Energy-efficient synthesis of ferrite powders and films

In recent years, there has been significant effort in the synthesis of nanocrystalline spinel ferrites due to their unique properties. Among them, zinc ferrite has been widely investigated for countless applications. As traditional ferrite synthesis methods are energy- and time-intensive, there is need for a resource-effective process that can prepare ferrites quickly and efficiently without compromising material quality. We report on a novel microwave-assisted soft-chemical synthesis technique in the liquid medium for synthesis of ZnFe2O4 powder below 100 °C, within 5 min. The use of β-diketonate precursors, featuring direct metal-to-oxygen bonds in their molecular structure, not only reduces process temperature and duration sharply, but also leads to water-soluble and non-toxic by-products. As synthesized powder is annealed at 300 °C for 2 hrs in a conventional anneal (CA) schedule. An alternative procedure, a 2-min rapid anneal at 300 °C (RA) is shown to be sufficient to crystallize the ferrite particles, which show a saturation magnetization (MS) of 38 emu/g, compared with 39 emu/g for a 2-hr CA. This signifies that our process is efficient enough to reduce energy consumption by ∼85% just by altering the anneal scheme. Recognizing the criticality of anneal process to the energy budget, a more energy-efficient variation of the reaction process was developed, which obviates the need for post-synthesis annealing altogether. It is shown that the process also can be employed to deposit crystalline thin films of ferrites.

Resonance raman detection and estimation in the aqueous phase using water dispersible cyclodextrin: reduced-graphene oxide sheets

Resonance Raman spectroscopy is a powerful analytical tool for detecting and identifying analytes, but the associated strong fluorescence background severely limits the use of the technique. Here, we show that by attaching beta-cyclodextrin (beta-CD) cavities to reduced graphene-oxide (rGO) sheets we obtain a water dispersible material (beta-CD: rGO) that combines the hydrophobicity associated with rGO with that of the cyclodextrin cavities and provides a versatile platform for resonance Raman detection. Planar aromatic and dye molecules that adsorb on the rGO domains and nonplanar molecules included within the tethered beta-CD cavities have their fluorescence effectively quenched. We show that it is possible using the water dispersible beta-CD: rGO sheets to record the resonance Raman spectra of adsorbed and included organic chromophores directly in aqueous media without having to extract or deposit on a substrate. This is significant, as it allows us to identify and estimate organic analytes present in water by resonance Raman spectroscopy.

Experimental Studies on the Kinematics of Cutting in Granular Materials

Slow flow in granular materials is characterized by high solid fraction and sustained inter-particle interaction. The kinematics of trawling or cutting is encountered in processes such as locomotion of organisms in sand; trawl gear movement on a soil deposit; plow movement; movement of rovers, earth moving equipment etc. Additionally, this configuration is very akin to shallow drilling configuration encountered in the mining and petroleum industries. An experimental study has been made in order to understand velocity and deformation fields in cutting of a model rounded sand. Under nominal plane strain conditions, sand is subjected to orthogonal cutting at different tool-rake angles. High-resolution optical images of the region of cutting were obtained during the flow of the granular ensemble around the tool. Interesting kinematics underlying the formation of a chip and the evolution of the deformation field is seen in these experiments. These images are also analyzed using a PIV algorithm and detailed information of the deformation parameters such as velocity, strain rate and volume change is obtained.

RF plasma MOCVD of Y2O3 thin films: Effect of RF self-bias on the substrates during deposition

Yttrium oxide (Y203) thin films have been deposited by radio frequency plasma assisted metal organic chemical vapor deposition (MOCVD) process using (2,2,6,6-tetramethy1-3,5-heptanedionate) yttrium (commonly known as Y(thd)3) precursor in a plasma of argon and oxygen gases at a substrate temperature of 350 C. The films have been deposited under influence of varying RF self-bias (-50 V to 175 V) on silicon, quartz, stainless steel and tantalum substrates. The deposited coatings are characterized by glancing angle X-ray diffraction (GIXRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), spectroscopic ellipsometry and scanning electron microscopy (SEM). GIXRD and FTIR results indicate deposition of Y2 03 (BCC structure) in all cases. However, XPS results indicate nonstoichiometric cubic phase deposition on the surface of deposited films. The degree of nonstoichiometry varies with bias during deposition. Ellipsometry results indicate that the refractive index for the deposited films is varying from 1.70 to 1.83 that is typical for Y203. All films are transparent in the investigated wavelength range 300-1200 nm. SEM results indicate that the microstructure of the films is changing with applied bias. Results indicate that it is possible to deposit single phase cubic Y203 thin films at low substrate temperature by RF plasma MOCVD process. RF self-bias that decides about the energy of impinging ions on the substrates plays an important role in controlling the texture of deposited Y203 films on the substrates. Results indicate that to control the structure of films and its texture, it is important to control the bias on the substrate during deposition. The films deposited at high bias level show degradation in the crystallinity and reduction of thickness. (C) 2013 Elsevier B.V. All rights reserved.

Morphological and electrochemical characterization of electrodeposited Zn-Ag nanoparticle composite coatings

Silver nanoparticles with an average size of 23 nm were chemically synthesized and used to fabricate Zn-Ag composite coatings. The Zn-Ag composite coatings were generated by electrodeposition method using a simple sulfate plating bath dispersed with 0.5, land 1.5 g/l of Ag nanoparticles. Scanning electron microscopy, X-ray diffraction and texture co-efficient calculations revealed that Ag nanoparticles appreciably influenced the morphology, micro-structure and texture of the deposit. It was also noticed that agglomerates of Ag nanopartides, in the case of high bath load conditions, produced defects and dislocations on the deposit surface. Ag nanoparticles altered the corrosion resistance property of Zn-Ag composite coatings as observed from Tafel polarization, electrochemical impedance analysis and an immersion test. Reduction in corrosion rate with increased charge transfer resistance was observed for Zn-Ag composite coatings when compared to a pure Zn coating. However, the particle concentration in the plating bath and their agglomeration state directly influenced the surface morphology and the subsequent corrosion behavior of the deposits. (C) 2013 Elsevier Inc. All rights reserved.

Using an Office Inkjet Printer to Define the Formation of Copper Films on Paper

A low-cost fabrication process for forming conductive copper lines on paper is presented. An office inkjet printer was used to deposit desired patterns of silver nitrate and tannic acid solutions sequentially on paper. Silver nitrate was instantaneously reduced in situ on paper by tannic acid at room temperature to form silver nanoparticles, which acted as catalysts for the subsequent electroless deposition of copper. The copper films were 1.8 mu m thick, and the sheet resistance of the copper film on paper was 9 Omega/square. A dual monopole ultrawide band antenna was fabricated on paper and its performance was equivalent to that of a similar antenna fabricated on a copper-film covered Kapton substrate using conventional lithographic processes. The paper-based conductive copper films fabricated using the facile process presented herein will aid the development of low-cost flexible circuits and sensors.

A method for predicting the consolidated undrained bearing capacity of shallow foundations

The effect of consolidation on the undrained bearing capacity of both rough and smooth strip and circular surface foundations is investigated, examining the influence of the magnitude and duration of an applied preload and the initial over-consolidation ratio of the deposit. The investigation comprised small strain finite-element analysis, with the soil response represented by Modified Cam Clay. The results are distilled into dimensionless and generalised forms, from which simple trends emerge. Based on these results, a simple method for predicting the consolidated undrained bearing capacity is proposed.

Precision control of drying using rhythmic dancing of sessile nanoparticle laden droplets

This work analyses the unique spatio-temporal alteration of the deposition pattern of evaporating nanoparticle laden droplets resting on a hydrophobic surface through targeted low frequency substrate vibrations. External excitation near the lowest resonant mode (n = 2) of the droplet initially de-pins and then subsequently re-pins the droplet edge creating pseudo-hydrophilicity (low contact angle). Vibration subsequently induces droplet shape oscillations (cyclic elongation and flattening) resulting in strong flow recirculation. This strong radially outward liquid flow augments nanoparticle transport, vaporization, and agglomeration near the pinned edge resulting in much reduced drying time under certain characteristic frequency of oscillations. The resultant deposit exhibits a much flatter structure with sharp, defined peripheral wedge topology as compared to natural drying. Such controlled manipulation of transport enables tailoring of structural and topological morphology of the deposits and offers possible routes towards controlling the formation and drying timescales which are crucial for applications ranging from pharmaceutics to surface patterning. (C) 2014 AIP Publishing LLC.

Biomechanics of substrate boring by fig wasps

Female insects of diverse orders bore into substrates to deposit their eggs. Such insects must overcome several biomechanical challenges to successfully oviposit, which include the selection of suitable substrates through which the ovipositor can penetrate without itself fracturing. In many cases, the insect may also need to steer and manipulate the ovipositor within the substrate to deliver eggs at desired locations before rapidly retracting her ovipositor to avoid predation. In the case of female parasitoid ichneumonid wasps, this process is repeated multiple times during her lifetime, thus testing the ability of the ovipositioning apparatus to endure fracture and fatigue. What specific adaptations does the ovipositioning apparatus of a female ichneumonoid wasp possess to withstand these challenges? We addressed this question using a model system composed of parasitoid and pollinator fig wasps. First, we show that parasitoid ovipositor tips have teeth-like structures, preferentially enriched with zinc, unlike the smooth morphology of pollinator ovipositors. We describe sensillae present on the parasitoid ovipositor tip that are likely to aid in the detection of chemical species and mechanical deformations and sample microenvironments within the substrate. Second, using atomic force microscopy, we show that parasitoid tip regions have a higher modulus compared with regions proximal to the abdomen in parasitoid and pollinator ovipositors. Finally, we use videography to film wasps during substrate boring and analyse buckling of the ovipositor to estimate the forces required for substrate boring. Together, these results allow us to describe the biomechanical principles underlying substrate boring in parasitoid ichneumonid wasps. Such studies may be useful for the biomimetic design of surgical tools and in the use of novel mechanisms to bore through hard substrates.

In situ formation of silver nanowire networks on paper

Simple, universally adaptable techniques for fabricating conductive patterns are required to translate laboratory-scale innovations into low-cost solutions for the developing world. Silver nanostructures have emerged as attractive candidates for forming such conductive patterns. We report here the in situ formation of conductive silver-nanowire networks on paper, thereby eliminating the need for either cost-intensive ink formulation or substrate preparation or complex post-deposition sintering steps. Reminiscent of the photographic process of `salt printing', a desktop office printer was used to deposit desired patterns of silver bromide on paper, which were subsequently exposed to light and then immersed in a photographic developer. Percolating silver nanowire networks that conformally coated the paper fibres were formed after 10 min of exposure to light from a commercial halogen lamp. Thus, conductive and patterned films with sheet resistances of the order of 4 Omega/rectangle can be easily formed by combining two widely used processes - inkjet printing and photographic development.

Enhancement of Corrosion Resistance of Zinc Coatings Using Green Additives

In the present work, morphology, microstructure, and electrochemical behavior of Zn coatings containing non-toxic additives have been investigated. Zn coatings were electrodeposited over mild steel substrates using Zn sulphate baths containing four different organic additives: sodium gluconate, dextrose, dextrin, and saccharin. All these additives are ``green'' and can be derived from food contents. Morphological and structural characterization using electron microscopy, x-ray diffraction, and texture co-efficient analysis revealed an appreciable alteration in the morphology and texture of the deposit depending on the type of additive used in the Zn plating bath. All the Zn coatings, however, were nano-crystalline irrespective of the type of additive used. Polarization and electrochemical impedance spectroscopic analysis, used to investigate the effect of the change in microstructure and morphology on corrosion resistance behavior, illustrated an improved corrosion resistance for Zn deposits obtained from plating bath containing additives as compared to the pure Zn coatings.

Breeding in bamboo: a novel anuran reproductive strategy discovered in Rhacophorid frogs of the Western Ghats, India

Amphibians exhibit extraordinarily diverse sets of reproductive strategies among vertebrates. Understanding life history strategies in an evolutionary framework is lacking for many amphibian species in the tropics. Here, we report a novel reproductive mode where adult frogs enter hollow internodes of bamboo via a small opening, deposit direct developing eggs, and provide parental care. This behaviour is observed in two species of the frog genus Raorchestes. The first description of this unique life history and details of nest site characteristics and embryo development are provided along with ecological comparisons. Evolution of novel reproductive modes and parental care are discussed in context of natural selection. Dearth of natural history information on amphibians in the Western Ghats and much of the South-East Asian region is highlighted with suggestions for further studies.(c) 2014 The Linnean Society of London, Biological Journal of the Linnean Society, 2014, 114, 1-11.

Deployment strategy for controlled morphologies in sessile, mixed colloidal droplets

Colloidal systems offer an effective medium to micro-engineer complex structures without involving sophisticated fabrication procedures. This article presents a deployment strategy of multiple droplets of different colloidal composition and utilizes the inherent capillary flow driven self assembly of nanoparticles to construct stacks of multiple materials on a given glass substrate. Here we used aqueous nano-crystalline titania and nano-amorphous silica solutions as the two materials. Initially, a pure nanotitania (nanosilica) droplet is deployed and allowed to dry partially. Subsequently, a second droplet of pure nanosilica (nanotitania) is deployed co-axially on the partially dried precipitate. The proposed deployment strategy allowed significant morphological differences when the deployment order of nanosilica and nanotitania were interchanged. Compositional analysis performed using EDX (Energy Dispersive X-ray spectroscopy) showed preferential deposition of nanosilica and nanotitania along the radial as well as the axial plane of the final deposit pattern. The underlying mechanism for such a phenomenon could be attributed to the contact line dynamics of a sessile double droplet. We also observe heteroaggregation of the nanosilica-nanotitania interaction along a narrow interface which resulted in nanotitania particles clustering into isolated islands embedded into a matrix of nanosilica particles. Overall, this work elucidates the evaporation driven dynamics of a mixed colloidal system which displays both macroscopic as well as microscopic phenomena. Such a system could be used to generate ordered arrays of functional materials with engineered micro to nano-scale properties.

Effect of W addition on the electrical switching of VO2 thin films

Vanadium Oxide has been a frontrunner in the field of oxide electronics because of its metal-insulator transition (MIT). The interplay of different structures of VO2 has played a crucial role in deciding the magnitude of the first order MIT. Substitution doping has been found to introduce different polymorphs of VO2. Hence the role of substitution doping in stabilizing the competing phases of VO2 in the thin film form remains underexplored. Consequently there have been reports both discounting and approving such a stabilization of competing phases in VO2. It is reported in the literature that the bandwidth of the hysteresis and transition temperature of VO2 can be tuned by substitutional doping of VO2 with W. In this work, we have adopted a novel technique called, Ultrasonic Nebulized Spray Pyrolysis of Aqueous Combustion Mixture (UNSPACM) to deposit VO2 and W- doped VO2 as thin films. XRD and Raman spectroscopy were used to investigate the role of tungsten on the structure of VO2 thin films. Morphology of the thin films was found to be consisting of globular and porous nanoparticles of size similar to 20nm. Transition temperature decreased with the addition of W. We found that for 2.0 at % W doping in VO2, the transition temperature has reduced from 68 degrees C to 25 degrees C. It is noted that W-doping in the process of reducing the transition temperature, alters the local structure and also increases room temperature carrier concentration. (c) 2016 Author(s).