Materials

Materials, Vol. 5, Pages 258-277: Ceramic Laser Materials

Jasbinder Sanghera — Thu, 09 Feb 2012 00:00:00 CET

Ceramic laser materials have come a long way since the first demonstration of lasing in 1964. Improvements in powder synthesis and ceramic sintering as well as novel ideas have led to notable achievements. These include the first Nd:yttrium aluminum garnet (YAG) ceramic laser in 1995, breaking the 1 KW mark in 2002 and then the remarkable demonstration of more than 100 KW output power from a YAG ceramic laser system in 2009. Additional developments have included highly doped microchip lasers, ultrashort pulse lasers, novel materials such as sesquioxides, fluoride ceramic lasers, selenide ceramic lasers in the 2 to 3 μm region, composite ceramic lasers for better thermal management, and single crystal lasers derived from polycrystalline ceramics. This paper highlights some of these notable achievements.

Materials, Vol. 5, Pages 248-257: Molecular Beam-Thermal Desorption Spectrometry (MB-TDS) Monitoring of Hydrogen Desorbed from Storage Fuel Cell Anodes

Rui F. M. Lobo — Mon, 06 Feb 2012 00:00:00 CET

Different types of experimental studies are performed using the hydrogen storage alloy (HSA) MlNi3.6Co0.85Al0.3Mn0.3 (Ml: La-rich mischmetal), chemically surface treated, as the anode active material for application in a proton exchange membrane fuel cell (PEMFC). The recently developed molecular beam—thermal desorption spectrometry (MB-TDS) technique is here reported for detecting the electrochemical hydrogen uptake and release by the treated HSA. The MB-TDS allows an accurate determination of the hydrogen mass absorbed into the hydrogen storage alloy (HSA), and has significant advantages in comparison with the conventional TDS method. Experimental data has revealed that the membrane electrode assembly (MEA) using such chemically treated alloy presents an enhanced surface capability for hydrogen adsorption.

Materials, Vol. 5, Pages 239-247: Aligned Layers of Silver Nano-Fibers

Andrii B. Golovin — Wed, 01 Feb 2012 00:00:00 CET

We describe a new dichroic polarizers made by ordering silver nano-fibers to aligned layers. The aligned layers consist of nano-fibers and self-assembled molecular aggregates of lyotropic liquid crystals. Unidirectional alignment of the layers is achieved by means of mechanical shearing. Aligned layers of silver nano-fibers are partially transparent to a linearly polarized electromagnetic radiation. The unidirectional alignment and density of the silver nano-fibers determine degree of polarization of transmitted light. The aligned layers of silver nano-fibers might be used in optics, microwave applications, and organic electronics.

Materials, Vol. 5, Pages 227-238: Optical Properties of Mg, Fe, Co-Doped Near-Stoichiometric LiTaO3 Single Crystals

Wei Tse Hsu — Mon, 30 Jan 2012 00:00:00 CET

Mg, Fe co-doped near-stoichiometric lithium tantalite (SLT) single crystals were grown by employing the zone-leveling Czochralski (ZLCz) technique. The optical properties, holographic parameters, as well as the composition of the grown crystals were measured. It was found that the Li/Ta ratio decreased with the doping of Mg and Fe ions. A red shift was observed in absorption spectrum for the Mg, Fe co-doped crystals compared to the undoped and Mg-doped ones. The effect of the iron ions (Fe2+ and Fe3+) was further discussed based on the specified absorption bands. Moreover, the occupation mechanism for the defects was discussed by using the IR absorption spectrum, which was attributed to the FeTa3− defects in the highly Fe-doped crystal. In addition, the holographic parameters were also found to be improved with a higher Fe/Ta ratio in the crystals.

Materials, Vol. 5, Pages 210-226: Stresses and Displacements in Functionally Graded Materials of Semi-Infinite Extent Induced by Rectangular Loadings

Hong-Tian Xiao — Mon, 30 Jan 2012 00:00:00 CET

This paper presents the stress and displacement fields in a functionally graded material (FGM) caused by a load. The FGM is a graded material of Si3N4-based ceramics and is assumed to be of semi-infinite extent. The load is a distributed loading over a rectangular area that is parallel to the external surface of the FGM and either on its external surface or within its interior space. The point-load analytical solutions or so-called Yue’s solutions are used for the numerical integration over the distributed loaded area. The loaded area is discretized into 200 small equal-sized rectangular elements. The numerical integration is carried out with the regular Gaussian quadrature. Weak and strong singular integrations encountered when the field points are located on the loaded plane, are resolved with the classical methods in boundary element analysis. The numerical integration results have high accuracy.

Materials, Vol. 5, Pages 192-209: Effective Heat and Mass Transport Properties of Anisotropic Porous Ceria for Solar Thermochemical Fuel Generation

Sophia Haussener — Thu, 19 Jan 2012 00:00:00 CET

High-resolution X-ray computed tomography is employed to obtain the exact 3D geometrical configuration of porous anisotropic ceria applied in solar-driven thermochemical cycles for splitting H2O and CO2. The tomography data are, in turn, used in direct pore-level numerical simulations for determining the morphological and effective heat/mass transport properties of porous ceria, namely: porosity, specific surface area, pore size distribution, extinction coefficient, thermal conductivity, convective heat transfer coefficient, permeability, Dupuit-Forchheimer coefficient, and tortuosity and residence time distributions. Tailored foam designs for enhanced transport properties are examined by means of adjusting morphologies of artificial ceria samples composed of bimodal distributed overlapping transparent spheres in an opaque medium.

Materials, Vol. 5, Pages 169-191: Generalized Fractional Derivative Anisotropic Viscoelastic Characterization

Harry H. Hilton — Wed, 18 Jan 2012 00:00:00 CET

Isotropic linear and nonlinear fractional derivative constitutive relations are formulated and examined in terms of many parameter generalized Kelvin models and are analytically extended to cover general anisotropic homogeneous or non-homogeneous as well as functionally graded viscoelastic material behavior. Equivalent integral constitutive relations, which are computationally more powerful, are derived from fractional differential ones and the associated anisotropic temperature-moisture-degree-of-cure shift functions and reduced times are established. Approximate Fourier transform inversions for fractional derivative relations are formulated and their accuracy is evaluated. The efficacy of integer and fractional derivative constitutive relations is compared and the preferential use of either characterization in analyzing isotropic and anisotropic real materials must be examined on a case-by-case basis. Approximate protocols for curve fitting analytical fractional derivative results to experimental data are formulated and evaluated.

Materials, Vol. 5, Pages 157-168: Preparation and Thermal Characterization of Annealed Gold Coated Porous Silicon

Kasra Behzad — Mon, 16 Jan 2012 00:00:00 CET

Porous silicon (PSi) layers were formed on a p-type Si wafer. Six samples were anodised electrically with a 30 mA/cm2 fixed current density for different etching times. The samples were coated with a 50–60 nm gold layer and annealed at different temperatures under Ar flow. The morphology of the layers, before and after annealing, formed by this method was investigated by scanning electron microscopy (SEM). Photoacoustic spectroscopy (PAS) measurements were carried out to measure the thermal diffusivity (TD) of the PSi and Au/PSi samples. For the Au/PSi samples, the thermal diffusivity was measured before and after annealing to study the effect of annealing. Also to study the aging effect, a comparison was made between freshly annealed samples and samples 30 days after annealing.

Materials, Vol. 5, Pages 156: Correction: Goto, H. et al. Liquid Crystalline π-Conjugated Copolymers Bearing a Pyrimidine Type Mesogenic Group. Materials 2009, 2, 22-37

Kohsuke Kawabata — Mon, 09 Jan 2012 00:00:00 CET

We found an error in the Scheme 1 in our paper published in Materials [1]. [...]

Materials, Vol. 5, Pages 135-155: Biodegradable Orthopedic Magnesium-Calcium (MgCa) Alloys, Processing, and Corrosion Performance

Meisam Salahshoor — Mon, 09 Jan 2012 00:00:00 CET

Magnesium-Calcium (Mg-Ca) alloy has received considerable attention as an emerging biodegradable implant material in orthopedic fixation applications. The biodegradable Mg-Ca alloys avoid stress shielding and secondary surgery inherent with permanent metallic implant materials. They also provide sufficient mechanical strength in load carrying applications as opposed to biopolymers. However, the key issue facing a biodegradable Mg-Ca implant is the fast corrosion in the human body environment. The ability to adjust degradation rate of Mg-Ca alloys is critical for the successful development of biodegradable orthopedic implants. This paper focuses on the functions and requirements of bone implants and critical issues of current implant biomaterials. Microstructures and mechanical properties of Mg-Ca alloys, and the unique properties of novel magnesium-calcium implant materials have been reviewed. Various manufacturing techniques to process Mg-Ca based alloys have been analyzed regarding their impacts on implant performance. Corrosion performance of Mg-Ca alloys processed by different manufacturing techniques was compared. In addition, the societal and economical impacts of developing biodegradable orthopedic implants have been emphasized.

Materials, Vol. 5, Pages 121-134: Metal-Exchanged β Zeolites as Catalysts for the Conversion of Acetone to Hydrocarbons

Aurora J. Cruz-Cabeza — Thu, 05 Jan 2012 00:00:00 CET

Various metal-β zeolites have been synthesized under similar ion-exchange conditions. During the exchange process, the nature and acid strength of the used cations modified the composition and textural properties as well as the Brönsted and Lewis acidity of the final materials. Zeolites exchanged with divalent cations showed a clear decrease of their surface Brönsted acidity and an increase of their Lewis acidity. All materials were active as catalysts for the transformation of acetone into hydrocarbons. Although the protonic zeolite was the most active in the acetone conversion (96.8% conversion), the metal-exchanged zeolites showed varied selectivities towards different products of the reaction. In particular, we found the Cu-β to have a considerable selectivity towards the production of isobutene from acetone (over 31% yield compared to 7.5% of the protonic zeolite). We propose different reactions mechanisms in order to explain the final product distributions.

Materials, Vol. 5, Pages 108-120: Advances in Retinal Tissue Engineering

Matthew Trese — Thu, 05 Jan 2012 00:00:00 CET

Retinal degenerations cause permanent visual loss and affect millions world-wide. Current treatment strategies, such as gene therapy and anti-angiogenic drugs, merely delay disease progression. Research is underway which aims to regenerate the diseased retina by transplanting a variety of cell types, including embryonic stem cells, fetal cells, progenitor cells and induced pluripotent stem cells. Initial retinal transplantation studies injected stem and progenitor cells into the vitreous or subretinal space with the hope that these donor cells would migrate to the site of retinal degeneration, integrate within the host retina and restore functional vision. Despite promising outcomes, these studies showed that the bolus injection technique gave rise to poorly localized tissue grafts. Subsequently, retinal tissue engineers have drawn upon the success of bone, cartilage and vasculature tissue engineering by employing a polymeric tissue engineering approach. This review will describe the evolution of retinal tissue engineering to date, with particular emphasis on the types of polymers that have routinely been used in recent investigations. Further, this review will show that the field of retinal tissue engineering will require new types of materials and fabrication techniques that optimize the survival, differentiation and delivery of retinal transplant cells.

Materials, Vol. 5, Pages 85-107: Acetic and Acrylic Acid Molecular Imprinted Model Silicone Hydrogel Materials for Ciprofloxacin-HCl Delivery

Alex Hui — Mon, 02 Jan 2012 00:00:00 CET

Contact lenses, as an alternative drug delivery vehicle for the eye compared to eye drops, are desirable due to potential advantages in dosing regimen, bioavailability and patient tolerance/compliance. The challenge has been to engineer and develop these materials to sustain drug delivery to the eye for a long period of time. In this study, model silicone hydrogel materials were created using a molecular imprinting strategy to deliver the antibiotic ciprofloxacin. Acetic and acrylic acid were used as the functional monomers, to interact with the ciprofloxacin template to efficiently create recognition cavities within the final polymerized material. Synthesized materials were loaded with 9.06 mM, 0.10 mM and 0.025 mM solutions of ciprofloxacin, and the release of ciprofloxacin into an artificial tear solution was monitored over time. The materials were shown to release for periods varying from 3 to 14 days, dependent on the loading solution, functional monomer concentration and functional monomer:template ratio, with materials with greater monomer:template ratio (8:1 and 16:1 imprinted) tending to release for longer periods of time. Materials with a lower monomer:template ratio (4:1 imprinted) tended to release comparatively greater amounts of ciprofloxacin into solution, but the release was somewhat shorter. The total amount of drug released from the imprinted materials was sufficient to reach levels relevant to inhibit the growth of common ocular isolates of bacteria. This work is one of the first to demonstrate the feasibility of molecular imprinting in model silicone hydrogel-type materials.

Materials, Vol. 5, Pages 47-84: Buckling of Carbon Nanotubes: A State of the Art Review

Hiroyuki Shima — Wed, 28 Dec 2011 00:00:00 CET

The nonlinear mechanical response of carbon nanotubes, referred to as their “buckling” behavior, is a major topic in the nanotube research community. Buckling means a deformation process in which a large strain beyond a threshold causes an abrupt change in the strain energy vs. deformation profile. Thus far, much effort has been devoted to analysis of the buckling of nanotubes under various loading conditions: compression, bending, torsion, and their certain combinations. Such extensive studies have been motivated by (i) the structural resilience of nanotubes against buckling, and (ii) the substantial influence of buckling on their physical properties. In this contribution, I review the dramatic progress in nanotube buckling research during the past few years.

Materials, Vol. 5, Pages 27-46: A Series of Supramolecular Complexes for Solar Energy Conversion via Water Reduction to Produce Hydrogen: An Excited State Kinetic Analysis of Ru(II),Rh(III),Ru(II) Photoinitiated Electron Collectors

Travis A. White — Tue, 27 Dec 2011 00:00:00 CET

Mixed-metal supramolecular complexes have been designed that photochemically absorb solar light, undergo photoinitiated electron collection and reduce water to produce hydrogen fuel using low energy visible light. This manuscript describes these systems with an analysis of the photophysics of a series of six supramolecular complexes, [{(TL)2Ru(dpp)}2RhX2](PF6)5 with TL = bpy, phen or Ph2phen with X = Cl or Br. The process of light conversion to a fuel requires a system to perform a number of complicated steps including the absorption of light, the generation of charge separation on a molecular level, the reduction by one and then two electrons and the interaction with the water substrate to produce hydrogen. The manuscript explores the rate of intramolecular electron transfer, rate of quenching of the supramolecules by the DMA electron donor, rate of reduction of the complex by DMA from the 3MLCT excited state, as well as overall rate of reduction of the complex via visible light excitation. Probing a series of complexes in detail exploring the variation of rates of important reactions as a function of sub-unit modification provides insight into the role of each process in the overall efficiency of water reduction to produce hydrogen. The kinetic analysis shows that the complexes display different rates of excited state reactions that vary with TL and halide. The role of the MLCT excited state is elucidated by this kinetic study which shows that the 3MLCT state and not the 3MMCT is likely that key contributor to the photoreduction of these complexes. The kinetic analysis of the excited state dynamics and reactions of the complexes are important as this class of supramolecules behaves as photoinitiated electron collectors and photocatalysts for the reduction of water to hydrogen.

Materials, Vol. 5, Pages 12-26: Statistical and Graphical Assessment of Circumferential and Radial Hardness Variation of AISI 4140, AISI 1020 and AA 6082 Aluminum Alloy

Hamad Al-Khalid — Fri, 23 Dec 2011 00:00:00 CET

Hardness homogeneity of the commonly used structural ferrous and nonferrous engineering materials is of vital importance in the design stage, therefore, reliable information regarding material properties homogeneity should be validated and any deviation should be addressed. In the current study the hardness variation, over wide spectrum radial locations of some ferrous and nonferrous structural engineering materials, was investigated. Measurements were performed over both faces (cross-section) of each stock bar according to a pre-specified stratified design, ensuring the coverage of the entire area both in radial and circumferential directions. Additionally the credibility of the apparatus and measuring procedures were examined through a statistically based calibration process of the hardness reference block. Statistical and response surface graphical analysis are used to examine the nature, adequacy and significance of the measured hardness values. Calibration of the apparatus reference block proved the reliability of the measuring system, where no strong evidence was found against the stochastic nature of hardness measures over the various stratified locations. Also, outlier elimination procedures were proved to be beneficial only at fewer measured points. Hardness measurements showed a dispersion domain that is within the acceptable confidence interval. For AISI 4140 and AISI 1020 steels, hardness is found to have a slight decrease trend as the diameter is reduced, while an opposite behavior is observed for AA 6082 aluminum alloy. However, no definite significant behavior was noticed regarding the effect of the sector sequence (circumferential direction).

Materials, Vol. 5, Pages 1-11: Structural and Mechanical Characterization of Zr58.5Ti8.2Cu14.2Ni11.4Al7.7 Bulk Metallic Glass

Konda G. Prashanth — Thu, 22 Dec 2011 00:00:00 CET

Thermal stability, structure and mechanical properties of the multi-component Zr58.5Ti8.2Cu14.2Ni11.4Al7.7 bulk metallic glass have been studied in detail. The glassy material displays good thermal stability against crystallization and a fairly large supercooled liquid region of 52 K. During heating, the alloy transforms into a metastable icosahedral quasicrystalline phase in the first stage of crystallization. At high temperatures, the quasicrystalline phase undergoes a transformation to form tetragonal and cubic NiZr2-type phases. Room-temperature compression tests of the as-cast sample show good mechanical properties, namely, high compressive strength of about 1,630 MPa and fracture strain of 3.3%. This is combined with a density of 6.32 g/cm3 and values of Poisson’s ratio and Young’s modulus of 0.377 and 77 GPa, respectively. The mechanical properties of the glass can be further improved by cold rolling. The compressive strength rises to 1,780 MPa and the fracture strain increases to 8.3% for the material cold-rolled to a diameter reduction of 10%.

Materials, Vol. 4, Pages 2231-2243: Non-Isothermal Kinetic Analysis of the Crystallization of Metallic Glasses Using the Master Curve Method

Joan Torrens-Serra — Tue, 20 Dec 2011 00:00:00 CET

The non-isothermal transformation rate curves of metallic glasses are analyzed with the Master Curve method grounded in the Kolmogorov-Johnson-Mehl-Avrami theory. The method is applied to the study of two different metallic glasses determining the activation energy of the transformation and the experimental kinetic function that is analyzed using Avrami kinetics. The analysis of the crystallization of Cu47Ti33Zr11Ni8Si1 metallic glassy powders gives Ea = 3.8 eV, in good agreement with the calculation by other methods, and a transformation initiated by an accelerating nucleation and diffusion-controlled growth. The other studied alloy is a Nanoperm-type Fe77Nb7B15Cu1 metallic glass with a primary crystallization of bcc-Fe. An activation energy of Ea = 5.7 eV is obtained from the Master Curve analysis. It is shown that the use of Avrami kinetics is not able to explain the crystallization mechanisms in this alloy giving an Avrami exponent of n = 1.

Materials, Vol. 4, Pages 2219-2230: Novel Repair Concept for Composite Materials by Repetitive Geometrical Interlock Elements

Werner Hufenbach — Tue, 20 Dec 2011 00:00:00 CET

Material adapted repair technologies for fiber-reinforced polymers with thermosetting matrix systems are currently characterized by requiring major efforts for repair preparation and accomplishment in all industrial areas of application. In order to allow for a uniform distribution of material and geometrical parameters over the repair zone, a novel composite interlock repair concept is introduced, which is based on a repair zone with undercuts prepared by water-jet technology. The presented numerical and experimental sensitivity analyses make a contribution to the systematic development of the interlock repair technology with respect to material and geometrical factors of influence. The results show the ability of the novel concept for a reproducible and automatable composite repair.

Materials, Vol. 4, Pages 2197-2218: In Vivo Degradation Behavior of the Magnesium Alloy LANd442 in Rabbit Tibiae

Berit Ullmann — Thu, 15 Dec 2011 00:00:00 CET

In former studies the magnesium alloy LAE442 showed promising in vivo degradation behavior and biocompatibility. However, reproducibility might be enhanced by replacement of the rare earth composition metal “E” by only a single rare earth element. Therefore, it was the aim of this study to examine whether the substitution of “E” by neodymium (“Nd”) had an influence on the in vivo degradation rate. LANd442 implants were inserted into rabbit tibiae and rabbits were euthanized after 4, 8, 13 and 26 weeks postoperatively. In vivo µCT was performed to evaluate the in vivo implant degradation behaviour by calculation of implant volume, density true 3-D thickness and corrosion rates. Additionally, weight loss, type of corrosion and mechanical stability were appraised by SEM/EDS-analysis and three-point bending tests. Implant volume, density and true 3-D thickness decreased over time, whereas the variance of the maximum diameters within an implant as well as the corrosion rate and weight loss increased. SEM examination revealed mainly pitting corrosion after 26 weeks. The maximum bending forces decreased over time. In comparison to LAE442, the new alloy showed a slower, but more uneven degradation behavior and less mechanical stability. To summarize, LANd442 appeared suitable for low weight bearing bones but is inferior to LAE442 regarding its degradation morphology and strength.

Materials, Vol. 4, Pages 2183-2196: Novel Concept to Detect an Optimum Thixoforming Condition of Al-Al3Ni Functionally Graded Material by Wavelet Analysis for Online Operation

Noriyoshi Kumazawa — Wed, 14 Dec 2011 00:00:00 CET

A novel technique to characterize the transition phenomenon from solid to melt of Al-Al3Ni functionally graded material (FGM) through a wavelet analysis for the development of a thixoforming system is investigated. Identification of an optimum semi-solid condition for thixoforming is necessary not only for the construction of a system but also the fabrication of a near-net-shape product with fine microstructure. An online wavelet analysis system using Haar’s wavelet function, which is applied for its simplicity compared with Daubechies’ wavelet function, is developed to find the optimum operating condition. A thixoforming system, which is constructed adapting a threshold value as an index, monitors successfully a discontinuity of deformation of Al-Al3Ni FGM with the temperature rise. Thus, the timing of an operation is not at pre-fixed temperature but at the time when the index related to a wavelet function is satisfied. The concept is confirmed to be suitable from the micro-structural observation of the Al-Al3Ni FGM product, because the product under the optimum condition is found to have refined Al3Ni grains, which change from coarse grains and are expected to improve the mechanical properties.

Materials, Vol. 4, Pages 2171-2182: Electrochromic Type E-Paper Using Poly(1H-Thieno[3,4-d]Imidazol-2(3H)-One) Derivatives by a Novel Printing Fabrication Process

Yoshiro Kondo — Wed, 14 Dec 2011 00:00:00 CET

In this study, we report poly(1H-thieno[3,4-d]imidazol-2(3H)-one) (pTIO) derivatives for an electrochromic (EC) type e-paper and its novel printing fabrication process. pTIO is a kind of conductive polymer (CP) s which are known as one of the EC materials. The electrochromism of pTIO is unique, because its color in doped state is almost transparent (pale gray). A transparent state is required to show a white color in a see-through view of an EC type e-paper. An electrochromism of CP has a good memory effect which is applicable for e-paper. The corresponding monomers of CP are able to be polymerized with an electrochemical method, which be made good use of for the fabrication process of e-paper. pTIO derivatives are copolymerized with other pi-conjugated X unit, which adjusts the color of electrochromism. Finally, we fabricated a segment matrix EC display using pTIO derivatives by ink-jet printing.

Materials, Vol. 4, Pages 2151-2170: Thermo-Electro-Mechanical Analysis of a Curved Functionally Graded Piezoelectric Actuator with Sandwich Structure

Zhi Yan — Mon, 12 Dec 2011 00:00:00 CET

In this work, the problem of a curved functionally graded piezoelectric (FGP) actuator with sandwich structure under electrical and thermal loads is investigated. The middle layer in the sandwich structure is functionally graded with the piezoelectric coefficient g31 varying continuously along the radial direction of the curved actuator. Based on the theory of linear piezoelectricity, analytical solutions are obtained by using Airy stress function to examine the effects of material gradient and heat conduction on the performance of the curved actuator. It is found that the material gradient and thermal load have significant influence on the electroelastic fields and the mechanical response of the curved FGP actuator. Without the sacrifice of actuation deflection, smaller internal stresses are generated by using the sandwich actuator with functionally graded piezoelectric layer instead of the conventional bimorph actuator. This work is very helpful for the design and application of curved piezoelectric actuators under thermal environment.

Materials, Vol. 4, Pages 2136-2150: Transient Thermal Stress Problem of a Functionally Graded Magneto-Electro-Thermoelastic Hollow Sphere

Yoshihiro Ootao — Mon, 12 Dec 2011 00:00:00 CET

This article is concerned with the theoretical analysis of the functionally graded magneto-electro-thermoelastic hollow sphere due to uniform surface heating. We analyze the transient thermoelastic problem for a functionally graded hollow sphere constructed of the spherical isotropic and linear magneto-electro-thermoelastic materials using a laminated composite mode as one of theoretical approximation in the spherically symmetric state. As an illustration, we carry out numerical calculations for a functionally graded hollow sphere constructed of piezoelectric and magnetostrictive materials and examine the behaviors in the transient state. The effects of the nonhomogeneity of material on the stresses, electric potential, and magnetic potential are investigated.

Materials, Vol. 4, Pages 2119-2135: Formulation Optimization of Gluten-Free Functional Spaghetti Based on Maize Flour and Oat Bran Enriched in b-Glucans

Lucia Padalino — Thu, 08 Dec 2011 00:00:00 CET

The aim of this work concerns the manufacturing process of gluten-free functional spaghetti based on maize flour and oat bran, enriched with b-glucans (22%). More specifically, the goal of the study was to obtain oat bran-loaded maize spaghetti with sensory properties close to unloaded pasta. To this aim, the study has been organized in two subsequent trials. In the first one, the oat bran amount added to spaghetti was continuously increased until the overall sensory quality of pasta reached the set sensory threshold (oat bran concentration = 20%). The second experimental step was aimed to improve the overall sensory quality of oat bran loaded maize spaghetti. In particular, an attempt was made to increase the sensory quality of spaghetti added with 20% oat bran by means of structuring agents. To this aim, the effects of different kinds of some hydrocolloids and egg white powder on the rheological properties of dough, as well as on quality attributes of pasta were examined. The rheological analysis showed that the addition of hydrocolloids and white egg to the dough enriched with 20% oat bran did not cause any substantial difference in the viscoelastic properties, compared to samples without any structuring agents. The best overall quality for both fresh and dry spaghetti was obtained by the addition of carboxymethylcellulose and chitosan at a concentration of 2%.

Materials, Vol. 4, Pages 2108-2118: Heat Conduction in a Functionally Graded Plate Subjected to Finite Cooling/Heating Rates: An Asymptotic Solution

Zhihe Jin — Thu, 08 Dec 2011 00:00:00 CET

This work investigates transient heat conduction in a functionally graded plate (FGM plate) subjected to gradual cooling/heating at its boundaries. The thermal properties of the FGM are assumed to be continuous and piecewise differentiable functions of the coordinate in the plate thickness direction. A linear ramp function describes the cooling/heating rates at the plate boundaries. A multi-layered material model and Laplace transform are employed to obtain the transformed temperatures at the interfaces between the layers. An asymptotic analysis and an integration technique are then used to obtain a closed form asymptotic solution of the temperature field in the FGM plate for short times. The thermal stress intensity factor (TSIF) for an edge crack in the FGM plate calculated based on the asymptotic temperature solution shows that the asymptotic solution can capture the peak TSIFs under the finite cooling rate conditions.

Materials, Vol. 4, Pages 2092-2107: Arsenic-Doped High-Resistivity-Silicon Epitaxial Layers for Integrating Low-Capacitance Diodes

Agata Sakic — Tue, 06 Dec 2011 00:00:00 CET

An arsenic doping technique for depositing up to 40-μm-thick high-resistivity layers is presented for fabricating diodes with low RC constants that can be integrated in closely-packed configurations. The doping of the as-grown epi-layers is controlled down to 5 × 1011 cm−3, a value that is solely limited by the cleanness of the epitaxial reactor chamber. To ensure such a low doping concentration, first an As-doped Si seed layer is grown with a concentration of 1016 to 1017 cm−3, after which the dopant gas arsine is turned off and a thick lightly-doped epi-layer is deposited. The final doping in the thick epi-layer relies on the segregation and incorporation of As from the seed layer, and it also depends on the final thickness of the layer, and the exact growth cycles. The obtained epi-layers exhibit a low density of stacking faults, an over-the-wafer doping uniformity of 3.6%, and a lifetime of generated carriers of more than 2.5 ms. Furthermore, the implementation of a segmented photodiode electron detector is demonstrated, featuring a 30 pF capacitance and a 90 Ω series resistance for a 7.6 mm2 anode area.

Materials, Vol. 4, Pages 2073-2091: Hydrogen

John O’M. Bockris — Wed, 30 Nov 2011 00:00:00 CET

The idea of a “Hydrogen Economy” is that carbon containing fuels should be replaced by hydrogen, thus eliminating air pollution and growth of CO2 in the atmosphere. However, storage of a gas, its transport and reconversion to electricity doubles the cost of H2 from the electrolyzer. Methanol made with CO2 from the atmosphere is a zero carbon fuel created from inexhaustible components from the atmosphere. Extensive work on the splitting of water by bacteria shows that if wastes are used as the origin of feed for certain bacteria, the cost for hydrogen becomes lower than any yet known. The first creation of hydrogen and electricity from light was carried out in 1976 by Ohashi et al. at Flinders University in Australia. Improvements in knowledge of the structure of the semiconductor-solution system used in a solar breakdown of water has led to the discovery of surface states which take part in giving rise to hydrogen (Khan). Photoelectrocatalysis made a ten times increase in the efficiency of the photo production of hydrogen from water. The use of two electrode cells; p and n semiconductors respectively, was first introduced by Uosaki in 1978. Most photoanodes decompose during the photoelectrolysis. To avoid this, it has been necessary to create a transparent shield between the semiconductor and its electronic properties and the solution. In this way, 8.5% at 25 °C and 9.5% at 50 °C has been reached in the photo dissociation of water (GaP and InAs) by Kainthla and Barbara Zeleney in 1989. A large consortium has been funded by the US government at the California Institute of Technology under the direction of Nathan Lewis. The decomposition of water by light is the main aim of this group. Whether light will be the origin of the post fossil fuel supply of energy may be questionable, but the maximum program in this direction is likely to come from Cal. Tech.

Materials, Vol. 4, Pages 2061-2072: Characterization of the Materials Synthesized by High Pressure-High Temperature Treatment of a Polymer Derived t-BC2N Ceramic

Wallace R. Matizamhuka — Tue, 29 Nov 2011 00:00:00 CET

Bulk B-C-N materials were synthesized under static high thermobaric conditions (20 GPa and 2,000 °C) in a multianvil apparatus from a polymer derived t-BC1.97N ceramic. The bulk samples were characterised using X-ray synchrotron radiation and analytical transmission electron microscopy in combination with electron energy loss spectroscopy. Polycrystalline B-C-N materials with a cubic type structure were formed under the applied reaction conditions, but the formation of a ternary cubic diamond-like c-BC2N compound, could not be unambiguously confirmed.

Materials, Vol. 4, Pages 2057-2060: Correction: Koush, Y.; Elliott, M.A. and Mathiak, K. Single Voxel Proton Spectroscopy for Neurofeedback at 7 Tesla. Materials 2011, 4, 1548–1563

Yury Koush — Thu, 24 Nov 2011 00:00:00 CET

In the published manuscript “Koush, Y.; Elliott, M.A. and Mathiak, K. Single Voxel Proton Spectroscopy for Neurofeedback at 7 Tesla. Materials 2011, 4, 1548-1563”, all estimates of T2* from the single voxel spectroscopy data were overestimated by a factor of 4. This was due to an incorrectly assumed four-fold lower sampling rate. The focus of the manuscript is on the relative changes in T2* with BOLD activation, and not on the absolute values. Therefore, none of the central claims are affected, but the scaling in most of the figures needs to be adjusted. The authors would like to make the following corrections to their published paper.

Materials, Vol. 4, Pages 2042-2056: Nanorod Self-Assembly in High Jc YBa2Cu3O7−x Films with Ru-Based Double Perovskites

Terry G. Holesinger — Thu, 17 Nov 2011 00:00:00 CET

Many second phase additions to YBa2Cu3O7−x (YBCO) films, in particular those that self-assemble into aligned nanorod and nanoparticle structures, enhance performance in self and applied fields. Of particular interest for additions are Ba-containing perovskites that are compatible with YBCO. In this report, we discuss the addition of Ba2YRuO6 to bulk and thick-film YBCO. Sub-micron, randomly oriented particles of this phase were found to form around grain boundaries and within YBCO grains in bulk sintered pellets. Within the limits of EDS, no Ru substitution into the YBCO was observed. Thick YBCO films were grown by pulsed laser deposition from a target consisting of YBa2Cu3Oy with 5 and 2.5 mole percent additions of Ba2YRuO6 and Y2O3, respectively. Films with enhanced in-field performance contained aligned, self-assembled Ba2YRuO6 nanorods and strained Y2O3 nanoparticle layers. A 0.9 µm thick film was found to have a self-field critical current density (Jc) of 5.1 MA/cm2 with minimum Jc(Q, H=1T) of 0.75 MA/cm2. Conversely, Jc characteristics were similar to YBCO films without additions when these secondary phases formed as large, disordered phases within the film. A 2.3 µm thick film with such a distribution of secondary phases was found to have reduced self-field Jc values of 3.4 MA/cm2 at 75.5 K and Jc(min, Q, 1T) of 0.4 MA/cm2.

Materials, Vol. 4, Pages 2017-2041: Dense CO2 as a Solute, Co-Solute or Co-Solvent in Particle Formation Processes: A Review

Ana V. M. Nunes — Wed, 16 Nov 2011 00:00:00 CET

The application of dense gases in particle formation processes has attracted great attention due to documented advantages over conventional technologies. In particular, the use of dense CO2 in the process has been subject of many works and explored in a variety of different techniques. This article presents a review of the current available techniques in use in particle formation processes, focusing exclusively on those employing dense CO2 as a solute, co-solute or co-solvent during the process, such as PGSS (Particles from gas-saturated solutions®), CPF (Concentrated Powder Form®), CPCSP (Continuous Powder Coating Spraying Process), CAN-BD (Carbon dioxide Assisted Nebulization with a Bubble Dryer®), SEA (Supercritical Enhanced Atomization), SAA (Supercritical Fluid-Assisted Atomization), PGSS-Drying and DELOS (Depressurization of an Expanded Liquid Organic Solution). Special emphasis is given to modifications introduced in the different techniques, as well as the limitations that have been overcome.

Materials, Vol. 4, Pages 2003-2016: The Rolling Transition in a Granular Flow along a Rotating Wall

Francois Rioual — Fri, 11 Nov 2011 00:00:00 CET

The flow of a dry granular material composed of spherical particles along a rotating boundary has been studied by the discrete element method (DEM). This type of flow is used, among others, as a process to spread particles. The flow consists of several phases. A compression phase along the rotating wall is followed by an elongation of the flow along the same boundary. Eventually, the particles slide or roll independently along the boundary. We show that the main motion of the flow can be characterized by a complex deformation rate of traction/compression and shear. We define numerically an effective friction coefficient of the flow on the scale of the continuum and show a strong decrease of this effective friction beyond a certain critical friction coefficient μ*. We correlate this phenomenon with the apparition of a new transition from a sliding regime to a rolling without sliding regime that we called the rolling transition; this dynamic transition is controlled by the value of the friction coefficient between the particle and the wall. We show that the spherical shape for the particles may represent an optimum for the flow in terms of energetic.

Materials, Vol. 4, Pages 1985-2002: Cellulose Isolation Methodology for NMR Analysis of Cellulose Ultrastructure

Marcus B. Foston — Mon, 07 Nov 2011 00:00:00 CET

In order to obtain accurate information about the ultrastructure of cellulose from native biomass by 13C cross polarization magic angle spinning (CP/MAS) NMR spectroscopy the cellulose component must be isolated due to overlapping resonances from both lignin and hemicellulose. Typically, cellulose isolation has been achieved via holocellulose pulping to remove lignin followed by an acid hydrolysis procedure to remove the hemicellulose components. Using 13C CP/MAS NMR and non-linear line-fitting of the cellulose C4 region, it was observed that the standard acid hydrolysis procedure caused an apparent increase in crystallinity of ~10% or less on the cellulose isolated from Populus holocellulose. We have examined the effect of the cellulose isolation method, particularly the acid treatment time for hemicellulose removal, on cellulose ultrastructural characteristics by studying these effects on cotton, microcrystalline cellulose (MCC) and holocellulose pulped Populus. 13C CP/MAS NMR of MCC indicated that holocellulose pulping and acid hydrolysis has little effect on the crystalline ultrastructural components of cellulose. Although any chemical method to isolate cellulose from native biomass will invariably alter substrate characteristics, especially those related to regions accessible to solvents, we found those changes to be minimal and consistent in samples of typical crystallinity and lignin/hemicellulose content. Based on the rate of the hemicellulose removal, as determined by HPLC-carbohydrate analysis and magnitude of cellulose ultrastructural alteration, the most suitable cellulose isolation methodology utilizes a treatment of 2.5 M HCl at 100 °C for a standard residence time between 1.5 and 4 h. However, for the most accurate crystallinity results this residence time should be determined empirically for a particular sample.

Materials, Vol. 4, Pages 1967-1984: Toughening of a Carbon-Fibre Composite Using Electrospun Poly(Hydroxyether of Bisphenol A) Nanofibrous Membranes Through Inverse Phase Separation and Inter-Domain Etherification

Kevin Magniez — Wed, 02 Nov 2011 00:00:00 CET

The interlaminar toughening of a carbon fibre reinforced composite by interleaving a thin layer (~20 microns) of poly(hydroxyether of bisphenol A) (phenoxy) nanofibres was explored in this work. Nanofibres, free of defect and averaging several hundred nanometres, were produced by electrospinning directly onto a pre-impregnated carbon fibre material (Toray G83C) at various concentrations between 0.5 wt % and 2 wt %. During curing at 150 °C, phenoxy diffuses through the epoxy resin to form a semi interpenetrating network with an inverse phase type of morphology where the epoxy became the co-continuous phase with a nodular morphology. This type of morphology improved the fracture toughness in mode I (opening failure) and mode II (in-plane shear failure) by up to 150% and 30%, respectively. Interlaminar shear stress test results showed that the interleaving did not negatively affect the effective in-plane strength of the composites. Furthermore, there was some evidence from DMTA and FT-IR analysis to suggest that inter-domain etherification between the residual epoxide groups with the pendant hydroxyl groups of the phenoxy occurred, also leading to an increase in glass transition temperature (~7.5 °C).

Materials, Vol. 4, Pages 1956-1966: Polyamide 6 Nanocomposites with Inorganic Particles Modified with Three Quaternary Ammonium Salts

Edcleide Maria Araujo — Wed, 02 Nov 2011 00:00:00 CET

The purpose of this study was to obtain polyamide 6 nanocomposites with national organically modified clay with three quaternary ammonium salts. The obtained results confirm the intercalation of molecules of salt in the clay layers, and a good interaction with the polymer, showing the formation of intercalated and/or partially exfoliated structures. The nanocomposites showed similar thermal stability compared to pure polymer, and the mechanical properties presented interesting and promising results.

Materials, Vol. 4, Pages 1941-1955: Advances in High-Field BOLD fMRI

Markus Barth — Wed, 02 Nov 2011 00:00:00 CET

This review article examines the current state of BOLD fMRI at a high magnetic field strength of 7 Tesla. The following aspects are covered: a short description of the BOLD contrast, spatial and temporal resolution, BOLD sensitivity, localization and spatial specificity, technical challenges as well as an outlook on future developments are given. It is shown that the main technical challenges of performing BOLD fMRI at high magnetic field strengths—namely development of array coils, imaging sequences and parallel imaging reconstruction—have been solved successfully. The combination of these developments has lead to the availability of high-resolution BOLD fMRI protocols that are able to cover the whole brain with a repetition time (TR) shorter than 3 s. The structural information available from these high-resolution fMRI images itself is already very detailed, which helps to co-localize structure and function. Potential future applications include whole-brain connectivity analysis on a laminar resolution and single subject examinations.

Materials, Vol. 4, Pages 1927-1940: Drug-Eluting Intraocular Lenses

Clara González-Chomón — Tue, 01 Nov 2011 00:00:00 CET

Notable advances in materials science and in surgical techniques make the management of cataract by replacement of the opaque crystalline with an intraocular lens (IOL), one of the most cost-effective interventions in current healthcare. The usefulness and safety of IOLs can be enhanced if they are endowed with the ability to load and to sustain drug release in the implantation site. Drug-eluting IOLs can prevent infections and untoward reactions of eye tissues (which lead to opacification) and also can act as drug depots for treatment of several other ocular pathologies. Such a myriad of therapeutic possibilities has prompted the design of drug-IOL combination products. Several approaches are under study, namely combination of the IOL with an insert in a single device, soaking in drug solutions, impregnation using supercritical fluids, coating with drug/polymer layers, and covalent grafting of the drug. The advantages/limitations of each technique are discussed in the present review on selected examples. Although more in vivo data are required, the information already available proves the interest of some approaches in ocular therapeutics.

Materials, Vol. 4, Pages 1906-1926: Hysteretic Tricolor Electrochromic Systems Based on the Dynamic Redox Properties of Unsymmetrically Substituted Dihydrophenanthrenes and Biphenyl-2,2'-Diyl Dications: Efficient Precursor Synthesis by a Flow Microreactor Method

Yusuke Ishigaki — Wed, 26 Oct 2011 00:00:00 CEST

A series of biphenyl-2,2'-diylbis(diarylmethanol)s 3, which have two kinds of aryl groups at the bay region, were efficiently obtained by integrated flow microreactor synthesis. The diols 3NO/NX are the precursors of unsymmetric biphenylic dications 2NO/NX2+, which are transformed into the corresponding dihydrophenanthrenes 1NO/NX via 2NO/NX+• upon reduction, when they exhibit two-stage color changes. On the other hand, the steady-state concentration of the intermediate 2NO/NX+• is negligible during the oxidation of 1NO/NX to 2NO/NX2+, which reflects unique tricolor electrochromicity with a hysteretic pattern of color change [color 1→color 2→color 3→color 1].

Materials, Vol. 4, Pages 1861-1905: Sol-Gel Behavior of Hydroxypropyl Methylcellulose (HPMC) in Ionic Media Including Drug Release

Sunil C. Joshi — Mon, 24 Oct 2011 00:00:00 CEST

Sol-gel transformations in HPMC (hydroxypropyl methylcellulose) are being increasingly studied because of their role in bio-related applications. The thermo-reversible behavior of HPMC is particularly affected by its properties and concentration in solvent media, nature of additives, and the thermal environment it is exposed to. This article contains investigations on the effects of salt additives in Hofmeister series on the HPMC gelation. Various findings regarding gelation with salt ions as well as with the ionic and non-ionic surfactants are presented. The gel formation in physiological salt fluids such as simulated gastric and intestine fluids is also examined with the interest in oral drug delivery systems. The processes of swelling, dissolution and dispersion of HPMC tablets in simulated bio-fluids are explored and the release of a drug from the tablet affected by such processes is studied. Explanations are provided based on the chemical structure and the molecular binding/association of HPMC in a media. The test results at the body or near-body temperature conditions helped in understanding the progress of the gelation process within the human body environment. The detailed interpretation of various molecule level interactions unfolded the sol-gel mechanisms and the influence of a few other factors. The obtained test data and the established mathematical models are expected to serve as a guide in customizing applications of HPMC hydrogels.

Materials, Vol. 4, Pages 1846-1860: A New Generation of X-ray Baggage Scanners Based on a Different Physical Principle

Konstantin Ignatyev — Mon, 17 Oct 2011 00:00:00 CEST

X-ray baggage scanners play a basic role in the protection of airports, customs, and other strategically important buildings and infrastructures. The current technology of baggage scanners is based on x-ray attenuation, meaning that the detection of threat objects relies on how various objects differently attenuate the x-ray beams going through them. This capability is enhanced by the use of dual-energy x-ray scanners, which make the determination of the x-ray attenuation characteristics of a material more precise by taking images with different x-ray spectra, and combining the information appropriately. However, this still has limitations whenever objects with similar attenuation characteristics have to be distinguished. We describe an alternative approach based on a different x-ray interaction phenomenon, x-ray refraction. Refraction is a familiar phenomenon in visible light (e.g., what makes a straw half immersed in a glass of water appear bent), which also takes place in the x-ray regime, only causing deviations at much smaller angles. Typically, these deviations occur at the boundaries of all objects. We have developed a system that, like other “phase contrast” based instruments, is capable of detecting such deviations, and therefore of creating precise images of the contours of all objects. This complements the material-related information provided by x-ray attenuation, and helps contextualizing the nature of the individual objects, therefore resulting in an increase of both sensitivity (increased detection rate) and specificity (reduced rate of false positives) of baggage scanners.

Materials, Vol. 4, Pages 1835-1845: The Origin of Tc Enhancement in Heterostructure Cuprate Superconductors

Doron L. Bergman — Mon, 17 Oct 2011 00:00:00 CEST

Recent experiments on heterostructures composed of two or more films of cuprate superconductors of different oxygen doping levels have shown a remarkable Tc enhancement (up to 50%) relative to single compound films. We provide a simple explanation of the enhancement which arises naturally from a collection of experimental works. We show that the enhancement could be caused by a structural change in the lattice, namely an increase in the distance of the apical oxygen from the copper-oxygen plane. This increase modifies the effective off-site interaction in the plane which in turn enhances the d-wave superconductivity order parameter. To illustrate this point we study the extended Hubbard model using the fluctuation exchange approximation.

Materials, Vol. 4, Pages 1818-1834: Multi-Echo-Based Echo-Planar Spectroscopic Imaging Using a 3T MRI Scanner

Jon K. Furuyama — Mon, 17 Oct 2011 00:00:00 CEST

The use of spin-echoes has been employed in an Echo-Planar Spectroscopic Imaging (EPSI) sequence to collect multiple phase encoded lines within a single TR in a Multi-Echo-based Echo-Planar Spectroscopic Imaging technique (MEEPSI). Despite the T2 dependence on the amplitude of the spin-echoes, the Full Width at Half Maximum (FWHM) of the derived multi-echo Point Spread Function (PSF) is shown to decrease, indicating an improved overall spatial resolution without requiring any additional scan time. The improved spatial resolution is demonstrated in the one-dimensional (1D) spatial profiles of the N-Acetyl Aspartate (NAA) singlet along the phase encode dimension in a gray matter phantom. Although the improved spatial resolution comes at the expense of spectral resolution, it is shown in vivo that peak broadening due to T2* decay is more significant than the loss of resolution from using spin-echoes and therefore does not affect the ability to quantify metabolites using the LCModel fitting algorithm.

Materials, Vol. 4, Pages 1805-1817: Fabrication of κ-Carrageenan Fibers by Wet Spinning: Spinning Parameters

Lingyan Kong — Tue, 11 Oct 2011 00:00:00 CEST

This study demonstrates the fabrication of κ-carrageenan fibers by a wet-spinning method and discusses three important spinning parameters: coagulation bath composition, spinning rate and post-spinning mechanical drawing. The as-spun fiber diameter decreased with KCl and ethanol concentration in the coagulation bath. In general, the ultimate tensile stress and elongation at break both increased for KCl concentration from 0.1 to 0.5 M with and without ethanol, with no significant change above 0.5 M. Spinning rate affected the dope flow and thus the polymer orientation (apparent viscosity) and fiber morphology. At spinning rates between 0.25 mL/min and 0.33 mL/min, the fiber diameter reached a minimum and the fiber surface was smooth. Both an increase and decrease from this spinning rate range increased the fiber diameter and roughness of the fiber surface. Post-spinning drawing of the fiber resulted in even smaller fiber diameter.

Materials, Vol. 4, Pages 1793-1804: Mesenchymal Stem Cells in Combination with Scaffolds for Bone Tissue Engineering

Laeticia Nassif — Tue, 11 Oct 2011 00:00:00 CEST

This article reviews past and current strategies of the use of bone graft substitutes along with the future biologic alternatives that can enhance the functional capabilities of those grafts. Many of these bone graft substitute alternatives include ceramic-based, allograft-based, factor-based and polymer-based whereas others are cell-based. The ways of achieving the goal of tissue engineering using stem cells and their lineage to regenerate tissue have been detailed with regard to both the generation of sufficient vascular invasion of the tissue to improve oxygen and nutrient supply, and the development of innovative physical/chemical stimuli to induce bone formation with the proper biomaterial to carry the cells. It is imperative to integrate basic polymer science with molecular biology and stem cell biology, in the design of new materials that perform very sophisticated signaling needed for integration and function.

Materials, Vol. 4, Pages 1776-1792: Evaluation of Titanium Alloys Fabricated Using Rapid Prototyping Technologies—Electron Beam Melting and Laser Beam Melting

Mari Koike — Mon, 10 Oct 2011 00:00:00 CEST

This study characterized properties of Ti-6Al-4V ELI (extra low interstitial, ASTM grade 23) specimens fabricated by a laser beam melting (LBM) and an electron beam melting (EBM) system for dental applications. Titanium alloy specimens were made into required size and shape for each standard test using fabrication methods. The LBM specimens were made by an LBM machine utilizing 20 µm of Ti-6Al-4V ELI powder. Ti-6Al-4V ELI specimens were also fabricated by an EBM using 40 µm of Ti-6Al-4V ELI powder (average diameter, 40 µm: Arcam ABÒ) in a vacuum. As a control, cast Ti-6Al-4V ELI specimens (Cast) were made using a centrifugal casting machine in an MgO-based mold. Also, a wrought form of Ti-6Al-4V ELI (Wrought) was used as a control. The mechanical properties, corrosion properties and grindability (wear properties) were evaluated and data was analyzed using ANOVA and a non-parametric method (α = 0.05). The strength of the LBM and wrought specimens were similar, whereas the EBM specimens were slightly lower than those two specimens. The hardness of both the LBM and EBM specimens was similar and slightly higher than that of the cast and wrought alloys. For the higher grindability speed at 1,250 m/min, the volume loss of Ti64 LBM and EBM showed no significant differences among all the fabrication methods. LBM and EBM exhibited favorable results in fabricating dental appliances with excellent properties as found for specimens made by other fabricating methods.

Materials, Vol. 4, Pages 1763-1775: Gelation and Retrogradation Mechanism of Wheat Amylose

Yukihiro Tamaki — Mon, 10 Oct 2011 00:00:00 CEST

The flow behavior, dynamic viscoelasticity, and optical rotation of aqueous solutions of wheat amylose were measured using a rheogoniometer and a polarimeter. The amylose solutions, at 25 °C, showed shear-thinning behavior at a concentration of 1.2%, but plastic behavior at 1.4 and 1.6%, the yield values of which were estimated to be 0.6 and 1.0 Pa, respectively. The viscosity of the wheat amylose increased a little with increase in temperature up to 10 or 20 °C at 1.2% or 1.4 and 1.6%, which was estimated to be a transition temperature. The elastic modulus increased with increase in concentration, and increased with increasing temperature up to 20, 25 and 30 °C, which was estimated to be a transition temperature, respectively, then decreased gradually but stayed at a large value even at high temperature (80 °C). A very low elastic modulus of the wheat amylose was observed upon addition of urea (4.0 M) and in alkaline solution (0.05 M NaOH) even at low temperature. The optical rotation of wheat amylose solution increased a little with decreasing temperature down to 25 °C, then increased rapidly with further decrease in the temperature. The mode of gelation mechanism of amylose molecules, which was previously proposed, was confirmed and a retrogradation mechanism of wheat amylose was proposed.

Materials, Vol. 4, Pages 1747-1762: Mechanical Properties of Titanium Nitride Nanocomposites Produced by Chemical Precursor Synthesis Followed by High-P,T Treatment

Edward Bailey — Thu, 06 Oct 2011 00:00:00 CEST

We investigated the high-P,T annealing and mechanical properties of nanocomposite materials with a highly nitrided bulk composition close to Ti3N4. Amorphous solids were precipitated from solution by ammonolysis of metal dialkylamide precursors followed by heating at 400–700 °C in flowing NH3 to produce reddish-brown amorphous/nanocrystalline materials. The precursors were then densified at 2 GPa and 200–700 °C to form monolithic ceramics. There was no evidence for N2 loss during the high-P,T treatment. Micro- and nanoindentation experiments indicate hardness values between 4–20 GPa for loads ranging between 0.005–3 N. Young's modulus values were measured to lie in the range 200–650 GPa. Palmqvist cracks determined from microindentation experiments indicate fracture toughness values between 2–4 MPa·m1/2 similar to Si3N4, SiC and Al2O3. Significant variations in the hardness may be associated with the distribution of amorphous/crystalline regions and the very fine grained nature (~3 nm grain sizes) of the crystalline component in these materials.

Materials, Vol. 4, Pages 1728-1746: Chitin-Methacrylate: Preparation, Characterization and Hydrogel Formation

Eugene Khor — Thu, 06 Oct 2011 00:00:00 CEST

Chitin-methacrylate (CM) was prepared by the reaction of methacrylic acid on chitin in 5% LiCl/DMAc in the presence of N,N’-dicyclocarbodiimide and dimethylaminopyridine. The resultant chitin-methacrylate product was isolated in 61% yield and was found to be readily water-soluble. The derivative was found to be a mixture of methacrylate and methacrylic-dimethylaminopyridine complex substituents at the C-6 position in approximately equal amounts. In order to evaluate the activity of the methacrylate double bond, a chitin-methacrylate water solution was photo-crosslinked in the presence of Irgacure 2959 photo-initiator to generate CM-hydrogel. The CM-hydrogel was evaluated for its biodegradability characteristics by enzymatic degradation with lysozyme solutions of varying concentrations. Completely water-soluble products were obtained within 48 h. In vitro cytotoxicity assays of the CM-hydrogel and its extract against three cell lines, NCTC clone 929, IMR-90 and MG-63, indicated the hydrogel was non-cytotoxic with cells able to adhere and proliferate well on the hydrogel.

Materials, Vol. 4, Pages 1705-1727: Polyacylurethanes as Novel Degradable Cell Carrier Materials for Tissue Engineering

Danijela Jovanovic — Thu, 06 Oct 2011 00:00:00 CEST

Polycaprolactone (PCL) polyester and segmented aliphatic polyester urethanes based on PCL soft segment have been thoroughly investigated as biodegradable scaffolds for tissue engineering. Although proven beneficial as long term implants, these materials degrade very slowly and are therefore not suitable in applications in which scaffold support is needed for a shorter time. A recently developed class of polyacylurethanes (PAUs) is expected to fulfill such requirements. Our aim was to assess in vitro the degradation of PAUs and evaluate their suitability as temporary scaffold materials to support soft tissue repair. With both a mass loss of 2.5–3.0% and a decrease in molar mass of approx. 35% over a period of 80 days, PAUs were shown to degrade via both bulk and surface erosion mechanisms. Fourier Transform Infra Red (FTIR) spectroscopy was successfully applied to study the extent of PAUs microphase separation during in vitro degradation. The microphase separated morphology of PAU1000 (molar mass of the oligocaprolactone soft segment = 1000 g/mol) provided this polymer with mechano-physical characteristics that would render it a suitable material for constructs and devices. PAU1000 exhibited excellent haemocompatibility in vitro. In addition, PAU1000 supported both adhesion and proliferation of vascular endothelial cells and this could be further enhanced by pre-coating of PAU1000 with fibronectin (Fn). The contact angle of PAU1000 decreased both with in vitro degradation and by incubation in biological fluids. In endothelial cell culture medium the contact angle reached 60°, which is optimal for cell adhesion. Taken together, these results support the application of PAU1000 in the field of soft tissue repair as a temporary degradable scaffold.

Materials, Vol. 4, Pages 1693-1704: Manganese-based Materials Inspired by Photosynthesis for Water-Splitting

Harvey J.M. Hou — Wed, 28 Sep 2011 00:00:00 CEST

In nature, the water-splitting reaction via photosynthesis driven by sunlight in plants, algae, and cyanobacteria stores the vast solar energy and provides vital oxygen to life on earth. The recent advances in elucidating the structures and functions of natural photosynthesis has provided firm framework and solid foundation in applying the knowledge to transform the carbon-based energy to renewable solar energy into our energy systems. In this review, inspired by photosynthesis robust photo water-splitting systems using manganese-containing materials including Mn-terpy dimer/titanium oxide, Mn-oxo tetramer/Nafion, and Mn-terpy oligomer/tungsten oxide, in solar fuel production are summarized and evaluated. Potential problems and future endeavors are also discussed.

Materials, Vol. 4, Pages 1648-1692: Synthesis of Binary Transition Metal Nitrides, Carbides and Borides from the Elements in the Laser-Heated Diamond Anvil Cell and Their Structure-Property Relations

Alexandra Friedrich — Wed, 28 Sep 2011 00:00:00 CEST

Transition metal nitrides, carbides and borides have a high potential for industrial applications as they not only have a high melting point but are generally harder and less compressible than the pure metals. Here we summarize recent advances in the synthesis of binary transition metal nitrides, carbides and borides focusing on the reaction of the elements at extreme conditions generated within the laser-heated diamond anvil cell. The current knowledge of their structures and high-pressure properties like high-(p; T) stability, compressibility and hardness is described as obtained from experiments.

Materials, Vol. 4, Pages 1632-1647: Effect of Molecular Flexibility on the Nematic-to-Isotropic Phase Transition for Highly Biaxial Molecular Non-Symmetric Liquid Crystal Dimers

Nerea Sebastián — Tue, 27 Sep 2011 00:00:00 CEST

In this work, a study of the nematic (N)–isotropic (I) phase transition has been made in a series of odd non-symmetric liquid crystal dimers, the α-(4-cyanobiphenyl-4’-yloxy)-ω-(1-pyrenimine-benzylidene-4’-oxy) alkanes, by means of accurate calorimetric and dielectric measurements. These materials are potential candidates to present the elusive biaxial nematic (NB) phase, as they exhibit both molecular biaxiality and flexibility. According to the theory, the uniaxial nematic (NU)–isotropic (I) phase transition is first-order in nature, whereas the NB–I phase transition is second-order. Thus, a fine analysis of the critical behavior of the N–I phase transition would allow us to determine the presence or not of the biaxial nematic phase and understand how the molecular biaxiality and flexibility of these compounds influences the critical behavior of the N–I phase transition.

Materials, Vol. 4, Pages 1619-1631: Coating of Carbon Fiber with Polyhedral Oligomeric Silsesquioxane (POSS) to Enhance Mechanical Properties and Durability of Carbon/Vinyl Ester Composites

Hassan Mahfuz — Wed, 21 Sep 2011 00:00:00 CEST

Our continuing quest to improve the performance of polymer composites under moist and saltwater environments has gained momentum in recent years with the reinforcement of inorganic nanoparticles into the polymer. The key to mitigate degradation of composites under such environments is to maintain the integrity of the fiber/matrix (F/M) interface. In this study, the F/M interface of carbon/vinyl ester composites has been modified by coating the carbon fiber with polyhedral oligomeric silsesquioxane (POSS). POSS is a nanostructured inorganic-organic hybrid particle with a cubic structure having silicon atoms at the core and linked to oxygen atoms. The advantage of using POSS is that the silicon atoms can be linked to a substituent that can be almost any chemical group known in organic chemistry. Cubic silica cores are ‘hard particles’ and are about 0.53 nm in diameter. The peripheral organic unit is a sphere of about 1–3 nm in diameter. Further, cubic structure of POSS remains intact during the polymerization process and therefore with appropriate functional groups, if installed on the fiber surface, would provide a stable and strong F/M interface. Two POSS systems with two different functional groups; namely, octaisobutyl and trisilanolphenyl have been investigated. A set of chemical and mechanical procedures has been developed to coat carbon fibers with POSS, and to fabricate layered composites with vinyl ester resin. Interlaminar shear and low velocity impact tests have indicated around 17–38% improvement in mechanical properties with respect to control samples made without the POSS coating. Saltwater and hygrothermal tests at various environmental conditions have revealed that coating with POSS reduces water absorption by 20–30% and retains the composite properties.

Materials, Vol. 4, Pages 1599-1618: Phase Stability and Elasticity of TiAlN

Igor A. Abrikosov — Thu, 15 Sep 2011 00:00:00 CEST

We review results of recent combined theoretical and experimental studies of Ti1−xAlxN, an archetypical alloy system material for hard-coating applications. Theoretical simulations of lattice parameters, mixing enthalpies, and elastic properties are presented. Calculated phase diagrams at ambient pressure, as well as at pressure of 10 GPa, show a wide miscibility gap and broad region of compositions and temperatures where the spinodal decomposition takes place. The strong dependence of the elastic properties and sound wave anisotropy on the Al-content offers detailed understanding of the spinodal decomposition and age hardening in Ti1−xAlxN alloy films and multilayers. TiAlN/TiN multilayers can further improve the hardness and thermal stability compared to TiAlN since they offer means to influence the kinetics of the favorable spinodal decomposition and suppress the detrimental transformation to w-AlN. Here, we show that a 100 degree improvement in terms of w-AlN suppression can be achieved, which is of importance when the coating is used as a protective coating on metal cutting inserts.

Materials, Vol. 4, Pages 1564-1598: On Structure and Properties of Amorphous Materials

Zbigniew H. Stachurski — Thu, 15 Sep 2011 00:00:00 CEST

Mechanical, optical, magnetic and electronic properties of amorphous materials hold great promise towards current and emergent technologies. We distinguish at least four categories of amorphous (glassy) materials: (i) metallic; (ii) thin films; (iii) organic and inorganic thermoplastics; and (iv) amorphous permanent networks. Some fundamental questions about the atomic arrangements remain unresolved. This paper focuses on the models of atomic arrangements in amorphous materials. The earliest ideas of Bernal on the structure of liquids were followed by experiments and computer models for the packing of spheres. Modern approach is to carry out computer simulations with prediction that can be tested by experiments. A geometrical concept of an ideal amorphous solid is presented as a novel contribution to the understanding of atomic arrangements in amorphous solids.

Materials, Vol. 4, Pages 1548-1563: Single Voxel Proton Spectroscopy for Neurofeedback at 7 Tesla

Yury Koush — Thu, 15 Sep 2011 00:00:00 CEST

Echo-planar imaging (EPI) in fMRI is regularly used to reveal BOLD activation in presubscribed regions of interest (ROI). The response is mediated by relative changes in T2* which appear as changes in the image pixel intensities. We have proposed an application of functional single-voxel proton spectroscopy (fSVPS) for real-time studies at ultra-high MR field which can be comparable to the EPI BOLD fMRI technique. A spin-echo SVPS protocol without water suppression was acquired with 310 repetitions on a 7T Siemens MR scanner (TE/TR = 20/1000 ms, flip angle α = 90°, voxel size 10 × 10 × 10 mm3). Transmitter reference voltage was optimized for the voxel location. Spectral processing of the water signal free induction decay (FID) using log-linear regression was used to estimate the T2* change between rest and activation of a functional task. The FID spectrum was filtered with a Gaussian window around the water peak, and log-linear regression was optimized for the particular ROI by adoption of the linearization length. The spectroscopic voxel was positioned on an ROI defined from a real-time fMRI EPI BOLD localizer. Additional online signal processing algorithms performed signal drift removal (exponential moving average), despiking and low-pass filtering (modified Kalman filter) and, finally, the dynamic feedback signal normalization. Two functional tasks were used to estimate the sensitivity of the SVPS method compared to BOLD signal changes, namely the primary motor cortex (PMC, left hand finger tapping) and visual cortex (VC, blinking checkerboard). Four healthy volunteers performed these tasks and an additional session using real-time signal feedback modulating their activation level of the PMC. Results show that single voxel spectroscopy is able to provide a good and reliable estimation of the BOLD signal changes. Small data size and FID signal processing instead of processing entire brain volumes as well as more information revealed from the acquired total water spectrum, i.e., direct estimation of the T2* values and B0 changes, make SVPS proton spectroscopy suitable and advantageous for real-time neurofeedback studies. Particular challenges of ultra-high field spectroscopy due to the non-linearity in the spectral information, e.g., poor main magnetic field homogeneity and the absence of motion correction for the SVPS sequence may lead to the special artifacts in the control signal which still need to be addressed. The contrast to noise ratio (CNR), experimental statistic (t-values) and percent signal change were used as quality parameters to estimate the method performance. The potential and challenges of the spectroscopic approach for fMRI studies needs to be further investigated.

Materials, Vol. 4, Pages 1543-1547: Two Types of Inulin Fructotransferases

Kazutomo Haraguchi — Wed, 07 Sep 2011 00:00:00 CEST

Inulin is a polysaccharide contained in chicory, dahlia, and other plants. An oligosaccharide DFA III is produced from inulin using a microbial enzyme, inulin fructotransferase (DFA III producing) [EC 2.4.1.93]. The oligosaccharide DFAIII has a unique functionality that accelerates the assimilation of minerals (Ca, Fe, and so on) from intestines. Therefore, it has a potential for the improvement of osteoporosis and iron deficiency anemia. The production of DFA III was industrialized in 2004 in Japan. Another oligosaccharide DFA I is produced from inulin by another enzyme, inulin fructotransferase (DFA I producing) [EC 2.4.1.200]. The oligosaccharide DFA I has half the sweetness of sucrose. The genes of the two enzymes were cloned and the nucleotide sequences were determined. The deduced amino acid sequences of two enzyme genes had a homology of 49.8%.

Materials, Vol. 4, Pages 1528-1542: Sorption of Aromatic Compounds with Copolymer Sorbent Materials Containing β-Cyclodextrin

Lee D. Wilson — Mon, 29 Aug 2011 00:00:00 CEST

Urethane copolymer sorbent materials that incorporate β-cyclodextrin (CD) have been prepared and their sorption properties with chlorinated aromatic compounds (i.e., pentachlorophenol, 2,4-dichlorophenol and 2,4-dichlorophenoxy acetic acid) have been evaluated. The sorption properties of granular activated carbon (GAC) were similarly compared in aqueous solution at variable pH conditions. The sorbents displayed variable BET surface areas as follows: MDI-X copolymers (< 101 m2/g), CDI-X copolymers (< 101 m2/g), and granular activated carbon (GAC ~103 m2/g). The sorption capacities for the copolymers sorbents are listed in descending order, as follows: GAC > CDI-3 copolymer ≈ MDI-3 copolymer. The sorption capacity for the aromatic adsorbates with each sorbent are listed in descending order, as follows: 2,4-dichlorophenol > 2,4-dichlorophenoxy acetic acid > pentachlorophenol. In general, the differences in the sorption properties of the copolymer sorbents with the chlorinated organics were related to the following factors: (i) surface area of the sorbent; (ii) CD content and accessibility; and (iii) and the chemical nature of the sorbent material.

Materials, Vol. 4, Pages 1519-1527: Spinning Carbon Nanotube Nanothread under a Scanning Electron Microscope

Weifeng Li — Mon, 29 Aug 2011 00:00:00 CEST

Nanothread with a diameter as small as one hundred nanometers was manufactured under a scanning electron microscope. Made directly from carbon nanotubes, and inheriting their superior electrical and mechanical properties, nanothread may be the world’s smallest man-made fiber. The smallest thread that can be spun using a bench-top spinning machine is about 5 microns in diameter. Nanothread is a new material building block that can be used at the nanoscale or plied to form yarn for applications at the micro and macro scales. Preliminary electrical and mechanical properties of nanothread were measured. The resistivity of nanothread is less than 10−5 Ω∙m. The strength of nanothread is greater than 0.5 GPa. This strength was obtained from measurements using special glue that cures in an electron microscope. The glue weakened the thread, thus further work is needed to obtain more accurate measurements. Nanothread will have broad applications in enabling electrical components, circuits, sensors, and tiny machines. Yarn can be used for various macroscale applications including lightweight antennas, composites, and cables.

Materials, Vol. 4, Pages 1483-1518: Matrices for Sensors from Inorganic, Organic, and Biological Nanocomposites

Claudio Nicolini — Wed, 24 Aug 2011 00:00:00 CEST

Matrices and sensors resulting from inorganic, organic and biological nanocomposites are presented in this overview. The term nanocomposite designates a solid combination of a matrix and of nanodimensional phases differing in properties from the matrix due to dissimilarities in structure and chemistry. The nanoocomposites chosen for a wide variety of health and environment sensors consist of Anodic Porous Allumina and P450scc, Carbon nanotubes and Conductive Polymers, Langmuir Blodgett Films of Lipases, Laccases, Cytochromes and Rhodopsins, Three-dimensional Nanoporous Materials and Nucleic Acid Programmable Protein Arrays.

Materials, Vol. 4, Pages 1469-1482: The Effect of Synovial Fluid Enzymes on the Biodegradability of Collagen and Fibrin Clots

Matthew Palmer — Mon, 22 Aug 2011 00:00:00 CEST

Recently there has been a great deal of interest in the use of biomaterials to stimulate wound healing. This is largely due to their ability to centralize high concentrations of compounds known to promote wound healing at a needed location. Joints present a unique challenge to using scaffolds because of the presence of enzymes in synovial fluid which are known to degrade materials that would be stable in other parts of the body. The hypothesis of this study was that atelocollagen scaffolds would have greater resistance to enzymatic degradation than scaffolds made of gelatin, fibrin and whole blood. To test this hypothesis, collagen and fibrin-based scaffolds were placed in matrix metallopeptidase-1 (MMP-1), elastase, and plasmin solutions at physiologic concentrations, and the degradation of each scaffold was measured at varying time points. The atelocollagen scaffolds had a significantly greater resistance to degradation by MMP-1, elastase and plasmin over the fibrin based scaffolds. The results suggest that atelocollagen-based scaffolds may provide some protection against premature degradation by synovial fluid enzymes over fibrin-based matrices.

Materials, Vol. 4, Pages 1440-1468: Simulation of Granular Flows and Pile Formation in a Flat-Bottomed Hopper and Bin, and Experimental Verification

Shinichi Yuu — Mon, 22 Aug 2011 00:00:00 CEST

Granular flows of 200 μm particles and the pile formation in a flat-bottomed hopper and bin in the presence of air and in a vacuum were predicted based on three-dimensional numerically empirical constitutive relations using Smoothed Particle Hydrodynamics and Computational Fluid Dynamics methods. The constitutive relations for the strain rate independent stress have been obtained as the functions of the Almansi strain including the large deformation by the same method as Yuu et al. [1]. The constitutive relations cover the elastic and the plastic regions including the flow state and represent the friction mechanism of granular material. We considered the effect of air on the granular flow and pile by the two-way coupling method. The granular flow patterns, the shapes of piles and the granular flow rates in the evolution are compared with experimental data measured under the same conditions. There was good agreement between these results, which suggests that the constitutive relations and the simulation method would be applicable for predicting granular flows and pile formation with complex geometry including free surface geometry. We describe the mechanisms by which the air decreases the granular flow rate and forms the convergence granular flow below the hopper outlet.

Materials, Vol. 4, Pages 1426-1439: Low and High Field Magnetic Resonance for in Vivo Analysis of Seeds

Ljudmilla Borisjuk — Tue, 16 Aug 2011 00:00:00 CEST

Low field NMR has been successfully used for the evaluation of seed composition and quality, but largely only in crop species. We show here that 1.5T NMR provides a reliable means for analysing the seed lipid fraction present in a wide range of species, where both the seed size and lipid concentration differed by >10 fold. Little use of high field NMR has been made in seed research to date, even though it potentially offers many opportunities for studying seed development, metabolism and storage. Here we demonstrate how 17.5T and 20T NMR can be applied to image seed structure, and analyse lipid and metabolite distribution. We suggest that further technical developments in NMR/MRI will facilitate significant advances in our understanding of seed biology.

Materials, Vol. 4, Pages 1417-1425: Preparation of Chitin Nanofibers from Mushrooms

Shinsuke Ifuku — Fri, 12 Aug 2011 00:00:00 CEST

Chitin nanofibers were isolated from the cell walls of five different types of mushrooms by the removal of glucans, minerals, and proteins, followed by a simple grinding treatment under acidic conditions. The Chitin nanofibers thus obtained have a uniform structure and a long fiber length. The width of the nanofibers depended on the type of mushrooms and varied in the range 20 to 28 nm. The Chitin nanofibers were characterized by elemental analyses, FT-IR spectra, and X-ray diffraction profiles. The results showed that the α-chitin crystal structure was maintained and glucans remained on the nanofiber surface.

Materials, Vol. 4, Pages 1399-1416: Deacetylation of Chitosan: Material Characterization and in vitro Evaluation via Albumin Adsorption and Pre-Osteoblastic Cell Cultures

Youling Yuan — Fri, 12 Aug 2011 00:00:00 CEST

Degree of deacetylation (DDA) and molecular weight (MW) of chitosans are important to their physical and biological properties. In this study, two chitosans, HS (DDA = 73.3%) and AT (DDA = 76.8%), were deacetylated with 45% sodium hydroxide under nitrogen atmosphere at 80 °C or 90 °C for up to 120 min, to obtain two series of chitosans. The polymers produced were characterized for MW by gel permeation chromatography, DDA by titration and UV-vis methods, and crystallinity, hydrophilicity and thermal stability by X-ray diffraction, water contact angle and differential scanning calorimetry respectively. Films, made by solution casting in dilute acetic acid at ambient conditions, were evaluated for biological activity by albumin adsorption and the attachment and growth of a pre-osteoblast cell line. Chitosans with between 80–93% DDA’s (based on titration) were reproducibly obtained. Even though deacetylation under nitrogen was supposed to limit chain degradation during decetylation, MW decreased (by maximum of 37.4% of HS and 63.0% for AT) with increasing deacetylation reaction time and temperature. Crystallinity and decomposition temperature increased and water contact angles decreased with processing to increase DDA. Significantly less albumin was absorbed on films made with 93% DDA chitosans as compared with the original materials and the AT chitosans absorbed less than the HS chitosans. The cells on higher DDA chitosan films grew faster than those on lower DDA films. In conclusion, processing conditions increased DDA and influenced physicochemical and biological properties. However, additional studies are needed to unambiguously determine the influence of DDA or MW on in vitro and in vivo performance of chitosan materials for bone/implant applications.

Materials, Vol. 4, Pages 1384-1398: Synthesis and Hydrolytic Degradation of Substituted Poly(DL-Lactic Acid)s

Hideto Tsuji — Wed, 10 Aug 2011 00:00:00 CEST

Non-substituted racemic poly(DL-lactic acid) (PLA) and substituted racemic poly(DL-lactic acid)s or poly(DL-2-hydroxyalkanoic acid)s with different side-chain lengths, i.e., poly(DL-2-hydroxybutanoic acid) (PBA), poly(DL-2-hydroxyhexanoic acid) (PHA), and poly(DL-2-hydroxydecanoic acid) (PDA) were synthesized by acid-catalyzed polycondensation of DL-lactic acid (LA), DL-2-hydroxybutanoic acid (BA), DL-2-hydroxyhexanoic acid (HA), and DL-2-hydroxydecanoic acid (DA), respectively. The hydrolytic degradation behavior was investigated in phosphate-buffered solution at 80 and 37 °C by gravimetry and gel permeation chromatography. It was found that the reactivity of monomers during polycondensation as monitored by the degree of polymerization (DP) decreased in the following order: LA > DA > BA > HA. The hydrolytic degradation rate traced by DP and weight loss at 80 °C decreased in the following order: PLA > PDA > PHA > PBA and that monitored by DP at 37 °C decreased in the following order: PLA > PDA > PBA > PHA. LA and PLA had the highest reactivity during polymerization and hydrolytic degradation rate, respectively, and were followed by DA and PDA. BA, HA, PBA, and PHA had the lowest reactivity during polymerization and hydrolytic degradation rate. The findings of the present study strongly suggest that inter-chain interactions play a major role in the reactivity of non-substituted and substituted LA monomers and degradation rate of the non-substituted and substituted PLA, along with steric hindrance of the side chains as can be expected.

Materials, Vol. 4, Pages 1375-1383: Large-Scale Growth of Tubular Aragonite Whiskers through a MgCl2-Assisted Hydrothermal Process

Minyan Ren — Mon, 08 Aug 2011 00:00:00 CEST

In this paper, we have developed a facile MgCl2-assissted hydrothermal synthesis route to grow tubular aragonite whiskers on a large scale. The products have been characterized by powder X-ray diffraction (XRD), optical microscopy, and scanning electronic microscopy (SEM). The results show the as-grown product is pure tubular aragonite crystalline whiskers with a diameter of 5–10 mm and a length of 100–200 mm, respectively. The concentration of Mg2+ plays an important role in determining the quality and purity of the products. Furthermore, the method can be extended to fabricate CaSO4 fibers. The high quality of the product and the mild conditions used mean that the present route has good prospects for the growth of inorganic crystalline whiskers.

Materials, Vol. 4, Pages 1360-1374: Osteoinductivity Assessment of BMP-2 Loaded Composite Chitosan-Nano-Hydroxyapatite Scaffolds in a Rat Muscle Pouch

Benjamin T. Reves — Tue, 02 Aug 2011 00:00:00 CEST

The objective of this study was to evaluate the osteoinductivity of composite chitosan-nano-hydroxyapatite scaffolds in a rat muscle pouch model. Previous in vitro characterization demonstrated the ability of the scaffolds to promote bone regeneration and as a carrier for local delivery of BMP-2. Composite microspheres were prepared using a co-precipitation method, and scaffolds were fabricated using an acid wash to adhere beads together. To determine the in vivo osteoinductivity of the scaffolds, the following groups (n = 6) were implanted into muscle pouches created in the latissimus dorsi of Sprague Dawley rats: (A) lyophilized scaffolds without rhBMP-2, (B) lyophilized scaffolds with rhBMP-2, (C) non-lyophilized scaffolds with rhBMP-2, and (D) absorbable collagen sponge with rhBMP-2 (control). Groups B, C, and D were loaded with 4 mL of a 9.0 μg/mL solution of rhBMP-2 for 48 h. The rats were sacrificed after one month and samples were analyzed for amount of residual implant material, new bone, and osteoid. Although the experimental groups displayed minimal degradation after one month, all of the scaffolds contained small amounts of woven bone and considerable amounts of osteoid. Approximately thirty percent of the open space available for tissue ingrowth in the scaffolds contained new bone or osteoid in the process of mineralization. The ability of the composite scaffolds (with and without BMP-2) to promote ectopic bone growth in vivo was demonstrated.

Materials, Vol. 4, Pages 1345-1359: Uniaxial Tension Test of Slender Reinforced Early Age Concrete Members

Yoichi Mimura — Tue, 02 Aug 2011 00:00:00 CEST

The present study aims to obtain the tensile properties of early age concrete based on a uniaxial tension test employing RC slender members. First, the paper shows that concrete strain is equal to the strain of rebar at the mid-span of the RC member. The tensile Young’s modulus and the strain capacity of early age concrete are estimated using strain measurements. The experiment indicated that the tensile Young’s modulus at an early age is higher than the compressive modulus. This observation was similar to one found in a previous investigation which used a direct tension test of early age concrete. Moreover, the paper describes how an empirical equation for mature concrete can be applied to the relation between uniaxial tensile strength and splitting tensile strength even in early age concrete. Based on a uniaxial tension test, the paper proposes an empirical equation for the relationship between standard bond stresses and relative slip.

Materials, Vol. 4, Pages 1333-1344: Resonant Mode Reduction in Radiofrequency Volume Coils for Ultrahigh Field Magnetic Resonance Imaging

Yong Pang — Thu, 28 Jul 2011 00:00:00 CEST

In a multimodal volume coil, only one mode can generate homogeneous Radiofrequency (RF) field for Magnetic Resonance Imaging. The existence of other modes may increase the volume coil design difficulties and potentially decreases coil performance. In this study, we introduce common-mode resonator technique to high and ultrahigh field volume coil designs to reduce the resonant mode while maintain the homogeneity of the RF field. To investigate the design method, the common-mode resonator was realized by using a microstrip line which was split along the central to become a pair of parallel transmission lines within which common-mode currents exist. Eight common-mode resonators were placed equidistantly along the circumference of a low loss dielectric cylinder to form a volume coil. Theoretical analysis and comparison between the 16-strut common-mode volume coil and a conventional 16-strut volume coil in terms of RF field homogeneity and efficiency was performed using Finite-Difference Time-Domain (FDTD) method at 298.2 MHz. MR imaging experiments were performed by using a prototype of the common-mode volume coil on a whole body 7 Tesla scanner. FDTD simulation results showed the reduced number of resonant modes of the common-mode volume coil over the conventional volume coil, while the RF field homogeneity of the two type volume coils was kept at the same level. MR imaging of a water phantom and a kiwi fruit showing the feasibility of the proposed method for simplifying the volume coil design is also presented.

Materials, Vol. 4, Pages 1321-1332: Calcium Sulfate with Stearic Acid as an Encouraging Carrier for Reindeer Bone Protein Extract

Hanna Tölli — Thu, 21 Jul 2011 00:00:00 CEST

Various bone proteins and growth factors in specific concentrations are required for bone formation. If the body cannot produce sufficient quantities of these factors, bone trauma can be healed with an implant that includes the required factors in a carrier. This study was designed to evaluate various calcium salt candidates that can be used as carrier with reindeer bone protein extract to induce ectopic bone formation in the muscle pouch model of mouse. The bone protein extract was either impregnated into the disc form of carrier or mixed with carrier powder before implantation. The radiographic analysis indicated increased bone formation in all of the active groups containing the bone protein extract compared to the controls within 21 days follow-up. The highest bone formation was seen in the group with calcium sulfate with stearic acid where new bone and calcified cartilage were clearly visible. The greatest bone formation occurred in the groups that had bone protein extract readily available. This indicates that the bone forming factors in sufficient concentrations are required at the early stage of bone formation. The calcium sulfate with stearic acid was the most suitable and effective carrier for reindeer bone protein extract.

Materials, Vol. 4, Pages 1309-1320: Boronization and Carburization of Superplastic Stainless Steel and Titanium-Based Alloys

Masafumi Matsushita — Mon, 18 Jul 2011 00:00:00 CEST

Bronization and carburization of fine-grain superplastic stainless steel is reviewed, and new experimental results for fine grain Ti88.5Al4.5V3Fe2Mo2 are reported. In superplastic duplex stainless steel, the diffusion of carbon and boron is faster than in non-superplastic duplex stainless steel. Further, diffusion is activated by uniaxial compressive stress. Moreover, non-superplastic duplex stainless steel shows typical grain boundary diffusion; however, inner grain diffusion is confirmed in superplastic stainless steel. The presence of Fe and Cr carbides or borides is confirmed by X-ray diffraction, which indicates that the diffused carbon and boron react with the Fe and Cr in superplastic stainless steel. The Vickers hardness of the carburized and boronized layers is similar to that achieved with other surface treatments such as electro-deposition. Diffusion of boron into the superplastic Ti88.5Al4.5V3Fe2Mo2 alloy was investigated. The hardness of the surface exposed to boron powder can be increased by annealing above the superplastic temperature. However, the Vickers hardness is lower than that of Ti boride.

Materials, Vol. 4, Pages 1287-1308: The Hardness and Strength Properties of WC-Co Composites

Ronald W. Armstrong — Thu, 14 Jul 2011 00:00:00 CEST

The industrially-important WC-Co composite materials provide a useful, albeit complicated materials system for understanding the combined influences on hardness and strength properties of the constituent WC particle strengths, the particle sizes, their contiguities, and of Co binder hardness and mean free paths, and in total, the volume fraction of constituents. A connection is made here between the composite material properties, especially including the material fracture toughness, and the several materials-type considerations of: (1) related hardness stress-strain behaviors; (2) dislocation (viscoplastic) thermal activation characterizations; (3) Hall-Petch type reciprocal square root of particle or grain size dependencies; and (4) indentation and conventional fracture mechanics results. Related behaviors of MgO and Al2O3 crystal and polycrystal materials are also described for the purpose of making comparisons.

Materials, Vol. 4, Pages 1271-1286: Cavitation During Superplastic Forming

John Campbell — Fri, 08 Jul 2011 00:00:00 CEST

Cavitation is the opening of pores during superplastic forming, typically at grain boundary triple points or on second phase grain boundary particles during slip of grain boundaries. Theories for the initiation of cavitation are reviewed. It seems that cavitation is unlikely to occur by processes intrinsic to metals such as dislocation mechanisms or point defect condensation. It is proposed that cavitation can only occur at non-bonded interfaces such as those introduced extrinsically (i.e., from the outside) during the original casting of the metal. These defects, known as oxide bifilms, are naturally introduced during pouring of the liquid metal, and are frozen into the solid, often pushed by dendritic growth into grain boundaries where they are difficult to detect because of their extreme thinness, often measured in nanometres. Their unbonded central interface acts as a crack and can initiate cavitation. Second phase precipitates probably do not nucleate and grow on grain boundaries but grow on bifilms in the boundaries, explaining the apparent association between boundaries, second phase particles and failure initiation. Improved melting and casting techniques can provide metal with reduced or zero bifilm population for which cavitation would not be possible, promising significant improvements in superplastic behaviour.

Materials, Vol. 4, Pages 1260-1270: Study of the Distribution of Radiative Defects and Reabsorption of the UV in ZnO Nanorods-Organic Hybrid White Light Emitting Diodes (LEDs)

Ijaz Hussain — Fri, 08 Jul 2011 00:00:00 CEST

In this study, the low temperature aqueous chemical growth (ACG) method was employed to synthesized ZnO nanorods to process-organic hybrid white light emitting diodes (LEDs) on glass substrate. Electroluminescence spectra of the hybrid white LEDs demonstrate the combination of emission bands arising from radiative recombination of the organic and ZnO nanorods (NRs). Depth resolved luminescence was used for probing the nature and spatial distribution of radiative defects, especially to study the re-absorption of ultraviolet (UV) in this hybrid white LEDs structure. At room temperature the cathodoluminescence (CL) spectra intensity of the deep band emission (DBE) is increased with the increase of the electron beam penetration depth due to the increase of defect concentration at the ZnO NRs/Polyfluorene (PFO) interface and probably due to internal absorption of the UV. A strong dependency between the intensity ratio of the UV to the DBE bands and the spatial distribution of the radiative defects in ZnO NRs has been found. The comparison of the CL spectra from the PFO and the ZnO NRs demonstrate that PFO has a very weak violet-blue emission band, which confirms that most of the white emission components originate from the ZnO NRs.

Materials, Vol. 4, Pages 1249-1259: Migration Capacity and Viability of Human Primary Osteoblasts in Synthetic Three-dimensional Bone Scaffolds Made of Tricalciumphosphate

Anika Jonitz — Fri, 08 Jul 2011 00:00:00 CEST

In current therapeutic strategies, bone defects are filled up by bone auto- or allografts. Since they are limited by insufficient availability and donor site morbidity, it is necessary to find an appropriate alternative of synthetic porous bone materials. Because of their osteoconductive characteristics, ceramic materials like tricalciumphosphate (TCP) are suitable to fill up bone defects. Another advantage of TCP implants is the ability of patient-specific engineering. Objective of the present in-vitro study was to analyze the migration capacity and viability of human primary osteoblasts in porous three-dimensional TCP scaffolds in a static cell culture. To obtain data of the cellular supply with nutrients and oxygen, we determined the oxygen concentration and the pH value within the 3D scaffold compared to the surrounding medium using microsensors. After eight days of cultivation we found cells on all four planes. During incubation, the oxygen concentration within the scaffold decreased by approximately 8%. Furthermore, we could not demonstrate an increasing acidification in the core of the TCP scaffold. Our results suggest that osteoblasts could migrate and survive within the macroporous TCP scaffolds. The selected size of the macropores prevents overgrowth of cells, whereby the oxygen and nutrients supply is sufficiently guaranteed.

Materials, Vol. 4, Pages 1238-1248: Influence of Surface Processing on the Biocompatibility of Titanium

Kornelia Wirsching — Wed, 06 Jul 2011 00:00:00 CEST

Surface conditioning of titanium middle ear implants results in an improved biocompatibility, which can be characterized by the properties of fibroblasts cultured on conditioned surfaces. Titanium has been established as a favorable biomaterial in ossicular chain reconstruction. The epithelization of the surface of the implants is important for their integration and stable positioning in the middle ear. Mouse fibroblast cells were cultured on platelets made from pure Grade 2 titanium. Platelets that had been etched along their production process were compared to unetched platelets. The DNA in the cell nuclei was stained with DAPI and the actin filaments of the cytoskeleton were stained with FITC-conjugated phalloidin in order to analyze the cells grown on etched and unetched platelets by fluorescence microscopy. SEM (scanning electron microscopic) images were used to compare the surface structure of etched and unetched titanium platelets. There was a statistically significant increase of the area covered by the cytoplasm and increased actin expression by fibroblasts grown on the etched titanium platelets. In addition, the area of the platelets covered by nuclei on the etched platelets exceeded on average the one on unetched platelets, although this difference was not significant. The SEM pictures comparing unetched and etched titanium platelets showed a clear difference in surface structure. Surface conditioning of titanium implants improved the epithelization by fibroblasts and consequently etched titanium should be the preferred biomaterial for reconstructive middle ear surgery.

Materials, Vol. 4, Pages 1224-1237: Defects Identification and Effects of Annealing on Lu2(1-x)Y2xSiO5 (LYSO) Single Crystals for Scintillation Application

Samuel Blahuta — Fri, 01 Jul 2011 00:00:00 CEST

The nature, properties and relative concentrations of electronic defects were investigated by Thermoluminescence (TL) in Lu2(1-x)Y2xSiO5 (LYSO) single crystals. Ce and Tb-doped single crystals, grown by the Czochralski technique (CZ), revealed similar traps in TL. LYSO:Ce single crystals were grown by the Floating-Zone technique (FZ) with increasing oxygen concentration in the growth atmosphere. TL intensity is strongly dependent on the oxygen content of the material, and oxygen vacancies are proven to be the main electronic defects in LYSO. The effects of oxidizing and reducing annealing post-treatment on these defects were investigated. While oxidizing treatments efficiently reduce the amount of electronic defects, reducing treatments increase the amount of existing traps. In a thermally assisted tunneling mechanism, the localization of oxygen vacancies around the dopant is discussed. They are shown to be in the close vicinity of the dopant, though not in first neighbor positions.

Materials, Vol. 4, Pages 1194-1223: Micrograin Superplasticity: Characteristics and Utilization

Farghalli A. Mohamed — Fri, 01 Jul 2011 00:00:00 CEST

Micrograin Superplasticity refers to the ability of fine-grained materials (1 µm < d < 10 μm, where d is the grain size) to exhibit extensive neck-free elongations during deformation at elevated temperatures. Over the past three decades, good progress has been made in rationalizing this phenomenon. The present paper provides a brief review on this progress in several areas that have been related to: (a) the mechanical characteristics of micrograin superplasticity and their origin; (b) the effect of impurity content and type on deformation behavior, boundary sliding, and cavitation during superplastic deformation; (c) the formation of cavity stringers; (d) dislocation activities and role during superplastic flow; and (e) the utilization of superplasticity.

Materials, Vol. 4, Pages 1182-1193: Experimental Determination of the Fluorescence Quantum Yield of Semiconductor Nanocrystals

Julien Laverdant — Thu, 30 Jun 2011 00:00:00 CEST

Many studies have considered the luminescence of colloidal II–VI nanocrystals, both in solution at a collective scale and at an individual scale by confocal microscopy. The quantum yield is an important figure of merit for the optical quality of a fluorophore. We detail here a simple method to determine the quantum yield of nanocrystals in solution as a function of the absorption. For this purpose, we choose rhodamine 101 as a reference dye to measure the nanocrystal fluorescence quantum yield. The influence of the concentration on quantum yield is therefore studied for both the reference and the solutions of nanocrystals and is found to be critical for the acuity of the method. Different types of nanocrystals are studied to illustrate different quantum yield evolutions with the concentration.

Materials, Vol. 4, Pages 1168-1181: Delocalization of Electrons in Strong Insulators at High Dynamic Pressures

William J. Nellis — Tue, 21 Jun 2011 00:00:00 CEST

Systematics of material responses to shock flows at high dynamic pressures are discussed. Dissipation in shock flows drives structural and electronic transitions or crossovers, such as used to synthesize metallic liquid hydrogen and most probably Al2O3 metallic glass. The term “metal” here means electrical conduction in a degenerate system, which occurs by band overlap in degenerate condensed matter, rather than by thermal ionization in a non-degenerate plasma. Since H2 and probably disordered Al2O3 become poor metals with minimum metallic conductivity (MMC) virtually all insulators with intermediate strengths do so as well under dynamic compression. That is, the magnitude of strength determines the split between thermal energy and disorder, which determines material response. These crossovers occur via a transition from insulators with electrons localized in chemical bonds to poor metals with electron energy bands. For example, radial extents of outermost electrons of Al and O atoms are 7 a0 and 4 a0, respectively, much greater than 1.7 a0 needed for onset of hybridization at 300 GPa. All such insulators are Mott insulators, provided the term “correlated electrons” includes chemical bonds.

Materials, Vol. 4, Pages 1144-1167: In Vivo Corrosion of Two Novel Magnesium Alloys ZEK100 and AX30 and Their Mechanical Suitability as Biodegradable Implants

Tim Andreas Huehnerschulte — Tue, 21 Jun 2011 00:00:00 CEST

In magnesium alloys, the components used modify the alloy properties. For magnesium implants in contact with bone, rare earths alloys are commonly examined. These were shown to have a higher corrosion resistance than other alloys and a high mechanical strength, but their exact composition is hard to predict. Therefore a reduction of their content could be favorable. The alloys ZEK100 and AX30 have a reduced content or contain no rare earths at all. The aim of the study was to investigate their in vivo degradation and to assess the suitability of the in vivo µCT for the examination of their corrosion. Implants were inserted in rabbit tibiae. Clinical examinations, X-rays and in vivo µCT scans were done regularly. Afterwards implants were analyzed with REM, electron dispersive X-ray (EDX), weighing and mechanical testing. The in vivo µCT is of great advantage, because it allows a quantification of the corrosion rate and qualitative 3D assessment of the corrosion morphology. The location of the implant has a remarkable effect on the corrosion rate. Due to its mechanical characteristics and its corrosion behavior, ZEK100 was judged to be suitable, while AX30, which displays favorable degradation behavior, has too little mechanical strength for applications in weight bearing bones.

Materials, Vol. 4, Pages 1132-1143: Optical Properties of ZnO Nanoparticles Capped with Polymers

Shingo Tachikawa — Fri, 17 Jun 2011 00:00:00 CEST

Optical properties of ZnO nanoparticles capped with polymers were investigated. Polyethylene glycol (PEG) and polyvinyl pyrrolidone (PVP) were used as capping reagents. ZnO nanoparticles were synthesized by the sol-gel method. Fluorescence and absorption spectra were measured. When we varied the timing of the addition of the polymer to the ZnO nanoparticle solution, the optical properties were drastically changed. When PEG was added to the solution before the synthesis of ZnO nanoparticles, the fluorescence intensity increased. At the same time, the total particle size increased, which indicated that PEG molecules had capped the ZnO nanoparticles. The capping led to surface passivation, which increased fluorescence intensity. However, when PEG was added to the solution after the synthesis of ZnO nanoparticles, the fluorescence and particle size did not change. When PVP was added to the solution before the synthesis of ZnO nanoparticles, aggregation of nanoparticles occurred. When PVP was added to the solution after the synthesis of ZnO nanoparticles, fluorescence and particle size increased. This improvement of optical properties is advantageous to the practical usage of ZnO nanoparticles, such as bioimaging

Materials, Vol. 4, Pages 1117-1131: Teriparatide Therapy as an Adjuvant for Tissue Engineering and Integration of Biomaterials

Robinder S. Dhillon — Wed, 15 Jun 2011 00:00:00 CEST

Critically sized large bone defects commonly result from trauma, radical tumor resections or infections. Currently, massive allografting remain as the clinical standard to treat these critical defects. Unfortunately, allograft healing is limited by the lack of osteogenesis and bio-integration of the graft to the host bone. Based on its widely studied anabolic effects on the bone, we have proposed that teriparatide [recombinant parathyroid hormone (PTH1–34)] could be an effective adjuvant for massive allograft healing. In support of this theory, here we review studies that have demonstrated that intermittent PTH1–34 treatment enhances and accelerates the skeletal repair process via a number of mechanisms including: effects on mesenchymal stem cells (MSC), angiogenesis, chondrogenesis, bone formation and remodeling. We also review the current literature on the effects of PTH1–34 therapy on bone healing, and discuss this drug’s long term potential as an adjuvant for endogenous tissue engineering.

Materials, Vol. 4, Pages 1104-1116: The Role Played by Computation in Understanding Hard Materials

John Edward Lowther — Tue, 14 Jun 2011 00:00:00 CEST

In the last decade, computation has played a valuable role in the understanding of materials. Hard materials, in particular, are only part of the application. Although materials involving B, C, N or O remain the most valued atomic component of hard materials, with diamond retaining its distinct superiority as the hardest, other materials involving a wide variety of metals are proving important. In the present work the importance of both ab-initio approaches and molecular dynamics aspects will be discussed with application to quite different systems. On one hand, ab-initio methods are applied to lightweight systems and advanced nitrides. Following, the use of molecular dynamics will be considered with application to strong metals that are used for high temperature applications.

Materials, Vol. 4, Pages 1096-1103: Correlation of Nitrogen Sorption and Confocal Laser Scanning Microscopy for the Analysis of Amino Group Distributions on Mesoporous Silica

Nando Gartmann — Thu, 09 Jun 2011 00:00:00 CEST

Aminopropylalkoxysilanes are frequently used for the functionalization of mesoporous silica. The analysis of amino group distributions on arrays of silica nanochannels by a combination of nitrogen sorption and confocal laser scanning microscopy provides valuable insight into the mechanisms underlying the interaction of these silanes with mesoporous silica surfaces. Tendencies towards external surface functionalization, non-uniform distribution in the pores, and hydrolysis of the silica framework are shown to depend to a large extent on the mobility of the aminopropylalkoxysilane molecules, which can be adjusted by the number and type of alkoxy groups.

Materials, Vol. 4, Pages 1087-1095: Fabrication of Multiferroic Co-Substituted BiFeO3 Epitaxial Films on SrTiO3 (100) Substrates by Radio Frequency Magnetron Sputtering

Husne Ara Begum — Thu, 09 Jun 2011 00:00:00 CEST

The 10 at.% Co-substituted BiFeO3 films (of thickness 50 nm) were successfully prepared by radio frequency (r.f.) magnetron sputtering on SrTiO3 (100) substrates with epitaxial relationships of [001](001)Co-BiFeO3//[001](001)SrTiO3. In this study, a single phase Co-substituted BiFeO3 epitaxial film was fabricated by r.f. magnetron sputtering. Sputtering conditions such as Ar, O2 gas pressure, annealing temperature, annealing atmosphere, and sputtering power were systematically changed. It was observed that a low Ar gas pressure and low sputtering power is necessary to suppress the formation of the secondary phases of BiOx. The Co-substituted BiFeO3 films were crystalized with post-annealing at 600 °C in air. The process window for single phase films is narrower than that for pure BiFeO3 epitaxial films. By substituting Fe with Co in BiFeO3, the magnetization at room temperature increased to 20 emu/cm3. This result suggests that Co-substituted BiFeO3 films can be used in spin-filter devices.

Materials, Vol. 4, Pages 1034-1086: Storage Phosphors for Medical Imaging

Paul Leblans — Thu, 09 Jun 2011 00:00:00 CEST

Computed radiography (CR) uses storage phosphor imaging plates for digital imaging. Absorbed X-ray energy is stored in crystal defects. In read-out the energy is set free as blue photons upon optical stimulation. In the 35 years of CR history, several storage phosphor families were investigated and developed. An explanation is given as to why some materials made it to the commercial stage, while others did not. The photo stimulated luminescence mechanism of the current commercial storage phosphors, BaFBr:Eu2+ and CsBr:Eu2+ is discussed. The relation between storage phosphor plate physical characteristics and image quality is explained. It is demonstrated that the morphology of the phosphor crystals in the CR imaging plate has a very significant impact on its performance.

Materials, Vol. 4, Pages 1023-1033: A Mechanochemical Approach to Porous Silicon Nanoparticles Fabrication

Luigi Russo — Tue, 07 Jun 2011 00:00:00 CEST

Porous silicon samples have been reduced in nanometric particles by a well known industrial mechanical process, the ball grinding in a planetary mill; the process has been extended to crystalline silicon for comparison purposes. The silicon nanoparticles have been studied by X-ray diffraction, infrared spectroscopy, gas porosimetry and transmission electron microscopy. We have estimated crystallites size from about 50 nm for silicon to 12 nm for porous silicon. The specific surface area of the powders analyzed ranges between 100 m2/g to 29 m2/g depending on the milling time, ranging from 1 to 20 h. Electron microscopy confirms the nanometric size of the particles and reveals a porous structure in the powders obtained by porous silicon samples which has been preserved by the fabrication conditions. Chemical functionalization during the milling process by a siloxane compound has also been demonstrated.

Materials, Vol. 4, Pages 1013-1022: Synthesis and Properties of a Chiroptically Active Oligomer from 3,4-Ethylenedioxythiophene and (–)-Myrtenal

Hirotsugu Kawashima — Mon, 30 May 2011 00:00:00 CEST

Oxidative polycondensation of 3,4-ethylenedioxythiophene and (–)-myrtenal was carried out with POCl3. A p-conjugated system thus constructed consists of aromatic and quinoidal alternating structure linked via methine groups. We examined iodine doping effect for the resultant material with electron spin resonance spectroscopy. Circular dichroism spectra in chloroform solution showed blue-shift with increase of iodine concentration. This result indicates that the doping process can tune chiroptical activity of the chiral π-conjugated system.

Materials, Vol. 4, Pages 991-1012: Antiviral Activity of Metal-Containing Polymers—Organotin and Cisplatin-Like Polymers

Michael R. Roner — Fri, 27 May 2011 00:00:00 CEST

Polymers containing platinum and to a lesser extent tin, have repeatedly demonstrated antitumor activity in vitro and in vivo against a variety of cell and tumor types. The mechanisms responsible for the antitumor activity include inducing a delay in cell proliferation and sister chromatid exchanges blocking tumor growth. As most DNA and some RNA viruses require, and even induce, infected cells to initiate DNA replication and subsequent cell division, compounds with antitumor activity will very likely also possess antiviral activity. This article examines the use of metal-containing polymers as a novel class of antivirals.

Materials, Vol. 4, Pages 980-990: Luminescent Afterglow Behavior in the M2Si5N8: Eu Family (M = Ca, Sr, Ba)

Koen Van den Eeckhout — Fri, 27 May 2011 00:00:00 CEST

Persistent luminescent materials are able to emit light for hours after being excited. The majority of persistent phosphors emit in the blue or green region of the visible spectrum. Orange- or red-emitting phosphors, strongly desired for emergency signage and medical imaging, are scarce. We prepared the nitrido-silicates Ca2Si5N8:Eu (orange), Sr2Si5N8:Eu (reddish), Ba2Si5N8:Eu (yellowish orange), and their rare-earth codoped variants (R = Nd, Dy, Sm, Tm) through a solid state reaction, and investigated their luminescence and afterglow properties. In this paper, we describe how the persistent luminescence is affected by the type of codopant and the choice and ratio of the starting products. All the materials exhibit some form of persistent luminescence, but for Sr2Si5N8:Eu,R this is very weak. In Ba2Si5N8:Eu the afterglow remains visible for about 400 s, and Ca2Si5N8:Eu,Tm shows the brightest and longest afterglow, lasting about 2,500 s. For optimal persistent luminescence, the dopant and codopant should be added in their fluoride form, in concentrations below 1 mol%. A Ca3N2 deficiency of about 5% triples the afterglow intensity. Our results show that Ba2Si5N8:Eu(,R) and Ca2Si5N8:Eu(,R) are promising persistent phosphors for applications requiring orange or red light.

Materials, Vol. 4, Pages 963-979: Microstructural and Process Characterization of Conductive Traces Printed from Ag Particulate Inks

David A. Roberson — Thu, 26 May 2011 00:00:00 CEST

Conductive inks are key enablers for the use of printing techniques in the fabrication of electronic systems. Focus on the understanding of aspects controlling the electrical performance of conductive ink is paramount. A comparison was made between microparticle Ag inks and an Ag nanoparticle ink. The microstructures resulting from thermal cure processes were characterized morphologically and also in terms of their effect on the resistivity of printed traces. For microparticle inks, the variability of resistivity measurements between samples as defined by coefficient of variation (CV) was greater than 0.1 when the resistivity was 10 to 50 times that of bulk Ag. When the resistivity was lower (~1.4 times that of bulk Ag) the CV of sample sets was less than 0.1. In the case of the nanoparticle ink, resistivity was found to decrease by a factor ranging from 1.2 to 1.5 after doubling the amount of layers printed prior to curing though it was expected to remain the same. Increasing the amount of layers printed also enhanced the sintering process.

Materials, Vol. 4, Pages 952-962: Study of Ni Metallization in Macroporous Si Using Wet Chemistry for Radio Frequency Cross-Talk Isolation in Mixed Signal Integrated Circuits

Xi Zhang — Wed, 25 May 2011 00:00:00 CEST

A highly conductive moat or Faraday cage of through-the-wafer thickness in Si substrate was proposed to be effective in shielding electromagnetic interference thereby reducing radio frequency (RF) cross-talk in high performance mixed signal integrated circuits. Such a structure was realized by metallization of selected ultra-high-aspect-ratio macroporous regions that were electrochemically etched in p− Si substrates. The metallization process was conducted by means of wet chemistry in an alkaline aqueous solution containing Ni2+ without reducing agent. It is found that at elevated temperature during immersion, Ni2+ was rapidly reduced and deposited into macroporous Si and a conformal metallization of the macropore sidewalls was obtained in a way that the entire porous Si framework was converted to Ni. A conductive moat was as a result incorporated into p− Si substrate. The experimentally measured reduction of crosstalk in this structure is 5~18 dB at frequencies up to 35 GHz.

Materials, Vol. 4, Pages 941-951: Layer Transfer from Chemically Etched 150 mm Porous Si Substrates

Barbara Terheiden — Mon, 23 May 2011 00:00:00 CEST

We demonstrate for the first time the successful layer transfer of an epitaxially grown monocrystalline Si film from a purely chemically etched porous Si substrate of 150 mm diameter to a glass carrier. The surface conditioning for all Si layer transfer processes based on porous Si has been, up to now without exception, carried out by electrochemical etching. In contrast, our chemical stain etching process uses an aqueous HF-rich HF/HNO3 solution. The porosity increases with increasing doping concentration of the Si substrate wafer and with increasing porous layer thickness. In contrast to the electrochemically etched double layers, the porosity profile of the stain etched substrates is highest at the original wafer surface and lowest at the interface between the porous layer and the Si bulk. The epitaxy process is adapted to the high porosity at the surface with regard to the reorganization of the porous layer.

Materials, Vol. 4, Pages 929-940: Nanohardness and Residual Stress in TiN Coatings

Luis Carlos Hernández — Tue, 17 May 2011 00:00:00 CEST

TiN films were prepared by the Cathodic arc evaporation deposition method under different negative substrate bias. AFM image analyses show that the growth mode of biased coatings changes from 3D island to lateral when the negative bias potential is increased. Nanohardness of the thin films was measured by nanoindentation, and residual stress was determined using Grazing incidence X ray diffraction. The maximum value of residual stress is reached at −100 V substrate bias coinciding with the biggest values of adhesion and nanohardness. Nanoindentation measurement proves that the force-depth curve shifts due to residual stress. The experimental results demonstrate that nanohardness is seriously affected by the residual stress.

Materials, Vol. 4, Pages 908-928: Magnetic Nanoparticles Embedded in a Silicon Matrix

Petra Granitzer — Tue, 17 May 2011 00:00:00 CEST

This paper represents a short overview of nanocomposites consisting of magnetic nanoparticles incorporated into the pores of a porous silicon matrix by two different methods. On the one hand, nickel is electrochemically deposited whereas the nanoparticles are precipitated on the pore walls. The size of these particles is between 2 and 6 nm. These particles cover the pore walls and form a tube-like arrangement. On the other hand, rather well monodispersed iron oxide nanoparticles, of 5 and 8 nm respectively, are infiltrated into the pores. From their size the particles would be superparamagnetic if isolated but due to magnetic interactions between them, ordering of magnetic moments occurs below a blocking temperature and thus the composite system displays a ferromagnetic behavior. This transition temperature of the nanocomposite can be varied by changing the filling factor of the particles within the pores. Thus samples with magnetic properties which are variable in a broad range can be achieved, which renders this composite system interesting not only for basic research but also for applications, especially because of the silicon base material which makes it possible for today’s process technology.

Materials, Vol. 4, Pages 893-907: Role of Titanium Surface Topography and Surface Wettability on Focal Adhesion Kinase Mediated Signaling in Fibroblasts

Christine J. Oates — Mon, 09 May 2011 00:00:00 CEST

Changes of titanium surface roughness and surface free energy may influence protein absorption that increases cell differentiation through activation of focal adhesion kinase related pathways. However, the influence of titanium surface roughness and hydrophilicity on fibroblast behavior is not well understood. The aim of this study was to investigate the influence of topography and hydrophilicity on fibroblast attachment, spreading, morphology, intracellular signaling, proliferation, and collagen I mRNA levels. Using a cellular FAK knockout (FAK−/−) model and wild-type (WT) controls, we also investigated the contribution of adhesion in fibroblasts cultured on smooth (PT), sand-blasted, large grit, acid-etched (SLA) and hydrophilic SLA topographies. Loss of FAK did not significantly affect fibroblast attachment to any surface, but SLA and hydrophilic SLA surface attenuated spreading of WT cells significantly more than FAK−/− fibroblasts. Both FAK−/− and WT cells formed numerous focal adhesions on PT surfaces, but significantly less on SLA and hydrophilic SLA surfaces. In WT cells, phosphorylation levels of FAK were lower on SLA and hydrophilic SLA in comparison with PT 24 h post seeding. Labeling of cells with antibodies to cortactin showed that FAK−/−cells contained significantly more cortactin-rich focal adhesion in comparison with WT cells on PT surfaces, but not on SLA or hydrophilic SLA. ERK 1/2 phosphorylation was highest in WT cells on all surfaces which correlated with collagen I expression levels. We conclude that fibroblasts are sensitive to changes in surface roughness and hydrophilicity, with adhesive interactions mediated through FAK, an important modulator of fibroblast response.

Materials, Vol. 4, Pages 869-892: Thermodynamic Origin of the Vitreous Transition

Robert Tournier F. — Mon, 09 May 2011 00:00:00 CEST

The vitreous transition is characterized by a freezing of atomic degrees of freedom at a temperature Tg depending on the heating and cooling rates. A kinetic origin is generally attributed to this phenomenon instead of a thermodynamic one which we develop here. Completed homogeneous nucleation laws reflecting the energy saving due to Fermi energy equalization of nascent crystals and their melt are used. They are applied to bulk metallic glasses and extended to inorganic glasses and polymers. A transition T*g among various Tg corresponds to a crystal homogeneous nucleation temperature, leading to a preliminary formation of a cluster distribution during the relaxation time preceding the long steady-state nucleation time of crystals in small samples. The thermally-activated energy barrier ΔG*2ls/kBT at T*g for homogeneous nucleation is nearly the same in all glass-forming melts and determined by similar values of viscosity and a thermally-activated diffusion barrier from melt to cluster. The glass transition T*g is a material constant and a linear function of the energy saving associated with charge transfers from nascent clusters to the melt. The vitreous transition and the melting temperatures alone are used to predict the free-volume disappearance temperature equal to the Vogel-Fulcher-Tammann temperature of fragile glass-forming melts, in agreement with many viscosity measurements. The reversible thermodynamic vitreous transition is determined by the disappearance temperature T*g of the fully-relaxed enthalpy Hr that is not time dependent; the observed specific heat jump at T*g is equal to the proportionality coefficient of Hr with (T*g − Ta) for T ≤ T*g as expected from the enthalpy excess stored by a quenched undercooled melt at the annealing temperature Ta and relaxed towards an equilibrium vitreous state. However, the heat flux measurements found in literature over the last 50 years only gave an out-of-equilibrium Tg since the enthalpy is continuous at T*g without visible heat jump.