrite was prepared by using autocombustion technique (flash). The microstructure and magnetic properties are studied. The results of XRD and TEM clarified that, this ferrite is nanosized with particle size (39 nm). Magnetic measurements showed a ferromagnetic behavior with T_C = 613 K, the saturation magnetization M_s = 13.71 emu/g, remanent magnetization M_r = 0.1694 emu/g and, coercivity H_c = 25.6 Oe. Natural material, egg white used as an aqueous medium to extend prepare nanoparticles better than other chemical interesting materials.     

Investigations on structural,electrical and magnetic properties of nickel substituted La-ferrites

Nanocrystalline nickel substituted La-ferrites, LaNi_xFe_1−xO₃ (where x = 0, 0.2, 0.4, 0.6 and 1.0) were synthesized by sol–gel autocombustion method. X-ray diffraction (XRD) technique was used to confirm the phase formation. The lattice parameter (a) decreases with increase of Ni content. The surface morphology and elemental analysis of the samples were studied by using scanning electron microscopy (SEM) and energy dispersive X-ray spectrometer (EDS). The electrical properties of the samples were measured by two-probe method. The hysteresis parameters viz. saturation magnetization (M_s), coercivity (H_C) and remanence (M_r) are reported as a function of nickel content. The substitution of nickel plays an important role in changing the structural, electrical and magnetic properties of La-ferrites.     

Kinetics of formation of barium tungstate in equimolar powder mixture of BaCO<Subscript>3</Subscript> and WO<Subscript>3</Subscript>

The formation of Barium monotungstate (BaWO₄) particles in equimolar powder mixtures of BaCO₃ and WO₃ was examined under isothermal and non-isothermal conditions upon heating in air at 25–1200 °C, using thermogravimetry. Concurrence of the observed mass loss (due to the release of CO₂) to the occurrence of the formation reaction was evidenced. Accordingly, the extent of reaction (x) was determined as a function of time (t) or temperature (T). The x–t and x–T data thus obtained were processed using well established mathematical apparatus and methods, in order to characterize nature of reaction rate-determining step, and derive isothermal and non-isothermal kinetic parameters. Moreover, the reaction mixture quenched at various temperatures (600–1,000 °C) in the reaction course was analyzed by various spectroscopic and microscopic techniques, for material characterization. The results obtained indicated that the reaction rate may be controlled by unidirectional diffusion of WO₃ species across the product layer (BaWO₄), which was implied to form on the barium carbonate particles. The isothermally determined activation energy (118–125 kJ/mol) was found to be more credible than that (245 kJ/mol) determined non-isothermally.     

The role of spin states of dimethylgermylene in photoinduced processes

A joint consideration of the previous references and our own data has pointed to the possibility of the appearance of both S₀ and T₁ spin states of Me₂Ge: in photoinduced processes. The absorption band at 430 nm should be attributed to the ground S₀ state of Me₂Ge:, and the absorption band at 480 nm should relate to the excited T₁ state of Me₂Ge:. In addition, the rate constants of addition to multiple bonds amount to 10⁴–10⁷ M⁻¹ s⁻¹ for the singlet particles and ∼10¹⁰ M⁻¹ s⁻¹ (diffusion controlled) for the triplet particles, respectively.     

Non-isothermal oxidation kinetics of single- and multi-walled carbon nanotubes up to 1273 K in ambient

Non-isothermal oxidation kinetics of single- and multi-walled carbon nanotubes (CNTs) have been studied using thermogravimetry up to 1273 K in ambient using multiple heating rates. One single heating rate based model-fitting technique and four multiple heating rates based model-free isoconversional methods were used for this purpose. Depending on nanotube structure and impurity content, average activation energy (E _a), pre-exponential factor (A), reaction order (n), and degradation mechanism changed considerably. For multi-walled CNTs, E _a and A evaluated using model-fitting technique were ranged from 142.31 to 178.19 kJ mol⁻¹, respectively, and from 1.71 × 10⁵ to 5.81 × 10⁷ s⁻¹, respectively, whereas, E _a for single-walled CNTs ranged from 83.84 to 148.68 kJ mol⁻¹ and A from 2.55 × 10² to 1.18 × 10⁷ s⁻¹. Although, irrespective of CNT type, the model-fitting method resulted in a single kinetic triplet i.e., E _a, A, and reaction mechanism, model-free isoconversional methods suggested that thermal oxidation of these nanotubes could be either a simple single-step mechanism with almost constant activation energy throughout the reaction span or a complex process involving multiple mechanisms that offered varying E _a with extent of conversion. Criado method was employed to predict degradation mechanism(s) of these CNTs.     

Kinetics of oxidation of hydroquinone to <Emphasis Type="Italic">p</Emphasis>-benzoquinone catalyzed by microporous metal-organic frameworks M<Subscript>3</Subscript>(BTC)<Subscript>2</Subscript> [M = copper(II), cobalt(II), or nickel(II); BTC = benzene-1,3,5-tricarboxylate] using molecular oxygen

The kinetics of oxidation of hydroquinone (H₂Q) to p-benzoquinone (Q) catalyzed by microporous metal-organic frameworks (MOFs) using molecular oxygen has been investigated. MOF catalysts with different metals and pore sizes, i.e. M₃(BTC)₂(H₂O) _x (M = Cu^II (1), Co^II (2), or Ni^II (3); BTC = benzene-1,3,5-tricarboxylate; x = 3 for MOF 1 and 12 for 2 and 3), were used to catalyze the oxidation reaction. The apparent first-order reaction rate constant increased with increasing temperature, molar ratio of catalyst/H₂Q, and pH of the medium. A kinetic model for the heterogeneous catalysis is proposed, and the apparent activation energy (E _a), the association constants between the hydroquinone and the catalyst (K _s), and the first-order rate constants for product formation in the MOF channels (k _N) were calculated.     

Kinetics of non-isothermal oxidation of anhydrous milk fat rich in conjugated linoleic acid using differential scanning calorimetry

Anhydrous milk fat (AMF) with low, medium, and high content of conjugated linoleic acid (L-, M-, and H-CLA) was oxidized using differential scanning calorimetry (DSC) at five different heating rates (3, 6, 9, 12, and 15 °C min⁻¹) in a temperature range of 100–350 °C. For the first time, kinetic oxidation parameters of AMF rich in CLA are reported. DSC spectra were analyzed to locate the start temperature (T _s), onset temperature (T _on), and maximum heat flow temperature (T _p). These reference points were further used to calculate the effective activation energy (E) and pre-exponential factor (z) using the Ozawa-Flynn-Wall method. The T _s shifts to lower values as the CLA content increases, while the T _on and T _p were less affected by the CLA content. The calculated kinetic parameters not only depend on the ratio between unsaturated to saturated fatty acids but also on the selected reference points. For the L-CLA sample, the E values calculated from T _s, T _on, and T _p were 146.51, 114.11, and 121.31 kJ mol⁻¹, respectively. For the M-CLA sample, the E values calculated were 112.42, 104.06, and 87.41 kJ mol⁻¹, respectively. For the H-CLA sample, the E values calculated were 87.60, 82.42, and 73.64 kJ mol⁻¹, respectively. These variations in E values do not have any physical background according to the compensation effect. In non-isothermal oxidation of AMF, several reactions with different kinetic parameters simultaneously take place and DSC only detects those reactions that have the highest exothermal effect. The T _s is the most consistent reference point to calculate E and z values.     

Design of plasticized proton conducting Chitosan:Dextran based biopolymer blend electrolytes for EDLC application: Structural,impedance and electrochemical studies

In this work, for the use of an electrical double-layer capacitor (EDLC) device applications, the fabrication and characterization of solid polymer electrolytes (SPEs) based on chitosan-dextran (CS-DN) blended polymer doped and plasticized with ammonium thiocyanate (NH₄SCN) and glycerol are studied, respectively. The Fourier transform infrared (FTIR) spectroscopy method has been used to investigate the structural behavior of electrolytes. It was observed that the FTIR bands are shifted and decreased in their intensities with the increased glycerol plasticizer content and it results in the complex formation. According to the electrical impedance spectra (EIS), the electrolyte incorporated with high contents of plasticizer (42 wt%) revealed the highest ionic conductivity of (3.08 × 10⁻⁴ S/cm). The electrical equivalent circuits (EEC) were used to investigate the circuit elements of the electrolytes further. Increasing glycerol plasticizers verified an improvement in ions density number (n), mobility (μ), and diffusion coefficient (D). The transference number measurements (TNM) indicated that the predominant charge carriers in the conduction process are ions where the (t_ion) is 0.95. According to the linear sweep voltammetry (LSV) study, the uppermost conducting sample was found to have sufficient anode stability with a breakdown voltage of 1.9 V that can be used in electrochemical devices. The absence of peaks in the cyclic voltammetry (CV) demonstrated that the charge storage mechanism within the constructed EDLC is fully capacitive. Based on this finding, the starting specific capacitance (C_s), energy density (E_d), and power density (P_d) have been identified to be 118F/g, 13.2 Wh/kg, and 1560 W/kg, respectively. Throughout its 100 cycles, the equivalence series resistance ESR value was between 53 and 117 Ω.     

Structural,optical and microwave dielectric properties of Ba1−xSrxWO4 ceramics prepared by solid state reaction route

In this paper, Barium Strontium Tungstate (Ba_1−xSr_x)WO₄ crystals with (x = 0; 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 and 1.0) were prepared by standard wet milling ceramic preparation method. These crystals were structurally characterized by X-ray diffraction (XRD), Fourier transform Raman (FT-Raman) and Fourier transform infrared (FT-IR) spectroscopic techniques. The shape, growth and average crystal size distribution of these crystals were investigated by a scanning electron microscope (SEM). Their optical properties were investigated by ultraviolet visible (UV–vis) absorption and photoluminescence (PL) measurements. XRD patterns, Rietveld refinements data, FT-Raman and FT-IR spectroscopies indicate that all the crystals present a scheelite-type tetragonal structure without deleterious phases. FT-Raman spectra exhibited 6 Raman active modes in range from 100 to 1000 cm⁻¹, while the FT-IR spectra presented 2 infrared active modes in range from 500 to 1000 cm⁻¹. SEM micrographs showed well sintered BaWO₄ grains, while the substitution of Sr induced modifications in the shape and reduction in the grain size. UV–vis absorption measurements evidenced an increase in the values of the optical band gap (from 4.36 to 4.53 eV) with the increase of Sr into BaWO₄ lattice. Dielectric constant, temperature coefficient of resonant frequency (τ_f), quality factors were measured with Hakki–Coleman technique. The value of τ_f found −43.68 ppm/°C for BaWO₄ which increased to −21.40 ppm/°C for the SrWO₄.     

The microstructure and magnetic properties of Ni<Subscript>0.4</Subscript>Zn<Subscript>0.6</Subscript>Fe<Subscript>2</Subscript>O<Subscript>4</Subscript> films prepared by spin-coating method

Nickel zinc ferrite (Ni_0.4Zn_0.6Fe₂O₄) films on Si (100) substrate were synthesized using a spin-coating method. The crystallinity of the Ni_0.4Zn_0.6Fe₂O₄ films with the thickness of about 386 nm became better as the annealing temperature increased. The films have smooth surface, relatively good packing density and uniform thickness. The volatilization of Zn is serious at 900 °C. With the increase of annealing temperature, the saturation magnetization M _s increases in the temperature ranging from 400 to 700 °C, however, decreases above 700 °C, and the coercivity H _c increases in the temperature range 400–800 °C, decreases above 800 °C. After annealed at 700 °C for 2 h in air with the heating rate 2 °C/min, the film shows a maximum saturation magnetization M _s of 349 emu/cc and low coercivity H _c of 66 Oe. The M _s is higher than others which prepared by this method, however, the H _c is lower. The M _s of Ni_0.4Zn_0.6Fe₂O₄ films annealed at 700 °C increases with increasing annealing time and the H _c changes slightly.     

尖晶石结构MFe2O4(M=Ca,Mg,Cu,Zn)纳米晶粉末的制备和磁性能

采用新型氨基凝胶自燃法成功制备出尖晶石结构MFe₂O₄（M=Ca,Mg,Cu,Zn）纳米晶粉末。对合成粉体样品的物相、形貌和磁性能进行了详细的研究。经能量色散X射线谱分析确定了合成MFe₂O₄粉末的高纯度。系统地研究了所合成的MFe₂O₄纳米晶粉末的磁性能。所有样品的磁滞回线均较窄,表明了它们具有软磁的特征。经测试得出4种铁氧体的饱和磁化强度（M_s）分别为2.1,29.3,24.1和4.2 emu·g^-1;剩余磁化强度（M_r）分别为0.2,2.3,11.4和0.2 emu·g^-1。这4种铁氧体样品的M_r/M_s值均小于0.5。对CaFe₂O₄和MgFe₂O₄两种典型铁氧体的零场冷却和场冷磁性能作了详细的研究。其中CaFe₂O₄样品的磁化强度在75 K以下有不一致的变化趋势,这是由于其发生了磁相变。     

An investigation of the relationship between microstructure and permeation properties of ZSM-5 membranes

The influence of membrane microstructure on the transport properties of ZSM-5 membranes was investigated. Two zeolite membranes with (1 0 1)- and (0 0 2)-orientations were grown layer-by-layer onto seeded alumina support. The membrane morphology was kept constant as well as the shape of the individual crystal grains that made up the polycrystalline zeolite membrane layer. The membrane microstructure were characterized and quantified using six microstructural parameters that include membrane thickness (τ), grain size (d), grain morphology (M), zeolite population (N), crystal intergrowth (I_c) and film orientation. Eight different gases including He, H₂, N₂, Ar, CH₄, n-C₄H₁₀, i-C₄H₁₀ and SF₆ were used as molecular probes to investigate the transport processes through the membrane of different thicknesses. By maintaining a comparable non-zeolite flow, it was demonstrated that the (1 0 1)- and (0 0 2)-oriented ZSM-5 membranes have comparable transport resistance. Also, the results of the multi-thickness comparison using the different sized molecular probes indicate a strong similarity in the transport mechanism and diffusion pathway through these two membranes. The experiment suggests that the grain boundary is the main non-zeolite diffusion pathway in the membrane and their elimination through grain growth can result in better membrane performance.     

Improved magnetic properties of self-composite SrFe12O19 powder prepared by Fe3O4 nanoparticles

Sintered polycrystalline strontium hexaferrite, which is one of the most widely used permanent magnetic materials, has been applied in many areas such as electrical and mechanical transductor devices. Improving the coercivity (H_cJ) of M-type strontium hexaferrite with a nominal composition SrFe₁₂O₁₉ (SrM) plays an essential role to adapt to many modern applications, but is limited by the process and purity of raw materials. In this work, we prepared SrM powders with different iron resources, sintering temperatures, and Fe/Sr atom ratios. It was found that using Fe₃O₄ nanoparticles with a Fe/Sr atom ratio of 12 at 1100 °C performed the self-composites with 70% nano-size and 30% micro-size, which had the best performance. The coercivity reaches 348.9 kA/m, which is improved compared to pure SrM obtained by other iron resources in the solid-state method. This process shows a unique formation mechanism and the resulting self-composite microstructure eventually causes enhancement in the properties, which provides a new way for high-performance hexaferrites.     

Metal–metal bond cleavage of carbene complexes by halogens: The crystal and molecular structures of ax-[Mn2(CO)9{C(OEt)2-thienyl}], [Mn(CO)4(I){C(OEt)2-thienyl}] and eq-[Mn2(CO)9{C(NH2)2-thienyl}]

The metal–metal bond in [M₂(CO)₉{C(OEt)R}] (M = Mn (1), Re (2), R = 2-thienyl (a), 2-bithienyl (b)) is readily cleaved with halogens to afford cis-[M(CO)₄(X){C(OEt)R}] (M = Mn (3), X = I; M = Re (4), X = Br). In the binuclear manganese complex, the carbene ligand is found in an axial position due to steric reasons, whereas the electronically favoured equatorial position is found for the carbene ligands in the corresponding rhenium complexes and in [Mn₂(CO)₉{C(NH₂)thienyl}] (5a), containing a sterically less demanding NH₂-substituent.     

The effect of gamma irradiation on electrical and dielectric properties of organic-based Schottky barrier diodes (SBDs) at room temperature

The effect of ⁶⁰Co (γ-ray) irradiation on the electrical and dielectric properties of Au/Polyvinyl Alcohol (Ni,Zn-doped)/n-Si Schottky barrier diodes (SBDs) has been investigated by using capacitance-voltage (C-V) and conductance-voltage (G/ω-V) measurements at room temperature and 1 MHz. The real capacitance and conductance values were obtained by eliminating series resistance (R_s) effect in the measured capacitance (C_m) and conductance (G_m) values through correction. The experimental values of the dielectric constant (ε′), dielectric loss (ε″), loss tangent (tanδ), ac electrical conductivity (σ_ac) and the real (M′) and imaginary (M″) parts of the electrical modulus were found to be strong functions of radiation and applied bias voltage, especially in the depletion and accumulation regions. In addition, the density distribution of interface states (N_ss) profile was obtained using the high-low frequency capacitance (C_HF-C_LF) method for before and after irradiation. The N_ss-V plots give two distinct peaks for both cases, namely before radiation and after radiation, and those peaks correspond to two different localized interface states regions at M/S interface. The changes in the dielectric properties in the depletion and accumulation regions stem especially from the restructuring and reordering of the charges at interface states and surface polarization whereas those in the accumulation region are caused by series resistance effect.     

Structural and electrical characteristics of ALD-HfO2/n-Si gate stack with SiON interfacial layer for advanced CMOS technology

We report the fabrication of an ultra-thin silicon oxynitride (SiON) as an interfacial layer (IL) for n-Si/ALD-HfO₂ gate stack with reduced leakage current. The XRD, AFM, FTIR, FESEM and EDAX characterizations have been performed for structural and morphological studies. Electrical parameters such as dielectric constant (K), interface trap density (D_it), leakage current density (J), effective oxide charge (Q_eff), barrier height (Φ_bo), ideality factor (ƞ), breakdown-voltage (V_br) and series resistance (R_s) were extracted through C-V, G-V and I-V measurements. The determined values of K, D_it, J, Q_eff, Φ_bo, ƞ, V_br and R_s are 14.4, 0.5 × 10 ¹¹ eV⁻¹ cm⁻², 2.2 × 10⁻⁹ A/cm², 0.3 × 10¹³ cm⁻², 0.42, 2.1, −0.33 and 14.5 MΩ respectively. SiON growth prior to HfO₂ deposition has curtailed the problem of high leakage current density and interfacial traps due to sufficient amount of N₂ incorporated at the interface.     

Study on the Effect of Nano and Active Particles of Alumina on Natural Rubber–Alumina Composites in the Presence of Epoxidized Natural Rubber as Compatibilizer

Natural rubber composites with alumina of different particle sizes (28 nm nano particles, 200 nm active particles and > 1000 nm raw alumina) were prepared by the usual rubber processing technique. Epoxidized natural rubber (ENR) was used in the composites as compatibilizer. Cure characteristics and mechanical properties of all composites were analyzed. The values of minimum rheometric torque (M_L), maximum rheometric torque (M_H) and torque difference (M_H – M_L) increased. Maximum enhancement was observed for the nano-filled composites. It endorses the view that nano alumina reveals highest interaction with natural rubber in presence of ENR. Scorch time and optimum cure time values for nano-composites were highest among all types of composites. Vulcanization reaction for the sulfur curing system of the composites was found to follow first order rate kinetics. Specific rate constant decreased with decreasing particle size in composites. Crosslink densities of composite-vulcanizates showed increasing trend with decreasing particle size of alumina. Mechanical properties of the composite vulcanizates increased with decreasing particle size of alumina - nano composites exhibiting much higher mechanical strength. Results of oxidative resistance reveal that particle size of alumina in composite vulcanizates has a significant impact on aging behavior.     

Ca<Superscript>2+</Superscript> and Mg<Superscript>2+</Superscript> incorporated barium hexaferrites: structural and magnetic properties

BaM hexaferrites substituted with both Ca²⁺ and Mg²⁺ ions, namely, Ba_1-2×Ca_xMg_xFe₁₂O₁₉ (0.0?≤?x?≤?0.1), synthesized during a sol–gel auto-combustion route. The hexaferrite phase and morphology of all samples were investigated using X-ray powder diffraction, a field emission scanning electron microscope, a high-resolution transmission microscope, and Fourier transform infrared spectroscopy. In addition, an M-type hexagonal structure was confirmed using XRD for all samples. FE-SEM and TEM revealed the shape of the hexagonal plate. Measurements of the magnetization versus the field M(H) of Ba_1-2×Ca_xMg_xFe₁₂O₁₉ (0.0?≤?x?≤?0.1) nanohexaferrites were conducted at 300 and 10?K. A hard-ferrimagnetic behavior at both 300 and 10?K was noted for the different products produced. The squareness ratio indicates the uniaxial anisotropy for various products. The deduced values of saturation magnetization (M_s) in all substituted samples are higher than in the pristine sample (x?=?0). The Ba_0.96Ca_0.02Mg_0.02Fe₁₂O₁₉ nanosized hexaferrite showed the highest values of M_s, remanence M_r, magneton number (n_B), and magnetocrystalline anisotropy constant (K_eff). In contrast, the values of the coercive field (H_c) and intrinsic coercivity (H_ci) diminish with the increase in the amount of the substituted Ca and Mg elements.

Open image in new window