Spark plasma sintering of novel ZrB2-SiC-TiSi2 composites with better mechanical properties

We report here the development of ultrafine grained ZrB2-SiC composites using TiSi2 as the sintering aid and spark plasma sintering (SPS) as the processing technique. It was observed that the presence of TiSi2 improved the sinterability of the composites, such that near theoretical densification (99.9%) could be achieved for ZrB2-18 wt.% SiC-5 wt.% TiSi2 composites after SPS at 1600 degrees C for 10 min at 50 MPa. Use of innovative multi stage sintering (MSS) route, which involved holding the samples at lower (intermediate) temperatures for some time before holding at the final temperature, while keeping the net holding time to 10 min, allowed attainment of full densification of ZrB2-18 wt.% SiC-2.5 wt.% TiSi2 at a still lower final temperature of 1500 degrees C at 30 MPa. TEM observations, which revealed the presence of anisotropic ZrB2 grains with faceted grain boundaries and TiSi2 at the intergranular regions, suggested the occurrence of liquid phase sintering in the presence of TiSi2. No additional phase was detected in XRD as well as TEM, which confirmed the absence of any sintering reaction. The as developed composites possessed an excellent combination of Vickers hardness and indentation toughness, both of which increased with increase in TiSi2 content, such that the ZrBi2-18 wt.% SiC-5 wt.% TiSi2 (SPS processed at 1600 degrees C) possessed hardness of similar to 20 GPa and indentation toughness of similar to 5 MPa m(1/2). The use of MSS SPS at 1500 degrees C for ZrBi2-18 wt.% SiC-2.5 wt.% TiSi2 composite resulted in improvement in hardness of up to similar to 27 GPa and attainment of high flexural strength of similar to 455 MPa. (C) 2011 Elsevier B.V. All rights reserved.

Defect-Free Hyperbranched Polydithioacetal via Melt Polymerization

Degree of branching (DB) describes the level of structural perfection of a hyperbranched polymer when compared to its defect-free analogue, namely the dendrimer. The strategy most commonly used to achieve high DB values, specifically while using AB(2) type self-condensations, is to design an AB2 monomer wherein the reaction of the first B-group leads to an enhancement of the reactivity of the second one. In the present study, we show that an AB2 monomer carrying a dimethylacetal unit and a thiol group undergoes a rapid self-condensation in the melt under acid-catalysis to yield a hyperbranched polydithioacetal with no linear defects. NMR studies using model systems reveal that the intermediate monothioacetal is relatively unstable under the polymerization conditions and transforms rapidly to the dithioacetal; because this second step occurs irreversibly during polymer formation, it leads to a defect-free hyperbranched polydithioacetal. TGA studies of the polymerization process provided some valuable insights into the kinetics of polymerization. An additional virtue of this approach is that the numerous terminal dimethylacetal groups are very labile and can be quantitatively transformed by treatment with a variety of functional thiols; the terminal dimethylacetals were, thus, reacted with various thiols, such as dodecanethiol, benzyl mercaptan, ethylmercaptopropionate, and so on, to demonstrate the versatility of these systems as sulfur-rich hyperscaffolds to anchor different kinds of functionality on their periphery.

Carrier concentration dependence of donor activation energy in n-type GaN epilayers grown on Si (111) by plasma-assisted MBE

The n-type GaN layers were grown by plasma-assisted MBE and either intentionally doped with Si or unintentionally doped. The optical characteristics of a donor level in Si-doped, GaN were studied in terms of photoluminescence (PL) spectroscopy as a function of electron concentration. Temperature dependent PL measurements allowed us to estimate the activation energy of a Si-related donor from temperature-induced decay of PL intensity. PL peak positions, full width at half maximum of PL and activation energies are found to be proportional to the cube root of carrier density. The involvement of donor levels is supported by the temperature-dependent electron concentration measurements. (C) 2012 Elsevier Ltd. All rights reserved.

Valence band offset at GaN/beta-Si3N4 and beta-Si3N4/Si(111) heterojunctions formed by plasma-assisted molecular beam epitaxy

Ultra thin films of pure beta-Si3N4 (0001) were grown on Si (111) surface by exposing the surface to radio- frequency nitrogen plasma with a high content of nitrogen atoms. Using beta-Si3N4 layer as a buffer layer, GaN epilayers were grown on Si (111) substrate by plasma-assisted molecular beam epitaxy. The valence band offset (VBO) of GaN/beta-Si3N4/ Si heterojunctions is determined by X-ray photoemission spectroscopy. The VBO at the beta-Si3N4 /Si interface was determined by valence-band photoelectron spectra to be 1.84 eV. The valence band of GaN is found to be 0.41 +/- 0.05 eV below that of beta-Si3N4 and a type-II heterojunction. The conduction band offset was deduced to be similar to 2.36 eV, and a change of the interface dipole of 1.29 eV was observed for GaN/ beta-Si3N4 interface formation. (c) 2011 Elsevier B.V. All rights reserved.

Realization of thermally durable close-packed 2D gold nanoparticle arrays using self-assembly and plasma etching

Realization of thermally and chemically durable, ordered gold nanostructures using bottom-up self-assembly techniques are essential for applications in a wide range of areas including catalysis, energy generation, and sensing. Herein, we describe a modular process for realizing uniform arrays of gold nanoparticles, with interparticle spacings of 2 nm and above, by using RF plasma etching to remove ligands from self-assembled arrays of ligand-coated gold nanoparticles. Both nanoscale imaging and macroscale spectroscopic characterization techniques were used to determine the optimal conditions for plasma etching, namely RF power, operating pressure, duration of treatment, and type of gas. We then studied the effect of nanoparticle size, interparticle spacing, and type of substrate on the thermal durability of plasma-treated and untreated nanoparticle arrays. Plasma-treated arrays showed enhanced chemical and thermal durability, on account of the removal of ligands. To illustrate the application potential of the developed process, robust SERS (surface-enhanced Raman scattering) substrates were formed using plasma-treated arrays of silver-coated gold nanoparticles that had a silicon wafer or photopaper as the underlying support. The measured value of the average SERS enhancement factor (2 x 10(5)) was quantitatively reproducible on both silicon and paper substrates. The silicon substrates gave quantitatively reproducible results even after thermal annealing. The paper-based SERS substrate was also used to swab and detect probe molecules deposited on a solid surface.

Sliding wear behavior of plasma nitrided Austenitic Stainless Steel Type AISI 316LN in the temperature range from 25 to 400 degrees C at 10(-4) bar

There is a research knowledge gap for the dry wear data of nitride treated Stainless Steel in high temperature and high vacuum environment. In order to fill this gap, plasma nitriding was done on austenitic Stainless Steel type AISI 316LN (316LN SS) and dry sliding wear tests have been conducted at 25 degrees C, 200 degrees C and 400 degrees C in high vacuum of 1.6 x 10(-4) bar. The two different slider material (316LN SS and Colmonoy) and two different sliding speeds (0.0576 m/s and 0.167 m/s) have been used. The tribological parameters such as friction coefficient, wear mechanism and volume of metal loss have been evaluated. Scanning Electron Microscopy (SEM) was used to study the surface morphology of the worn pins and rings. Electronic balancing machine was used to record the mass of metal loss during wear tests. The 2D optical profilometer was used to measure the depth of the wear track. The Plasma Nitride treated 316LN SS rings (PN rings) exhibit excellent wear resistance against 316LN SS pin and Colmonoy pin at all temperatures. However, PN ring vs. Colmonoy pin Pair shows better wear resistance than PN ring vs. 316LN SS pin Pair at higher temperature. (C) 2012 Elsevier B.V. All rights reserved.

Synthesis and characterization of nano silicon and titanium nitride powders using atmospheric microwave plasma technique

We have demonstrated a simple, scalable and inexpensive method based on microwave plasma for synthesizing 5 to 10 g/h of nanomaterials. Luminescent nano silicon particles were synthesized by homogenous nucleation of silicon vapour produced by the radial injection of silicon tetrachloride vapour and nano titanium nitride was synthesized by using liquid titanium tetrachloride as the precursor. The synthesized nano silicon and titanium nitride powders were characterized by XRD, XPS, TEM, SEM and BET. The characterization techniques indicated that the synthesized powders were indeed crystalline nanomaterials.

In Situ Electrochemical Polymerization at Air-Water Interface: Surface-Pressure-Induced, Graphene-Oxide-Assisted Preferential Orientation of Polyaniline

In situ electrochemical polymerization of aniline in a Langmuir trough under applied surface pressure assists in the preferential orientation of polyaniline (PANI) in planar polaronic structure. Exfoliated graphene oxide (EGO) spread on water surface is used to bring anilinium cations present in the subphase to air-water interface through electrostatic interactions. Subsequent electrochemical polymerization of aniline under applied surface pressure in the Schaefer mode results in EGO/PANT composite with PANT in planar polaronic form. The orientation of PANI is confirmed by electrochemical and Raman spectroscopic studies. This technique opens up possibilities of 2-D polymerization at the air-water interface. Electrochemical sensing of hydrogen peroxide is used to differentiate the activity of planar and coiled forms of PANI toward electrocatalytic reactions.

Microstructure and dry sliding wear resistance evaluation of plasma nitrided austenitic stainless steel type AISI 316LN against different sliders

In this work, Plasma Nitriding was carried out at a temperature of 570 degrees C on nuclear grade austenitic stainless steel type AISI 316 LN (316LN SS) in a gas mixture of 20% N-2-80% H-2 to improve the surface hardness and thereby sliding wear resistance. The Plasma Nitride (PN) treated surface has been characterized by Vickers microhardness measurements, Scanning Electron Microscopic (SEM) examination, X-ray Diffraction (XRD) and sliding wear assessment. The average thickness of the PN layer was found to be 70 mu m. Microhardness measurements showed a significant increase in the hardness from 210 HV25g (unnitrided sample) to 1040 HV25g (Plasma Nitrided sample). The XRD reveals that PN layer consists of CrN, Fe4N and Fe3N phases along with austenite phase. The tribological parameters such as the friction coefficient and wear mechanism have been evaluated at ambient conditions for PN treated ring (PN ring) vs. ASTM A453 grade 660 pin (ASTM pin), PN ring vs. Nickel based alloy hard faced pin (Colmonoy pin), PN ring vs. 316LN SS pin and 316LN SS ring vs. 316LN SS pin. The wear tracks have been analyzed by SEM, Energy Dispersive X-ray Analysis (EDX) and Optical Profilometry. The untreated 316LN SS ring vs. 316LN SS pin produced severe wear and was characterized by a combination of delamination and adhesion wear mechanism, whereas wear mechanism of the PN rings reveals mild abrasion and a transfer layer from pin materials. (C) 2012 Elsevier B.V. All rights reserved.

In vitro bioactivity and cytocompatibility properties of spark plasma sintered HA-Ti composites

The present study reports the results of the detailed in vitro bioactivity and cytocompatibility properties of the hydroxyapatite (HA) and the HA-titanium (HA-Ti) composite with varying amount of Ti (5, 10, and 20 wt %), densified using spark plasma sintering process (SPS). Using this technique and tailoring suitable processing parameters, it has been possible to retain both HA and Ti in the sintered ceramics. Importantly, the uniquely designed SPS processing with suitably chosen parameters enables in achieving better mechanical properties, such as higher indentation fracture toughness (similar to 1.5 MPa m1/2) in HA-Ti composites compared with HA. X-ray diffraction and scanning electron microscopic (SEM) observations reveal good bioactivity of the HA-Ti composites with the formation of thick, flaky, and porous apatite layer when immersed in simulated body fluid at 37 degrees C and pH of 7.4. Atomic absorption spectroscopic analysis of the simulated body fluid solution reveals dynamic changes in Ca+2 ion concentration with more dissolution of Ca+2 ion from the HA-20Ti composite. However, the measurements with inductively coupled plasma spectrometer do not record dissolution of Ti+4 ions. Transmission electron microscopic analysis indicates weak crystalline nature of the apatite and confirms the formation of fine-scale apatite crystals. MTT assay, fluorescence, and SEM study demonstrate good cell viability and cell adhesion/proliferation of the Saos -2 cells, cultured on the developed composites under standard culture condition, and the difference in cell viability has been discussed in reference to substrate composition and roughness. Overall, HA-Ti composites exhibit comparable and even better in vitro bioactivity and cytocompatibility properties than HA. (c) 2012 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2013.

Thermal degradation kinetics of thermoresponsive poly(N-isopropylacrylamide-co-N,N-dimethylacrylamide) copolymers prepared via RAFT polymerization

Reversible addition-fragmentation chain transfer polymerization at 70 A degrees C in N,N-dimethylformamide was used to prepare poly(N-isopropylacrylamide-co-N,N-dimethylacrylamide) copolymers in various compositions to afford well-defined polymers with pre-determined molecular weight, narrow molecular weight distribution, and precise chain end structure. The copolymer compositions were determined by H-1 NMR spectroscopy. The reactivity ratios of N-isopropylacrylamide (NIPAM) and N,N-dimethylacrylamide (DMA) were calculated as r (NIPAM) = 0.838 and r (DMA) = 1.105, respectively, by the extended Kelen-Tudos method at high conversions. The lower critical solution temperature of PNIPAM can be altered by changing the DMA content in the copolymer chain. Differential scanning calorimetry and thermogravimetric analysis at different heating rates were carried out on these copolymers to understand the nature of thermal degradation and to determine its kinetics. Different kinetic models were applied to estimate various parameters like the activation energy, the order, and the frequency factor. These studies are important to understand the solid state polymer degradation of N-alkyl substituted polymers, which show great potential in the preparation of miscible polymer blends due to their ability to interact through hydrogen bonding.

Densification kinetics, phase assemblage and hardness of spark plasma sintered Cu-10 wt% TiB2 and Cu-10 wt% TiB2-10 wt% Pb composites

The present work demonstrates the synthesis of Cu-10 wt% TiB2 composites with a theoretical density of more than 90% by tailoring the spark plasma sintering (SPS) conditions in the temperature range of 400-700 degrees C. Interestingly, 10 wt% Pb addition to Cu-10 wt% TiB2 lowers the sinter density and the difference in the densification behavior of the investigated compositions was discussed in reference to the current profile recorded during a SPS cycle. The sintering kinetics and phase assemblage were also discussed in reference to surface melting of the constituents prior to bulk melting temperature, temperature dependent wettability of Pb on Cu, diffusion kinetics of Cu as well as the formation of various oxides. An important result is that a high hardness of around 2 GPa and relative density close to 92% qtheoretical was achieved for the Cu-10 wt% TiB2-10 wt% Pb composite, and such a combination has never been achieved before using any conventional processing route.

On the densification mechanisms and properties of Cu-Pb and Cu-Pb-TiB2 nanocomposites densified using spark plasma sintering

The present paper is aimed to understand the sub-processes triggered by rapid heating during spark plasma sintering as well as to assess the extent to which densification and properties of metallic materials can be enhanced using such superfast consolidation process. Using nanocrystalline Cu-Pb as a model system, the influence of Pb as well as TiB2 addition on the densification mechanisms and properties are discussed. Importantly, a high hardness of 2 GPa is achieved in Cu-based nanocomposites. (C) 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Spark plasma sintering may lead to phase instability and inferior mechanical properties: A case study with TiB2

In contrast to the widely reported beneficial aspects of spark plasma sintering in developing materials with better properties, we report here two interesting aspects recorded with difficult-to-sinter titanium diboride: (a) in situ formation of second phase (TiB) and (b) inferior hardness (by similar to 30%) and elastic modulus (by similar to 20%) for spark plasma sintered TiB2, with respect to hot pressed TiB2. The formation of TiB is discussed with reference to the enhanced reaction kinetics in the presence of pulsed electric field. (C) 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Dynamics and Regulation of RecA Polymerization and De-Polymerization on Double-Stranded DNA

The RecA filament formed on double-stranded (ds) DNA is proposed to be a functional state analogous to that generated during the process of DNA strand exchange. RecA polymerization and de-polymerization on dsDNA is governed by multiple physiological factors. However, a comprehensive understanding of how these factors regulate the processes of polymerization and de-polymerization of RecA filament on dsDNA is still evolving. Here, we investigate the effects of temperature, pH, tensile force, and DNA ends (in particular ssDNA overhang) on the polymerization and de-polymerization dynamics of the E. coli RecA filament at a single-molecule level. Our results identified the optimal conditions that permitted spontaneous RecA nucleation and polymerization, as well as conditions that could maintain the stability of a preformed RecA filament. Further examination at a nano-meter spatial resolution, by stretching short DNA constructs, revealed a striking dynamic RecA polymerization and de-polymerization induced saw-tooth pattern in DNA extension fluctuation. In addition, we show that RecA does not polymerize on S-DNA, a recently identified novel base-paired elongated DNA structure that was previously proposed to be a possible binding substrate for RecA. Overall, our studies have helped to resolve several previous single-molecule studies that reported contradictory and inconsistent results on RecA nucleation, polymerization and stability. Furthermore, our findings also provide insights into the regulatory mechanisms of RecA filament formation and stability in vivo.