The Effects of Nitrogen Bonding on Hardness of AIN/CrN Multilayer Hard Coatings

AIN/CrN multilayer hard coatings with various bilayer thicknesses were fabricated by a reactive sputtering process. The microstructural and mechanical characterizations of multilayer coatings were investigated through transmission electron microscope (TEM) observations and the hardness measurements by nano indentation. In particular, the variation of chemical bonding states of the bilayer nitrides was elucidated by near edge X-ray absorption fine structure (NEXAFS) spectroscopy. Many broken nitrogen bonds were formed by decreasing the bilayer thickness of AIN/CrN multilayer coatings. Existence of optimum AIN/CrN multilayer coatings thickness for maximum hardness could be explained by the competition of softening by the formation of broken nitrogen bonds and strengthening induced by decreasing bilayer thickness.

Micromechanisms of damage nucleation during contact deformation of columnar multilayer nitride coatings

In order to resolve some missing micromechanistic details regarding contact deformation in nitride multilayer coatings we report here observations from cross-sectional transmission electron microscopy and focused ion beam studies of the Vickers indentations on TiN/TiAlN multilayer films of various total thicknesses as well as bilayer periods. The study of damage induced by contact deformation in a nitride multilayer coating is complemented by stress calculated using an analytical model. Kinked boundaries of sliding columns give rise to cracks which propagate at an angle to the indentation axis under a combination of compressive and shear stresses. It is seen that multilayers provide more distributed columnar sliding, thereby reducing the stress intensity factor for shear cracking, while interfacial dislocations provide a stress relief mechanism by enabling lateral movement of material. (C) 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Nonlinear viscoelasticity of freestanding and polymer-anchored vertically aligned carbon nanotube foams

Vertical arrays of carbon nanotubes (VACNTs) show unique mechanical behavior in compression, with a highly nonlinear response similar to that of open cell foams and the ability to recover large deformations. Here, we study the viscoelastic response of both freestanding VACNT arrays and sandwich structures composed of a VACNT array partially embedded between two layers of poly(dimethylsiloxane) (PDMS) and bucky paper. The VACNTs tested are similar to 2 mm thick foams grown via an injection chemical vapor deposition method. Both freestanding and sandwich structures exhibit a time-dependent behavior under compression. A power-law function of time is used to describe the main features observed in creep and stress-relaxation tests. The power-law exponents show nonlinear viscoelastic behavior in which the rate of creep is dependent upon the stress level and the rate of stress relaxation is dependent upon the strain level. The results show a marginal effect of the thin PDMS/bucky paper layers on the viscoelastic responses. At high strain levels (epsilon - 0.8), the peak stress for the anchored CNTs reaches similar to 45 MPa, whereas it is only similar to 15MPa for freestanding CNTs, suggesting a large effect of PDMS on the structural response of the sandwich structures. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.3699184]

Low temperature charge transport and microwave absorption of carbon coated iron nanoparticles-polymer composite films

In this paper, the low temperature electrical conductivity and microwave absorption properties of carbon coated iron nanoparticles-polyvinyl chloride composite films are investigated for different filler fractions. The filler particles are prepared by the pyrolysis of ferrocene at 980 degrees C and embedded in polyvinyl chloride matrix. The high resolution transmission electron micrographs of the filler material have shown a 5 nm thin layer graphitic carbon covering over iron particles. The room temperature electrical conductivity of the composite film changes by 10 orders of magnitude with the increase of filler concentration. A percolation threshold of 2.2 and an electromagnetic interference shielding efficiency (EMI SE) of similar to 18.6 dB in 26.5-40 GHz range are observed for 50 wt% loading. The charge transport follows three dimensional variable range hopping conduction. (C) 2012 Elsevier Ltd. All rights reserved.

The force distribution function of an oscillator model of polymer stretching at constant velocity

Recent simulations of the stretching of tethered biopolymers at a constant speed v (Ponmurugan and Vemparala, 2011 Phys. Rev. E 84 060101(R)) have suggested that for any time t, the distribution of the fluctuating forces f responsible for chain deformation is governed by a relation of the form P(+ f)/ P(- f) = expgamma f], gamma being a coefficient that is solely a function of v and the temperature T. This result, which is reminiscent of the fluctuation theorems applicable to stochastic trajectories involving thermodynamic variables, is derived in this paper from an analytical calculation based on a generalization of Mazonka and Jarzynski's classic model of dragged particle dynamics Mazonka and Jarzynski, 1999 arXiv:cond-\textbackslashmat/9912121v1]. However, the analytical calculations suggest that the result holds only if t >> 1 and the force fluctuations are driven by white rather than colored noise; they further suggest that the coefficient gamma in the purported theorem varies not as v(0.15)T-(0.7), as indicated by the simulations, but as vT(-1).

Electromechanical dynamics and optimization of pectoral fin-based ionic polymer-metal composite underwater propulsor

Ionic polymer-metal composites are soft artificial muscle-like bending actuators, which can work efficiently in wet environments such as water. Therefore, there is significant motivation for research on the development and design analysis of ionic polymer-metal composite based biomimetic underwater propulsion systems. Among aquatic animals, fishes are efficient swimmers with advantages such as high maneuverability, high cruising speed, noiseless propulsion, and efficient stabilization. Fish swimming mechanisms provide biomimetic inspiration for underwater propulsor design. Fish locomotion can be broadly classified into body and/or caudal fin propulsion and median and/or paired pectoral fin propulsion. In this article, the paired pectoral fin-based oscillatory propulsion using ionic polymer-metal composite for aquatic propulsor applications is studied. Beam theory and the concept of hydrodynamic function are used to describe the interaction between the beam and water. Furthermore, a quasi-steady blade element model that accounts for unsteady phenomena such as added mass effects, dynamic stall, and the cumulative Wagner effect is used to obtain hydrodynamic performance of the ionic polymer-metal composite propulsor. Dynamic characteristics of ionic polymer-metal composite fin are analyzed using numerical simulations. It is shown that the use of optimization methods can lead to significant improvement in performance of the ionic polymer-metal composite fin.

Self-Assembly and Catalytic Activity of Metal Nanoparticles Immobilized in Polymer Membrane Prepared via Layer-by-Layer Approach

Densely packed nanoparticles distributed in a stable and robust thin film is a highly preferred system for utilizing the various applications of nanoparticles. Here, we report covalent bond mediated layer-by-layer (LbL) self-assembled thin films of nanoparticles embedded in polymer membrane. Polymer with complementary functional group is utilized for fabrication of thin film via covalent bonding. UV-visible spectroscopy, atomic force microscopy (AFM) and scanning electron microscopy (SEM) were used to monitor the growth of LbL thin film. Subsequently, the composite thin film is used for catalysis of an organic electron transfer reaction of p-nitrophenol to p-aminophenol by sodium borohydride. The catalytic activity of these composite films is assayed multiple times, proving its applicability as a catalyst. The kinetic data obtained by monitoring reduction of p-nitrophenol suggest that the reaction rates are directly related to the sizes of the nanoparticle and porosity of the membrane.

Thermal degradation kinetics of poly(trimethylol propane triacrylate)/poly(hexane diol diacrylate) interpenetrating polymer network

Interpenetrating polymer networks (IPNs) of trimethylol propane triacrylate (TMPTA) and 1,6-hexane diol diacrylate (HDDA) at different weight ratios were synthesized. Temperature modulated differential scanning calorimetry (TMDSC) was used to determine whether the formation resulted in a copolymer or interpenetrating polymer network (IPN). These polymers are used as binders for microstereolithography (MSL) based ceramic microfabrication. The kinetics of thermal degradation of these polymers are important to optimize the debinding process for fabricating 3D shaped ceramic objects by MSL based rapid prototyping technique. Therefore, thermal and thermo-oxidative degradation of these IPNs have been studied by dynamic and isothermal thermogravimetry (TGA). Non-isothermal model-free kinetic methods have been adopted (isoconversional differential and KAS) to calculate the apparent activation energy (E a) as a function of conversion (α) in N 2 and air. The degradation of these polymers in N 2 atmosphere occurs via two mechanisms. Chain end scission plays a dominant role at lower temperature while the kinetics is governed by random chain scission at higher temperature. Oxidative degradation shows multiple degradation steps having higher activation energy than in N 2. Isothermal degradation was also carried out to predict the reaction model which is found to be decelerating. It was shown that the degradation of PTMPTA follows a contracting sphere reaction model in N 2. However, as the HDDA content increases in the IPNs, the degradation reaction follows Avrami-Erofeev model and diffusion governed mechanisms. The intermediate IPN compositions show both type of mechanism. Based on the above study, debinding strategy for MSL based microfabricated ceramic structure has been proposed. © 2012 Elsevier B.V.

Electrochemical studies on Zn/nano-CeO 2 electrodeposited composite coatings

The Zn-CeO 2 composite coatings through electrodeposition technique were successfully fabricated on mild steel substrate. As a comparison pure zinc coating was also prepared. The concentration of CeO 2 nanoparticles was varied in the electrolytic bath and the composites were electrodeposited both in the presence and absence of cetyltriammonium bromide (CTAB). The performance of the CeO 2 nanoparticles towards the deposition, crystal structure, texture, surface morphology and electrochemical corrosion behavior was studied. For characterizations of the electrodeposits, the techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM) were used. Both the additives ceria and surfactant polarize the reduction processes and thus influence the deposition process, surface nature and the electrochemical properties. The electrochemical experiments like potentiodynamic polarization and electrochemical impedance spectroscopic (EIS) studies carried out in 3.5 wt. NaCl solution explicit higher corrosion resistance by CeO 2 incorporated coating in the presence of surfactant. © 2012 Elsevier B.V. All rights reserved.

Dynamics of rotating composite beams: A comparative study between CNT reinforced polymer composite beams and laminated composite beams using spectral finite elements

This paper presents a spectral finite element formulation for uniform and tapered rotating CNT embedded polymer composite beams. The exact solution to the governing differential equation of a rotating Euler-Bernoulli beam with maximum centrifugal force is used as an interpolating function for the spectral element formulation. Free vibration and wave propagation analysis is carried out using the formulated spectral element. The present study shows the substantial effect of volume fraction and L/D ratio of CNTs in a beam on the natural frequency, impulse response and wave propagation characteristics of the rotating beam. It is found that the CNTs embedded in the matrix can make the rotating beam non-dispersive in nature at higher rotation speeds. Embedded CNTs can significantly alter the dynamics of polymer-nanocomposite beams. The results are also compared with those obtained for carbon fiber reinforced laminated composite rotating beams. It is observed that CNT reinforced rotating beams are superior in performance compared to laminated composite rotating beams. © 2012 Elsevier Ltd. All rights reserved.

Synchrotron Small-Angle X-ray Scattering Studies of Hemoglobin Nonaggregation Confined inside Polymer Capsules

The effect of confinement on the structure of hemoglobin (Hb) within polymer capsules was investigated here. Hemoglobin transformed from an aggregated state in solution to a nonaggregated state when confined inside the polymer capsules. This was directly confirmed using synchrotron small-angle X-ray scattering (SAXS) studies. The radius of gyration (R-g) and polydispersity (p) of the proteins in the confined state were smaller compared to those in solution. In fact, the R-g value is very similar to theoretical values obtained using protein structures generated from the Protein Databank. In the temperature range (25-85 degrees C, Tm 59 degrees C), the R-g values for the confined Hb remained constant. This observation is in contrary to the increasing R-g values obtained for the bare Hb in solution. This suggested higher thermal stability of Hb when confined inside the polymer capsule than when in solution. Changes in protein configuration were also reflected in the protein function. Confinement resulted in a beneficial enhancement of the electroactivity of Hb. While Hb in solution showed dominance of the cathodic process (Fe3+ -> Fe2+), efficient reversible Fe3+/Fe2+ redox response is observed in the case of the confined Hb. This has important protein functional implications. Confinement allows the electroactive heme to take up positions favorable for various biochemical activities such as sensing of analytes of various sizes from small to macromolecules and controlled delivery of drugs.

Non-destructive evaluation of porosity and its effect on mechanical properties of carbon fiber reinforced polymer composite materials

In this work, an attempt is made to induce porosity of varied levels in carbon fiber reinforced epoxy based polymer composite laminates fabricated using prepregs by varying the fabrication parameters such as applied vacuum, autoclave pressure and curing temperature. Different NDE tools have been utilized to evaluate the porosity content and correlate with measurable parameters of different NDE techniques. Primarily, ultrasonic imaging and real time digital X-ray imaging have been tried to obtain a measurable parameter which can represent or reflect the amount of porosity contained in the composite laminate. Also, effect of varied porosity content on mechanical properties of the CFRP composite materials is investigated through a series of experimental investigations. The outcome of the experimental approach has yielded interesting and encouraging trend as a first step towards developing an NDE tool for quantification of effect of varied porosity in the polymer composite materials.

Non-destructive evaluation of porosity and its effect on mechanical properties of carbon fiber reinforced polymer composite materials

Structural adhesive bonding is widely used to execute assemblies in automobile and aerospace structures. The quality and reliability of these bonded joints must be ensured during service. In this context non destructive evaluation of these bonded structures play an important role. Evaluation of adhesively bonded composite single lap shear joints has been attempted through experimental approach. Series of tests, non-destructive as well as destructive were performed on different sets of carbon fiber reinforced polymer (CFRP) composite lap joint specimens with varied bond quality. Details of the experimental investigations carried out and the outcome are presented in this paper.

Polymer thin film structures for ultra-low cost biosensing

Reflectance change due to binding of molecules on thin film structures has been exploited for bio-molecular sensing by several groups due to its potential in the development of sensitive, low cost, easy to fabricate, large area sensors with high multiplexing capabilities. However, all of these sensing platforms have been developed using traditional semiconductor materials and processing techniques, which are expensive. This article presents a method to fabricate disposable thin film reflectance biosensors using polymers, such as polycarbonate, which are 2-3 orders of magnitude cheaper than conventional semiconductor and dielectric materials and can be processed by alternate low cost methods, leading to significant reduction in consumable costs associated with diagnostic biosensing. (C) 2011 Elsevier GmbH. All rights reserved.

Polymer microfabrication by scanning based microstereolithography: Optical design and material functionality

Several research groups have attempted to optimize photopolymerization parameters to increase the throughput of scanning based microstereolithography (MSL) systems through modified beam scanning techniques. Efforts in reducing the curing line width have been implemented through high numerical aperture (NA) optical setups. However, the intensity contour symmetry and the depth of field of focus have led to grossly non-vertical and non-uniform curing profiles. This work tries to review the photopolymerization process in a scanning based MSL system from the aspect of material functionality and optical design. The focus has been to exploit the rich potential of photoreactor scanning system in achieving desired fabrication modalities (minimum curing width, uniform depth profile, and vertical curing profile) even with a reduced NA optical setup and a single movable stage. The present study tries to manipulate to its advantage the effect of optimized lower c] (photoinitiator (PI) concentration) in reducing the minimum curing width to similar to 10-20 mu m even with a higher spot size (similar to 21.36 mu m) through a judiciously chosen ``monomer-PI'' system. Optimization on grounds of increasing E-max (maximum laser exposure energy at surface) by optimizing the scan rate provides enough time for the monomer or resin to get cured across the entire resist thickness (surface to substrate similar to 10-100 mu m), leading to uniform depth profiles along the entire scan lengths. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4750975]