Ceramic-metal reaction welding

In bonding ceramic oxides to metals, two reaction mechanisms have been utilized. These are (1) a surface or microscopic reaction, between close-packed ceramic oxides, quartz, and glasses and the noble metals (e.g. Pt, Pd, Au, Ag), maintaining a sharp discontinuity at the interface, (2) a bulk or macroscopic reaction between the same oxides and other transition metals (e.g. Fe, Co, Ni) producing a diffusional type interface. Both have common reaction conditions and occur: (a) below the melting point of the lowest melting component, (b) in any atmosphere compatible with all components at the operating temperature, (c) under little or no pressure, and (d) without deformation.The progress of several Type 1 reactions has been followed by direct observation at elevated temperatures and high resolution in a modified transmission electron microscope. It has thereby been established that this reaction proceeds with the formation of an intermediate phase, liquid-like at temperatures below the melting point of any of the components.Bonds have also been examined using electron scanning microscopy, electron probe microanalysis, and optical microscopy. Vacuum tight bonds can be produced and shear tests indicate that strength is generally limited by the strength of oxide components.     

The influence of source material composition on morphology and optical properties of ZnO nanostructures

We investigated the influence of the composition of the source materials on the morphology and optical properties of ZnO nanostructures. The source materials consisted of a mixture of ZnO and carbon, or ZnO, carbon, and another metal oxide (In2O3, MnO2, or V2O5). The addition of a different metal oxide to the source materials is a commonly used method to achieve doping and/or alteration of the morphology of ZnO nanostructures. For each metal oxide additive, we investigated the influence of different forms of carbon (graphite, carbon nanofibers, and single wall carbon nanotubes). Obtained nanostructures were studied using scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, selected area electron diffraction, and photoluminescence. The morphology and the optical properties of the obtained nanostructures were strongly dependent on the source material composition. Possible reasons for observed differences are discussed.     

Synthesis of Fe-group metal oxide nanostructures by thermal oxidation and their magnetic properties

In this paper, we review the preparation of Fe-group metal oxide nanostructures by the thermal oxidation method developed in our lab. By this method, we have prepared several kinds of nanostructures, including nanowires and nanoleaves. The magnetic properties of these nanostructures have also been studied. By carefully controlling the reacting time, temperature, and humidity, we have prepared alpha-Fe2O3, gamma-Fe2O3, Fe3O4, and Co3O4 nanowires and alpha-Fe2O3 nanoleaves by heating the substrates in proper atmosphere. The alpha-Fe2O3 and Co3O4 nanowires are produced by directly oxygenating pure metal at 550 to approximately 650 degrees C and 480-520 degrees C, separately. The gamma-Fe2O3 and Fe3O4 nanowires are produced by reducing as-prepared alpha-Fe2O3 nanowires in a mixture of N2 and H2. The nanowires are about 10-20 microm, with diameter of about 20 to approximately 100 nm. Most of the nanowire arrays are grown vertically from the surface of the substrate at a high surface density (10(8)-10(9) cm(-2)). Compared with the nanowires prepared by hydrothermal process and template method, Most of our nanowires are structurally uniform and single crystallites. The magnetic properties of these nanostructures are also studied, and demonstrate some novel properties.     

Metal catalyst adsorption effects in the growth of carbon nanostructures on mesoporous material

Mesoporous silica films were used as host for metal-based (Me = Fe, Co, Ni) nanoparticles via wet impregnation at pH = 5. A hydrogen ion beam was used to reduce the metallic oxide and hydroxides, previously detected by X-ray photoelectron spectroscopy, in metals. Chemical vapor deposition processes at three different conditions varying the acetylene-nitrogen proportion were performed on the mesoporous films decorated by different metal-based nanoparticles. The grown carbon nanostructures were characterized by high-resolution transmission electron microscopy and scanning electron microscopy. The ability to grow carbon nanostructures decreases in the following order: Fe > Co > Ni. When pure acetylene is used, iron allows to form graphene sheets around the metal catalyst like carbon nanocapsules, whereas cobalt allows to form structures that seem to be carbon nanotubes. Nitrogen leads to control the size and shape of carbon nanocapsules for iron catalyst and avoid the growth of such carbon nanotube-like structures for cobalt catalyst.     

Synthesis of core-shell nanostructures of Co3O4@SiO2 with controlled shell thickness (5-20 nm) and hollow shells of silica

Synthesis of uniform silica shell over Co3O4 nanoparticles was carried out using the colloidal solutions of Tergitol and cyclohexane. The shell could be controlled to a thickness of up to 20 nm by varying different parameters such as the amount of tetraethylorthosilicate, concentration of Co3O4 nanoparticles, reaction time and the presence of water and 1-octanol. Control of the amount of water (required for hydrolysis) appears to be the key factor for controlling the shell thickness. The methodology used is suitable to form shell over nanoparticles (present in powder form; synthesized at high temperature) which have high degree of agglomeration. Hollow shells of silica were obtained by the dissolution of the oxide core of Co3O4@SiO2 core-shell nanostructures. The composition of these core-shell nanostructures was confirmed by high-resolution transmission electron microscopy and elemental mapping by energy dispersive X-ray analysis. The hollow shells were characterized by using TEM, EDX and IR. Electron paramagnetic resonance studies of the core-shell nanostructures indicate the presence of free radicals on silica shell due to the presence of dangling bonds in the silica. Increase in the magnetic susceptibility was observed for these core-shell nanostructures.     

Filling single-wall carbon nanotubes with d- and f-metal chloride and metal nanowires

Nanowires of magnetic metals (Fe, Co, Ho, Gd) have been synthesized inside the hollow interiors of single-wall carbon nanotubes (SWNTs) by filling SWNTs with precursor metal chlorides and subsequent reduction. SWNTs have been filled by either the melt-phase sealed-tube reaction or a solution-phase method. Among the metal chlorides investigated in this study, HoCl3 and GdCl3 filled the SWNTs to a significantly higher extent. The nanowires have been imaged by transmission electron microscopy (TEM), high-resolution transmission electron microscopy, and scanning transmission electron microscopy (STEM). X-ray energy dispersive spectroscopy carried out in conjunction with TEM and STEM confirmed the presence of metal chloride and metal nanowires.     

Microstructure and optical properties of Ag-doped ZnO nanostructures prepared by a wet oxidation doping process

Silver-doped zinc oxide (Ag:ZnO) nanostructures were prepared by a facile and efficient wet oxidation method. This method included two steps: metallic Zn thin films mixed with Ag atoms were prepared by magnetron sputtering as the precursors, and then the precursors were oxidized in an O(2) atmosphere with water vapour present to form Ag:ZnO nanostructures. By controlling the oxidation conditions, pure ZnO and Ag:ZnO nanobelts/nanowires with a thickness of ～ 20 nm and length of up to several tens of microns were synthesized. Scanning electron microscopy, transmission electron microscopy, cathodoluminescence and low temperature photoluminescence (PL) measurements were adopted to characterize the microstructure and optical properties of the prepared samples. The results indicated that Ag doping during magnetron sputtering was a feasible method to tune the optical properties of ZnO nanostructures. For the Ag:ZnO nanostructures, the intensity of ultraviolet emission was increased up to three times compared with the pure ones. The detailed PL intensity variation with the increasing temperature is also discussed based on the ionization energy of acceptor in ZnO induced by Ag dopants.     

Fullerenes as precursors for nanocapsule formation

We have shown that Ni metal particles when melted in the presence of C₆₀ form graphitic layers around themselves with the Ni remaining as pure metal and without any evidence of carbide formation. We have successfully encapsulated particles over several orders of magnitude of size from ∼10 nm to several microns. The process has been observed taking place in real time using transmission electron microscopy (TEM). The process was not observed when graphite powder was used instead of C₆₀ powder and the Ni similarly heated to melting point, using the electron beam. Heating a mixture of Ni and C₆₀ powders together in a conventional manner also produced encapsulated Ni particles. This suggests that the encapsulation method is thermal in nature although the electron beam does offer the ability to control the process for individual particles. Further research has shown that the encapsulation process can also occur at temperatures as low as 800° C by a catalytic route. We have extended the work of heating a metal in the presence of fullerenes and have effectively encapsulated other metals such as Fe, Co, Ho, Cu and Au.     

A fine cobalt-toughened Al2O3-TiC ceramic and its wear resistance

Mechanical ball milling is the most common method for mixing ceramic powders with a ductile phase such as metal particles. In this paper, a new powder processing way is presented. Al2O3 and TiC powders are coated with a layer of metal cobalt using the chemical deposition process. The thickness of the metal cobalt film can be controlled by adjusting the deposition conditions. The Co-coated Al2O3 (Al2O3–Co) and TiC (Tic–Co) powders are mixed at the rate of 7:3 and hot-press sintered into a fine Al2O3–TiC–Co (ATC) ceramic. The main properties, erosion behaviour, abrasion behaviour, wear mechanism and wear resistance of Al2O3-TiC-Co and Al2O3–30 wt% TiC (AT30) ceramics are determined by transmission electron microscopy, scanning electron microscopy, energy dispersive X-ray spectroscopy, etc. It is shown that the ATC ceramic possesses improved mechanical properties. Because of the existence of metal cobalt in the grain boundaries, the bonding strength between grains is increased, and this prevents spalling of grains during wear. Experimentation indicates that ATC is more resistant to wear than Al2O3–TiC ceramic. The relationship between their mechanical properties and wear resistance is also discussed in this paper.     

Relative larvicidal property of common oxide nanostructures against Culex quinquefasciatus

Common oxide nanostructures such as silicon‐di‐oxide, magnesium‐oxide, zinc‐oxide, and copper‐oxide (CuO) having useful functional and bioactive properties have been synthesised and characterised. All these nanostructures have been found to be larvicidal towards Culex quinquefasciatus mosquito especially against lower instars in comparison with higher instars in 48 h. Only, CuO is larvicidal against late instar stages after 48 h. Moreover, CuO is larvicidal against first instar stages after 24 h (LC₅₀ 157 mg/l). However, none of these nanostructures are pupicidal. Post mortality larval morphology was found to be distorted under bright field microscopy and scanning electron microscopy images of affected larval surface appeared to be rough and uneven. Fluorescent images showed that nanostructures infiltrated inside visceral organs of larvae. Nanostructures also caused tissue oxidative stress in larvae. These results indicate that above stated oxide nanostructures are effective larvicidal agents against early instar stages of Culex larvae.Inspec keywords: biodegradable materials, oxidation, optical microscopy, fluorescence, cellular biophysics, biological tissues, diseases, scanning electron microscopy, toxicology, biological techniquesOther keywords: late instar stages, bright field microscopy, scanning electron microscopy images, tissue oxidative stress, oxide nanostructures, silicon‐dioxide, magnesium‐oxide, zinc‐oxide, copper‐oxide, functional properties, bioactive properties, larvicidal property, larvicidal agents, Culex quinquefasciatus mosquito, Culex larvae     

Hydrothermal synthesis of transition metal oxide nanomaterials in HEPES buffer solution

Various transition metal oxide (Co₃O₄, Mn₃O₄ and ZnO) nanostructures were readily synthesized in HEPES buffer solution (200 mmol/L, pH 7.40) via a simple hydrothermal method. The products were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED) and energy dispersive X-ray spectroscopy (EDX). It was found that the morphologies of the as-obtained transition metal oxide nanostructures were affected by the reaction temperature, HEPES/metal salt molar ratio and metal precursor. HEPES with two free nitrogen atoms (piperazine group) and terminal hydroxyl groups plays a critical role as a reactant and surfactant to prevent the transition metal oxide nanomaterials from aggregation.     

Fullerenes as precursors for nanocapsule formation

Abstract

We have shown that Ni metal particles when melted in the presence of C₆₀ form graphitic layers around themselves with the Ni remaining as pure metal and without any evidence of carbide formation. We have successfully encapsulated particles over several orders of magnitude of size from ～10 nm to several microns. The process has been observed taking place in real time using transmission electron microscopy (TEM). The process was not observed when graphite powder was used instead of C₆₀ powder and the Ni similarly heated to melting point, using the electron beam. Heating a mixture of Ni and C₆₀ powders together in a conventional manner also produced encapsulated Ni particles. This suggests that the encapsulation method is thermal in nature although the electron beam does offer the ability to control the process for individual particles. Further research has shown that the encapsulation process can also occur at temperatures as low as 800° C by a catalytic route. We have extended the work of heating a metal in the presence of fullerenes and have effectively encapsulated other metals such as Fe, Co, Ho, Cu and Au.     

Large-scale metal oxide nanostructures on template-patterned microbowls: A simple method for growth of hierarchical structures

Hierarchical structures-metal oxide nanostructures on desired patterns of metal oxide microbowls have been successfully fabricated by combining the unique advantages of two simple techniques: template assisted self-assembly technique by which polystyrene micro/nanospheres could be readily patterned and positioned on a large scale and hot-plate technique by which metal oxide nanostructures could be easily formed. Instead of using microspheres as mask to locate the catalyst for subsequent nanostructure growth, in this work we directly employed the patterned polystyrene microspheres as a template where the metal films (Fe, Cu, Zn and Co) were deposited and the hierarchical structures were formed subsequently by a one-step low temperature (250 °C-400 °C) heating process in atmosphere. With the feasibilities like patterning, positioning and fabricating the hierarchical structures with large surface area, this simple and practical method exhibits potentials for the synthesis of a unique building block: nanostructures on the desired patterns of micro/nanobowls, for future nanoscience and nanotechnology.     

Controlled synthesis of germanium nanowires and nanotubes with variable morphologies and sizes

We report on the controlled growth of germanium (Ge) nanostructures in the form of both nanowire (NW) and nanotube (NT) with ultrahigh aspect ratios and variable diameters. The nanostructures are grown inside a porous anodic aluminum oxide (AAO) template by low-temperature chemical vapor deposition (CVD) assisted by an electrodeposited metal nanorod catalyst. Depending on the choice of catalytic metals (Au, Ni, Cu, Co) and germane (GeH(4)) concentration during CVD, either Ge NWs or NTs can be synthesized at low growth temperatures (310-370 °C). Furthermore, Ge NWs and NTs with two or more branches can be grown from the same stem while using AAO with branched channels as templates. Transmission electron microscopy studies show that NWs are single crystalline and that branches grow epitaxially from the stem of NWs with a crystalline direction independent of diameter. As-grown NTs are amorphous but can crystallize via postannealing at 400 °C in Ar/H(2) atmosphere, with a wall thickness controllable between 6 and 18 nm in the CVD process. The yield and quality of the NTs are critically dependent on the choice of the catalyst, where Ni appears the best choice for Ge NT growth among Ni, Cu, Co, and Au. The synthesis of structurally uniform and morphologically versatile Ge nanostructures may open up new opportunities for integrated Ge-nanostructure-based nanocircuits, nanodevices, and nanosystems.     

Synthesis of Fe(2)O(3)/TiO(2) nanorod-nanotube arrays by filling TiO(2) nanotubes with Fe

Synthesis of hematite (α-Fe(2)O(3)) nanostructures on a titania (TiO(2)) nanotubular template is carried out using a pulsed electrodeposition technique. The TiO(2) nanotubes are prepared by the sonoelectrochemical anodization method and are filled with iron (Fe) by pulsed electrodeposition. The Fe/TiO(2) composite is then annealed in an O(2) atmosphere to convert it to Fe(2)O(3)/TiO(2) nanorod-nanotube arrays. The length of the Fe(2)O(3) inside the TiO(2) nanotubes can be tuned from 50 to 550?nm by changing the deposition time. The composite material is characterized by scanning electron microscopy, transmission electron microscopy and diffuse reflectance ultraviolet-visible studies to confirm the formation of one-dimensional Fe(2)O(3)/TiO(2) nanorod-nanotube arrays. The present approach can be used for designing variable one-dimensional metal oxide heterostructures.     

pH‐Dependent Galvanic Replacement of Supported and Colloidal Cu2O Nanocrystals with Gold and Palladium

Galvanic replacement reactions (GRRs) on nanoparticles (NPs) are typically performed between two metals, i.e., a solid metal NP and a replacing salt solution of a more noble metal. The solution pH in GRRs is commonly considered an irrelevant parameter. Yet, the solution pH plays a major role in GRRs involving metal oxide NPs. Here, Cu₂O nanocrystals (NCs) are studied as galvanic replacement (GR) precursors, undergoing replacement by gold and palladium, with the resulting nanostructures showing a strong dependence on the pH of the replacing metal salt solution. GRRs are reported for the first time on supported (chemically deposited) oxide NCs and the results are compared with those obtained with corresponding colloidal systems. Control of the pH enables production of different nanostructures, from metal‐decorated Cu₂O NCs to uniformly coated Cu₂O‐in‐metal (Cu₂O@Me) core–shell nanoarchitectures. Improved metal nucleation efficiencies at low pHs are attributed to changes in the Cu₂O surface charge resulting from protonation of the oxide surface. GR followed by etching of the Cu₂O cores provides metal nanocages that collapse upon drying; the latter is prevented using a sol–gel silica overlayer stabilizing the metal nanocages. Metal‐replaced Cu₂O NCs and their corresponding stabilized nanostructures may be useful as photocatalysts, electrocatalysts, and nanosensors.     

Cu2O-Au nanocomposites with novel structures and remarkable chemisorption capacity and photocatalytic activity

The decomposition of CuH nanoparticles in aqueous solution has been successfully developed as a novel method for the preparation of Cu₂O nanoparticles. In particular, we found that the decomposition of CuH nanoparticles in aqueous solution could be catalyzed by Au colloids, forming Cu₂O-Au nanocomposites. The composition and structure of the resulting Cu₂O-Au nanocomposites have been characterized in detail by inductively coupled plasma atomic emission spectroscopy, powder X-ray diffraction, N₂ adsorption-desorption isotherms, infrared spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy and transmission electron microscopy. Their visible-light-driven photocatalytic activity toward various dye molecules has also been investigated. Depending on the Au:Cu ratio, Cu₂O-Au nanocomposites exhibit different novel nanostructures including a beautiful flower-like nanostructure that consists of polycrystalline Cu₂O, amorphous Cu₂O and Au colloids. We propose that the rapidly-generated bubbles of H₂ during the course of the catalytic decomposition reaction drive the simultaneously-formed Cu₂O to form amorphous curved thin foils and might also act as a template to assemble curved thin foils of amorphous Cu₂O, polycrystalline Cu₂O and Au colloids into uniform nanostructures. A Cu₂O-Au nanocomposite with a Cu:Au ratio of 40 exhibits remarkable chemisorption capacity and visible-light-driven photocatalytic activity towards methyl orange and acid orange 7 and is a promising chemisorption-photocatalysis integrated catalyst. The catalytic decomposition of the metal hydride might open up a new approach for the fabrication of other metal/metal oxide nanocomposites with novel nanostructures and properties.      

Morphological transformations induced by Co impurity in ZnO nanostructures prepared by rf-sputtering and their physical properties

Growth of uniform and vertically well aligned nanorods is a difficult process and becomes more complicated in case of ZnO nanorods on silicon (Si) substrate due to thermal instability of the Si substrate and large lattice mismatch (~?40%) between the substrate and the ZnO nanorods array. Growth of ZnO nanorods assisted by metal ion via rf-sputtering is a good technique; however, it needs many parameters to be controlled for desired growth and morphology of nanostructures. In this work, we report the morphological transformations of ZnO nanostructured thin film by simply controlling the concentration of Cobalt (Co) impurity in sputtering target. With the introduction of Co ions in ZnO matrix, the initial coalescence grain structure (pyramidal morphology) changes into columnar grains and as the concentration of Co ions increases further, a highly oriented ZnO nanorods array is obtained. The possible mechanism with the help of schematic diagram is also proposed for the morphological transformation of ZnO nanostructures. The vertically aligned nanorods show good optical properties as well as robust ferromagnetism at room temperatures. It has also been observed that with the dopant conc. increasing there was a significant decrease in the band gap energy. The structure and morphology of rf-sputtered nanostructured thin films were investigated by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy and selected area electron diffraction. Interestingly, with Co conc. increasing in ZnO matrix results in decreasing LO modes in Raman spectroscopy. It can have strong influence on the magnetic properties of the material. The good optical and strong ferromagnetic properties of the ZnO nanorods, suggest its possible applications in the fields of lasers, spintronics and medical applications.     

Simple and efficient biomimetic synthesis of Mn3O4 hierarchical structures and their application in water treatment

Biotemplate synthesis of functional materials is interesting owing to low cost, high yield and easy way of preparation. Recently, we have developed a simple and cost effective biomimetic synthesis of hierarchical network like nanostructures of manganese oxide (Mn3O4). Readily available eggshell membrane with nucleating and capping sites were used as a template in our synthesis. The prepared material was characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray (EDX) analysis and X-ray Diffraction (XRD). The surface area was calculated using the Brunauer-Emmett-Teller (BET) theory, and pore size distribution was obtained by Barrett-Joyner-Helenda (BJH) method. The prepared Mn3O4 showed good ability to remove organic pollutants from water and expected to be useful in effluent treatment in textile industry.     

Dopant induced bandgap narrowing in Y-doped zinc oxide nanostructures

In this report, hydrothermal synthesis and the absorption properties of the cubic shaped zinc oxide nanostructures doped with different amount of yttrium (Y) metal cation (0 to 15 at.%) are demonstrated. The structural and optical properties of chemically synthesized pure and Y doped ZnO powders are investigated by using powder X-ray diffraction (XRD), field emission scanning electron spectroscopy (FESEM) and transmission electron microscopy (TEM), ultraviolet-visible (UV-vis) absorbance, photoluminescence (PL), and Fourier transform infra-red spectroscopy (FT-IR). It is found that the dopant ions stabilize in wurtzite hexagonal phase of ZnO upto the concentration of less than 6 at.%, which is mainly due to the fact that the ZnO lattice expands and the optical bandgap energy decreases at this level. Increasing the dopant concentration to greater than 6 at.% leads to a contraction of the lattice, which in turn produces a significant structural disorder evidenced by shift in the XRD peaks due to additional interstitial incorporation of Y. The vibrational modes of the metal oxide groups have been identified from the IR transmission spectra. The optical absorption results show that the optical bandgap energy of Y:ZnO nanocrystals is much less as compared to that of the pure bulk ZnO particles. Doping ZnO with trivalent Y produces excess number of electrons in the conduction band and thus, shifts the absorption edge and narrows down to 80 meV approximately. PL spectra are used to study the dependence of doping on the deep-level emission, which show an enhanced blue emission after Y doping. The existence of near band edge (NBE) emission and blue emission, related to zinc interstitials are observed in the luminescence spectra of Zn(1-x)Y(x)O nanostructures.