Hydrometallurgical Extraction of Zinc and Copper – A 57Fe-Mössbauer and XRD Approach

The most commonly used route in the hydrometallurgical extraction of zinc and copper from a sulphide ore is the concentrate–roast–leach–electro winning process. In the present investigation a zinc–copper ore from the Maranda mine, located in the Murchison Greenstone Belt, South Africa, containing sphalerite (ZnS) and chalcopyrite (CuFeS₂), was studied. The ⁵⁷Fe-Mössbauer spectrum of the concentrate yielded pyrite, chalcopyrite and clinochlore, consistent with XRD data. Optimal roasting conditions were found to be 900°C for 3 h and the calcine produced contained according to X-ray diffractometry equal amounts of franklinite (ZnFe₂O₄) and zinc oxide (ZnO) and half the amount of willemite (Zn₂SiO₄). The Mössbauer spectrum showed predominantly franklinite (59%), hematite (6%) and other Zn- or Cu-depleted ferrites (35%). The latter could not be detected by XRD analyses as peak overlapping with other species occurred. Leaching was done with HCl, H₂SO₄ and HNO₃, to determine which process would result in maximum recovery of Zn and Cu. More than 80% of both were recovered by using either one of the three techniques. From the residue of the leaching, the Fe-compounds were precipitated and <1% of the Zn and Cu was not recovered.     

Visible light activated photo-catalytic effect and local structure of iron silicate glass prepared by sol-gel method

A relationship between methylene blue (MB) decomposition ability under visible light and local structure of xFe₂O₃·(100-x)SiO₂ glass abbreviated as xFS prepared by sol-gel method was investigated by ⁵⁷Fe-Mössbauer spectroscopy, X-ray diffractometry (XRD) and ultraviolet-visible light absorption spectroscopy (UV-Vis). Mössbauer spectra of xFS glass with x of 10, 30 and 50 annealed at 1000 °C for 3 h were mainly composed of a paramagnetic doublet due to fayalite (Fe₂SiO₄), and magnetic sextets due to magnetite (Fe₃O₄) or hematite (α-Fe₂O₃). The absorption area (A) of α-Fe₂O₃ gradually increased from 0.0 to 10.3 and 100 % with the increasing Fe₂O₃ content (x) of annealed xFS glass. A leaching test performed by 20 mL of MB aqueous solution and 40 mg of annealed 50FS glass showed that MB concentration decreased from 16.2 to 4.7 μmol L^?1 after 2 h with the first order rate constant of 1.8 × 10^?4 s^?1. These results prove that annealed iron silicate glass containing α-Fe₂O₃ can decompose MB effectively under visible light irradiation.     

Decrease of superparamagnetic fraction at room temperature in ultrafine CoFe2O4 particles by Ag doping

Co_1???x Ag _x Fe₂O₄ nanoparticles have been prepared by the combustion route. The average crystallite sizes for compositions with x = 0 and 0.2 are found to be 36 and 33 nm respectively from the XRD line broadening. Compared to the pure CoFe₂O₄, Ag-doping reduces the intrinsic magnetization values (M, M _r), but enhances coercivity (H _c). Mössbauer spectra show two sextets, indicating occupancies of tetrahedral and octahedral sites by Fe^3?+?. Hyperfine fields of 505 and 477 kOe in pure CoFe₂O₄ have been found for octahedral and tetrahedral sites respectively at liquid nitrogen temperature. The hyperfine field decreases with Ag-doping which also corroborates the magnetization studies. EPR study confirms the room temperature ferromagnetic behavior for Co_1???x Ag _x Fe₂O₄ (x = 0.2). The room temperature Mössbauer studies on x?=?0.0 and 0.2 show the ferromagnetic sextets (95%) along with superparamagnetic doublet (5%). However, x = 0.6 sample shows the ferromagnetic sextets only at room temperature. Highly Ag doped samples could be useful for the fabrication of the high-density magnetic materials as well as magnetic drug delivery.     

Magnetic properties of bioactive glass-ceramics containing nanocrystalline zinc ferrite

Glass-ceramics with finely dispersed zinc ferrite (ZnFe₂O₄) nanocrystallites were obtained by heat treatment of x(ZnO,Fe₂O₃)(65?x)SiO₂20(CaO,P₂O₅)15Na₂O (6≤x≤21 mole%) glasses. X-ray diffraction patterns of the glass-ceramic samples revealed the presence of calcium sodium phosphate [NaCaPO₄] and zinc ferrite [ZnFe₂O₄] as major crystalline phases. Zinc ferrite present in nanocrystalline form contributes to the magnetic properties of the glass-ceramic samples. Magnetic hysteresis cycles of the glass-ceramic samples were obtained with applied magnetic field sweeps of ±20 kOe and ±500 Oe, in order to evaluate the potential of these glass-ceramics for hyperthermia treatment of cancer. The evolution of magnetic properties in these samples, viz., from a partially paramagnetic to fully ferrimagnetic nature has been explored using magnetometry and X-ray diffraction studies.     

Structural and magnetic investigations of sub-nano Mn-Mg ferrite prepared by wet method

Manganese-magnesium ferrite nanoparticles Mn_1−xMg_xFe₂O₄; 0≤x≤0.25 were prepared by the co-precipitation route. The samples were characterized by X-ray diffraction (XRD), which confirms the single phase spinel structure. Crystallite size, calculated from the (3 1 1) peak using the Scherrer formula, was found to increase with increasing Mg²⁺ concentrations and was found to be within the range 3-6 nm. TEM was also used to characterize the microstructure of nanosized Mn_1−xMg_xFe₂O₄. Nominal composition of the samples was determined by Atomic Absorption analysis (AA). Hysteresis loops of manganese-magnesium ferrite were obtained at room temperature and revealed lower saturation magnetization values associated with nanocrystalline Mn_1−xMg_xFe₂O₄ particles. This behavior was attributed to structural distortion of surface spins compared to that of the bulk one.     

Local structure and water cleaning ability of iron oxide nanoparticles prepared by hydro-thermal reaction

Nanoparticles (NPs) of Fe₃O₄ and γFe₂O₃ synthesized by hydrothermal reaction were characterized by X-ray diffractometry (XRD), ⁵⁷Fe-Mössbauer spectroscopy and field emission scanning electron microscopy (FE-SEM). A decrease in concentration of methylene blue (MB) aqueous solution due to bulk Fe⁰-NP γFe₂O₃ mixture with the mass ratio of 3:7 was measured by ultraviolet-visible light absorption spectroscopy (UV-Vis). The Mössbauer spectrum of NP Fe₃O₄ prepared from hydrothermal reaction was composed of two sextets with absorption area (A), isomer shift (δ) and internal magnetic field (H _int) of 56.3 %, 0.34_±0.03 mm s^???1 and 49.0_±0.30 T for tetrahedral (T _d) Fe^III, and 43.7 %, 0.66_±0.11 mm s^???1 and 44.0_±0.71 T for octahedral (O _h) Fe^II?+?III. The Fe^II/Fe^III ratio was determined to be 0.280 for NP Fe₃O₄, giving ‘x’ of 0.124 in Fe_3???xO_4. These results show that NP Fe₃O₄ prepared by hydrothermal reaction was not regular but nonstoichiometric Fe₃O₄. Consistent results were observed for XRD patterns of NP Fe_3???xO₄ indicating sharp intense peaks at 2Θ of 30.2, 35.7 and 43.3° with a large linewidth of 0.44°, yielding the crystallite size of 29–37 nm from the Scherrer’s equation. Iso-thermal annealing of NP Fe_3???xO₄ at 250 °C for 30 min resulted in the precipitation of NP γFe₂O₃ with δ of 0.33_±0.03 mm s^???1 and H _intof 46.4_±0.27 T due to magnetic tetrahedral Fe^III. The Debye temperature of NP Fe_3???xO₄ was respectively estimated to be 267_±5.45 K for Fe $^{\mathrm{III}}(T_{\mathrm{d}})$ and 282_±7.17 K for Fe $^{\mathrm{II+III}}(O_{\mathrm{h}})$ , both of which were smaller than that obtained for bulk Fe₃O₄ of 280_±4.15 K and 307_±5.70 K, indicating that the chemical environment of iron of NPs is less rigid than that of the bulk compounds. A leaching test using methylene blue (MB) and mixture of bulk Fe⁰-NP γFe₂O₃ (3:7) showed a remarkable decrease in MB concentration from 1.90 × 10^???2 to 9.49 × 10^???4 mM for 24 h with the first order rate constant (k _MB) of 2.1 × 10^???3 min^???1. This result verifies that MB decomposing ability is enhanced by using NP γFe₂O₃ compared with the k _MB of 1.1 × 10^???4 min^???1 previously obtained from the leaching test using MB and bulk mixture of Fe⁰???γFe₂O₃ (3:7).     

Synthesis and magnetic properties of La-substituted M-type Sr hexaferrites

Single-phase M-type hexagonal ferrites Sr_1−xLa_xFe₁₂O₁₉ (0≤x≤1) were prepared by a ceramic route. The stability limits of the ferrite phases were determined with a combination of various microscopy techniques, electron-probe micro-analysis, powder X-ray diffraction and thermal analysis. SrFe₁₂O₁₉ (x=0) is stable up to 1420 °C, whereas LaFe₁₂O₁₉ (x=1) exists between 1360 and 1400 °C only. The lattice parameters of Sr_1−xLa_xFe₁₂O₁₉ exhibit a linear variation with x, i.e. a₀ slightly increases and c₀ decreases with x, leading to a decrease of the unit cell volume with x. The saturation magnetization at T=5 K decreases with increasing La concentration. Room temperature Mössbauer analysis shows that the Fe³⁺/Fe²⁺ valence change occurs in the 2a sites for the whole composition range.     

Magnetic and Mössbauer studies on nanocrystalline Co1−x Li x Fe2O4 (x = 0, 0.2)

Ultrafine particles of Co_1???x Li _x Fe₂O₄ (x?= 0, 0.2) samples are prepared by glycine–nitrate combustion route. X-ray diffraction and transmission electron microscopy studies show that the samples have cubic spinel structure and average crystallite sizes of x?= 0 and 0.2 are 36 and 44 nm respectively. Vibrating sample magnetometer studies revealed the ferromagnetic nature of the samples. Li-doped CoFe₂O₄ sample showed higher values of coercive field, remanent magnetization and saturation magnetization compared to pure CoF₂O₄ indicating the enhancement of magnetic interactions. Mössbauer spectra at 77 K exhibited two broad sextets indicating that Fe^3?+? ions occupy both tetrahedral and octahedral sites. From these studies, it is concluded that Co_1???x Li _x Fe₂O₄ (x?= 0, 0.2) samples exhibit an inverse spinel structure. At room temperature, two sextets are superimposed on a very broad non-Lorentzian background indicating the presence of superparamgnetic fraction in agreement with the microscopic observations.     

Mössbauer characterization of Fe-doped ZnO prepared by mechanical milling

The preparation of massive oxides Zn₁??? _x Fe _x O by means of mechanical milling in diverse gaseous atmospheres and starting with different powder mixtures was investigated. ZnO powder with 10 at.% admixture of Fe, FeO or Fe₂O₃, were milled during 1, 4 or 16 h and characterized by X-ray diffraction and Mössbauer spectroscopy. Different phases were obtained according to the initial conditions (precursor used, atmosphere, etc.) and phase’s formation enthalpies.     

Synthesis and characterizations of water-based ferrofluids of substituted ferrites [Fe1−xBxFe2O4, B=Mn,Co (x=0–1)] for biomedical applications

Nanomagnetic particles have great potential in the biomedical applications like MRI contrast enhancement, magnetic separation, targeting delivery and hyperthermia. In this paper, we have explored the possibility of biomedical applications of [Fe_1−xB_xFe₂O₄, B=Mn, Co] ferrite. Superparamagnetic particles of substituted ferrites [Fe_1−xB_xFe₂O₄, B=Mn, Co (x=0–1)] and their fatty acid coated water base ferrofluids have been successfully prepared by co-precipitation technique using NH4OH/TMAH (Tetramethylammonium hydroxide) as base. In vitro cytocompatibility study of different magnetic fluids was done using HeLa (human cervical carcinoma) cell lines. Co²⁺-substituted ferrite systems (e.g. CoFe₂O₄) is more toxic than Mn²⁺-substituted ferrite systems (e.g. MnFe₂O₄, Fe_0.6Mn_0.4Fe₂O₄). The later is as cytocompatible as Fe₃O₄. Thus, Fe_1−xMn_xFe₂O₄ could be useful in biomedical applications like MRI contrast agent and hyperthermia treatment of cancer.     

Heat treatment effects on spinel phase of Zn x Ni1 − x Fe2O4 and MnFe2O4 nanoferrites

We report the effects of heat treatment on Zn _x Ni_1???x Fe₂O₄ (x?= 0, 0.5 and 1.0) and MnFe₂O₄ ferrite nanoparticles. The as-prepared compounds were sintered from 400°C to 1100°C. Pure ZnFe₂O₄ (x?= 1.0) and MnFe₂O₄ could be obtained under low reaction temperature of 200°C. NiFe₂O₄ (x?= 0) and Zn_0.5Ni_0.5Fe₂O₄ (x?= 0.5) nanoferrites crystallized with single phase cubic spinel structure after annealing at 600°C. The single phase cubic spinel structure of these compounds was destroyed after annealing at temperature above 700°C. The magnetization measurements indicate superparamagnetic behavior of the nanosized compounds produced.     

X-ray spectroscopic investigation of some spinel structures

K-absorption edges of cations in the manganites of magnesium, nickel, copper, zinc and cadmium and ferrite samples of composition, Mg_1?x Mn_x Fe₂O₄ (x=0, 0·25, 0·50, 0·75, 1·0), have been recorded employing a 40 cm curved mica crystal spectrograph of transmission type. It is observed that the absorption edges for the specimen shift towards the shorter wavelength side of the metal edge position. Shifts of both the absorption edges and the main absorptoin peaks for ferrites and manganites have been compared with compounds in which the oxidation state of the cation is well known. It is found that the manganese ions in these ferrites and manganites exist in valence states two and three respectively while iron in the ferrite samples is present in oxidation state three. An attempt has been made to interpret the observed absorption edge features in the light of neutron and X-ray diffraction studies on the same ferrite and manganite samples.     

Effect of lanthanum ions on magnetic properties of Y3Fe5O12 nanoparticles

Lanthanum ion (La³⁺)-substituted garnet nanoparticles Y_3?x La _x Fe₅O₁₂ (x = 0.0, 0.2, 0.4, 0.6, 0.8, and 1.0) were fabricated by a sol–gel method. Their crystalline structures and magnetic properties were investigated by using X-ray diffraction (XRD), vibrating sample magnetometer (VSM), and Mössbauer spectrum. The XRD results show that samples of Y_3?x La _x Fe₅O₁₂ (0.0 ≤ x ≤ 0.8) are all single phase and the sizes of particles range from 32 to 65 nm. Those of Y₂LaFe₅O₁₂ consisted of peaks from garnet and LaFeO₃ structures. Compared to pure YIG, the saturation magnetization is larger when the La concentration x = 0.2. However, with increasing La concentration (x), it decreases obviously. Meanwhile, may be due to the enhancement of the surface spin effects, the saturation magnetization rises as the particle size is increased. Different from the pure YIG, the Mössbauer spectra of Y_2.8La_0.2Fe₅O₁₂ and Y_2.2La_0.8Fe₅O₁₂ are composed of four sets of six-line hyperfine patterns. The results tell us that the substitution of La³⁺ ions with large ionic radius (1.061 Å) will give rise to a microscopic structure distortion of the a- and d-sites to different degrees, and the Zeeman sextets from a- and d-sites begin to split into two sub-sextets, which is helpful to explain the phenomenon observed in the study of the magnetic property.     

Complex permittivity, complex permeability and microwave absorption properties of ferrite-paraffin polymer composites

We have investigated the electromagnetic (EM) characteristics of Co_xMn_1−xFe₂O₄ spinel ferrite (where x=0.0, 0.5 and 1.0) nanoparticles (NPs)/paraffin nanocomposite material at 8-20 GHz. Co_xMn_1−xFe₂O₄ NPs have been synthesized by cetyltrimethylammonium assisted hydrothermal route using NaOH. A variation in complex dielectric permittivity and magnetic permeability at room temperature with frequency in the range 8-20 GHz has been studied. Particles showed phase purity and crystallinity in powder X-ray diffraction (XRD) analysis. At the same time, Co_xMn_1−xFe₂O₄ NPs demonstrated a spinel cubic structure from XRD results. A reflection loss of −46.60 dB was found at 10.5 GHz for an absorber thickness of 2 mm. Co_xMn_1−xFe₂O₄ may be attractive candidates for EM wave absorption materials.     

Influence of differential stress on the galvanic interaction of pyrite–chalcopyrite

The effect of stress action on pyrite–chalcopyrite galvanic corrosion was investigated using polarization curves and electrochemical impedance spectroscopy (EIS) measurements. When stress increased from 0 to 4?×?10⁵ Pa, the corrosion current density of pyrite–chalcopyrite increased from 5.678 to 6.719 μA cm^?2, and the corrosion potential decreased from 281.634 to 270.187 mV, accompanied by a decrease in polarization resistance from 25.09 to 23.79 Ω·cm². EIS results show there have three time constants in the Nyquist diagrams, which indicated the presence of different steps during the corrosion process. Stress dramatically enhanced pyrite–chalcopyrite galvanic corrosion by affecting the Cu_1???x Fe_1???y S₂ film and the double layer, whereas had little impact on the adsorption species. When the stress changed from 0 to 4?×?10⁵ Pa, the pore resistance and capacitance of the Cu_1???x Fe_1???y S₂ film, R _p and Q _p, changed by 25.72 and 72.28 %, respectively. The adsorption species resistance, R _sl, and capacitance, Q _sl, only changed by 9.77 and 2.31 %, respectively.     

Magnetic interactions in Cu-substituted manganese ferrites

A series of Mn_1−xCu_xFe₂O₄, with x=0, 0.25, 0.50, 0.75 and 1.0, spinel ferrites were prepared by standard ceramic method, to study the effect of compositional variation on magnetic susceptibility, saturation magnetization (M_s), Curie temperature (T_c) and magnetic moments (μ_B). The Curie temperatures have been evaluated by measuring the ac susceptibility using the mutual inductance technique. On increasing Cu contents from 0.0 to 0.50, the saturation magnetization increases while the Curie temperature decreases. On further increase in Cu contents, x>0.50 a decreasing trend in M_s is exhibited while T_c continues to decrease. This effect can be partially related to the low magnetic moments of Cu⁺² ions. The dominant interaction in all ferrite samples is A-B interaction which is due to the negative values of the characteristic temperature θ(K) showing that the magnetic ordering is antiferromagnetic. The Y-K angle increases gradually with increasing copper contents and extrapolates to 90° for CuFe₂O₄. From the computation of Y-K angles for Mn_1−xCu_xFe₂O₄, it can be concluded that the mixed copper ferrites exhibit a non-collinearity of the Y-K type while MnFe₂O₄ shows a Neel type of ordering.     

Microwave absorption properties of Al- and Cr-substituted M-type barium hexaferrite

Aluminum- and chromium-substituted barium ferrite particles with single magnetic domain were prepared using self-propagating combustion method. The crystalline structure, size, coercivity and microwave absorption property of the particles were investigated by means of X-ray diffraction, transmission electron microscopy, vibrating sample magnetometry and vector network analyzer. The results show that the crystalline structure of BaFe_12−xAl_xO₁₉ is still hexagonal. But when the chromium substitution amount y exceeds 0.6, the extra chromium ions cannot enter the lattice of BaFe_12−yCr_yO₁₉. After Fe³⁺ is partly substituted with Al³⁺ and Cr³⁺, the microwave absorption properties of barium ferrite are improved. The maximum absorption reaches 34.76 dB. The ferromagnetic resonance is an important channel of barium ferrite to absorb microwaves with high frequency. Aluminum and chromium substitutions change the ferromagnetic resonant frequency of barium ferrite. The multipeak phenomenon of the ferromagnetic resonance increases the microwave absorption capability of barium ferrite.     

Magnetization and Mössbauer study of double layer perovskites La1.5Ca1.5Mn2 − x Fe x O7 prepared by sol–gel method

Magnetization and Mössbauer studies have been made for understanding magnetic behavior of three double perovskite systems La_1.5Ca_1.5Mn_2???x Fe _x O₇ corresponding to x = 0.05, 0.10 and 0.50. These have been prepared following sol–gel route. Substitution of Fe does not lead to any major change in the tetragonal cell but increased iron leads to greater distortion in octahedral site. The three samples undergo paramagnetic–ferromagnetic transition. Curie temperature (T _c) for the system with 0.05 Fe is ～150 K which is lower than (190 K) for the system without iron; with 0.50 Fe T _c goes below 50 K. Iron goes as Fe^3?+? and replaces Mn in ab plane. With increasing Fe the valence states of Mn get re-distributed in a way that number of the Jahn–Teller ions Mn^3?+? increases and that of the pairs of Mn^3?+?–O–Mn^4?+? experiencing double exchange decreases.     

Optical spectroscopic analysis of Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> doped CuO containing phosphate glass

The effect of Fe₂O₃ in sodium zinc phosphate glass system containing CuO with the chemical composition 40P₂O₅:38ZnO:1CuO:(21 ? x)Na₂O:xFe₂O₃ (where x = 1, 2, 3, 4, 5 and 6 mol%) has been studied. The glass formability of the prepared samples was examined by means of XRD which proved that there are no natural crystal contents. Archimedes method has been employed to measure the density of the prepared glass samples hence, the molar volume was calculated. The density and the molar volume were found to be increased by increasing Fe₂O₃ content. The optical spectroscopic analysis for the obtained glass samples has been carried out over the whole range (190–1000 nm) for studying the effect of bandpass absorption glass filter, its color peak center and UV cut-off. The center for bandpass filter is found to exhibit a red shift by increasing Fe₂O₃ content. Moreover, all glass samples showed a bandstop in UV-range which was increased by increasing Fe₂O₃ content. The results reveal the practicality of this glass composition in optical color glass bandpass filter for UV preventing applications such as UV-Laser protection.     

A 236 GHz Fe3+ EPR Study of Nanoparticles of the Ferromagnetic Room-Temperature Semiconductor Sn1−x Fe x O2 (x = 0.005)

High-frequency (236 GHz) electron paramagnetic resonance (EPR) studies of Fe³⁺ ions at 255 K are reported in a Sn_1?x Fe _x O₂ powder with x = 0.005, which is a ferromagnetic semiconductor at room temperature. The observed EPR spectrum can be simulated reasonably well as the overlap of spectra due to four magnetically inequivalent high-spin (HS) Fe³⁺ ions (S = 5/2). The spectrum intensity is calculated, using the overlap I(BL) + (I(HS1) + I(HS2) + I(HS3) + I(HS4)) × exp(?0.00001B), where B is the magnetic field intensity in Gauss, I represents the intensity of an EPR line (HS1, HS2, HS3, HS4), and BL stands for the baseline (the exponential factor, as found by fitting to the experimental spectrum, is related to the Boltzmann population distribution of energy levels at 255 K, which is the temperature of the sample in the spectrometer). These high-frequency EPR results are significantly different from those at X-band. The large values of the zero-field splitting parameter (D) observed here for the four centers at the high frequency of 236 GHz are beyond the capability of X-band, which can only record spectra of ions with much smaller D values than those reported here.