Laboratory-scale fluidized bed rig for high-temperature tube wastage studies

As part of a study of the wear of candidate heat exchanger tube materials for use in fluidized bed combustors, two similar laboratory-scale rigs have been built and characterized. Specimens of selected alloys are carried on counter-rotating rotors immersed in a fluidized bed, and are exposed to particle impact velocities of up to approximately 3 ms-1 at temperatures up to 1000°C. The performance of this design of apparatus has been investigated in detail. The effects of several experimental variables have been studied, including angle of particle impact, specimen speed, position of the rotor within the fluidized bed, duration of exposure, bed material particle size, degradation of the bed material, degree of fluidization of the bed, and size of specimen. In many cases the results obtained with steel specimens at elevated temperatures are similar to those observed with polymeric specimens at low temperatures.

Deposition of carbon nitride films using an electron cyclotron wave resonance plasma source

Hydrogenated amorphous carbon nitride (a-C:N:H) has been synthesized using a high plasma density electron cyclotron wave resonance (ECWR) technique using N2 and C2H2 as source gases, at different ratios and a fixed ion energy (80 eV). The composition, structure and bonding state of the films were investigated and related to their optical and electrical properties. The nitrogen content in the film rises rapidly until the N2/C2H2 gas ratio reaches 2 and then increases more gradually, while the deposition rate decreases steeply, placing an upper limit for the nitrogen incorporation at 30 at%. For nitrogen contents above 20 at%, the band gap and sp3-bonded carbon fraction decrease from 1.7 to 1.1 eV and approximately 65 to 40%, respectively. Films with higher nitrogen content are less dense than the original hydrogenated tetrahedral amorphous carbon (ta-C:H) film but, because they have a relatively high band gap (1.1 eV), high resistivity (109 Ω cm) and moderate sp3-bonded carbon fraction (40%), they should be classed as polymeric in nature.

Nitrogen incorporation into tetrahedral hydrogenated amorphous carbon

Structural changes induced by the incorporation of nitrogen into ta-C : H films have been studied by Electron Energy Loss Spectroscopy, X-Ray Photoelectron Spectroscopy, Fourier Transformed Infrared Spectroscopy and Ultraviolet-Visible Spectroscopy. ta-C:H films have been synthesised using a low pressure Electron Cyclotron Wave Resonance (ECWR) source which provides a plasma beam with a high degree of ionisation and dissociation. Nitrogen was incorporated by adding N2 to the C2H2 plasma used for the deposition of ta-C : H films. The N/C atomic ratio in the films rises rapidly until the N2/C2H2 gas ratio reaches three, and then increases more gradually, while the deposition rate decreases steeply. Chemical sputtering of the forming films and the formation of molecular nitrogen within the films limit the maximum nitrogen content to about N/C = 0.6. For low nitrogen content the films retain their diamond-like properties, however as N/C atomic ratio increases, a polymeric-like material is formed, with >C=N- structures and terminating C=N and NH groups that decrease the connectivity of the network.

Perturbation of the stability of amyloid fibrils through alteration of electrostatic interactions.

The self-assembly of proteins and peptides into polymeric amyloid fibrils is a process that has important implications ranging from the understanding of protein misfolding disorders to the discovery of novel nanobiomaterials. In this study, we probe the stability of fibrils prepared at pH 2.0 and composed of the protein insulin by manipulating electrostatic interactions within the fibril architecture. We demonstrate that strong electrostatic repulsion is sufficient to disrupt the hydrogen-bonded, cross-β network that links insulin molecules and ultimately results in fibril dissociation. The extent of this dissociation correlates well with predictions for colloidal models considering the net global charge of the polypeptide chain, although the kinetics of the process is regulated by the charge state of a single amino acid. We found the fibrils to be maximally stable under their formation conditions. Partial disruption of the cross-β network under conditions where the fibrils remain intact leads to a reduction in their stability. Together, these results support the contention that a major determinant of amyloid stability stems from the interactions in the structured core, and show how the control of electrostatic interactions can be used to characterize the factors that modulate fibril stability.

SU8 bio-chemical sensor microarrays

Microfabricated cantilevers have recently attracted considerable attention as novel label-free chemical and biological biosensors which translate surface reactions into nanomechanical bending motion. However these studies have primarily focused on commercially available silicon cantilevers and relatively little work has been performed on cantilevers fabricated from other materials. Polymeric materials, offer significant advantages over silicon by virtue of the low Young's modulus, ease of microfabrication and reduced cost. In this paper, we report a non-vacuum fabrication process to produce arrays of SU8 cantilevers and demonstrate their application as chemical sensors using in situ reference cantilevers. © 2006 Elsevier B.V. All rights reserved.

Friction of sliding surfaces carrying adsorbed lubricant layers

In concentrated contacts the behaviour of lubricants is much modified by the high local pressures: changes can arise both from molecular ordering within the very thin film lubricant layers present at the interface as well as from the deposition on the component surfaces of more solid-like polymeric boundary layers. These 'third bodies' separating the solid surfaces may have rheological or mechanical properties very different from those observed in the bulk. Classical elasto-hydrodynamic theory considers the entrapped lubricant to exhibit a piezo-viscous behaviour while the conventional picture of more solid boundary lubricant layers views their shear strength r as being linearly dependent on local pressure p, so that T = TO + ap where TO and a are constants. If TO is relatively small, then the coefficient of friction \i = T Ip ~ a and so Amonton's laws are recovered. However, the properties of adsorbed or deposited surface films, or indeed other third bodies such as debris layers, may be more complex than this. A preliminary study has looked quantitatively at the influence of the pressure dependence of the shear strength of any surface layer on the overall friction coefficient of a contact which is made up of an array of asperities whose height varies in a Gaussian manner. Individual contact points may be elastic or plastic. The analysis results in plots of coefficient of friction versus the service or load parameter PIH&NRa where P is the nominal pressure on the contact, HS the hardness of the deforming surface, N the asperity density, R the mean radius of curvature of the asperities, and a is the standard deviation of their height distribution. In principle, any variation oft withp can be incorporated into the model; however, in this initial study we have used data on colloidal suspensions from the group at the Ecole Centrale de Lyon as well as examining the effect of functional relationships of somewhat greater complexity than a simple linear form. Results of the analysis indicate that variations in fj. are possible as the load is varied which depend on the statistical spread of behaviour at individual asperity contacts. The value of this analysis is that it attempts to combine the behaviour of films on the molecular scale with the topography of real engineering surfaces and so give an indication of the effects at the full-size or macro-scale that can be achieved by chemical or molecular surface engineering.

Nanoindentation measurements of bone viscoelasticity as a function of hydration state

Bone is an anisotropic material, and its mechanical properties are determined by its microstructure as well as its composition. Mechanical properties of bone are a consequence of the proportions of, and the interactions between, mineral, collagen and water. Water plays an important role in maintaining the mechanical integrity of the composite, but the manner in which water interacts within the ultrastructure is unclear. Dentine being an isotropic two-dimensional structure presents a homogenous composite to examine the dehydration effects. Nanoindentation methods for determining the viscoelastic properties have recently been developed and are a subject of great interest. Here, one method based on elastic-viscoelastic correspondence for 'ramp and hold' creep testing (Oyen, J. Mater. Res., 2005) has been used to analyze viscoelastic behavior of polymeric and biological materials. The method of 'ramp and hold' allows the shear modulus at time zero to be determined from fitting of the displacement during the maximum load hold. Changes in the viscoelastic properties of bone and dentine were examined as the material was systematically dehydrated in a series of water:solvent mixes. Samples of equine dentine were sectioned and cryo-polished. Shear modulus was obtained by nanoindentation using spherical indenters with a maximum load hold of 120s. Samples were tested in different solvent concentrations sequentially, 70% ethanol to 50% ethanol, 70 % ethanol to 100% ethanol, 70% ethanol to 70% methanol to 100% methanol, and 70% ethanol to 100% acetone, after storage in each condition for 24h. By selectively removing and then replacing water from the composite, insights in to the ultrastructure of the tissue can be gained from the corresponding changes in the experimentally determined moduli, as well as an understanding of the complete reversibility of the dehydration process. © 2006 Materials Research Society.

Poroelastic indentation analysis for hydrated biological tissues

Indentation techniques are employed for the measurement of mechanical properties of a wide range of materials. In particular, techniques focused at small length-scales, such as nanoindentation and AFM indentation, allow for local characterization of material properties in heterogeneous materials including natural tissues and biomimetic materials. Typical elastic analysis for spherical indentation is applicable in the absence of time-dependent deformation, but is inappropriate for materials with time-dependent responses. Recent analyses for the viscoelastic indentation problem, based on elastic-viscoelastic correspondence, have begun to address the issue of time-dependent deformation during an indentation test. The viscoelastic analysis has been shown to fit experimental indentation data well, and has been demonstrated as useful for characterization of viscoelasticity in polymeric materials and in hydrated mineralized tissues. However, a viscoelastic analysis is not necessarily sufficient for multi-phase materials with fluid flow. In the current work, a poroelastic analysis-based on fluid motion through a porous elastic network-is used to examine spherical indentation creep responses of hydrated biological materials. Both analytical and finite element approaches are considered for the poroelastic Hertzian indentation problem. Modeling results are compared with experimental data from nanoindentation of hydrated bone immersed in water and polar solvents (ethanol, methanol, acetone). Baseline (water-immersed) bone responses are characterized using the poroelastic model and numerical results are compared with altered hydration states due to polar solvents. © 2007 Materials Research Society.

Perylene-based fluorescent liquid crystal dye guest-host mixtures

We present a study on a series of dye guest-host mixtures using fluorescent perylene-based molecules as the guest dye in an organosiloxane host. These hosts have temperature-independent switching, at room temperature, through 90° for fields of the order of 10 Vrms/μm. Perylene molecules have been grafted onto the organosiloxane moiety via an alkyl spacer producing novel and rugged fluorescent dyes that are readily miscible in the host. Micro-separation of the low molar mass siloxane groups in the mesophases tend to form smectic phases. These planes produce an effective two-dimensional polymer backbonethat engenders the rugged mechanical properties of polymeric liquid crystals onto these low molar mass ferroelectric liquid crystals. In this study we show how the introduction of the dye molecules affects the electro-optic properties of the organosiloxane host. © 2001 OPA (Overseas Publishers Association) N.V. Published by license under the Gordon and Breach Science Publishers imprint, a member of the Taylor & Francis Group,.

Fabrication and electromechanical characterization of near-field electrospun composite fibers.

We report the use of near-field electrospinning (NFES) as a route to fabricate composite electrodes. Electrodes made of composite fibers of multi-walled carbon nanotubes in polyethylene oxide (PEO) are formed via liquid deposition, with precise control over their configuration. The electromechanical properties of free-standing fibers and fibers deposited on elastic substrates are studied in detail. In particular, we examine the elastic deformation limit of the resulting free-standing fibers and find, similarly to bulk PEO composites, that the plastic deformation onset is below 2% of tensile strain. In comparison, the apparent deformation limit is much improved when the fibers are integrated onto a stretchable, elastic substrate. It is hoped that the NFES fabrication protocol presented here can provide a platform to direct-write polymeric electrodes, and to integrate both stiff and soft electrodes onto a variety of polymeric substrates.

Polymer waveguide-based backplanes for board-level optical interconnects

Optical interconnects are increasingly considered for use in high-performance electronic systems. Multimode polymer waveguides are a promising technology for the formation of optical backplane as they enable cost-effective integration of optical links onto standard printed circuit boards. In this paper, two different types of polymer waveguide-based optical backplanes are presented. The first one implements a passive shuffle architecture enabling non-blocking on-board optical interconnection between different cards/modules, while the second one deploys a regenerative bus architecture allowing the interconnection of an arbitrary number of electrical cards over a common optical bus. The polymer materials and the multimode waveguide components used to form the optical backplanes are presented, while details of the interconnection architectures and design of the backplanes are described. Proof-of-principle demonstrators fabricated onto low-cost FR4 substrates, including a 10-card 1 Tb/s-capacity passive shuffle router and 4-channel 3-card polymeric bus modules, are reported and their optical performance characteristics are presented. Low-loss, low-crosstalk on-board interconnection is achieved and error-free (BER10 12) 10 Gb/s communication between different card/module interfaces is demonstrated in both polymeric backplane systems. © 2012 IEEE.

Direct-write conductive fibres for soft electronics

We report the use of near-field electrospinning (NFES) as a route to fabricate composite electrodes. Electrodes made of composite fibers of carbon nanotubes in polyethylene oxide (PEO) are formed via liquid deposition, with precise control over their configuration. The electromechanical properties of free-standing fibers and fibers deposited on elastic substrates are studied in detail. We then examine the elastic deformation limit of the resulting free-standing fibers and find, similarly to bulk PEO composites, that the plastic deformation onset is below 2% of tensile strain. In comparison, the apparent deformation limit is much improved when the fibers are integrated onto a stretchable, elastic substrate. It is hoped that the NFES fabrication protocol presented here can provide a platform to direct-write polymeric electrodes, and to integrate both stiff and soft electrodes onto a variety of polymeric substrates. © 2012 IEEE.

Failure mechanisms in fibrous scaffolds.

Polymeric fibrous scaffolds have been considered as replacements for load-bearing soft tissues, because of their ability to mimic the microstructure of natural tissues. Poor toughness of fibrous materials results in failure, which is an issue of importance to both engineering and medical practice. The toughness of fibrous materials depends on the ability of the microstructure to develop toughening mechanisms. However, such toughening mechanisms are still not well understood, because the detailed evolution at the microscopic level is difficult to visualize. A novel and simple method was developed, namely, a sample-taping technique, to examine the detailed failure mechanisms of fibrous microstructures. This technique was compared with in situ fracture testing by scanning electron microscopy. Examination of three types of fibrous networks showed that two different failure modes occurred in fibrous scaffolds. For brittle cracking in gelatin electrospun scaffolds, the random network morphology around the crack tip remained during crack propagation. For ductile failure in polycaprolactone electrospun scaffolds and nonwoven fabrics, the random network deformed via fiber rearrangement, and a large number of fiber bundles formed across the region in front of the notch tip. These fiber bundles not only accommodated mechanical strain, but also resisted crack propagation and thus toughened the fibrous scaffolds. Such understanding provides insight for the production of fibrous materials with enhanced toughness.

Using mesoscopic models to design strong and tough biomimetic polymer networks

Using computational modeling, we investigate the mechanical properties of polymeric materials composed of coiled chains, or "globules", which encompass a folded secondary structure and are cross-linked by labile bonds to form a macroscopic network. In the presence of an applied force, the globules can unfold into linear chains and thereby dissipate energy as the network is deformed; the latter attribute can contribute to the toughness of the material. Our goal is to determine how to tailor the labile intra- and intermolecular bonds within the network to produce material exhibiting both toughness and strength. Herein, we use the lattice spring model (LSM) to simulate the globules and the cross-linked network. We also utilize our modified Hierarchical Bell model (MHBM) to simulate the rupture and reforming of N parallel bonds. By applying a tensile deformation, we demonstrate that the mechanical properties of the system are sensitive to the values of N in and N out, the respective values of N for the intra- and intermolecular bonds. We find that the strength of the material is mainly controlled by the value of N out, with the higher value of N out providing a stronger material. We also find that, if N in is smaller than N out, the globules can unfold under the tensile load before the sample fractures and, in this manner, can increase the ductility of the sample. Our results provide effective strategies for exploiting relatively weak, labile interactions (e.g., hydrogen bonding or the thiol/disulfide exchange reaction) in both the intra- and intermolecular bonds to tailor the macroscopic performance of the materials. © 2011 American Chemical Society.

Failure mechanisms in fibrous scaffolds

Polymeric fibrous scaffolds have been considered as replacements for load-bearing soft tissues, because of their ability to mimic the microstructure of natural tissues. Poor toughness of fibrous materials results in failure, which is an issue of importance to both engineering and medical practice. The toughness of fibrous materials depends on the ability of the microstructure to develop toughening mechanisms. However, such toughening mechanisms are still not well understood, because the detailed evolution at the microscopic level is difficult to visualize. A novel and simple method was developed, namely, a sample-taping technique, to examine the detailed failure mechanisms of fibrous microstructures. This technique was compared with in situ fracture testing by scanning electron microscopy. Examination of three types of fibrous networks showed that two different failure modes occurred in fibrous scaffolds. For brittle cracking in gelatin electrospun scaffolds, the random network morphology around the crack tip remained during crack propagation. For ductile failure in polycaprolactone electrospun scaffolds and nonwoven fabrics, the random network deformed via fiber rearrangement, and a large number of fiber bundles formed across the region in front of the notch tip. These fiber bundles not only accommodated mechanical strain, but also resisted crack propagation and thus toughened the fibrous scaffolds. Such understanding provides insight for the production of fibrous materials with enhanced toughness. © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.