Effect of mechanical milling on the structural, magnetic and dielectric properties of coprecipitated ultrafine zinc ferrite

Nanosized ZnFe2O4 particles containing traces of a-Fe2O3 by intent were produced by low temperature chemical coprecipitation methods. These particles were subjected to high-energy ball milling. These were then characterised using X-ray diffraction, magnetisation and dielectric studies. The effect of milling on zinc ferrite particles have been studied with a view to ascertaining the anomalous behaviour of these materials in the nanoregime. X-ray diffraction and magnetisation studies carried out show that these particles are associated with strains and it is the surface effects that contribute to the magnetisation. Hematite percentage, probably due to decomposition of zinc ferrite, increases with milling. Dielectric behaviour of these particles is due to interfacial polarisation as proposed by Koops. Also the defects caused by the milling produce traps in the surface layer contributes to dielectric permittivity via spin polarised electron tunnelling between grains. The ionic mechanism is enhanced in dielectrics with the rise in temperature which results in the increase of dielectric permittivity with temperature.

Catalysis by Polymer Supported Dendrimers, their Metal Complexes and Nanoparticle Conjugates

The present thesis has described the development of some heterogeneous catalysts based on polymer supported dendrimers. Attachment of dendrimers to crosslinked polymer produced new catalysts with combined benefits of both dendrimers and heterogeneous catalysts. These were used as heterogeneous catalysts in selected reactions. All possible attempts were taken to avoid halogenated and aromatic solvents and toxic reagents. In short the present work has dealt with development of environmental friendly catalysts based on dendrimers.

Polypropylene/metal oxide nanocomposites: fiber spinning and evaluation”

PP has been getting much attention over the years because it is a very durable polymer commonly used in aggressive environments including automotive battery casings, fuel containers etc. They are used to make bottles, fibers for clothing, components in cars etc. However, it has some shortcomings such as low dimensional and thermal stability. Materials such as metal oxides with sizes of the order 1–50 nm have received a great deal of attention because of their versatile applications in polymer/ inorganic nanocomposites, optoelectronic devices, biomedical materials, and other areas. They are stable under harsh process conditions and also regarded as safe materials to human beings and animals. In the present investigation, PP is modified by incorporating metal oxide nanoparticles such as ZnO and TiO2 by simple melt mixing method. Melt spinning method was used to prepare PP/metal oxide nanocomposite fibers. Various studies have been carried out on these composites and fibers. In the first part of the study, ZnO nanoparticles were prepared from ZnCl2 and NaOH in presence of chitosan, PVA, ethanol and starch. This is a simple and inexpensive method compared to other methods. Change in morphology and particle size of ZnO were studied. Least particle size was obtained in chitosan medium. The particles were characterized by using XRD, SEM, TEM, TGA and EDAX. Antibacterial properties of ZnO prepared in chitosan medium (NZO) and commercial zinc oxide (CZO) were evaluated using a gram positive and a gram negative bacteria

Artificial neural network modeling for surface roughness prediction in cylindrical grinding of Al‐SiCp metal matrix composites and ANOVA analysis

Metal matrix composites (MMC) having aluminium (Al) in the matrix phase and silicon carbide particles (SiCp) in reinforcement phase, ie Al‐SiCp type MMC, have gained popularity in the re‐cent past. In this competitive age, manufacturing industries strive to produce superior quality products at reasonable price. This is possible by achieving higher productivity while performing machining at optimum combinations of process variables. The low weight and high strength MMC are found suitable for variety of components

The Surface Plasmon Resonance of Supported Noble Metal Nanoparticles: Characterization, Laser Tailoring, and SERS Application

This work deals with the optical properties of supported noble metal nanoparticles, which are dominated by the so-called Mie resonance and are strongly dependent on the particles’ morphology. For this reason, characterization and control of the dimension of these systems are desired in order to optimize their applications. Gold and silver nanoparticles have been produced on dielectric supports like quartz glass, sapphire and rutile, by the technique of vapor deposition under ultra-high vacuum conditions. During the preparation, coalescence is observed as an important mechanism of cluster growth. The particles have been studied in situ by optical transmission spectroscopy and ex situ by atomic force microscopy. It is shown that the morphology of the aggregates can be regarded as oblate spheroids. A theoretical treatment of their optical properties, based on the quasistatic approximation, and its combination with results obtained by atomic force microscopy give a detailed characterization of the nanoparticles. This method has been compared with transmission electron microscopy and the results are in excellent agreement. Tailoring of the clusters’ dimensions by irradiation with nanosecond-pulsed laser light has been investigated. Selected particles are heated within the ensemble by excitation of the Mie resonance under irradiation with a tunable laser source. Laser-induced coalescence prevents strongly tailoring of the particle size. Nevertheless, control of the particle shape is possible. Laser-tailored ensembles have been tested as substrates for surface-enhanced Raman spectroscopy (SERS), leading to an improvement of the results. Moreover, they constitute reproducible, robust and tunable SERS-substrates with a high potential for specific applications, in the present case focused on environmental protection. Thereby, these SERS-substrates are ideally suited for routine measurements.

Model catalyst studies of the strong metal-support interaction: Surface structure identified by STM on Pd nanoparticles on TiO2(110)

Model catalysts of Pd nanoparticles and films on TiO2 (I 10) were fabricated by metal vapour deposition (MVD). Molecular beam measurements show that the particles are active for CO adsorption, with a global sticking probability of 0.25, but that they are deactivated by annealing above 600 K, an effect indicative of SMSI. The Pd nanoparticles are single crystals oriented with their (I 11) plane parallel to the surface plane of the titania. Analysis of the surface by atomic resolution STM shows that new structures have formed at the surface of the Pd nanoparticles and films after annealing above 800 K. There are only two structures, a zigzag arrangement and a much more complex "pinwheel" structure. The former has a unit cell containing 7 atoms, and the latter is a bigger unit cell containing 25 atoms. These new structures are due to an overlayer of titania that has appeared on the surface of the Pd nanoparticles after annealing, and it is proposed that the surface layer that causes the SMSI effect is a mixed alloy of Pd and Ti, with only two discrete ratios of atoms: Pd/Ti of 1: 1 (pinwheel) and 1:2 (zigzag). We propose that it is these structures that cause the SMSI effect. (c) 2005 Elsevier Inc. All rights reserved.

Purification and electron cryomicroscopy of coronavirus particles

Intact, enveloped coronavirus particles vary widely in size and contour, and are thus refractory to study by traditional structural means such as X-ray crystallography. Electron microscopy (EM) overcomes some problems associated with particle variability and has been an important tool for investigating coronavirus ultrastructure. However, EM sample preparation requires that the specimen be dried onto a carbon support film before imaging, collapsing internal particle structure in the case of coronaviruses. Moreover, conventional EM achieves image contrast by immersing the specimen briefly in heavy-metal-containing stain, which reveals some features while obscuring others. Electron cryomicroscopy (cryo-EM) instead employs a porous support film, to which the specimen is adsorbed and flash-frozen. Specimens preserved in vitreous ice over holes in the support film can then be imaged without additional staining. Cryo-EM, coupled with single-particle image analysis techniques, makes it possible to examine the size, structure and arrangement of coronavirus structural components in fully hydrated, native virions. Two virus purification procedures are described.

Silica coated noble metal nanoparticle hydrosols as supported catalyst precursors

Synthesis of well-defined nanoparticles has been intensively pursued not only for their fundamental scientific interest, but also for many technological applications. One important development of the nanomaterial is in the area of chemical catalysis. We have now developed a new aqueous-based method for the synthesis of silica encapsulated noble metal nanoparticles in controlled dimensions. Thus, colloid stable silica encapsulated similar to 5 nm platinum nanoparticle is synthesized by a multi-step method. The thickness of the silica coating could be controlled using a different amount of silica precursor. These particles supported on a high surface area alumina are also demonstrated to display a superior hydrogenation activity and stability against metal sintering after thermal activation.

Aerogel-coated metal nanoparticle colloids as novel entities for the synthesis of defined supported metal catalysts

Nanometer metal particles of tailored size (3-5 nm) and composition prepared via inverse microemulsion were encapsulated by ultrathin coatings (<2.5 nm) of inorganic porous aerogels covered with surface -OH groups. These composite materials formed metastable colloids in solvent(s), and the organic surfactant molecules were subsequently removed without leading to aggregation (the ethanolic colloid solution was shown to be stable against flocculation for at least weeks). We demonstrate that the totally inorganic-based composite colloids, after the removal of surfactant, can be anchored to conventional solid supports (gamma-alumina, carbons) upon mixing. Application of a high temperature resulted in the formation of strong covalent linkages between the colloids and the support because of the condensation of surface groups at the interface. Detailed characterizations (X-ray diffraction (XRD), pore analysis, transmission electron microscopy (TEM), CO chemisorption) and catalytic testing (butane combustion) showed that there was no significant metal aggregation from the fine metal particles individually coated with porous aerogel oxide. Most of these metal sites on the coated nanoparticles with and without support are fully accessible by small molecules hence giving extremely active metal catalysts. Thus, the product and technology described may be suitable to synthesize these precursor entities of defined metal sizes (as inks) for wash coat/impregnation applications in catalysis. The advantages of developing inorganic nanocomposite chemical precursors are also discussed.

Characterization of Metal and Trace Element Contents of Particulate Matter (PM10) Emitted by Vehicles Running on Brazilian FuelsHydrated Ethanol and Gasoline with 22% of Anhydrous Ethanol

Emission of fine particles by mobile sources has been a matter of great concern due to its potential risk both to human health and the environment. Although there is no evidence that one sole component may be responsible for the adverse health outcomes, it is postulated that the metal particle content is one of the most important factors, mainly in relation to oxidative stress. Data concerning the amount and type of metal particles emitted by automotive vehicles using Brazilian fuels are limited. The aim of this study was to identify inhalable particles (PM10) and their trace metal content in two light-duty vehicles where one was fueled with ethanol while the other was fueled with gasoline mixed with 22% of anhydrous ethanol (gasohol); these engines were tested on a chassis dynamometer. The elementary composition of the samples was evaluated by the particle-induced x-ray emission technique. The experiment showed that total emission factors ranged from 2.5 to 11.8 mg/km in the gasohol vehicle, and from 1.2 to 3 mg/km in the ethanol vehicle. The majority of particles emitted were in the fine fraction (PM2.5), in which Al, Si, Ca, and Fe corresponded to 80% of the total weight. PM10 emissions from the ethanol vehicle were about threefold lower than those of gasohol. The elevated amount of fine particulate matter is an aggravating factor, considering that these particles, and consequently associated metals, readily penetrate deeply into the respiratory tract, producing damage to lungs and other tissues.

Magnetic characterization of ferrihydrite nanoparticles synthesized by hydrolysis of Fe metal-organic precursor

We investigate the formation of ferrihydrite nanoparticles (NPs) by hydrolysis of the Fe(III) alkoxide Fe(O(t)Bu)(3). Controlled amounts of water, up to 3.0 vol%, were added to the precursor solution yielding a series of hydrolyzed samples ranging from P0.0 (the unreacted precursor) to P3.0. X-ray diffraction (XRD) analysis evidenced the formation of high-crystalline ferrihydrite NP in sample P3.0, with grain size estimate of about 3.2 nm. The transition from the molecular precursor to the formation of crystalline magnetic NPs was followed through magnetization measurements M(T) and M(H), as well as Mossbauer spectroscopy (MS). M(T) measurements indicate a paramagnetic (PM) behavior for sample P0.0, characteristic of binuclear Fe-O-Fe units, which evolves to a superparamagnetic (SPM) behavior, with an energy barrier for the blocking process estimated for sample P3.0 as E(a) = 4.9 x 10(-21) J (E(a)/k(B) = 355 K), resulting in a high effective anisotropy constant K(eff) = 290 kJ/m(3). Magnetization loops at 5 K progressively change from PM-like to ferromagnetic-like shape upon increasing the hydrolysis process, although hysteresis (H(c) approximate to 500 Oe) only is apparent for P2.0 and higher. MS spectra at room temperature are PM/SPM doublets for all samples, while the MS spectra at T = 4.2 K reveal increasingly well-defined magnetic ordering as hydrolysis of the precursor stepwise progresses until well-crystallized ferrihydrite particles are formed. (C) 2008 Elsevier B.V. All rights reserved.

Microstructural, Mechanical and Tribological Characterisation of CVD and PVD Coatings for Metal Cutting Applications

The present thesis focuses on characterisation of microstructure and the resulting mechanical and tribological properties of CVD and PVD coatings used in metal cutting applications. These thin and hard coatings are designed to improve the tribological performance of cutting tools which in metal cutting operations may result in improved cutting performance, lower energy consumption, lower production costs and lower impact on the environment.  In order to increase the understanding of the tribological behaviour of the coating systems a number of friction and wear tests have been performed and evaluated by post-test microscopy and surface analysis. Much of the work has focused on coating cohesive and adhesive strength, surface fatigue resistance, abrasive wear resistance and friction and wear behaviour under sliding contact and metal cutting conditions. The results show that the CVD deposition of accurate crystallographic phases, e.g. α-Al2O3 rather than κ-Al2O3, textures and multilayer structures can increase the wear resistance of Al2O3. However, the characteristics of the interfaces, e.g. topography as well as interfacial porosity, have a strong impact on coating adhesion and consequently on the resulting properties.  Through the deposition of well designed bonding and template layer structures the above problems may be eliminated. Also, the presence of macro-particles in PVD coatings may have a significant impact on the interfacial adhesive strength, increasing the tendency to coating spalling and lowering the surface fatigue resistance, as well as increasing the friction in sliding contacts. Finally, the CVD-Al2O3 coating topography influences the contact conditions in sliding as well as in metal cutting. In summary, the work illuminates the importance of understanding the relationships between deposition process parameters, composition and microstructure, resulting properties and tribological performance of CVD and PVD coatings and how this knowledge can be used to develop the coating materials of tomorrow.

Simulação computacional de medidas estereológicas em estruturas de metal duro (WC-Co)

This work focuses on the creation and applications of a dynamic simulation software in order to study the hard metal structure (WC-Co). The technological ground used to increase the GPU hardware capacity was Geforce 9600 GT along with the PhysX chip created to make games more realistic. The software simulates the three-dimensional carbide structure to the shape of a cubic box where tungsten carbide (WC) are modeled as triangular prisms and truncated triangular prisms. The program was proven effective regarding checking testes, ranging from calculations of parameter measures such as the capacity to increase the number of particles simulated dynamically. It was possible to make an investigation of both the mean parameters and distributions stereological parameters used to characterize the carbide structure through cutting plans. Grounded on the cutting plans concerning the analyzed structures, we have investigated the linear intercepts, the intercepts to the area, and the perimeter section of the intercepted grains as well as the binder phase to the structure by calculating the mean value and distribution of the free path. As literature shows almost consensually that the distribution of the linear intercepts is lognormal, this suggests that the grain distribution is also lognormal. Thus, a routine was developed regarding the program which made possible a more detailed research on this issue. We have observed that it is possible, under certain values for the parameters which define the shape and size of the Prismatic grain to find out the distribution to the linear intercepts that approach the lognormal shape. Regarding a number of developed simulations, we have observed that the distribution curves of the linear and area intercepts as well as the perimeter section are consistent with studies on static computer simulation to these parameters.

Stratified Sampling Applied to Estimation of the Volumetric Fraction of Alumina in Cast Metal Matrix Composites

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Analysis of Semi-solid Processing for Metal Matrix Composite Synthesis Using Factorial Design

The main goal in this work is to conduct a quantitative analysis of the mechanical stir casting process for obtaining particulate metal matrix composites. A combined route of stirring at semi-solid state followed by stirring at liquid state is proposed. A fractional factorial design was developed to investigate the influence and interactions of factors as: time, rotation, initial fraction and particle size, on the incorporated fraction. The best incorporations were obtained with all factors at high levels, as well as that very long stirring periods have no strong influence being particle size and rotation the most important factors on the incorporated fraction. Particle wetting occurs during stirring at semisolid state, highlighting the importance of the interactions between particles and the alloy globularized phase. The role of the alloying element Mg as a wettability-promoting agent is discussed. The shear forces resulting from the stirring system is emphasized and understood as the effect of rotation itself added to the propeller blade geometry.