Pulsed Electrical Stimulation and Surface Charge Induced Cell Growth on Multistage Spark Plasma Sintered Hydroxyapatite-Barium Titanate Piezobiocomposite

The primary purpose of the present work was to illustrate whether cell proliferation can be enhanced on electroactive bioceramic composite, when the cells are cultured in the presence of external electrical stimulation. The two different aspects of the influence of electric field (E-field) application toward stimulating the growth/proliferation of bone/connective tissue cells in vitro, (a) intermittent delivery of extremely low strength pulsed electrical stimulation (0.5-4V/cm, 400s DC pulse) and (b) surface charge generated by electrical poling (10kV/cm) of hydroxyapatite (HA)-BaTiO3 piezobiocomposite have been demonstrated. The experimental results establish that the cell growth can be enhanced using the new culture protocol of the intermittent delivery of electrical pulses within a narrow range of stimulation parameters. The optimal E-field strength for enhanced cellular response for mouse fibroblast L929 and osteogenic cells is in the range of 0.5-1V/cm. The MTT 3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyl tetrazolium bromide] assay results suggested the increased viability of E-field treated cells over 7d in culture, implicating the positive impact of electrical pulses on proliferation behavior. The alizarin red assay results showed noticeable increase in Ca-deposition on the E-field treated samples in comparison to their untreated counterparts. The negatively charged surfaces of developed piezocomposite stimulated the cell growth in a statistically noticeable manner as compared with the uncharged or positively charged surfaces of similar composition.

MHD arcjet onset boundary of high specific impulse Plasma Thrusters

Magnetoplasmadynamic thrusters are known to enter a strongly unstable regime, calledas onset in the literature, under high specific impulse operation. This paper probes the early signs of onset in relatively moderate specific impulse operation by a single fluid plasma thruster simulation. The procedure involves solving the combined Maxwell’s-Navier-Stokes equation, with an onset criterion of radial current reaching close to zero values near the electrodes. Thruster parameters are varied starting from voltage potential, plasma temperature and cathodic radius. Onset curves are plotted which can provide important engine-specific information in order to understand the onset performance of the plasma thruster.

Microstructure-Wear Resistance Correlation and Wear Mechanisms of Spark Plasma Sintered Cu-Pb Nanocomposites

The dispersion of a softer phase in a metallic matrix reduces the coefficient of friction (COF), often at the expense of an increased wear rate at the tribological contact. To address this issue, unlubricated fretting wear tests were performed on spark plasma sintered Cu-Pb nanocomposites against bearing steel. The sintering temperature and the Pb content as well as the fretting parameters were judiciously selected and varied to investigate the role of microstructure (grain size, second-phase content) on the wear resistance properties of Cu-Pb nanocomposites. A combination of the lowest wear rate (similar to 1.5 x 10(-6) mm(3)/Nm) and a modest COF (similar to 0.4) was achieved for Cu-15 wt pct Pb nanocomposites. The lower wear rate of Cu-Pb nanocomposites with respect to unreinforced Cu is attributed to high hardness (similar to 2 to 3.5 GPa) of the matrix, Cu2O/Fe2O3-rich oxide layer formation at tribological interface, and exuding of softer Pb particles. The wear properties are discussed in reference to the characteristics of transfer layer on worn surface as well as subsurface damage probed using focused ion beam microscopy. Interestingly, the flash temperature has been found to have insignificant effect on the observed oxidative wear, and alternative mechanisms are proposed. Importantly, the wear resistance properties of the nanocomposites reveal a weak Hall-Petch-like relationship with grain size of nanocrystalline Cu. (C) The Minerals, Metals & Materials Society and ASM International 2013

Direct Characterizing of Densification Mechanisms during Spark Plasma Sintering

Spark plasma sintering (SPS) is a convenient and rapid means of producing dense ceramic compacts. However, the mechanisms responsible for rapid densification have not been identified satisfactorily, with different studies using an indirect approach yielding varied values for the densification parameters. This study involved SPS in high purity nanocrystalline alumina with temperatures ranging from 1173 to 1423K and stresses from 25 to 100MPa. A direct approach, with analyses at a constant density, revealed a stress exponent of similar to 1 and an inverse grain size dependence of similar to 3, consistent with Coble creep process. Whereas the direct approach gives a stress exponent of similar to 1, the indirect approach used previously gives stress exponents ranging from similar to 2.2 to 3.5 with the same data, thereby revealing potentially spurious values of the densification parameters from conventional indirect approaches to characterizing densification. The rapid densification during SPS is related to the finer grain sizes retained with the rapid heating rates and the imposed stress that enhances the driving force for densification.

Enzymatic degradation of polymers: a brief review

Recently, research on polymer has drawn much attention mainly due to the ever increasing application of these polymeric materials in several areas such as food packaging industry, agricultural industry and biomedical research. However, increasing industrial use of polymers has led to the environmentally critical issue of waste disposal. Further, the successful implication of polymeric materials in biomedical applications depends on the biodegradability of the concerned polymer. Various enzymes play an important role in the biodegradation of polymers. The present review describes the enzyme mediated biodegradation of various polymers including synthetic, natural and blends of these materials. Detailed examples of enzymatic degradation of polymers are illustrated from current scientific literature with the discussion on various factors that can influence the degradation. In addition, different techniques that are generally applied to assess the degradation process as well as degradation products have been described. Finally, a special emphasis is given to the investigation of the kinetics of polymer degradation by enzymes.

Controlling Conformations of Diketopyrrolopyrrole-Based Conjugated Polymers: Role of Torsional Angle

Transport of charge carriers through conjugated polymers is strongly influenced by the presence and distribution of structural disorders. In the present work, structural defects caused by the presence of torsional.. angle were investigated in a diketopyrrolopyrrole (DPP)-based conjugated polymer. Two new copolymers of DPP were synthesized with varying torsional angles to trace the role of structural disorder. The optical properties of these copolymers in solution and thin film reveal the strong influence of torsional angle on their photophysical properties. A strong influence was observed on carrier transport properties of polymers in organic field-effect transistors (OFET) device geometry. The polymers based on phenyl DPP with higher torsional angle (PPTDPP-OD-TEG) resulted in high threshold voltage with less charge carrier mobility as compared to the polymer based on thiophene DPP (2DPP-OD-TEG) bearing a lower torsional angle. Carrier mobility and the molecular orientation of the conjugated polymers were correlated on the basis of grazing incidence X-ray scattering measurements showing the strong role of torsional angle introduced in the form of structural disorder. The results presented in this Article provide a deep insight into the sensitivity of structural disorder and its impact on the device performance of DPP-based conjugated polymers.

Mechanochemical Synthesis of Amide Functionalized Porous Organic Polymers

Two porous organic polymers decorated with the amide functionality were synthesized mechanochemically and their properties were compared with the ones prepared by conventional solution mediated method. All the POPs were subjected to gas and water vapor sorption studies. The mechanochemically synthesized POPs have less surface area and show moderate adsorption properties compared to the solution mediated POPs. The amide based POPs show remarkable stability in water and concentrated acids.

Selenium in Diketopyrrolopyrrole-based Polymers: Influence on Electronic Properties and Charge Carrier Mobilities

Diketopyrrolopyrrole (DPP)-based pi-conjugated copolymers with thiophene have exceptionally high electron mobilities. This paper investigates electronic properties and charge carrier mobilities of selenophene containing analogues. Two new copolymers, with alternating thiophene DPP (TDPP) and selenophene DPP (SeDPP) units, were synthesized. Two side-chains, hexyl (Hex) and triethylene glycol (TEG) were employed, yielding polymers designated as PTDPPSeDPP-Hex and PTDPPSeDPP-TEG. Selenophene systems have smaller band gaps, with concomitant enhancement of the stability of the reduced state. For both polymers, ambipolar mobilities were observed in organic field-effect transistors (OFET). Grazing incidence X-ray diffraction (GIXD) data indicates preferential edge-on orientation of PTDPPSeDPP-TEG, which leads to superior charge transport properties of the TEG substituted polymer, as compared to its Hex analogue. Time-dependent-density functional theory (TDDFT) calculations corroborate the decrease in the optical band gap with the inclusion of selenophene. Ambipolar charge transport is rationalized by exceptionally wide conduction bands. Delta SCF calculations confirm the larger electron affinity, and therefore the greater stability, of the reduced form of the selenophene-containing DPP polymer in presence of chloroform.

Microstructure Development, Nanomechanical, and Dynamic Compression Properties of Spark Plasma Sintered TiB2-Ti-Based Homogeneous and Bi-layered Composites

The growing threats due to increased use of small-caliber armor piercing projectiles demand the development of new light-weight body armor materials. In this context, TiB2 appears to be a promising ceramic material. However, poor sinterability and low fracture toughness remain two major issues for TiB2. In order to address these issues together, Ti as a sinter-aid is used to develop TiB2-(x wt pct Ti), (x = 10, 20) homogeneous composites and a bi-layered composite (BLC) with each layer having Ti content of 10 and 20 wt pct. The present study uniquely demonstrates the efficacy of two-stage spark plasma sintering route to develop dense TiB2-Ti composites with an excellent combination of nanoscale hardness (similar to 36 GPa) and indentation fracture toughness (similar to 12 MPa m(1/2)). In case of BLC, these properties are not compromised w.r.t. homogeneous composites, suggesting the retention of baseline material properties even in the bi-layer design due to optimal relief of residual stresses. The better indentation toughness of TiB2-(10 wt pct Ti) and TiB2-(20 wt pct Ti) composites can be attributed to the observed crack deflection/arrest, indicating better damage tolerance. Transmission electron microscope investigation reveals the presence of dense dislocation networks and deformation twins in alpha-Ti at the grain boundaries and triple pockets, surrounded by TiB2 grains. The dynamic strength of around 4 GPa has been measured using Split Hopkinson Pressure Bar tests in a reproducible manner at strain rates of the order of 600 s(-1). The damage progression under high strain rate has been investigated by acquiring real time images for the entire test duration using ultra-high speed imaging. An attempt has been made to establish microstructure-property correlation and a simple analysis based on Mohr-Coulomb theory is used to rationalize the measured strength properties.

Use of side-chain for rational design of n-type diketopyrrolopyrrole-based conjugated polymers: what did we find out?

The primary role of substituted side chains in organic semiconductors is to increase their solubility in common organic solvents. In the recent past, many literature reports have suggested that the side chains play a critical role in molecular packing and strongly impact the charge transport properties of conjugated polymers. In this work, we have investigated the influence of side-chains on the charge transport behavior of a novel class of diketopyrrolopyrrole (DPP) based alternating copolymers. To investigate the role of side-chains, we prepared four diketopyrrolopyrrole-diketopyrrolopyrrole (DPP-DPP) conjugated polymers with varied side-chains and carried out a systematic study of thin film microstructure and charge transport properties in polymer thin-film transistors (PTFTs). Combining results obtained from grazing incidence X-ray diffraction (GIXD) and charge transport properties in PTFTs, we conclude side-chains have a strong influence on molecular packing, thin film microstructure, and the charge carrier mobility of DPP-DPP copolymers. However, the influence of side-chains on optical properties was moderate. The preferential ``edge-on'' packing and dominant n-channel behavior with exceptionally high field-effect electron mobility values of >1 cm(2) V-1 s(-1) were observed by incorporating hydrophilic (triethylene glycol) and hydrophobic side-chains of alternate DPP units. In contrast moderate electron and hole mobilities were observed by incorporation of branched hydrophobic side-chains. This work clearly demonstrates that the subtle balance between hydrophobicity and hydrophilicity induced by side-chains is a powerful strategy to alter the molecular packing and improve the ambipolar charge transport properties in DPP-DPP based conjugated polymers. Theoretical analysis supports the conclusion that the side-chains influence polymer properties through morphology changes, as there is no effect on the electronic properties in the gas phase. The exceptional electron mobility is at least partially a result of the strong intramolecular conjugation of the donor and acceptor as evidenced by the unusually wide conduction band of the polymer.

Explosives Sensing by Using Electron-Rich Supramolecular Polymers: Role of Intermolecular Hydrogen Bonding in Significant Enhancement of Sensitivity

We demonstrate here that supramolecular interactions enhance the sensitivity towards detection of electron-deficient nitro-aromatic compounds (NACs) over discrete analogues. NACs are the most commonly used explosive ingredients and are common constituents of many unexploded landmines used during World WarII. In this study, we have synthesised a series of pyrene-based polycarboxylic acids along with their corresponding discrete esters. Due to the electron richness and the fluorescent behaviour of the pyrene moiety, all the compounds act as sensors for electron-deficient NACs through a fluorescence quenching mechanism. A Stern-Volmer quenching constant determination revealed that the carboxylic acids are more sensitive than the corresponding esters towards NACs in solution. The high sensitivity of the acids was attributed to supramolecular polymer formation through hydrogen bonding in the case of the acids, and the enhancement mechanism is based on an exciton energy migration upon excitation along the hydrogen-bond backbone. The presence of intermolecular hydrogen bonding in the acids in solution was established by solvent-dependent fluorescence studies and dynamic light scattering (DLS) experiments. In addition, the importance of intermolecular hydrogen bonds in solid-state sensing was further explored by scanning tunnelling microscopy (STM) experiments at the liquid-solid interface, in which structures of self-assembled monolayer of the acids and the corresponding esters were compared. The sensitivity tests revealed that these supramolecular sensors can even detect picric acid and trinitrotoluene in solution at levels as low as parts per trillion (ppt), which is much below the recommended permissible level of these constituents in drinking water.

New low band gap 2-(4-(trifluoromethyl)phenyl)-1H-benzod]imidazole and benzo1,2-c; 4,5-c `]bis1,2,5]thiadiazole based conjugated polymers for organic photovoltaics

Two new low band gap D-A structured conjugated polymers, PBDTTBI and PBDTBBT, based on 2-(4-(trifluoromethyl)phenyl)-1H-benzod]imidazole and benzo1,2-c; 4,5-c']bis1,2,5]thiadiazole acceptor units with benzo1,2-b; 3,4-b']dithiophene as a donor unit have been designed and synthesized via a Stille coupling reaction. The incorporation of the benzo1,2-c; 4,5-c']bis1,2,5]thiadiazole unit into PBDTBBT has significantly altered the optical and electrochemical properties of the polymer. The optical band gap estimated from the onset absorption edge is similar to 1.88 eV and similar to 1.1 eV, respectively for PBDTTBI and PBDTBBT. It is observed that PBDTBBT exhibited a deeper HOMO energy level (similar to 4.06 eV) with strong intramolecular charge transfer interactions. Bulk heterojunction solar cells fabricated with a configuration of ITO/PEDOT: PSS/PBDTBBT: PC71BM/Al exhibited a best power conversion efficiency of 0.67%, with a short circuit current density of 4.9 mA cm(-2), an open-circuit voltage of 0.54 V and a fill factor of 25%.

Semipolar and nonpolar GaN epi-films grown on m-sapphire by plasma assisted molecular beam epitaxy

We hereby report the development of non-polar epi-GaN films of usable quality, on an m-plane sapphire. Generally, it is difficult to obtain high-quality nonpolar material due to the planar anisotropic nature of the growth mode. However, we could achieve good quality epi-GaN films by involving controlled steps of nitridation. GaN epilayers were grown on m-plane (10-10) sapphire substrates using plasma assisted molecular beam epitaxy. The films grown on the nitridated surface resulted in a nonpolar (10-10) orientation while without nitridation caused a semipolar (11-22) orientation. Room temperature photoluminescence study showed that nonpolar GaN films have higher value of compressive strain as compared to semipolar GaN films, which was further confirmed by room temperature Raman spectroscopy. The room temperature UV photodetection of both films was investigated by measuring the I-V characteristics under UV light illumination. UV photodetectors fabricated on nonpolar GaN showed better characteristics, including higher external quantum efficiency, compared to photodetectors fabricated on semipolar GaN. X-ray rocking curves confirmed better crystallinity of semipolar as compared to nonpolar GaN which resulted in faster transit response of the device. (C) 2014 AIP Publishing LLC.

Investigations on pressure and thickness profiles in carbon fiber-reinforced polymers during vacuum assisted resin transfer molding

Systematic experiments have been carried out by monitoring the in-situ pressure and thickness profiles for three different configurations, viz., flat plate, flat plate with a central circular hole, and an L-section using vacuum assisted resin transfer molding (VARTM) process. The effect of anisotropy on resin flow has been quantified by considering uni-directional carbon fiber preforms with 0 degrees and 90 degrees orientation to the flow direction for each configuration. A quasi-isotropic 45 degrees/0 degrees/-45 degrees/90 degrees](S) layup has also been included for flat plate case. Additionally, the study has been extended to understand the effect of using high permeability medium for each configuration. Fluid pressure profiles and thickness variation profiles have been obtained using an array of pressure sensors and linear variable differential transformers for each configuration. Experimental data reveal that anisotropy (due to changing fiber orientations), configuration, and gravity significantly change fluid pressure and displacement fields obtained during VARTM.

Gold Catalyzed Plasma Assisted Growth of Germanium Nanoneedles

A systematic study of Gold catalyzed growth of Ge nanoneedles by PECVD at low temperatures (<400 degrees C) is presented. Morphology, growth rate and aspect ratio of the needles are studied as a function of power, gas flow rate and chamber pressure. Nanoneedles were grown at pre-defined positions with catalytic particles obtained by e-Beam Lithography and lift off. This opens up the possibility of using Ge Nano needles in photovoltaic, nanoelectronics and nanosensor device applications.