Stimuli-responsive weak polyelectrolyte multilayer films: A thin film platform for self triggered multi-drug delivery

Polyelectrolyte multilayer (PEM) thin film composed of weak polyelectrolytes was designed by layer-by-layer (LbL) assembly of poly(allylamine hydrochloride) (PAH) and poly(methacrylic acid) (PMA) for multi-drug delivery applications. Environmental stimuli such as pH and ionic strength showed significant influence in changing the film morphology from pore-free smooth structure to porous structure and favored triggered release of loaded molecules. The film was successfully loaded with bovine serum albumin (BSA) and ciprofloxacin hydrochloride (CH) by modulating the porous polymeric network of the film. Release studies showed that the amount of release could be easily controlled by changing the environmental conditions such as pH and ionic strength. Sustained release of loaded molecules was observed up to 8 h. The fabricated films were found to be biocompatible with epithelial cells during in-vitro cell culture studies. PEM film reported here not only has the potential to be used as self-responding thin film platform for transdermal drug delivery, but also has the potential for further development in antimicrobial or anti-inflammatory coatings on implants and drug-releasing coatings for stents. (C) 2015 Elsevier B.V. All rights reserved.

On the contributions of different micromechanisms for enhancement in the strength of TI-6Al-4V alloy upon B addition: A nanomechanical analysis

The addition of small amount of boron to Ti and it alloys refines the as-cast microstructure and enhances the mechanical properties. In this paper, we employ nanoindentation on each of the constituent phases in the microstructure and `rule-of-mixture' type analysis to examine their relative contributions to the strength enhancement in a Ti-6Al-4V alloy modified with 0.3 wt% B. Our results indicate to two main contributors to the relatively higher flow strength of B-modified alloy vis-a-vis the base alloy: (a) strengthening of alpha phase due to the reduction in the effective slip length that occurs as a result of the microstructural refinement that occurs upon B addition, and (b) composite strengthening caused by the TiB whiskers present in the alloy. (C) 2015 Elsevier B.V. All rights reserved.

Size Effects on Strength in the Transition from Single-to-Polycrystalline Behavior

During the transition from single crystalline to polycrystalline behavior, the available data show the strength increasing or decreasing as the number of grains in a cross section is reduced. Tensile experiments were conducted on polycrystalline Ni with grain sizes (d) between 16 and 140 mu m and varying specimen thickness (t), covering a range of lambda (-t/d) between similar to 0.5 and 20. With a decrease in lambda, the data revealed a consistent trend of strength being independent of lambda at large lambda, an increase in strength, and then a decrease in strength. Microstructural studies revealed that lower constraints enabled easier rotation of the surface grains and texture evolution, independent of the specimen thickness. In specimen interiors, there was a greater ease of rotation in thinner samples. Measurements of misorientation deviations within grains revealed important differences in the specimen interiors. A simple model is developed taking into account the additional geometrically necessary dislocations due to variations in the behavior of surface and interior grains, leading to additional strengthening. A suitable combination of this strengthening and surface weakening can give rise to wide range of possibilities with a decrease in lambda, including weakening, strengthening, and strengthening and weakening.

On the Structural Stability of Melt Spun Ribbons of Fe95-x Zr (x) B4Cu1 (x=7 and 9) Alloys and Correlation with Their Magnetic Properties

Melt spun ribbons of Fe95-x Zr (x) B4Cu1 with x = 7 (Z7B4) and 9 (Z9B4) alloys have been prepared, and their structure and magnetic properties have been evaluated using XRD, DSC, TEM, VSM, and Mossbauer spectroscopy. The glass forming ability (GFA) of both alloys has been calculated theoretically using thermodynamical parameters, and Z9B4 alloy is found to possess higher GFA than that of Z7B4 alloy which is validated by XRD results. On annealing, the amorphous Z7B4 ribbon crystallizes into nanocrystalline alpha-Fe, whereas amorphous Z9B4 ribbon shows two-stage crystallization process, first partially to bcc solid solution which is then transformed to nanocrystalline alpha-Fe and Fe2Zr phases exhibiting bimodal distribution. A detailed phase analysis using Mossbauer spectroscopy through hyperfine field distribution of phases has been carried out to understand the crystallization behavior of Z7B4 and Z9B4 alloy ribbons. In order to understand the phase transformation behavior of Z7B4 and Z9B4 ribbons, molar Gibbs free energies of amorphous, alpha-Fe, and Fe2Zr phases have been evaluated. It is found that in case of Z7B4, alpha-Fe is always a stable phase, whereas Fe2Zr is stable at higher temperature for Z9B4. (C) The Minerals, Metals & Materials Society and ASM International 2015

Microstructure Formation in Dissimilar Metal Welds: Electron Beam Welding of Ti/Ni

We present results for electron beam welding of a binary Ti/Ni dissimilar metal couple. The difference in physical properties of the base metals and metallurgical features (thermodynamics and kinetics) of the system influence both macroscopic transport and microstructure development in the weld. Microstructures near the fusion interfaces are markedly different from those inside the weld region. At the Ti side, Ti2Ni dendrites are observed to grow toward the fusion interface, while in the Ni side, layered growth of gamma-Ni, Ni3Ti, and Ni3Ti + NiTi eutectic is observed. Different morphologies of the latter eutectic constitute the predominant microstructure inside the weld metal region. These results are compared and contrasted with those from laser welding of the same binary couple, and a scheme of solidification is proposed to explain the observations. This highlights notable departures from welding of similar and other dissimilar metals such as a significant asymmetry in heat transport that governs progress of solidification from each side of the couple, and a lack of unique liquidus isotherm characterizing the liquid-solid front.

Evolution of Texture and Microstructure in Deformed and Annealed Copper-Iron Multilayer

The effect of multiple phases on the evolution of texture during cold rolling and annealing of a copper-iron multilayer, fabricated by accumulative roll bonding, has been studied. The presence of an iron layer affects the deformation texture of the copper layer only at very large strains. On the other hand, a strong effect of copper on iron is observed at both small and large strains. At smaller strains, the larger deformation carried by the copper suppresses the texture development in the iron, whereas, at higher strains, selection of specific orientation relationship at the interface influences the texture of the iron layer. Shear banding and continuous dynamic recrystallization were found to influence the evolution of texture in the copper layer. The influence of large plastic deformation on the recrystallization behavior of copper is demonstrated with the suppression of typical fcc annealing texture components, described as constrained recrystallization. Evolution of typical annealing texture component is suppressed because of the multilayer microstructure. The plane of the interface formed during deformation is determined by a combination of the rolling texture of individual phases, constrained annealing, and the tendency to form a low-energy interface between the two phases during annealing.

Macroporous three-dimensional graphene oxide foams for dye adsorption and antibacterial applications

Several reports illustrate the wide range applicability of graphene oxide (GO) in water remediation. However, a few layers of graphene oxide tend to aggregate under saline conditions thereby reducing its activity. The effects of aggregation can be minimized by having a random arrangement of GO layers in a three dimensional architecture. The current study emphasizes the potential benefits of highly porous, ultralight graphene oxide foams in environmental applications. These foams were prepared by a facile and cost effective lyophilization technique. The 3D architecture allowed the direct use of these foams in the removal of aqueous pollutants without any pretreatment such as ultrasonication. Due to its macroporous nature, the foams exhibited excellent adsorption abilities towards carcinogenic dyes such as rhodamine B (RB), malachite green (MG) and acriflavine (AF) with respective sorption capacities of 446, 321 and 228 mg g(-1) of foam. These foams were also further investigated for antibacterial activities against E. coli bacteria in aqueous and nutrient growth media. The random arrangement of GO layers in the porous foam architecture allowed it to exhibit excellent antibacterial activity even under physiological conditions by following the classical wrapping-perturbation mechanism. These results demonstrate the vast scope of GO foam in water remediation for both dye removal and antibacterial activity.

Outstanding dielectric constant and piezoelectric coefficient in electrospun nanofiber mats of PVDF containing silver decorated multiwall carbon nanotubes: assessing through piezoresponse force microscopy

In order to enhance the piezoelectric b-phase, PVDF was electrospun from DMF solution. The enhanced b-phase was discerned by comparing the electrospun fibers against the melt mixed samples. While both the processes resulted in phase transformation of a-to electroactive b-polymorph in PVDF, the fraction of b-phase was strongly dependent on the adopted process. Two different nanoscopic particles: carboxyl functionalized multiwall carbon nanotubes (CNTs) and silver (Ag) decorated CNTs were used to further enhance the piezoelectric coefficient in the electrospun fibers. Fourier transform infrared spectroscopy (FTIR) and wide-angle X-ray diffraction (XRD) supports the development of piezoelectric b-phase in PVDF. It was concluded that electrospinning was the best technique for inducing the b-polymorph in PVDF. This was attributed to the high voltage electrostatic field that generates extensional forces on the polymer chains that aligns the dipoles in one direction. The ferroelectric and piezoelectric measurement on electrospun fibers were studied using piezo-response force microscope (PFM). The Ag-CNTs filled PVDF electrospun fibers showed the highest piezoelectric coefficient (d(33) = 54 pm V-1) in contrast to PVDF/CNT fibers (35 pm V-1) and neat PVDF (30 pm V-1). This study demonstrates that the piezoelectric coefficient can be enhanced significantly by electrospinning PVDF containing Ag decorated nanoparticles.

Microstructural evolution and strength variability in microwires

Tensile experiments on cold-drawn Ni microwires with diameters from similar to 115 to 50 gm revealed high strengths, with significant strength variability for finer wires with diameters less than similar to 50 gm. The wires showed pronounced necking at fracture. The coarser wires with diameters > 50 mu m exhibited conventional ductile cup-cone fracture, with dimples in the central zone and peripheral shear lips, whereas finer wires failed by shear with knife or chisel-edge fractures. Shear bands were observed in all samples. Further, through- section microscopy of selected fractured samples revealed that the shear bands did not go across the enitre specimen for the coarser wires. The shear bands led to grain fragmention, with a reduction in grain aspect ratio as well as rotations away from the initial < 111 > orientations. The strength data were analysed based on a Weibull approach. The data could be rationalized in terms of failure from volume defects in coarser wires, with a high Weibull modulus, and from surface defects in finer wires, with a low Weibull modulus and greater variability. (C) 2015 Elsevier B.V. All rights reserved.

Effect of semi-solid heat treatment on elevated temperature plasticity of 304L stainless steel

The present work explores the potential of semi-solid heat treatment technique by elucidating its effect on the plastic behavior of 304L SS in hot working domain. To accomplish this objective, hot isothermal compression tests on 304L SS specimens with semi-solid heat treatment and conventional annealing heat treatment have been carried out within a temperature range of 1273-1473 K and strain rates ranging from 0.01 to 1 s(-1). The dynamic flow behavior of this steel in its conventional heat-treated condition and semi-solid heat-treated condition has been characterized in terms of strain hardening, temperature softening, strain rate hardening, and dynamic flow softening. Extensive microstructural investigation has been carried out to corroborate the results obtained from the analysis of flow behavior. Detailed analysis of the results demonstrates that semi-solid heat treatment moderates work hardening, strain rate hardening, and temperature sensitivity of 304L SS, which is favorable for hot deformation. The post-deformation hardness values of semi-solid heat-treated steel and conventionally heat-treated steel were found to remain similar despite the pre-deformation heat treatment conditions. The results obtained demonstrate the potential of semi-solid heat treatment as a pre-deformation heat treatment step to effectively reduce the strength of the material to facilitate easier deformation without affecting the post-deformation properties of the steel.

Anti-corrosive and anti-microbial properties of nanocrystalline Ni-Ag coatings

Anti-corrosive and anti-bacterial properties of electrodeposited nanocrystalline Ni-Ag coatings are illustrated. Pure Ni, Ni-7 at.% Ag, & Ni-14 at.% Ag coatings were electrodeposited on Cu substrate. Coating consisted of Ni-rich and Ag-rich solid solution phases. With increase in the Ag content, the corrosion resistance of the Ni-Ag coating initially increased and then decreased. The initial increase was due to the Ni-Ag solid solution. The subsequent decrease was due to the increased galvanic coupling between the Ag-rich and Ni-rich phases. For all Ag contents, the corrosion resistance of the Ni-Ag coating was higher than the pure Ni coating. Exposure to Sulphate Reducing Bacteria (SRB) revealed that the extent of bio-fouling decreased with increase in the Ag content. After 2 month exposure to SRB, the Ni-Ag coatings demonstrated less loss in corrosion resistance (58% for Ni-7 at.% Ag and 20% for Ni-14 at.% Ag) when compared pure Ni coating (115%). (C) 2016 Elsevier B.V. All rights reserved.

Investigations on structural, magnetic and electronic structure of Gd-doped ZnO nanostructures synthesized using sol-gel technique

GdxZn1-xO (x = 0, 0.02, 0.04 and 0.06) nanostructures have been synthesized using sol-gel technique and characterized to understand their structural and magnetic properties. X-ray diffraction (XRD) results show that Gd (0, 2, 4 and 6 %)-doped ZnO nanostructures crystallized in the wurtzite structure having space group C3(v) (P6(3)mc). Photoluminescence and Raman studies of Gd-doped ZnO powder show the formation of singly ionized oxygen vacancies. X-ray absorption spectroscopy reveals that Gd replaces the Zn atoms in the host lattice and maintains the crystal symmetry with slight lattice distortion. Gd L-3-edge spectra reveal charge transfer between Zn and Gd dopant ions. O K-edge spectra also depict the charge transfer through the oxygen bridge (Gd-O-Zn). Weak magnetic ordering is observed in all Gd-doped ZnO samples.

Anti-corrosive and anti-microbial properties of nanocrystalline Ni-Ag coatings

Anti-corrosive and anti-bacterial properties of electrodeposited nanocrystalline Ni-Ag coatings are illustrated. Pure Ni, Ni-7 at.% Ag, & Ni-14 at.% Ag coatings were electrodeposited on Cu substrate. Coating consisted of Ni-rich and Ag-rich solid solution phases. With increase in the Ag content, the corrosion resistance of the Ni-Ag coating initially increased and then decreased. The initial increase was due to the Ni-Ag solid solution. The subsequent decrease was due to the increased galvanic coupling between the Ag-rich and Ni-rich phases. For all Ag contents, the corrosion resistance of the Ni-Ag coating was higher than the pure Ni coating. Exposure to Sulphate Reducing Bacteria (SRB) revealed that the extent of bio-fouling decreased with increase in the Ag content. After 2 month exposure to SRB, the Ni-Ag coatings demonstrated less loss in corrosion resistance (58% for Ni-7 at.% Ag and 20% for Ni-14 at.% Ag) when compared pure Ni coating (115%). (C) 2016 Elsevier B.V. All rights reserved.

Orientation Selection and Microstructural Evolution in Directionally Solidified Tb0.3Dy0.7Fe1.95

Tb0.3Dy0.7Fe1.95 alloy was directionally solidified by using a modified Bridgman technique at a wide range of growth rates of 5 to 100 cm/h. The directionally grown samples exhibited plane front solidification morphology up to a growth rate of 90 cm/h. Typical island banding feature was observed closer to the chilled end, which eventually gave rise to irregular peritectic coupled growth (PCG). The PCG gained prominence with an increase in the growth rate. The texture study revealed formation of strong aOE (c) 311 > texture in a lower growth rate regime, aOE (c) 110 > and ``rotated aOE (c) 110 > aEuroe in an intermediate growth regime, and aOE (c) 112 > in a higher growth rate regime. In-depth analysis of the atomic configuration of a solid-liquid interface revealed that the growth texture is influenced by the kinetics of atomic attachment to the solid-liquid interface, which is intimately related to a planar packing fraction and an atomic stacking sequence of the interfacial plane. The mechanism proposed in this article is novel and will be useful in addressing the orientation selection mechanism of topologically closed packed intermetallic systems. The samples grown at a higher growth rate exhibit larger magnetostriction (lambda) and d lambda/dH owing to the absence of pro-peritectic (Tb,Dy)Fe-3 and formation of aOE (c) 112 > texture, which lies closer to the easy magnetization direction (EMD).