Systematic study of the synthesis of nanostructured multiferroic films and their structural, electronic and magnetic properties

<p>Multiferroics are unique materials that display multiple ferroic properties (ferroelectricity, ferromagnetism and ferroelasticity) simultaneously. A number of materials containing bismuth have intrinsic multiferroic properties, including BiFeO₃ and BiCrO₃. Among them, BiFeO₃ has attracted widespread attention because BiFeO₃ was the first material to display multiferroic behaviour at ambient temperature. A weak ferromagnetism occurs only at low temperatures depending on synthesis conditions. This thesis reports the structural, magnetic and optical properties of nanostructured BiFeO₃ thin films prepared by two novel approaches of ion beam sputtering and ion implantation techniques. Nanocrystalline BiFeO₃ films were prepared at ambient temperature by sputtering and thermal annealing at 500 °C in an oxygen atmosphere. The annealing resulted in the formation of multiferroic BiFeO₃ phase with a reduction of iron oxide and bismuth phases. Superparamagnetism was observed and could be attributed to magnetite and maghemite nanoparticles. The magnetic properties were mainly due to magnetite and maghemite nanoparticles. The saturation magnetic moment was 60% lower after annealing, which was due to Fe in phases of iron oxide being incorporated into BiFeO₃ nanoparticles. An exchange bias was observed before and after annealing. The exchange bias cannot be attributed to BiFeO₃ structure. Instead, the exchange has likely arisen from magnetite and maghemite cores with spin-disordered shells. Piezoelectric responses measured by piezoelectric force microscopy confirmed the presence of BiFeO₃ ferroelectric material. The Magneto-optical Kerr effect (MOKE) and optical studies were used to calculate an anomalously high Verdet constant. The MOKE and magnetic circular dichroism (MCD) displayed a significant modification in function of the wavelength. Further increasing the annealing temperature lead to an increase in iron oxide phases, while increasing the annealing duration reduced the iron oxide phases, however this increases the fraction of Bi₂Fe₄O₉ and Bi₂O₃. Another approach to synthesise BiFeO₃ thin film was investigated by bismuth ion implantation into iron oxide thin film. An as-made iron oxide film subsequently implanted with bismuth and annealed showed a 6.5% reduction of the ferromagnetic phase fraction. An annealed iron oxide film subsequently implanted with bismuth and annealed show that the ferromagnetic phase was present at less than 4% while Fe₃O₄ and γ-Fe₂O₃ increased to 7%. The coercive field is affected by annealing. However, this field is not affected by the bismuth implantation. For the first-time, a preliminary investigation reporting the implantation of Bi then Fe then O into SiO₂:Si was made with the aim to synthesise BiFeO₃ films and magnetic nanoparticles. The implantation of Fe then O then Bi into SiO₂:Si contained a mix of iron oxides: α-Fe₂O₃ and Fe₃O₄, as confirmed by Raman spectroscopy and X-ray diffraction, while γ-Fe₂O₃ was most likely also present in the film. The as-implanted sample displayed a sign of a superparamagnetic phase that was lost with annealing the sample. Preliminary investigations of another multiferroic material, BiCrO₃, were carried out. Thin films of BiCrO₃ were prepared by ion beam sputtering and annealing the sample in an oxygen atmosphere which lead to BiCrxOy with chromium oxides and bismuth oxide phases. Magnetic enhancement was observed when annealing above 700 °C. Annealing in an oxygen atmosphere followed by an argon atmosphere created a superparamagnetic phase that was not visible under other annealing conditions.</p>

Systematic study of the synthesis of nanostructured multiferroic films and their structural, electronic and magnetic properties

<p>Multiferroics are unique materials that display multiple ferroic properties (ferroelectricity, ferromagnetism and ferroelasticity) simultaneously. A number of materials containing bismuth have intrinsic multiferroic properties, including BiFeO₃ and BiCrO₃. Among them, BiFeO₃ has attracted widespread attention because BiFeO₃ was the first material to display multiferroic behaviour at ambient temperature. A weak ferromagnetism occurs only at low temperatures depending on synthesis conditions. This thesis reports the structural, magnetic and optical properties of nanostructured BiFeO₃ thin films prepared by two novel approaches of ion beam sputtering and ion implantation techniques. Nanocrystalline BiFeO₃ films were prepared at ambient temperature by sputtering and thermal annealing at 500 °C in an oxygen atmosphere. The annealing resulted in the formation of multiferroic BiFeO₃ phase with a reduction of iron oxide and bismuth phases. Superparamagnetism was observed and could be attributed to magnetite and maghemite nanoparticles. The magnetic properties were mainly due to magnetite and maghemite nanoparticles. The saturation magnetic moment was 60% lower after annealing, which was due to Fe in phases of iron oxide being incorporated into BiFeO₃ nanoparticles. An exchange bias was observed before and after annealing. The exchange bias cannot be attributed to BiFeO₃ structure. Instead, the exchange has likely arisen from magnetite and maghemite cores with spin-disordered shells. Piezoelectric responses measured by piezoelectric force microscopy confirmed the presence of BiFeO₃ ferroelectric material. The Magneto-optical Kerr effect (MOKE) and optical studies were used to calculate an anomalously high Verdet constant. The MOKE and magnetic circular dichroism (MCD) displayed a significant modification in function of the wavelength. Further increasing the annealing temperature lead to an increase in iron oxide phases, while increasing the annealing duration reduced the iron oxide phases, however this increases the fraction of Bi₂Fe₄O₉ and Bi₂O₃. Another approach to synthesise BiFeO₃ thin film was investigated by bismuth ion implantation into iron oxide thin film. An as-made iron oxide film subsequently implanted with bismuth and annealed showed a 6.5% reduction of the ferromagnetic phase fraction. An annealed iron oxide film subsequently implanted with bismuth and annealed show that the ferromagnetic phase was present at less than 4% while Fe₃O₄ and γ-Fe₂O₃ increased to 7%. The coercive field is affected by annealing. However, this field is not affected by the bismuth implantation. For the first-time, a preliminary investigation reporting the implantation of Bi then Fe then O into SiO₂:Si was made with the aim to synthesise BiFeO₃ films and magnetic nanoparticles. The implantation of Fe then O then Bi into SiO₂:Si contained a mix of iron oxides: α-Fe₂O₃ and Fe₃O₄, as confirmed by Raman spectroscopy and X-ray diffraction, while γ-Fe₂O₃ was most likely also present in the film. The as-implanted sample displayed a sign of a superparamagnetic phase that was lost with annealing the sample. Preliminary investigations of another multiferroic material, BiCrO₃, were carried out. Thin films of BiCrO₃ were prepared by ion beam sputtering and annealing the sample in an oxygen atmosphere which lead to BiCrxOy with chromium oxides and bismuth oxide phases. Magnetic enhancement was observed when annealing above 700 °C. Annealing in an oxygen atmosphere followed by an argon atmosphere created a superparamagnetic phase that was not visible under other annealing conditions.</p>

Initial Dynamic Susceptibility of Maghemite Nanoparticles Dispersed in Surface-Treated Polymeric Template

Magnetic nanocomposites based on maghemite nanoparticles supported (ex situ route) on styrene- divinilbenzene (Sty-DVB) copolymer templates were produced and characterized for their structure and morphology. The as-produced nanocomposites were further chemically-treated with different oxidant agents and surface-coated with stearic acid. X-ray diffraction and transmission electron microscopy data show that the incorporated nanoparticles are preserved despite the aggressive chemical treatments employed. From the dynamical susceptibility measurements performed on the nanocomposites, the values of the saturation magnetization (76 emu/g) and the effective magnetic anisotropy (1.7 × 104 J/m3) were obtained, in excellent agreement with the values reported in the literature for maghemite. This finding strongly supports the preservation of the magnetic properties of the supported nanosized maghemite throughout the entire samples’ processing.

Innovative functional polymerization of pyrrole-N-propionic acid onto WS2 nanotubes using cerium-doped maghemite nanoparticles for photothermal therapy

Tungsten disulfide nanotubes (WS2-NTs) were found to be very active for photothermal therapy. However, their lack of stability in aqueous solutions inhibits their use in many applications, especially in biomedicine. Few attempts were made to chemically functionalize the surface of the NTs to improve their dispersability. Here, we present a new polymerization method using cerium-doped maghemite nanoparticles (CM-NPs) as magnetic nanosized linkers between the WS2-NT surface and pyrrole-N-propionic acid monomers, which allow in situ polymerization onto the composite surface. This unique composite is magnetic, and contains two active entities for photothermal therapy—WS2 and the polypyrrole. The photothermal activity of the composite was tested at a wavelength of 808 nm, and significant thermal activity was observed. Moreover, the polycarboxylated polymeric coating of the NTs enables effective linkage of additional molecules or drugs via covalent bonding. In addition, a new method was established for large-scale synthesis of CM-NPs and WS2-NT-CM composites.

Nanomagnetic Polymeric Absorbent Based on Alginate and Gamma-Maghemite Synthesized In Situ for Wastewater Treatment from Metallurgical Industry

A nanomagnetic absorbent based on calcium alginate was produced successfully with the maghemite nanoparticles synthesized in situ, i.e., together with the polysaccharide crosslinking reaction. Physicochemical properties of the absorbent were analyzed and its ability to remove Ni(II) and Mn(II) ions from a real metallurgical industry wastewater was evaluated. Kinetic studies of the adsorption of these heavy metals were realized. To ascertain the most suitable quantity of absorbent to remove Ni(II) and Mn(II) from the wastewater, the absorbent mass was varied and adsorption kinetics was also evaluated. The competitiveness between the metals was evaluated to understand the adsorption mechanism. The samples were characterized by transmission electron microscopy, vibrating sample magnetometry, X-ray diffractometry and Mössbauer spectroscopy. The absorbent prepared, in this work, can be classified as a hydrogel. It presented predominant spherical morphology and micrometric dimension, containing atoms of iron and calcium dispersed uniformly in their internal and external surfaces. The synthesized maghemite nanoparticles presented superparamagnetic behavior. Results showed that the adsorption equilibrium time for both ions was about 60 min. The removal percentages from wastewater were 60.5% for nickel and 56.6% for manganese, using 300 mg of hydrogel. Results revealed that the adsorption mechanism is by ionic change between calcium and heavy metals.

Study of Photodegradation Performance and Ability of Lead Removal of Synthesized Maghemite Nanoparticles Using Ziziphus Jujuba Extract

Today, Water pollutants such as heavy metals and dyes are very important dangers to the nature. Metals such as lead, chromium, mercury and arsenic are examples of heavy metals which are toxic to living things, even sometime at the lowest concentrations. For resolve this challenge, Magnetic nanoparticles are attractive compound because of their advantages such as high efficiency, fast recovery capability, high surface area, easy transportation and inexpensive. We presented an easy and eco-friendly route for the synthesis of iron oxide nanoparticles using Ziziphus jujuba extract. In order to determine the physical, chemical and optical properties of the synthesized samples, Fourier-transform infrared (FT-IR), powder X-ray diffraction (PXRD), vibrating sample magnetometer (VSM), field emission scanning electron microscope (FESEM), energy dispersive X-ray (EDX), transmission electron microscopy (TEM), and Raman analyses were deployed. PXRD results showed that the synthesized nanoparticles have maghemite form of (γ-Fe2O3). FESEM and TEM results demonstrated that the size of these nanoparticles was in range of 20-50 nm, and had spherical shapes. Raman spectrum confirmed the cubic structure of γ-Fe2O3 NPs. Survey of magnetic properties showed that the synthesized maghemite nanoparticles (γ-Fe2O3 NPs) were superparamagnetic. The ability to remove lead from aqueous solution was investigated using these nanoparticles. The results showed that the synthesized nanoparticles were capable of removing 96% of lead at pH = 7 and 1 mg/L loading of nanoparticles. The photocatalytic activity of γ-Fe2O3 NPs was studied on methylene blue (MB) dye; as a result, MB at pH =7 and 1 gr dosage of γ-Fe2O3 had the highest removal percentage (92.8%) during 160 minute using γ-Fe2O3 which calcined at 400 ˚C. The reusability results showed that after four cycles of using the γ-Fe2O3-400, the obtained degradation of methylene blue was about 87.1%. Thus, synthesized γ-Fe2O3 NPs can be a good alternative for removing heavy metals and industrial dyes from contaminated waters.