Search results for: superparamagnetism

Authors: Navneet Kaur, S. D. Tiwari

Abstract:

Magnetic nanoparticles possess fascinating properties which make their behavior unique in comparison to corresponding bulk materials. Superparamagnetism is one such interesting phenomenon exhibited only by small particles of magnetic materials. In this state, the thermal energy of particles become more than their magnetic anisotropy energy, and so particle magnetic moment vectors fluctuate between states of minimum energy. This situation is similar to paramagnetism of non-interacting ions and termed as superparamagnetism. The magnetization of such systems has been described by Langevin function. But, the estimated fit parameters, in this case, are found to be unphysical. It is due to non-consideration of particle size distribution. In this work, analysis of magnetization data on NiO nanoparticles is presented considering the effect of particle size distribution. Nanoparticles of NiO of two different sizes are prepared by heating freshly synthesized Ni(OH)₂ at different temperatures. Room temperature X-ray diffraction patterns confirm the formation of single phase of NiO. The diffraction lines are seen to be quite broad indicating the nanocrystalline nature of the samples. The average crystallite size are estimated to be about 6 and 8 nm. The samples are also characterized by transmission electron microscope. Magnetization of both sample is measured as function of temperature and applied magnetic field. Zero field cooled and field cooled magnetization are measured as a function of temperature to determine the bifurcation temperature. The magnetization is also measured at several temperatures in superparamagnetic region. The data are fitted to an appropriate expression considering a distribution in particle size following a least square fit procedure. The computer codes are written in PYTHON. The presented analysis is found to be very useful for estimating the particle size distribution present in the samples. The estimated distributions are compared with those determined from transmission electron micrographs.

Keywords: anisotropy, magnetization, nanoparticles, superparamagnetism

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Authors: Priya Arora, Jaspreet K. Rajput

Abstract:

Superparamagnetism has accelerated the research and use of more economical and ecological magnetically separable catalysts due to their more efficient isolation by response to an applied magnetic field. Magnetite nanomaterials coated by SiO2 shell have received a great deal of focus in the last decades as it provides high stability and also easy further surface functionalization depending upon the application. In this protocol, Fe3O4 magnetic nanoparticles have been synthesized by co-precipitation combined with sonication method. Further, Fe3O4 superparamagnetic nanoparticles have been functionalized by various moieties to serve as efficient catalysts for multicomponent reactions. The functionalized nanoparticles were characterized by techniques like Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), scanning electron microscopy (SEM), vibrating sample magnetometer (VSM), thermogravimetric analysis (TGA), Brunauer-Emmett-Teller (BET) surface area analysis. The as prepared nanocatalysts can be reused for several times without any significant loss in its activity. The utilization of magnetic nanoparticles as catalysts for this reaction is one approach i.e. green, inexpensive, facile and widely applicable.

Keywords: functionalized, magnetite, multicomponent reactions, superparamagnetic

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Authors: Chandni Rani, S. D. Tiwari

Abstract:

Ferrihydrite is one of the distinct minerals in the family of oxides, hydroxides and oxyhydroxides of iron. It is a nanocrystalline material. It occurs naturally in different sediments, soil systems and also found in the core of ferritin, an iron storage protien. This material can also be synthesized by suitable chemical methods in laboratories. This is known as less crystalline Iron (III) Oxyhydroxide. Due to its poor crystallinity, there are very broad peaks in x-ray diffraction. Depending on the number of peaks in x-ray diffraction pattern, it is classified as two lines and six lines ferrihydrite. The average crystallite size for these two forms is found to be about 2nm to 5nm. The exact crystal structure of this system is still under debate. Out of these two forms, the six lines ferrihydrite is more ordered in comparison to two lines ferrihydrite. The magnetic behavior of two lines ferrihydrite nanoparticles is somewhat well studied. But the magnetic behavior of six lines ferrihydrite nanoparticles could not attract the attention of researchers much. This motivated us to work on the magnetic properties of six lines ferrihydrite nanoparticles. In this work, we present synthesis, structural characterization and magnetic behavior of 5 nm six lines ferrihydrite nanoparticles. X-ray diffraction and transmission electron microscope are used for structural characterization of this system. Magnetization measurements are performed to fit the data at different temperatures. Then the effect of magnetic moment distribution is also found. All these observations are discussed in detail.

Keywords: nanoparticles, magnetism, superparamagnetism, magnetic anisotropy

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Authors: Navneet Kaur, S. D. Tiwari

Abstract:

Superparamagnetism is an interesting phenomenon and observed in small particles of magnetic materials. It arises due to a reduction in particle size. In the superparamagnetic state, as the thermal energy overcomes magnetic anisotropy energy, the magnetic moment vector of particles flip their magnetization direction between states of minimum energy. Superparamagnetic nanoparticles have been attracting the researchers due to many applications such as information storage, magnetic resonance imaging, biomedical applications, and sensors. For information storage, thermal fluctuations lead to loss of data. So that nanoparticles should have high blocking temperature. And to achieve this, nanoparticles should have a higher magnetic moment and magnetic anisotropy constant. In this work, the magnetic anisotropy constant of the antiferromagnetic nanoparticles system is determined. Magnetic studies on nanoparticles of NiO (nickel oxide) are reported well. This antiferromagnetic nanoparticle system has high blocking temperature and magnetic anisotropy constant of order 105 J/m3. The magnetic study of NiO nanoparticles in the superparamagnetic region is presented. NiO particles of two different sizes, i.e., 6 and 8 nm, are synthesized using the chemical route. These particles are characterized by an x-ray diffractometer, transmission electron microscope, and superconducting quantum interference device magnetometry. The magnetization vs. applied magnetic field and temperature data for both samples confirm their superparamagnetic nature. The blocking temperature for 6 and 8 nm particles is found to be 200 and 172 K, respectively. Magnetization vs. applied magnetic field data of NiO is fitted to an appropriate magnetic expression using a non-linear least square fit method. The role of particle size distribution and magnetic anisotropy is taken in to account in magnetization expression. The source code is written in Python programming language. This fitting provides us the magnetic anisotropy constant for NiO and other magnetic fit parameters. The particle size distribution estimated matches well with the transmission electron micrograph. The value of magnetic anisotropy constants for 6 and 8 nm particles is found to be 1.42 X 105 and 1.20 X 105 J/m3, respectively. The obtained magnetic fit parameters are verified using the Neel model. It is concluded that the effect of magnetic anisotropy should not be ignored while studying the magnetization process of nanoparticles.

Keywords: anisotropy, superparamagnetic, nanoparticle, magnetization

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Authors: Anahita Mortazavi Manesh, Mojtaba Bagherzadeh

Abstract:

Metalloporphyrins are well known to mimic the activity of monooxygenase enzymes. In this regard, metalloporphyrin complexes have been largely employed as valuable biomimetic catalysts, owing to the critical roles they play in oxygen transfer processes in catalytic oxidation reactions. Investigating in this area is based on different strategies to design selective, stable and high turnover catalytic systems. Immobilization of expensive metalloporphyrin catalysts onto supports appears to be a good way to improve their stability, selectivity and the catalytic performance because of the support environment and other advantages with respect to recovery, reuse. In other words, supporting metalloporphyrins provides a physical separation of active sites, thus minimizing catalyst self-destruction and dimerization of unhindered metalloporphyrins. Furthermore, heterogeneous catalytic oxidations have become an important target since their process are used in industry, helping to minimize the problems of industrial waste treatment. Hence, the immobilization of these biomimetic catalysts is much desired. An attractive approach is the preparation of the heterogeneous catalyst involves immobilization of complexes on silica coated magnetic nano-particles. Fe3O4@SiO2 magnetic nanoparticles have been studied extensively due to their superparamagnetism property, large surface area to volume ratio and easy functionalization. Using heterogenized homogeneous catalysts is an attractive option to facile separation of catalyst, simplified product work-up and continuity of catalytic system. Homogeneous catalysts immobilized on magnetic nanoparticles (MNPs) surface occupy a unique position due to combining the advantages of both homogeneous and heterogeneous catalysts. In addition, superparamagnetic nature of MNPs enable very simple separation of the immobilized catalysts from the reaction mixture using an external magnet. In the present work, an efficient heterogeneous catalyst was prepared by immobilizing manganese porphyrin on functionalized magnetic nanoparticles through the amino propyl linkage. The prepared catalyst was characterized by elemental analysis, FT-IR spectroscopy, X-ray powder diffraction, atomic absorption spectroscopy, UV-Vis spectroscopy, and scanning electron microscopy. Application of immobilized metalloporphyrin in the oxidation of various organic substrates was explored using Gas chromatographic (GC) analyses. The results showed that the supported Mn-porphyrin catalyst (Fe3O4@SiO2-NH2@MnPor) is an efficient and reusable catalyst in oxidation reactions. Our catalytic system exhibits high catalytic activity in terms of turnover number (TON) and reaction conditions. Leaching and recycling experiments revealed that nanocatalyst can be recovered several times without loss of activity and magnetic properties. The most important advantage of this heterogenized catalytic system is the simplicity of the catalyst separation in which the catalyst can be separated from the reaction mixture by applying a magnet. Furthermore, the separation and reuse of the magnetic Fe3O4 nanoparticles were very effective and economical.

Keywords: Fe3O4 nanoparticle, immobilized metalloporphyrin, magnetically separable nanocatalyst, oxidation reactions

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Authors: Ece A. Irmak, Amdulla O. Mekhrabov, M. Vedat Akdeniz

Abstract:

There is a growing interest on the synthesis and characterization of nanoalloys since the unique chemical, and physical properties of nanoalloys can be tuned and, consequently, new structural motifs can be created by varying the type of constituent elements, atomic and magnetic ordering, as well as size and shape of the nanoparticles. Due to the fine size effects, magnetic nanoalloys have considerable attention with their enhanced mechanical, electrical, optical and magnetic behavior. As an important magnetic nanoalloy, the novel application area of Fe-Ni based nanoalloys is expected to be widened in the chemical, aerospace industry and magnetic biomedical applications. Noble metals have been using in biomedical applications for several years because of their surface plasmon properties. In this respect, iron-nickel nanoalloys are promising materials for magnetic biomedical applications because they show novel properties such as superparamagnetism and surface plasmon resonance property. Also, there is great attention for the usage Fe-Ni based nanoalloys as radar absorbing materials in aerospace and stealth industry due to having high Curie temperature, high permeability and high saturation magnetization with good thermal stability. In this study, FeNi₃ bimetallic nanoalloys were synthesized by mechanical alloying in a planetary high energy ball mill. In mechanical alloying, micron size powders are placed into the mill with milling media. The powders are repeatedly deformed, fractured and alloyed by high energy collision under the impact of balls until the desired composition and particle size is achieved. The experimental studies were carried out in two parts. Firstly, dry mechanical alloying with high energy dry planetary ball milling was applied to obtain FeNi₃ nanoparticles. Secondly, dry milling was followed by surfactant-assisted ball milling to observe the surfactant and solvent effect on the structure, size, and properties of the FeNi₃ nanoalloys. In the first part, the powder sample of iron-nickel was prepared according to the 1:3 iron to nickel ratio to produce FeNi₃ nanoparticles and the 1:10 powder to ball weight ratio. To avoid oxidation during milling, the vials had been filled with Ar inert gas before milling started. The powders were milled for 80 hours in total and the synthesis of the FeNi₃ intermetallic nanoparticles was succeeded by mechanical alloying in 40 hours. Also, regarding the particle size, it was found that the amount of nano-sized particles raised with increasing milling time. In the second part of the study, dry milling of the Fe and Ni powders with the same stoichiometric ratio was repeated. Then, to prevent agglomeration and to obtain smaller sized nanoparticles with superparamagnetic behavior, surfactants and solvent are added to the system, after 40-hour milling time, with the completion of the mechanical alloying. During surfactant-assisted ball milling, heptane was used as milling medium, and as surfactants, oleic acid and oleylamine were used in the high energy ball milling processes. The characterization of the alloyed particles in terms of microstructure, morphology, particle size, thermal and magnetic properties with respect to milling time was done by X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, vibrating-sample magnetometer, and differential scanning calorimetry.

Keywords: iron-nickel systems, magnetic nanoalloys, mechanical alloying, nanoalloy characterization, surfactant-assisted ball milling

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