Investigation of the mechanical behavior of kangaroo humeral head cartilage tissue by a porohyperelastic model based on the strain-rate-dependent permeability

Solid–interstitial fluid interaction, which depends on tissue permeability, is significant to the strain-rate-dependent mechanical behavior of humeral head (shoulder) cartilage. Due to anatomical and biomechanical similarities to that of the human shoulder, kangaroos present a suitable animal model. Therefore, indentation experiments were conducted on kangaroo shoulder cartilage tissues from low (10−4/s) to moderately high (10−2/s) strain-rates. A porohyperelastic model was developed based on the experimental characterization; and a permeability function that takes into account the effect of strain-rate on permeability (strain-rate-dependent permeability) was introduced into the model to investigate the effect of rate-dependent fluid flow on tissue response. The prediction of the model with the strain-rate-dependent permeability was compared with those of the models using constant permeability and strain-dependent permeability. Compared to the model with constant permeability, the models with strain-dependent and strain-rate-dependent permeability were able to better capture the experimental variation at all strain-rates (p<0.05). Significant differences were not identified between models with strain-dependent and strain-rate-dependent permeability at strain-rate of 5×10−3/s (p=0.179). However, at strain-rate of 10−2/s, the model with strain-rate-dependent permeability was significantly better at capturing the experimental results (p<0.005). The findings thus revealed the significance of rate-dependent fluid flow on tissue behavior at large strain-rates, which provides insights into the mechanical deformation mechanisms of cartilage tissues.

Nanoindentation study of the mechanical behavior of TiO2 nanotube arrays

Titanium dioxide (TiO2) nanotube arrays are attracting increasing attention for use in solar cells, lithium-ion batteries, and biomedical implants. To take full advantage of their unique physical properties, such arrays need to maintain adequate mechanical integrity in applications. However, the mechanical performance of TiO2 nanotube arrays is not well understood. In this work, we investigate the deformation and failure of TiO2 nanotube arrays using the nanoindentation technique. We found that the load–displacement response of the arrays strongly depends on the indentation depth and indenter shape. Substrate-independent elastic modulus and hardness can be obtained when the indentation depth is less than 2.5% of the array height. The deformation mechanisms of TiO2 nanotube arrays by Berkovich and conical indenters are closely associated with the densification of TiO2 nanotubes under compression. A theoretical model for deformation of the arrays under a largeradius conical indenter is also proposed.

Electronic Structure of Vacancy Ordered Spinels, $GaMo_{4}S_{8}$ and $GaV_{4}S_{8}$, from ab Initio Calculations

We report ab initio calculations for the band dispersions and total as well as partial densities of states for vacancy ordered, clustered spinels, GaMo4S8 and GaV4S8. Results are presented for the high temperature cubic phase for both compounds. Additionally, we discuss results of similar calculations for GaMo4S8 in an idealized cubic structure, as well as the nonmagnetic and the ferromagnetic states of the low temperature rhombohedral structure. Comparison of these results allows us to discuss the unusual aspects of the electronic structure of this interesting class of compounds, and provide estimates of the crystal-field and exchange splitting strengths.

Elevated temperature mechanical properties of hollow flange channel sections

The fire performance of cold-formed steel members is an important criterion to be verified for their successful use in structural applications. However, lack of clear design guidance on their fire performance has inhibited their usage in buildings. Their elevated temperature mechanical properties, i.e., yield strengths, elastic moduli and stress–strain relationships, are imperative for the fire design. In the past many researchers have proposed elevated temperature mechanical property reduction factors for cold-formed steels, however, large variations exist among them. The LiteSteel Beam (LSB), a hollow flange channel section, is manufactured by a combined cold-forming and electric resistance welding process. Its web, inner and outer flange elements have different yield strengths due to varying levels of cold-working caused by their manufacturing process. Elevated temperature mechanical properties of LSBs are not the same even within their cross-sections. Therefore an experimental study was undertaken to determine the elevated temperature mechanical properties of steel plate elements in LSBs. Elevated temperature tensile tests were performed on web, inner and outer flange specimens taken from LSBs, and their results are presented in this paper including their comparisons with previous studies. Based on the test results and the proposed values from previous studies and fire design standards, suitable predictive equations are proposed for the determination of elevated temperature mechanical properties of LSB web and flange elements. Suitable stress–strain models are also proposed for the plate elements of this cold-formed and welded hollow flange channel section.

Increasing ionic conductivity and mechanical strength of a plastic electrolyte by inclusion of a polymer

in this contribution we present a soft matter solid electrolyte which was obtained by inclusion of a polymer (polyacrylonitrile, PAN) in LiClO4/LiTFSI-succinonitrile (SN), a semi-solid organic plastic electrolyte. Addition of the polymer resulted in considerable enhancement in ionic conductivity as well as mechanical strength of LiX-SN (X=ClO4, TFSI) plastic electrolyte. Ionic conductivity of 92.5%-[1 M LiClO4-SN]:7.5%-PAN (PAN amount as per SN weight) composite at 25 degrees C recorded a remarkably high value of 7 x 10(-3) Omega(-1) cm(-1), higher by few tens of order in magnitude compared to 1 M LiClO4-SN. Composite conductivity at sub-ambient temperature is also quite high. At -20 degrees C, the ionic conductivity of (100 -x)%-[1 M LiClO4-SN]:x%-PAN composites are in the range 3 x 10(-5)-4.5 x 10(-4) Omega(-1) cm(-1), approximately one to two orders of magnitude higher with respect to 1 M LiClO4-SN electrolyte conductivity. Addition of PAN resulted in an increase of the Young's modulus (Y) from Y -> 0 for LiClO4-SN to a maximum of 0.4MPa for the composites. Microstructural studies based on X-ray diffraction, differential scanning calorimetry and Fourier transform infrared spectroscopy suggest that enhancement in composite ionic conductivity is a combined effect of decrease in crystallinity and enhanced trans conformer concentration. (c) 2008 Elsevier Ltd. All rights reserved.

Synthesis by mechanical alloying and thermoelectric properties of Cu2Te

Hexagonal Cu-2 Te has been synthesised by mechanical alloying from elemental powders. The milling time required for the synthesis is longer than that reported for other tellurides. The mechanical grinding of the bulk Cu2Te obtained by the melting route does not change the structure. Prolonged milling as well as grinding beyond 40 h lead to a decrease in grain size to nanometer level. The cold compaction of milled or ground powders exhibit much smaller Seebeck coefficient (thermopower). However, cold compaction of samples milled for longer time (>150 h) lead to the thermopower values close to that of the bulk indicating significant improvement of rheological properties at room temperature for powders milled for long times.

The high temperature mechanical characteristics of superplastic 3 mol% yttria stabilized zirconia

A detailed study was undertaken to characterize the deformation behavior of a superplastic 3 mol% yttria-stabilized tetragonal zirconia (3YTZ) over a wide range of strain rates, temperatures and grain sizes. The experimental data were analyzed in terms of the following equation for high temperature deformation: Image Full-size image ∞ σn d−pexp(−Q/RT), where Image Full-size image is the strain rate, σ is the flow stress, d is the grain size, Q is the activation energy, R is the gas constant, T is the absolute temperature, and n and p are constants termed the stress exponent and the inverse grain size exponent, respectively. The experimental data over a wide range of stresses revealed a transition in stress exponent. Deformation in the low and high stress regions was associated with n not, vert, similar 3 and p not, vert, similar 1, and n not, vert, similar 2 and p not, vert, similar 3, respectively. The transition stress between the two regions decreased with increasing grain size. The activation energy was similar for both regions with a value of not, vert, similar 550 kJ mol−1. Microstructural measurements revealed that grains remained essentially equiaxed after the accumulation of large strains, and very limited concurrent grain growths occurred in most experiments. Assessment of possible rate controlling creep mechanisms and comparison with previous studied indicate that in the n not, vert, similar 2 region, deformation occurs by a grain boundary sliding process whose rate is independent of impurity content. Deformation in the n not, vert, similar 3 region is controlled by an interface reaction that is highly sensitive to impurity content. It is concluded that an increase in impurity content increases yttrium segregation to grain boundaries, which enhances the rate of the interface reaction, thereby decreasing the apparent transition stress between the n not, vert, similar 2 and n not, vert, similar 3 regions. This unified approach incorporating two sequential mechanisms can rationalize many of the apparently dissimilar results that have been reported previously for deformation of 3YTZ.

The influence of trace impurities on the mechanical characteristics of a superplastic 2 mol% yttria stabilized zirconia

In contrast to metallic alloys, the mechanical characteristics of superplastic ceramics are very sensitive to minor changes in levels of trace impurities. In the present study, the mechanical behavior of a 2 mol% yttria stabilized tetragonal zirconia was studied in tension and compression in two batches of material, with small variations in levels of trace impurities, to examine the influence of stress axis and impurity content on the deformation behavior. The mechanical properties of the material were characterized in terms of the expression: (epsilon)over dot proportional to sigma(n) where (epsilon)over dot is the strain rate, sigma is the stress and n is termed the stress exponent. The mechanical behavior of the ceramic was identical in tension and compression, for a material with a given level of impurity. The high purity specimens exhibited a transition from a stress exponent of similar to 3 to similar to 2 with an increase in stress, whereas the low purity material displayed only n similar to 2 behavior over the entire stress range studied. Detailed high resolution and analytical electron microscopy studies revealed that there was no amorphous phase at interfaces in both batches of material; however, segregation of Al at interfaces was detected only in the low purity material. The observed transition in stress exponents can be rationalized in terms of two sequential mechanisms: grain boundary sliding with n similar to 2 and interface reaction controlled grain boundary sliding with n similar to 3. The transition from n similar to 3 to similar to 2 occurred at lower stresses with an increase in the grain size and a decrease in the purity level.

Electronic structure studies and photocatalytic properties of cubic Bi1.5ZnNb1.5O7

The photocatalytic ability of cubic Bi1.5ZnNb1.5O7 (BZN) pyrochlore for the decolorization of an acid orange 7 (AO7) azo dye in aqueous solution under ultraviolet (UV) irradiation has been investigated for the first time. BZN catalyst powders prepared using low temperature sol-gel and higher temperature solid-state methods have been evaluated and their reaction rates have been compared.The experimental band gap energy has been estimated from the optical absorption edge and has been used as reference for theoretical calculations. The electronic band structure of BZN has been investigated using first-principles density functional theory (DFT) calculations for random, completely and partially ordered solid solutions of Zn cations in both the A and B sites of the pyrochlore structure.The nature of the orbitals in the valence band (VB) and the conduction band (CB) has been identified and the theoretical band gap energy has been discussed in terms of the DFT model approximations.

Self-assembly of indole-2-carboxylic acid at graphite and gold surfaces

Model systems are critical to our understanding of self-assembly processes. As such, we have studied the surface self-assembly of a small and simple molecule, indole-2-carboxylic acid (I2CA). We combine density functional theory gas-phase (DFT) calculations with scanning tunneling microscopy to reveal details of I2CA assembly in two different solvents at the solution/solid interface, and on Au(111) in ultrahigh vacuum (UHV). In UHV and at the trichlorobenzene/highly oriented pyrolytic graphite (HOPG) interface, I2CA forms epitaxial lamellar structures based on cyclic OH⋯O carboxylic dimers. The structure formed at the heptanoic acid/HOPG interface is different and can be interpreted in a model where heptanoic acid molecules co-adsorb on the substrate with the I2CA, forming a bicomponent commensurate unit cell. DFT calculations of dimer energetics elucidate the basic building blocks of these structures, whereas calculations of periodic two-dimensional assemblies reveal the epitaxial effects introduced by the different substrates.

The equilibrium geometry and electronic structure of Bi nanolines on clean and hydrogenated Si(001) surfaces

The equilibrium geometry, electronic structure and energetic stability of Bi nanolines on clean and hydrogenated Si(001) surfaces have been examined by means of ab initio total energy calculations and scanning tunnelling microscopy. For the Bi nanolines on a clean Si surface the two most plausible structural models, the Miki or M model (Miki et al 1999 Phys. Rev. B 59 14868) and the Haiku or H model (Owen et al 2002 Phys. Rev. Lett. 88 226104), have been examined in detail. The results of the total energy calculations support the stability of the H model over the M model, in agreement with previous theoretical results. For Bi nanolines on the hydrogenated Si(001) surface, we find that an atomic configuration derived from the H model is also more stable than an atomic configuration derived from the M model. However, the energetically less stable (M) model exhibits better agreement with experimental measurements for equilibrium geometry. The electronic structures of the H and M models are very similar. Both models exhibit a semiconducting character, with the highest occupied Bi-derived bands lying at ~0.5 eV below the valence band maximum. Simulated and experimental STM images confirm that at a low negative bias the Bi lines exhibit an 'antiwire' property for both structural models.

The electronic origin of contrast reversal in bias-dependent STM images of nanolines

Self-organized Bi lines that are only 1.5 nm wide can be grown without kinks or breaks on Si(0 0 1) surfaces to lengths of up to 500 nm. Constant-current topographical images of the lines, obtained with the scanning tunneling microscope, have a striking bias dependence. Although the lines appear darker than the Si terraces at biases below ≈∣1.2∣ V, the contrast reverses at biases above ≈∣1.5∣ V. Between these two ranges the lines and terraces are of comparable brightness. It has been suggested that this bias dependence may be due to the presence of a semiconductor-like energy gap within the line. Using ab initio calculations it is demonstrated that the energy gap is too small to explain the experimentally observed bias dependence. Consequently, at this time, there is no compelling explanation for this phenomenon. An alternative explanation is proposed that arises naturally from calculations of the tunneling current, using the Tersoff–Hamann approximation, and an examination of the electronic structure of the line.

The geometry of Bi nanolines on Si(0 0 1)

A study of the Bi nanoline geometry on Si(0 0 1) has been performed using a combination of ab initio theoretical technique and scanning tunnelling microscopy (STM). Our calculations demonstrate decisively that the recently proposed Haiku geometry is a lower energy configuration than any of the previously proposed line geometries. Furthermore, we have made comparisons between STM constant-current topographs of the lines and Tersoff–Haman STM simulations. Although the Haiku and the Miki geometries both reproduce the main features of the constant-current topographs, the simulated STM images of the Miki geometry have a dark stripe between the dimer rows that does not correspond well with experiment.

The electronic properties of Si(001)–Bi(2 × n)

A Bi 2 × n surface net was grown on the Si(001) surface and studied with inverse photoemission, scanning tunnelling microscopy and ab initio and empirical pseudopotential calculations. The experiments demonstrated that Bi adsorption eliminates the dimer related π1* and π2* surface states, produced by correlated dimer buckling, leaving the bulk bandgap clear of unoccupied surface states. Ab initio calculations support this observation and demonstrate that the surface states derived from the formation of symmetric Bi dimers do not penetrate the fundamental bandgap of bulk Si. Since symmetric Bi dimers are an important structural component of the recently discovered Bi nanolines, that self-organize on Si(001) above the Bi desorption temperature, a connection will be made between our findings and the electronic structure of the nanolines.

Two-dimensional self-assembly of a symmetry-reduced tricarboxylic acid

Investigations of the self-assembly of simple molecules at the solution/solid interface can provide useful insight into the general principles governing supramolecular chemistry in two dimensions. Here, we report on the assembly of 3,4′,5-biphenyl tricarboxylic acid (H3BHTC), a small hydrogen bonding unit related to the much-studied 1,3,5-benzenetricarboxylic acid (trimesic acid, TMA), which we investigate using scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. STM images show that H3BHTC assembles by itself into an offset zigzag chain structure that maximizes the surface molecular density in favor of maximizing the number density of strong cyclic hydrogen bonds between the carboxylic groups. The offset geometry creates “sticky” pores that promote solvent coadsorption. Adding coronene to the molecular solution produces a transformation to a high-symmetry host–guest lattice stabilized by a dimeric/trimeric hydrogen bonding motif similar to the TMA flower structure. Finally, we show that the H3BHTC lattice firmly immobilizes the guest coronene molecules, allowing for high-resolution imaging of the coronene structure.