Sonochemical synthesis of Gd3+ doped CoFe2O4 spinel ferrite nanoparticles and its physical properties

In this work, a facile and green method for gadolinium doped cobalt ferrite (CoFe2−xGdxO4; x = 0.00, 0.05, 0.10, 0.15, 0.20) nanoparticles by using ultrasonic irradiation was reported. The impact of Gd3+ substitution on the structural, magnetic, dielectric and electrical properties of cobalt ferrite nanoparticles was evaluated. The sonochemically synthesized spinel ferrite nanoparticles were characterized by X-ray Diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), vibrating sample magnetometer (VSM). X-ray diffraction (XRD) study confirmed the formation of single phase spinel ferrite of CoFe2−xGdxO4 nanoparticles. XRD results also revealed that ultrasonic irradiation seems to be favourable to achieve highly crystalline single crystal phase gadolinium doped cobalt ferrite nanoparticles without any post annealing process. Fourier Transform Infrared and Raman Spectra confirmed the formation of spinel ferrite crystal structure. X-ray photoelectron spectroscopy revealed the impact of Gd3+ substitution in CoFe2O4 nanoparticles on cation distribution at the tetrahedral and octahedral site in spinel ferrite crystal system. The electrical properties showed that the Gd3+ doped cobalt ferrite (CoFe2−xGdxO4; x = 0.20) exhibit enhanced dielectric constant (277 at 100 Hz) and ac conductivity (20.2 × 10−9 S/cm at 100 Hz). The modulus spectroscopy demonstrated the impact of Gd3+ substitution in cobalt ferrite nanoparticles on grain boundary relaxation time, capacitance and resistance. Magnetic property measurement revealed that the coercivity decreases with Gd3+ substitution from 234.32 Oe (x = 0.00) to 12.60 Oe (x = 0.05) and further increases from 12.60 Oe (x = 0.05) to 68.62 Oe (x = 0.20). Moreover, saturation magnetization decreases with Gd3+ substitution from 40.19 emu/g (x = 0.00) to 21.58 emu/g (x = 0.20). This work demonstrates that the grain size and cation distribution in Gd3+ doped cobalt ferrite nanoparticles synthesized by sonochemical method, is effective in controlling the structural, magnetic, and electrical properties, and can be find very promising applications. © 2017 Elsevier B.V.Ministry of Education, Youth and Sports of the Czech Republic - Program NPU I [LO1504

The effect of Co and Zn addition on densification and electrical properties of ceria-based nanopowders

CNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOCAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORIn this work, cobalt and zinc-doped Ce0.8Gd0.2O1.9 samples were prepared starting from a commercial nanopowder and compared to the undoped material. The powder samples were pressed and afterwards sintered by a two-step procedure, before characterization by X-Ray Diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM) and Impedance Spectroscopy (IS) in air. Cobalt or zinc additions are effective as sintering aid, allowing peak sintering temperatures around 1000 degrees C to reach densifications above of 93% of theoretical density, showing no evidence for the presence of secondary phases. The total conductivity at 800 degrees C of pressed Zn-doped samples (6.7x10(-2) S/cm) and Co-doped samples (7.5x10(-2) S/cm) is similar for undoped samples (7.2x10(-2) S/cm) showing that Zn and Co has a positive effect on densification without compromising the electrical conductivity.In this work, cobalt and zinc-doped Ce0.8Gd0.2O1.9 samples were prepared starting from a commercial nanopowder and compared to the undoped material. The powder samples were pressed and afterwards sintered by a two-step procedure, before characterization by X-Ray Diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM) and Impedance Spectroscopy (IS) in air. Cobalt or zinc additions are effective as sintering aid, allowing peak sintering temperatures around 1000 degrees C to reach densifications above of 93% of theoretical density, showing no evidence for the presence of secondary phases. The total conductivity at 800 degrees C of pressed Zn-doped samples (6.7x10(-2) S/cm) and Co-doped samples (7.5x10(-2) S/cm) is similar for undoped samples (7.2x10(-2) S/cm) showing that Zn and Co has a positive effect on densification without compromising the electrical conductivity.19510571063CNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOCAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOCAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORSem informaçãoSem informaçãoFinancial supports from CAPES and CNPq are greatly appreciated. We would like to thank Rita C. G. Vinhas (State University of Campinas, Campinas Campus, Brazil), for helping with the XPS measurements

Electrodeposition of rare earth-transition metal alloy thin films and nanostructures

Rare earth-transition metal alloys are of interest in MEMS and magnetic storage industries because of their unique magnetic properties. However, the applications of these alloys have been limited to bulk and thin film architectures because of the limitations of the contemporary vapor deposition technique to fabricate high aspect ratio nanostructures. The objective of this study is to develop an electrochemical process to deposit rare earth-transition metal alloys thus making it possible to deposit high aspect ratio nanostructures such as nanowires and nanotubes, which helps to tune their properties for specific applications. Electrodeposition of rare earth-transition metal alloys was achieved from an aqueous electrolyte kept under quiescent condition. The effect of cobalt (II) concentration, pH and deposition potential on rare earth-cobalt alloy electrodeposition was investigated. The alloy composition and the partial current densities exhibited a coupled deposition behavior between cobalt and rare earth. The rare earth concentration in the deposit and the current efficiency was found to depend on cobalt (II) concentration. Template electrodeposition of rare earth-transition metal alloy nanowires and nanotubes was demonstrated for the first time. Template deposition enabled the growth of several micron long deposits as compared to about 200 nm thick films deposited on planar substrate. Electrodeposition of rare earth-cobalt alloy nanotubes was observed from unmodified templates under low electrolyte pH, short deposition time and larger pore sizes. Also the composition of the deposit showed strong dependence to diffusion. The crystalline and magnetic properties investigation showed an amorphous deposit with small coercivity and squareness ratio. Compositionally modulated, electrodeposited, multilayered nanowires of CoGd/Co were also demonstrated. Based on the experimental results of rare earth-cobalt alloy deposition on planar electrodes and templates, an electrochemical reaction mechanism and a steady state kinetic model were presented. The mechanism showed a coupled behavior based on competitive adsorption of the intermediates. The kinetic model showed a good data fit between the experimental and simulated results

Structural, optical and magnetic properties of nanostructured Cr-substituted Ni-Zn spinel ferrites synthesized by a microwave combustion method

Nanoparticles of Cr3+-substituted Ni-Zn ferrites with a general formula Ni0.4Zn0.6-xCrxFe2O4 (x = 0.0 - 0.6) have been synthesized via a facile microwave combustion route. The crystalline phase has been characterized by XRD, TEM, FT-I and XPS revealing the spinel ferrite structure without extra phases. Crystallite sizes of 23 - 32 nm as estimated by XRD analyses, after corrections for crystal stains by Williamson-Hall method, are comparable to the average particle sizes observed by TEM which indicates successfully synthesized nanocrystals. Rietveld refinement analyses of the XRD patterns have inferred a monotonic decrease behavior of the lattice parameter with Cr doping in agreement with Vegard's law of solid solution series. Furthermore, cations distribution with an increased inversion factor indicate the B-site preference of Cr3+ ions. The oxidation states and cations distribution indicated by XPS results imply the Cr3+ doping on the account of Zn2+ ions and a partial reduction of Fe3+ to Fe2+ to keep the charge balance in a composition series of (Ni2+)0.4(Zn2+, Cr3+)0.6(Fe2+, Fe3+)2(O2-)4. The optical properties were explored by optical UV-Vis spectroscopy indicating allowed direct transitions with band gap energy that decreases from 3.9 eV to 3.7 eV with Cr doping. Furthermore, the photocatalytic activity for the degradation of methyl orange (MO) dye was investigated showing largely enhanced photodecomposition up to 30% of MO dye over Ni0.4Cr0.6Fe2O4 for 6 hours. A vibrating sample magnetometry (VSM) measurements at room temperature show further enhancement in the saturation magnetization of Ni0.4Zn0.6Fe2O4 , the highest in Ni-Zn ferrites, from about 60 to 70 emu/g with the increase of Cr concentration up to x = 0.1, while the coercivity shows a general increase in the whole range of Cr doping.Comment: 21 page, 9 figure

Fabrication and characterization of Ru-doped LiCuFe2O4 nanoparticles and their capacitive and resistive humidity sensor applications

Polycrystalline ruthenium-doped lithium-copper-ferrite ( Ru-LiCuFe2O4) nanoparticles (NPs) are synthesized using a simple and cost-effective chemical co-precipitation method and annealed at different temperatures for increasing the crystallinity. The transmission and scanning electron microscopy images have confirmed the presence of soft agglomerations and cuboids for the samples annealed at 1100 °C. X-ray photoelectron results along with Raman spectra have collectively demonstrated the presence of Ru in the structure of Ru-LiCuFe2O4 NPs. The dielectric properties of as-synthesized Ru-LiCuFe2O4 NPs are investigated using LCR meter where the smaller NPs demonstrates a higher dielectric constant. Also, the results of magnetic measurements of annealed Ru-LiCuFe2O4 NPs have corroborated a soft magnetic nature due to the pinning sites that endow lower coercivity, remanence and saturation magnetization than that of the pristine one. The variation of permittivity and electrical resistivity with respect to frequency under humidity conditions suggested that this material has a potential to use as capacitive and resistive humidity sensor. The results of this study open the doors for utilization of metal-doped magnetic ferrites for humidity sensing application

The influence of Ca2+ and Zn2+ doping on the development of sustainable pigments based on GdFeO3 perovskite: From a reddish colour towards a pure black

Black pigments are very commonly used and arouse widespread interest in the ceramic industry. Nevertheless, these pigments contain toxic elements that are detrimental to human health. In view of this, the present work is focused on the development of sustainable black pigments prepared by a coprecipitation method at 1200 °C. Samples with the nominal formula (Gd1–xCax)(Fe0.95Zn0.05)O2.975–x/2 (x = 0.00, 0.05, 0.10) showed single-phase orthorhombic perovskite. The presence of dopants played an important role in the reduction of Fe3+ to Fe2+ and caused different local distortions in the structure which explained the final black colouration of these pigments in comparison with the red GdFeO3 sample. The loss of symmetry and the increase in the number of d-d transitions of iron may explain the aforementioned changes. Co-doped pigments reached low C* values, improving on the purest black colour obtained in a commercial black ceramic pigment, which contains toxic elements. In addition to presenting good NIR solar reflectance values of up to 8%, the final colours of these pigments were also stable after their application in a commercial transparent glaze at 1080 °C that could be used for tiles.Funding for open access charge: CRUE-Universitat Jaume

From molecules to nanoparticles to functional materials

Functional nanomaterials have held a steady position at the frontier of materials science and engineering in the 21st century. “Molecular Designing of Nanoparticles with Controlled Morphological and Physicochemical Characteristics and Functional Materials Based on Them” was the title of the research project funded by the Ministry of Education, Science and Technological Development of the Republic of Serbia and performed between 2011 and 2019 in the interdisciplinary area of nanoscience and nanotechnologies. Research activities within this program were divided into five interrelated topics: 1) from molecules to nanoparticles; 2) advanced ceramics with improved functional properties; 3) electrode materials for lithium–ion batteries; 4) nano-calcium phosphate in preventive and regenerative medicine; 5) biodegradable microand nano-particles for the controlled delivery of medicaments. This report gives an insight into this bibliographically most impactful Serbian national project on nanotechnologies executed within the aforementioned nine-year cycle, 2011–2019, focusing here only on the results achieved in the past three years. The project provided an outstanding and internationally recognized contribution to synthesis, characterization and functional design of a number of materials systems, including pure and lanthanide–doped hydroxyapatite, zinc oxides, sodium cobaltates, lithium iron pyrophosphates, lithium iron silicates and a number of polymeric systems

Doctor of Philosophy

dissertationSpintronic devices are currently being researched as next-generation alternatives to traditional electronics. Electronics, which utilize the charge-carrying capabilities of electrons to store information, are fundamentally limited not only by size constraints, but also by limits on current flow and degradation, due to electro-migration. Spintronics devices are able to overcome these limitations, as their information storage is in the spin of electrons, rather than their charge. By using spin rather than charge, these current-limiting shortcomings can be easily overcome. However, for spintronic devices to be fully implemented into the current technology industry, their capabilities must be improved. Spintronic device operation relies on the movement and manipulation of spin-polarized electrons, in which there are three main processes that must be optimized in order to maximize device efficiencies. These spin-related processes are: the injection of spin-polarized electrons, the transport and manipulation of these carriers, and the detection of spin-polarized currents. In order to enhance the rate of spin-polarized injection, research has been focused on the use of alternative methods to enhance injection beyond that of a simple ferromagnetic metal/semiconductor injector interface. These alternatives include the use of oxide-based tunnel barriers and the modification of semiconductors and insulators for their use as ferromagnetic injector materials. The transport of spin-polarized carriers is heavily reliant on the optimization of materials' properties in order to enhance the carrier mobility and to quench spin-orbit coupling (SOC). However, a certain degree of SOC is necessary in order to allow for the electric-field, gate-controlled manipulation of spin currents. Spin detection can be performed via both optical and electrical techniques. Using electrical methods relies on the conversion between spin and charge currents via SOC and is often the preferred method for device-based applications. This dissertation presents experimental results on the use of oxides for fulfilling the three spintronic device requirements. In the case of spin injection, the study of dilute magnetic dielectrics (DMDs) shows the importance of doping on the magnetic properties of the resulting tunnel barriers. The study of spin transport in ZnO has shown that, even at room temperature, the spin diffusion length is relatively long, on the order of 100 nm. These studies have also probed the spin relaxation mechanics in ZnO and have shown that Dyakonov-Perel spin relaxation, operating according to Fermi-Dirac statistics, is the dominant spin relaxation mechanism in zinc oxide. Finally, spin detection in ZnO has shown that, similar to other semiconductors, by modifying the resistivity of the ZnO thin films, the spin Hall angle (SHA) can be enhanced to nearly that of metals. This is possible by enhancing extrinsic SOC due to skew-scattering from impurities as well as phonons. In addition, thermal spin injection has also been detected using ZnO, which results support the independently measured inverse spin-Hall effect studies. The work represented herein illustrates that oxide materials have the potential to enhance spintronic device potential in all processes pertinent to spintronic applications

Thin films of non-peripherally substituted liquid crystalline phthalocyanines A

This thesis was submitted for the degree of Doctor of Philosophy and awarded by Brunel University.Three non-peripherally substituted liquid crystalline bisphthalocyanine (Pc) compounds have been studied to examine the role of central metal ions lutetium (Lu), and gadolinium (Gd) and substituent chain lengths, i.e. octyl (C8H17) and hexyl (C6H13), in determining the physical properties. For the octyl substituted Pc molecules, the head-to-tail or Jaggregates within the as-deposited spun films produced a redshift of the optical absorption Q bands in relation to their 0.01 mgml-1 solutions. Annealing at 80˚C produced a well-ordered discotic liquid crystalline (LC) mesophase causing additional redshifts irrespective of the metal ion in case of C8LuPc2 and C8GdPc2. Formation of face-to-face or H-aggregated monomers led to blueshifts of the Q bands with respect to solution spectra for C6GdPc2, both as-deposited and annealed films. Stretching and bending vibrations of pyrrole, isoindole, and metal-nitrogen bonds in Pc rings showed Raman bands at higher energy for smaller metal ion. However, no change was observed for the difference in chain lengths. As-deposited C8LuPc2 and C6GdPc2 produced comparable Ohmic conductivity, of the value 67.55 Scm-1 and 42.31 Scm-1, respectively. C8GdPc2 exhibited two orders of magnitude less conductivity than the other two due to the size effect of the central ion and side chain length. On annealing, an increase of Ohmic conductivity was noticed in the isostructural octyl substituted phthalocyanines on contrary to a reduced conductivity in hexyl substituted one. An optical band shift of the C8LuPc2 and C8GdPc2 thin films occurred on oxidation by bromine vapour. Oxidations of Pc-coated ITO were also achieved by applying potential at 0.88 V and 0.96 V electrochemically for the C8LuPc2 and C8GdPc2 compounds, respectively. To explore the applications of these compounds in biosensing, in situ interaction studies between bromine oxidised compounds and biological cofactors nicotinamide adenine dinucleotide (NADH) and L-ascorbic acid (vitamin C) were carried out using optical absorption spectroscopy. Thin films of a non-peripherally octyl substituted LC lead phthalocyanine was exposed to 99.9 % pure hydrogen sulfide gas to produce hybrid nanocomposites consisting of lead sulphide quantum dots embedded in the analogous metal free phthalocyanine matrix. Trapping of charge carriers caused hysteresis in the current-voltage characteristics of the film on interdigitated gold electrodes. The charge hopping distance was found to be 9.05 nm, more than the percolation limit and responsible for forming two well-defined conducting states with potential application as a memristor