Optical properties of a nanomatch-like plasmonic structure

The optical properties of a match-like plasmonic nanostructure are numerically investigated using full-wave finite-difference time-domain analysis in conjunction with dispersive material models. This work is mainly motivated by the developed technique enabling reproducible fabrication of nanomatch structures as well as the growing applications that utilize the localized field enhancement in plasmonic nanostructures. Our research revealed that due to the pronounced field enhancement and larger resonance tunabilities, some nanomatch topologies show potentials for various applications in the field of, e.g., sensing as well as a novel scheme for highly reproducible tips in scanning near field optical microscopy, among others. Despite the additional degrees of freedom that are offered by the composite nature of the proposed nanomatch topology, the paper also reflects on a fundamental complication intrinsic to the material interfaces especially in the nanoscale: stoichiometric mixing. We conclude that the specificity in material modeling will become a significant issue in future research on functionalized composite nanostructures.

Modification of the magnetic properties of a heterometallic wheel by inclusion of a Jahn-Teller distorted Cu(II) ion

An investigation into the physical consequences of including a Jahn-Teller distorted Cu(II) ion within an antiferromagnetically coupled ring, [R(2)NH(2)][Cr(7)CuF(8)((O(2)C(t)Bu)(16))] is reported. Inelastic neutron scattering (INS) and electron paramagnetic resonance (EPR) spectroscopic data are simulated using a microscopic spin Hamiltonian, and show that the two Cr-Cu exchange interactions must be inequivalent. One Cr-Cu exchange is found to be antiferromagnetic and the other ferromagnetic. The geometry of the Jahn-Teller elongation is deduced from these results, and shows that a Jahn-Teller elongation axis must lie in the plane of the Cr(7)Cu wheel; the elongation is not observed by X-ray crystallography, due to positional disorder of the Cu site within the wheel. An electronic structure calculation confirms the structural distortion of the Cu site.

Exploratory studies on coordination chemistry of a redox-active bridging ligand: synthesis, properties and solid state structures of the complexes

The explorative coordination chemistry of the bridging ligand TTF-PPB is presented. Its strong binding ability to Co(II) and then to Ni(II) or Cu(II) in the presence of hexafluoroacetylacetonate (hfac(-)), forming new mono-and dinuclear complexes 1-3, is described. X-ray crystallographic studies have been conducted in the case of the free ligand TTF-PPB as well as its complexes [Co(TTF-PPB)(hfac)(2)] (1) and [Co(hfac)(2)(mu-TTF-PPB)Ni(hfac)(2)] (2). Each metal ion is bonded to two bidentate hfac-anions through their oxygen atoms and two nitrogen atoms of the PPB moiety with a distorted octahedral coordination geometry. Specifically, nitrogen donor atoms of TTF-PPB adopt a cis-coordination but not in the equatorial plane, which is quite rare. Electronic absorption, photoinduced intraligand charge transfer ((1)ILCT), and electrochemical behaviour of 1-3 have been investigated. UV-Vis spectroscopy shows very strong bands in the UV region consistent with ligand centred pi-pi* transitions and an intense broad band in the visible region corresponding to a spin-allowed pi-pi* (1)ILCT transition. Upon coordination, the (1)ILCT band is bathochromically shifted by 3100, 6100 and 5900 cm(-1) on going from 1 to 3. The electrochemical studies reveal that all of them undergo two reversible oxidation and one reversible reduction processes, ascribed to the successive oxidations of the TTF moiety and the reduction of the PPB unit, respectively.

Excited state properties of formamide in water solution: An ab initio study

We present ab initio quantum calculation of the optical properties of formamide in vapor phase and in water solution. We employ time dependent density functional theory for the isolated molecule and many-body perturbation theory methods for the system in solution. An average over several molecular dynamics snapshots is performed to take into account the disorder of the liquid. We find that the excited stateproperties of the gas-phase formamide are strongly modified by the presence of the water solvent: the geometry of the molecule is distorted and the electronic and optical properties are severely modified. The important interaction among the formamide and the water molecules forces us to use fully quantum methods for the calculation of the excited stateproperties of this system. The excitonic wave function is localized both on the solute and on part of the solvent.

PMMA-CNT matrices for vacuum electronic, biosensing and energy applications

Carbon nanotubes (CNTs) are interesting materials with extraordinary properties for various applications. Here, vertically-aligned multiwalled CNTs (VA-MWCNTs) are grown by our dual radio frequency plasma enhanced chemical vapor deposition (PECVD). After optimizing the synthesis processes, these VA-MWCNTs were fabricated in to a series of devices for applications in vacuum electronics, glucose biosensors, glucose biofuel cells, and supercapacitors In particular, we have created the so-called PMMA-CNT matrices (opened-tip CNTs embedded in poly-methyl methacrylate) that are promising components in a novel energy sensing, generation and storage (SGS) system that integrate glucose biosensors, biofuel cells, and supercapacitors. The content of this thesis work is described as follows: 1. We have first optimized the synthesis of VA-MWCNTs by our PECVD technique. The effects of CH4 flow rate and growth duration on the lengths of these CNTs were studied. 2. We have characterized these VA-MWCNTs for electron field emission. We noticed that as grown CNTs suffers from high emission threshold, poor emission density and poor long-term stability. We attempted a series of experiments to understand ways to overcome these problems. First, we decrease the screening effects on VA-MWCNTs by creating arrays of self-assembled CNT bundles that are catalyst-free and opened tips. These bundles are found to enhance the field emission stability and emission density. Subsequently, we have created PMMA-CNT matrices that are excellent electron field emitters with an emission threshold field of more than two-fold lower than that of the as-grown sample. Furthermore, no significant emission degradation was observed after a continuous emission test of 40 hours (versus much shorter tests in reported literatures). Based on the new understanding we learnt from the PMMA-CNT matrices, we further created PMMA-STO-CNT matrices by embedding opened-tip VA-MWCNTs that are coated with strontium titanate (SrTiO3) with PMMA. We found that the PMMA-STO-CNT matrices have all the desired properties of the PMMA-CNT matrices. Furthermore, PMMA-STO-CNT matrices offer much lower emission threshold field, about five-fold lower than that of as grown VA-MWCNTs. The new understandings we obtained are important for practical application of VA-MWCNTs in field emission devices. 3. Subsequently, we have functionalized PMMA-CNT matrices for glucose biosensing. Our biosensor was developed by immobilized glucose oxidase (GOχ) on the opened-tip CNTs exposed on the matrices. The durability, stability and sensitivity of the biosensor were studied. In order to understand the performance of miniaturized glucose biosensors, we have then investigated the effect of working electrode area on the sensitivity and current level of our biosensors. 4. Next, functionalized PMMA-CNT matrices were utilized for energy generation and storage. We found that PMMA-CNT matrices are promising component in glucose/O2 biofuel cells (BFCs) for energy generation. The construction of these BFCs and the effect of the electrode area on the power density of these BFCs were investigated. Then, we have attempted to use PMMA-CNT matrices as supercapacitors for energy storage devices. The performance of these supercapacitors and ways to enhance their performance are discussed. 5. Finally, we further evaluated the concept of energy SGS system that integrated glucose biosensors, biofuel cells, and supercapacitors. This SGS system may be implantable to monitor and control the blood glucose level in our body.

Functional ZnO nanostructures for electronic and energy applications

ZnO has proven to be a multifunctional material with important nanotechnological applications. ZnO nanostructures can be grown in various forms such as nanowires, nanorods, nanobelts, nanocombs etc. In this work, ZnO nanostructures are grown in a double quartz tube configuration thermal Chemical Vapor Deposition (CVD) system. We focus on functionalized ZnO Nanostructures by controlling their structures and tuning their properties for various applications. The following topics have been investigated: 1. We have fabricated various ZnO nanostructures using a thermal CVD technique. The growth parameters were optimized and studied for different nanostructures. 2. We have studied the application of ZnO nanowires (ZnONWs) for field effect transistors (FETs). Unintentional n-type conductivity was observed in our FETs based on as-grown ZnO NWs. We have then shown for the first time that controlled incorporation of hydrogen into ZnO NWs can introduce p-type characters to the nanowires. We further found that the n-type behaviors remained, leading to the ambipolar behaviors of hydrogen incorporated ZnO NWs. Importantly, the detected p- and n- type behaviors are stable for longer than two years when devices were kept in ambient conditions. All these can be explained by an ab initio model of Zn vacancy-Hydrogen complexes, which can serve as the donor, acceptors, or green photoluminescence quencher, depend on the number of hydrogen atoms involved. 3. Next ZnONWs were tested for electron field emission. We focus on reducing the threshold field (Eth) of field emission from non-aligned ZnO NWs. As encouraged by our results on enhancing the conductivity of ZnO NWs by hydrogen annealing described in Chapter 3, we have studied the effect of hydrogen annealing for improving field emission behavior of our ZnO NWs. We found that optimally annealed ZnO NWs offered much lower threshold electric field and improved emission stability. We also studied field emission from ZnO NWs at moderate vacuum levels. We found that there exists a minimum Eth as we scale the threshold field with pressure. This behavior is explained by referring to Paschen’s law. 4. We have studied the application of ZnO nanostructures for solar energy harvesting. First, as-grown and (CdSe) ZnS QDs decorated ZnO NBs and ZnONWs were tested for photocurrent generation. All these nanostructures offered fast response time to solar radiation. The decoration of QDs decreases the stable current level produced by ZnONWs but increases that generated by NBs. It is possible that NBs offer more stable surfaces for the attachment of QDs. In addition, our results suggests that performance degradation of solar cells made by growing ZnO NWs on ITO is due to the increase in resistance of ITO after the high temperature growth process. Hydrogen annealing also improve the efficiency of the solar cells by decreasing the resistance of ITO. Due to the issues on ITO, we use Ni foil as the growth substrates. Performance of solar cells made by growing ZnO NWs on Ni foils degraded after Hydrogen annealing at both low (300 °C) and high (600 °C) temperatures since annealing passivates native defects in ZnONWs and thus reduce the absorption of visible spectra from our solar simulator. Decoration of QDs improves the efficiency of such solar cells by increasing absorption of light in the visible region. Using a better electrolyte than phosphate buffer solution (PBS) such as KI also improves the solar cell efficiency. 5. Finally, we have attempted p-type doping of ZnO NWs using various growth precursors including phosphorus pentoxide, sodium fluoride, and zinc fluoride. We have also attempted to create p-type carriers via introducing interstitial fluorine by annealing ZnO nanostructures in diluted fluorine gas. In brief, we are unable to reproduce the growth of reported p-type ZnO nanostructures. However; we have identified the window of temperature and duration of post-growth annealing of ZnO NWs in dilute fluorine gas which leads to suppression of native defects. This is the first experimental effort on post-growth annealing of ZnO NWs in dilute fluorine gas although this has been suggested by a recent theory for creating p-type semiconductors. In our experiments the defect band peak due to native defects is found to decrease by annealing at 300 °C for 10 – 30 minutes. One of the major future works will be to determine the type of charge carriers in our annealed ZnONWs.

Analysis of transport properties of mechanically alloyed [Pb1-xSnxTe]

The work described in this thesis had two objectives. The first objective was to develop a physically based computational model that could be used to predict the electronic conductivity, Seebeck coefficient, and thermal conductivity of Pb1-xSnxTe alloys over the 400 K to 700 K temperature as a function of Sn content and doping level. The second objective was to determine how the secondary phase inclusions observed in Pb1-xSnxTe alloys made by consolidating mechanically alloyed elemental powders impact the ability of the material to harvest waste heat and generate electricity in the 400 K to 700 K temperature range. The motivation for this work was that though the promise of this alloy as an unusually efficient thermoelectric power generator material in the 400 K to 700 K range had been demonstrated in the literature, methods to reproducibly control and subsequently optimize the materials thermoelectric figure of merit remain elusive. Mechanical alloying, though not typically used to fabricate these alloys, is a potential method for cost-effectively engineering these properties. Given that there are deviations from crystalline perfection in mechanically alloyed material such as secondary phase inclusions, the question arises as to whether these defects are detrimental to thermoelectric function or alternatively, whether they enhance thermoelectric function of the alloy. The hypothesis formed at the onset of this work was that the small secondary phase SnO2 inclusions observed to be present in the mechanically alloyed Pb1-xSnxTe would increase the thermoelectric figure of merit of the material over the temperature range of interest. It was proposed that the increase in the figure of merit would arise because the inclusions in the material would not reduce the electrical conductivity to as great an extent as the thermal conductivity. If this were to be true, then the experimentally measured electronic conductivity in mechanically alloyed Pb1-xSnxTe alloys that have these inclusions would not be less than that expected in alloys without these inclusions while the portion of the thermal conductivity that is not due to charge carriers (the lattice thermal conductivity) would be less than what would be expected from alloys that do not have these inclusions. Furthermore, it would be possible to approximate the observed changes in the electrical and thermal transport properties using existing physical models for the scattering of electrons and phonons by small inclusions. The approach taken to investigate this hypothesis was to first experimentally characterize the mobile carrier concentration at room temperature along with the extent and type of secondary phase inclusions present in a series of three mechanically alloyed Pb1-xSnxTe alloys with different Sn content. Second, the physically based computational model was developed. This model was used to determine what the electronic conductivity, Seebeck coefficient, total thermal conductivity, and the portion of the thermal conductivity not due to mobile charge carriers would be in these particular Pb1-xSnxTe alloys if there were to be no secondary phase inclusions. Third, the electronic conductivity, Seebeck coefficient and total thermal conductivity was experimentally measured for these three alloys with inclusions present at elevated temperatures. The model predictions for electrical conductivity and Seebeck coefficient were directly compared to the experimental elevated temperature electrical transport measurements. The computational model was then used to extract the lattice thermal conductivity from the experimentally measured total thermal conductivity. This lattice thermal conductivity was then compared to what would be expected from the alloys in the absence of secondary phase inclusions. Secondary phase inclusions were determined by X-ray diffraction analysis to be present in all three alloys to a varying extent. The inclusions were found not to significantly degrade electrical conductivity at temperatures above ~ 400 K in these alloys, though they do dramatically impact electronic mobility at room temperature. It is shown that, at temperatures above ~ 400 K, electrons are scattered predominantly by optical and acoustical phonons rather than by an alloy scattering mechanism or the inclusions. The experimental electrical conductivity and Seebeck coefficient data at elevated temperatures were found to be within ~ 10 % of what would be expected for material without inclusions. The inclusions were not found to reduce the lattice thermal conductivity at elevated temperatures. The experimentally measured thermal conductivity data was found to be consistent with the lattice thermal conductivity that would arise due to two scattering processes: Phonon phonon scattering (Umklapp scattering) and the scattering of phonons by the disorder induced by the formation of a PbTe-SnTe solid solution (alloy scattering). As opposed to the case in electrical transport, the alloy scattering mechanism in thermal transport is shown to be a significant contributor to the total thermal resistance. An estimation of the extent to which the mean free time between phonon scattering events would be reduced due to the presence of the inclusions is consistent with the above analysis of the experimental data. The first important result of this work was the development of an experimentally validated, physically based computational model that can be used to predict the electronic conductivity, Seebeck coefficient, and thermal conductivity of Pb1-xSnxTe alloys over the 400 K to 700 K temperature as a function of Sn content and doping level. This model will be critical in future work as a tool to first determine what the highest thermoelectric figure of merit one can expect from this alloy system at a given temperature and, second, as a tool to determine the optimum Sn content and doping level to achieve this figure of merit. The second important result of this work is the determination that the secondary phase inclusions that were observed to be present in the Pb1-xSnxTe made by mechanical alloying do not keep the material from having the same electrical and thermal transport that would be expected from “perfect" single crystal material at elevated temperatures. The analytical approach described in this work will be critical in future investigations to predict how changing the size, type, and volume fraction of secondary phase inclusions can be used to impact thermal and electrical transport in this materials system.

MULTISCALE EXAMINATION AND MODELING OF ELECTRON TRANSPORT IN NANOSCALE MATERIALS AND DEVICES

For half a century the integrated circuits (ICs) that make up the heart of electronic devices have been steadily improving by shrinking at an exponential rate. However, as the current crop of ICs get smaller and the insulating layers involved become thinner, electrons leak through due to quantum mechanical tunneling. This is one of several issues which will bring an end to this incredible streak of exponential improvement of this type of transistor device, after which future improvements will have to come from employing fundamentally different transistor architecture rather than fine tuning and miniaturizing the metal-oxide-semiconductor field effect transistors (MOSFETs) in use today. Several new transistor designs, some designed and built here at Michigan Tech, involve electrons tunneling their way through arrays of nanoparticles. We use a multi-scale approach to model these devices and study their behavior. For investigating the tunneling characteristics of the individual junctions, we use a first-principles approach to model conduction between sub-nanometer gold particles. To estimate the change in energy due to the movement of individual electrons, we use the finite element method to calculate electrostatic capacitances. The kinetic Monte Carlo method allows us to use our knowledge of these details to simulate the dynamics of an entire device— sometimes consisting of hundreds of individual particles—and watch as a device ‘turns on’ and starts conducting an electric current. Scanning tunneling microscopy (STM) and the closely related scanning tunneling spectroscopy (STS) are a family of powerful experimental techniques that allow for the probing and imaging of surfaces and molecules at atomic resolution. However, interpretation of the results often requires comparison with theoretical and computational models. We have developed a new method for calculating STM topographs and STS spectra. This method combines an established method for approximating the geometric variation of the electronic density of states, with a modern method for calculating spin-dependent tunneling currents, offering a unique balance between accuracy and accessibility.

NANOSCALE ELECTROCHEMISTRY BY IN-SITU TRANSMISSION ELECTRON MICROSCOPY

Nanoscale research in energy storage has recently focused on investigating the properties of nanostructures in order to increase energy density, power rate, and capacity. To better understand the intrinsic properties of nanomaterials, a new and advanced in situ system was designed that allows atomic scale observation of materials under external fields. A special holder equipped with a scanning tunneling microscopy (STM) probe inside a transmission electron microscopy (TEM) system was used to perform the in situ studies on mechanical, electrical, and electrochemical properties of nanomaterials. The nanostructures of titanium dioxide (TiO2) nanotubes are characterized by electron imaging, diffraction, and chemical analysis techniques inside TEM. TiO2 nanotube is one of the candidates as anode materials for lithium ion batteries. It is necessary to study their morphological, mechanical, electrical, and electrochemical properties at atomic level. The synthesis of TiO2 nanotubes showed that the aspect ratio of TiO2 could be controlled by processing parameters, such as anodization time and voltage. Ammonium hydroxide (NH4OH) treated TiO2 nanotubes showed unexpected instability. Observation revealed the nanotubes were disintegrated into nanoparticles and the tubular morphology was vanished after annealing. The nitrogen compounds incorporated in surface defects weaken the nanotube and result in the collapse of nanotube into nanoparticles during phase transformation. Next, the electrical and mechanical properties of TiO2 nanotubes were studied by in situ TEM system. Phase transformation of anatase TiO2 nanotubes into rutile nanoparticles was studied by in situ Joule heating. The results showed that single anatase TiO2 nanotubes broke into ultrafine small anatase nanoparticles. On further increasing the bias, the nanoclusters of anatase particles became prone to a solid state reaction and were grown into stable large rutile nanoparticles. The relationship between mechanical and electrical properties of TiO2 nanotubes was also investigated. Initially, both anatase and amorphous TiO2 nanotubes were characterized by using I-V test to demonstrate the semiconductor properties. The observation of mechanical bending on TiO2 nanotubes revealed that the conductivity would increase when bending deformation happened. The defects on the nanotubes created by deformation helped electron transportation to increase the conductivity. Lastly, the electrochemical properties of amorphous TiO2 nanotubes were characterized by in situ TEM system. The direct chemical and imaging evidence of lithium-induced atomic ordering in amorphous TiO2 nanotubes was studied. The results indicated that the lithiation started with the valance reduction of Ti4+ to Ti3+ leading to a LixTiO2 intercalation compound. The continued intercalation of Li ions in TiO2 nanotubes triggered an amorphous to crystalline phase transformation. The crystals were formed as nano islands and identified to be Li2Ti2O4 with cubic structure (a = 8.375 Å). This phase transformation is associated with local inhomogeneities in Li distribution. Based on these observations, a new reaction mechanism is proposed to explain the first cycle lithiation behavior in amorphous TiO2 nanotubes.

Dosimetric properties of an amorphous silicon EPID for verification of modulated electron radiotherapy

Purpose: To investigate the dosimetric properties of an electronic portal imaging device (EPID) for electron beam detection and to evaluate its potential for quality assurance (QA) of modulated electron radiotherapy (MERT). Methods: A commercially available EPID was used to detect electron beams shaped by a photon multileaf collimator (MLC) at a source-surface distance of 70 cm. The fundamental dosimetric properties such as reproducibility, dose linearity, field size response, energy response, and saturation were investigated for electron beams. A new method to acquire the flood-field for the EPID calibration was tested. For validation purpose, profiles of open fields and various MLC fields (square and irregular) were measured with a diode in water and compared to the EPID measurements. Finally, in order to use the EPID for QA of MERT delivery, a method was developed to reconstruct EPID two-dimensional (2D) dose distributions in a water-equivalent depth of 1.5 cm. Comparisons were performed with film measurement for static and dynamic monoenergy fields as well as for multienergy fields composed by several segments of different electron energies. Results: The advantageous EPID dosimetric properties already known for photons as reproducibility, linearity with dose, and dose rate were found to be identical for electron detection. The flood-field calibration method was proven to be effective and the EPID was capable to accurately reproduce the dose measured in water at 1.0 cm depth for 6 MeV, 1.3 cm for 9 MeV, and 1.5 cm for 12, 15, and 18 MeV. The deviations between the output factors measured with EPID and in water at these depths were within ±1.2% for all the energies with a mean deviation of 0.1%. The average gamma pass rate (criteria: 1.5%, 1.5 mm) for profile comparison between EPID and measurements in water was better than 99% for all the energies considered in this study. When comparing the reconstructed EPID 2D dose distributions at 1.5 cm depth to film measurements, the gamma pass rate (criteria: 2%, 2 mm) was better than 97% for all the tested cases. Conclusions: This study demonstrates the high potential of the EPID for electron dosimetry, and in particular, confirms the possibility to use it as an efficient verification tool for MERT delivery.

A Pt(II) complex with both a phenanthroline and a tetrathiafulvalene-extended dithiolate ligand: Synthesis, crystal structure, electrochemical and spectroscopic properties

The reaction of 4,5-bis(2'-cyanoethylsulfanyl)-4',5'-dipropylthiotetrathiafulvalene with Pt(phen)Cl-2 (phen = 1,10-phenanthroline) with CsOH as base in CH3OH-THE affords the target complex I in 44% yield. This complex crystallizes in the monoclinic space group P2(1)/c, M = 790.01, a = 12.1732(12), b = 15.851(2), c = 14.5371(16) angstrom, beta = 107.693(12)degrees, V = 2672.4(5) angstrom(3) and Z = 4. It undergoes two reversible single-electron oxidation and two irreversible reduction processes. An intense electronic absorption band at 15200 cm(-1) (658 nm) in CH2Cl2 is assigned to the intramolecular mixed metal/ligand-to-ligand charge transfer (LLCT) from a tetrathiafulvalene-extended dithiolate-based HOMO to a phenanthroline-based LUMO. This band shifts hypsochromically with increasing solvent polarity. Systematic changes in the optical spectra upon oxidation allow precise tuning of the oxidation states of 1 and reversible control over its optical properties. Irradiation of 1 at 15625 cm(-1) (640 nm) in glassy solution below 150K results in emission from the (LLCT)-L-3 excited state. GRAPHICS (C) 2013 Elsevier Ltd. All rights reserved.

Supramolecular Organization of Dye Molecules in Zeolite L Channels: Synthesis, Properties, and Composite Materials

Sequential insertion of different dyes into the 1D channels of zeolite L (ZL) leads to supramolecular sandwich structures and allows the formation of sophisticated antenna composites for light harvesting, transport, and trapping. The synthesis and properties of dye molecules, host materials, composites, and composites embedded in polymer matrices, including two- and three-color antenna systems, are described. Perylene diimide (PDI) dyes are an important class of chromophores and are of great interest for the synthesis of artificial antenna systems. They are especially well suited to advancing our understanding of the structure–transport relationship in ZL because their core fits tightly through the 12-ring channel opening. The substituents at both ends of the PDIs can be varied to a large extent without influencing their electronic absorption and fluorescence spectra. The intercalation/insertion of 17 PDIs, 2 terrylenes, and 1 quaterrylene into ZL are compared and their interactions with the inner surface of the ZL nanochannels discussed. ZL crystals of about 500 nm in size have been used because they meet the criteria that must be respected for the preparation of antenna composites for light harvesting, transport, and trapping. The photostability of dyes is considerably improved by inserting them into the ZL channels because the guests are protected by being confined. Plugging the channel entrances, so that the guests cannot escape into the environment is a prerequisite for achieving long-term stability of composites embedded in an organic matrix. Successful methods to achieve this goal are described. Finally, the embedding of dye–ZL composites in polymer matrices, while maintaining optical transparency, is reported. These results facilitate the rational design of advanced dye–zeolite composite materials and provide powerful tools for further developing and understanding artificial antenna systems, which are among the most fascinating subjects of current photochemistry and photophysics.

Effects of Strand Geometry on Selected Properties of Long-Stand Structural Composite Lumber Made from Northeastern Hardwoods

Structural composite lumber (SCL) products often possess significantly higher design values than the top grades of solid lumber, making it a popular choice for both residential and commercial applications. The enhanced mechanical properties of SCL are mainly due to defect randomization and densification of the wood fiber, both largely functions of the size, shape and composition (species) of the wood element. Traditionally, SCL manufacturers have used thin, rectangular elements produced from either moderate density softwoods or low density hardwoods. Higher density hardwood species have been avoided, as they require higher pressures to adequately densify and consolidate the wood furnish. These higher pressures can lead to increased manufacturing costs, damage to the wood fiber and/or a product that is too dense, making it heavy and unreceptive to common mechanical fastening techniques. In the northeastern United States high density, diffuse-porous hardwoods (such as maple, beech and birch) are abundant. Use of these species as primary furnish for a SCL product may allow for a competitive advantage in terms of resource cost against products that rely on veneer grade logs. Proximity to this abundant and relatively inexpensive resource may facilitate entry of SCL production facilities in the northeastern United States, where currently none exist. However, modifications to current strand sizes, geometries or production techniques will likely be required to allow for use of these species. A new SCL product concept has been invented allowing for use of these high density hardwoods. The product, referred to as long-strand structural composite lumber (LSSCL), uses strands of significantly larger cross sectional areas and volumes than existing SCL products. In spite of the large strand size, satisfactory consolidation is achieved without excessive densification of the wood fiber through use of a symmetrical strand geometric cross-section. LSSCL density is similar to that of existing SCL products, but is due mainly to the inherent density of the species, rather than through densification. An experiment was designed and conducted producing LSSCL from both large (7/16”) and small (1/4”) strands, of both square and triangular geometric cross sections. Testing results indicate that the large, triangular strands produce LSSCL beams with projected design values of: Modulus of elasticity (MOEapp) – 1,750,000 psi; Allowable bending stress (Fb) – 2750 psi; Allowable shear stress (Fv) – 260 psi. Several modifications are recommended which may lead to improvement of these values, likely allowing for competition against existing SCL products.

Microstructure, magnetic and mechanical properties of Ni-Zn ferrites prepared by Powder Injection Moulding

Nowadays, the electronic industry demands small and complex parts as a consequence of the miniaturization of electronic devices. Powder injection moulding (PIM) is an emerging technique for the manufacturing of magnetic ceramics. In this paper, we analyze the sintering process, between 900 °C and 1300 °C, of Ni–Zn ferrites prepared by PIM. In particular, the densification behaviour, microstructure and mechanical properties of samples with toroidal and bar geometry were analyzed at different temperatures. Additionally, the magnetic behaviour (complex permeability and magnetic losses factor) of these compacts was compared with that of samples prepared by conventional powder compaction. Finally, the mechanical behaviour (elastic modulus, flexure strength and fracture toughness) was analyzed as a function of the powder loading of feedstock. The final microstructure of prepared samples was correlated with the macroscopic behaviour. A good agreement was established between the densities and population of defects found in the materials depending on the sintering conditions. In general, the final mechanical and magnetic properties of PIM samples were enhanced relative those obtained by uniaxial compaction.