Solid phase crystallization under continuous heating: kinetic and microstructure scaling laws

The kinetics and microstructure of solid-phase crystallization under continuous heating conditions and random distribution of nuclei are analyzed. An Arrhenius temperature dependence is assumed for both nucleation and growth rates. Under these circumstances, the system has a scaling law such that the behavior of the scaled system is independent of the heating rate. Hence, the kinetics and microstructure obtained at different heating rates differ only in time and length scaling factors. Concerning the kinetics, it is shown that the extended volume evolves with time according to αex = [exp(κCt′)]m+1, where t′ is the dimensionless time. This scaled solution not only represents a significant simplification of the system description, it also provides new tools for its analysis. For instance, it has been possible to find an analytical dependence of the final average grain size on kinetic parameters. Concerning the microstructure, the existence of a length scaling factor has allowed the grain-size distribution to be numerically calculated as a function of the kinetic parameters

Solid-phase microextraction as short-term sampling technique for BTEX occupational exposure

Solid phase microextraction (SPME) has been widely used for many years in various applications, such as environmental and water samples, food and fragrance analysis, or biological fluids. The aim of this study was to suggest the SPME method as an alternative to conventional techniques used in the evaluation of worker exposure to benzene, toluene, ethylbenzene, and xylene (BTEX). Polymethylsiloxane-carboxen (PDMS/CAR) showed as the most effective stationary phase material for sorbing BTEX among other materials (polyacrylate, PDMS, PDMS/divinylbenzene, Carbowax/divinylbenzene). Various experimental conditions were studied to apply SPME to BTEX quantitation in field situations. The uptake rate of the selected fiber (75 μm PDMS/CAR) was determined for each analyte at various concentrations, relative humidities, and airflow velocities from static (calm air) to dynamic (>200 cm/s) conditions. The SPME method also was compared with the National Institute of Occupational Safety and Health method 1501. Unlike the latter, the SPME approach fulfills the new requirement for the threshold limit value-short term exposure limit (TLV-STEL) of 2.5 ppm for benzene (8 mg/m3).

Recent Advances in Valorization Methods of Inorganic/Organic Solid, Liquid, and Gas Wastes

The main goal of this special issue was to gather contributions dealing with the latest breakthrough methods for providing value compounds and energy/fuel from waste valorization. Valorization is a relatively new approach in the area of industrial wastes management, a key issue to promote sustainable development. In this field, the recovery of value-added substances, such as antioxidants, proteins, vitamins, and so forth, from the processing of agroindustrial byproducts, is worth mentioning. Another important valorization approach is the use of biogas from waste treatment plants for the production of energy. Several approaches involving physical and chemical processes, thermal and biological processes that ensure reduced emissions and energy consumptions were taken into account. The papers selected for this topical issue represent some of the mostly researched methods that currently promote the valorization of wastes to energy and useful materials ...

Demonstration and Field Evaluation of Alternative Portland Cement Concrete Pavement Reinforcement Materials, HR-1069, 2003

Transverse joints are placed in portland cement concrete pavements to control the development of random cracking due to stresses induced by moisture and thermal gradients and restrained slab movement. These joints are strengthened through the use of load transfer devices, typically dowel bars, designed to transfer load across the joint from one pavement slab to the next. Epoxy coated steel bars are the materials of choice at the present time, but have experienced some difficulties with resistance to corrosion from deicing salts. The research project investigated the use of alternative materials, dowel size and spacing to determine the benefits and limitations of each material. In this project two types of fiber composite materials, stainless steel solid dowels and epoxy coated dowels were tested for five years in side by side installation in a portion of U.S. 65 near Des Moines, Iowa, between 1997 and 2002. The work was directed at analyzing the load transfer characteristics of 8-in. vs. 12-in. spacing of the dowels and the alternative dowel materials, fiber composite (1.5- and 1.88-in. diameter) and stainless steel (1.5-in. diameter), compared to typical 1.5-in. diameter epoxy-coated steel dowels placed on 12-in. spacing. Data were collected biannually within each series of joints and variables in terms of load transfer in each lane (outer wheel path), visual distress, joint openings, and faulting in each wheel path. After five years of performance the following observations were made from the data collected. Each of the dowel materials is performing equally in terms of load transfer, joint movement and faulting. Stainless steel dowels are providing load transfer performance equal to or greater than epoxy-coated steel dowels at the end of five years. Fiber reinforced polymer (FRP) dowels of the sizes and materials tested should be spaced no greater than 8 in. apart to achieve comparable performance to epoxy coated dowels. No evidence of deterioration due to road salts was identified on any of the products tested. The relatively high cost of stainless steel solid and FRP dowels was a limitation at the time of this study conclusion. Work is continuing with the subject materials in laboratory studies to determine the proper shape, spacing, chemical composition and testing specification to make the FRP and stainless (clad or solid) dowels a viable alternative joint load transfer material for long lasting portland cement concrete pavements.

Investigation of Materials for the Reduction and Prevention of Corrosion on Highway Maintenance Equipment, TR-472, 2009

The issue of corrosion of winter maintenance equipment is becoming of greater concern because of the increased use of liquid solutions of ice control chemicals, as opposed to their application in solid form. Being in liquid form, the ice control chemicals can more easily penetrate into the nooks and crannies on equipment and avoid being cleansed from the vehicle. Given this enhanced corrosive ability, methods must be found to minimize corrosion. The methods may include coatings, additives, cleansing techniques, other methods, and may also include doing nothing, and accepting a reduced equipment lifetime as a valid (perhaps) trade off with the enhanced benefits of using liquid ice control chemicals. In reality, some combination of these methods may prove to be optimal. Whatever solutions are selected, they must be relatively cheap and durable. The latter point is critical because of the environment in which maintenance trucks operate, in which scrapes, scratches and dents are facts of life. Protection methods that are not robust simply will not work. The purpose of this study is to determine how corrosion occurs on maintenance trucks, to find methods that would minimize the major corrosion mechanisms, and to

Selective ablation of photovoltaic materials with UV laser sources for monolithic interconnection of devices based on a-Si:H

Lasers are essential tools for cell isolation and monolithic interconnection in thin-film-silicon photovoltaic technologies. Laser ablation of transparent conductive oxides (TCOs), amorphous silicon structures and back contact removal are standard processes in industry for monolithic device interconnection. However, material ablation with minimum debris and small heat affected zone is one of the main difficulty is to achieve, to reduce costs and to improve device efficiency. In this paper we present recent results in laser ablation of photovoltaic materials using excimer and UV wavelengths of diode-pumped solid-state (DPSS) laser sources. We discuss results concerning UV ablation of different TCO and thin-film silicon (a-Si:H and nc-Si:H), focussing our study on ablation threshold measurements and process-quality assessment using advanced optical microscopy techniques. In that way we show the advantages of using UV wavelengths for minimizing the characteristic material thermal affection of laser irradiation in the ns regime at higher wavelengths. Additionally we include preliminary results of selective ablation of film on film structures irradiating from the film side (direct writing configuration) including the problem of selective ablation of ZnO films on a-Si:H layers. In that way we demonstrate the potential use of UV wavelengths of fully commercial laser sources as an alternative to standard backscribing process in device fabrication.

Electromagnetic Design of a Solid Steel Rotor Motor for Demanding Operation Environments

The solid-rotor induction motor provides a mechanically and thermally reliable solution for demanding environments where other rotor solutions are prohibited or questionable. Solid rotors, which are manufactured of single pieces of ferromagnetic material, are commonly used in motors in which the rotationspeeds exceed substantially the conventional speeds of laminated rotors with squirrel-cage. During the operation of a solid-rotor electrical machine, the rotor core forms a conductor for both the magnetic flux and the electrical current. This causes an increase in the rotor resistance and rotor leakage inductance, which essentially decreases the power factor and the efficiency of the machine. The electromagnetic problems related to the solid-rotor induction motor are mostly associated with the low performance of the rotor. Therefore, the main emphasis in this thesis is put on the solid steel rotor designs. The rotor designs studied in thisthesis are based on the fact that the rotor construction should be extremely robust and reliable to withstand the high mechanical stresses caused by the rotational velocity of the rotor. In addition, the demanding operation environment sets requirements for the applied materials because of the high temperatures and oxidizing acids, which may be present in the cooling fluid. Therefore, the solid rotors analyzed in this thesis are made of a single piece of ferromagnetic material without any additional parts, such as copper end-rings or a squirrel-cage. A pure solid rotor construction is rigid and able to keep its balance over a large speed range. It also may tolerate other environmental stresses such as corroding substances or abrasive particles. In this thesis, the main target is to improve the performance of an induction motor equipped with a solid steel rotor by traditional methods: by axial slitting of the rotor, by selecting a proper rotor core material and by coating the rotor with a high-resistive stainless ferromagnetic material. In the solid steel rotor calculation, the rotor end-effects have a significant effect on the rotor characteristics. Thus, the emphasis is also put on the comparison of different rotor endfactors. In addition, a corrective slip-dependent end-factor is proposed. The rotor designs covered in this thesis are the smooth solid rotor, the axially slitted solid rotor and the slitted rotor having a uniform ferromagnetic coating cylinder. The thesis aims at design rules for multi-megawatt machines. Typically, mega-watt-size solidrotor machines find their applications mainly in the field of electric-motor-gas-compression systems, in steam-turbine applications, and in various types of largepower pump applications, where high operational speeds are required. In this thesis, a 120 kW, 10 000 rpm solid-rotor induction motor is usedas a small-scale model for such megawatt-range solid-rotor machines. The performance of the 120 kW solid-rotor induction motors is determined by experimental measurements and finite element calculations.

The high-speed induction motor: calculating the effects of solid-rotor material on machine characteristics

A method for the analysis of high-speed solid-rotor induction motors in presented. The analysis is based on a new combination of the three dimensional linear method and the transfer matrix method. Both saturation and finite length effects are taken into account. The active region of the solid rotor is divided into saturated and unsaturated parts. The time dependence is assumed to be sinusoidal and phasor quantities are used in the solution. The method is applied to the calculation of smooth solid rotors manufactured of different materials. Six rotor materials are tested: three construction steels, pure iron, a cobaltiron alloy and an aluminium alloy. The results obtained by the method agree fairly well with the measurement quantities.

Sintesi i caracteritzacio dels materials multiferroics BiFeO3, La: BiFeO3 i Sr: BiFeO3

Recentment, ha crescut un notable interès pels materials multiferroics (o materials que presenten simultàniament propietats elèctriques i magnètiques), a causa de les seves múltiples aplicacions, sobretot en el camp de l"electrònica. Aquest article pretén donar a conèixer els materials multiferroics, tant des del punt de vista de la física fonamental com de la química de l"estat sòlid. Tanmateix, es presentarà un dels materials multiferroics actualment més estudiats i s"exposaran els detalls de la seva síntesi i caracterització habituals en la química de l"estat sòlid.

Importance of the embedding environment on the strain within small rings in siliceous materials

The effect of the local environment on the energetic strain within small (SiO)N rings (with N=2,3) in silica materials is investigated via periodic model systems employing density functional calculations. Through comparison of the energies of various nonterminated systems containing small rings in strained and relatively unstrained environments, with alpha quartz, we demonstrate how small ring strain is affected by the nature of the embedding environment. We compare our findings with numerous previously reported calculations, often predicting significantly different small-ring strain energies, leading to a critical assessment of methods of calculating accurate localized ring energies. The results have relevance for estimates of the strain-induced response (e.g., chemical, photo, and radio) of small silica rings, and the propensity for them to form in bulk glasses, thin films, and nanoclusters.

Solid phase extraction of iron and lead in environmental matrices on amberlite xad-1180/pv

A solid phase extraction procedure using Amberlite XAD-1180/Pyrocatechol violet (PV) chelating resin for the determination of iron and lead ions in various environmental samples was established. The procedure is based on the sorption of lead(II) and iron(III) ions onto the resin at pH 9, followed by elution with 1 mol/L HNO3 and determination by flame atomic absorption spectrometry. The influence of alkaline, earth alkaline and some transition metals, as interferents, are discussed. The recoveries for the spiked analytes were greater than 95%. The detection limits for lead and iron by FAAS were 0.37 µg/L and 0.20 µg/L, respectively. Validation of the method described here was performed by using three certified reference materials (SRM 1515 Apple Leaves, SRM 2711 Montana Soil and NRCC-SLRS-4 Riverine Water). The procedure was successfully applied to natural waters and human hair.

Preconcentration of copper from natural water samples using ligand-less in situ surfactant-based solid phase extraction prior to FAAS determination

In the present work, a simple and rapid ligand-less, in situ, surfactant-based solid phase extraction for the preconcentration of copper in water samples was developed. In this method, a cationic surfactant (n-dodecyltrimethylammonium bromide) was dissolved in an aqueous sample followed by the addition of an appropriate ion-pairing agent (ClO4-). Due to the interaction between the surfactant and ion-pairing agent, solid particles were formed and subsequently used for the adsorption of Cu(OH)2 and CuI. After centrifugation, the sediment was dissolved in 1.0 mL of 1 mol L-1 HNO3 in ethanol and aspirated directly into the flame atomic absorption spectrometer. In order to obtain the optimum conditions, several parameters affecting the performance of the LL-ISS-SPE, including the volumes of DTAB, KClO4, and KI, pH, and potentially interfering ions, were optimized. It was found that KI and phosphate buffer solution (pH = 9) could extract more than 95% of copper ions. The amount of copper ions in the water samples varied from 3.2 to 4.8 ng mL-1, with relative standard deviations of 98.5%-103%. The determination of copper in water samples was linear over a concentration range of 0.5-200.0 ng mL-1. The limit of detection (3Sb/m) was 0.1 ng mL-1 with an enrichment factor of 38.7. The accuracy of the developed method was verified by the determination of copper in two certified reference materials, producing satisfactory results.

Cuticular and Suberin Polymers of Edible Plants. Analysis by Gas Chromatographic-Mass Spectrometric and Solid State Spectroscopic Methods

Cutin and suberin are structural and protective polymers of plant surfaces. The epidermal cells of the aerial parts of plants are covered with an extracellular cuticular layer, which consists of polyester cutin, highly resistant cutan, cuticular waxes and polysaccharides which link the layer to the epidermal cells. A similar protective layer is formed by a polyaromatic-polyaliphatic biopolymer suberin, which is present particularly in the cell walls of the phellem layer of periderm of the underground parts of plants (e.g. roots and tubers) and the bark of trees. In addition, suberization is also a major factor in wound healing and wound periderm formation regardless of the plants’ tissue. Knowledge of the composition and functions of cuticular and suberin polymers is important for understanding the physiological properties for the plants and for nutritional quality when these plants are consumed as foods. The aims of the practical work were to assess the chemical composition of cuticular polymers of several northern berries and seeds and suberin of two varieties of potatoes. Cutin and suberin were studied as isolated polymers and further after depolymerization as soluble monomers and solid residues. Chemical and enzymatic depolymerization techniques were compared and a new chemical depolymerization method was developed. Gas chromatographic analysis with mass spectrometric detection (GC-MS) was used to assess the monomer compositions. Polymer investigations were conducted with solid state carbon-13 cross polarization magic angle spinning nuclear magnetic resonance spectroscopy (13C CP-MAS NMR), Fourier transform infrared spectroscopy (FTIR) and microscopic analysis. Furthermore, the development of suberin over one year of post-harvest storage was investigated and the cuticular layers from berries grown in the North and South of Finland were compared. The results show that the amounts of isolated cuticular layers and cutin monomers, as well as monomeric compositions vary greatly between the berries. The monomer composition of seeds was found to differ from the corresponding berry peel monomers. The berry cutin monomers were composed mostly of long-chain aliphatic ω-hydroxy acids, with various mid-chain functionalities (double-bonds, epoxy, hydroxy and keto groups). Substituted α,ω-diacids predominated over ω-hydroxy acids in potato suberin monomers and slight differences were found between the varieties. The newly-developed closed tube chemical method was found to be suitable for cutin and suberin analysis and preferred over the solvent-consuming and laborious reflux method. Enzymatic hydrolysis with cutinase was less effective than chemical methanolysis and showed specificity towards α,ω-diacid bonds. According to ₁₃C CP-MAS NMR and FTIR, the depolymerization residues contained significant amounts of aromatic structures, polysaccharides and possible cutan-type aliphatic moieties. Cultivation location seems to have effect on cuticular composition. The materials studied contained significant amounts of different types of biopolymers that could be utilized for several purposes with or without further processing. The importance of the so-called waste material from industrial processes of berries and potatoes as a source of either dietary fiber or specialty chemicals should be further investigated in detail. The evident impact of cuticular and suberin polymers, among other fiber components, on human health should be investigated in clinical trials. These by-product materials may be used as value-added fiber fractions in the food industry and as raw materials for specialty chemicals such as lubricants and emulsifiers, or as building blocks for novel polymers.

Defects in Persistent Luminescence Materials

Persistent luminescence materials can store energy from solar radiation or artificial lighting and release it over a period of several hours without a continuous excitation source. These materials are widely used to improve human safety in emergency and traffic signalization. They can also be utilized in novel applications including solar cells, medical diagnostics, radiation detectors and structural damage sensors. The development of these materials is currently based on methods based on trial and error. The tailoring of new materials is also hindered by the lack of knowledge on the role of their intrinsic and extrinsic lattice defects in the appropriate mechanisms. The goal of this work was to clarify the persistent luminescence mechanisms by combining ab initio density functional theory (DFT) calculations with selected experimental methods. The DFT approach enables a full control of both the nature of the defects and their locations in the host lattice. The materials studied in the present work, the distrontium magnesium disilicate (Sr₂MgSi₂O₇) and strontium aluminate (SrAl₂O₄) are among the most efficient persistent luminescence hosts when doped with divalent europium Eu²⁺ and co-doped with trivalent rare earth ions R³⁺ (R: Y, La-Nd, Sm, Gd-Lu). The polycrystalline materials were prepared with the solid state method and their structural and phase purity was confirmed by X-ray powder diffraction. Their local crystal structure was studied by high-resolution transmission electron microscopy. The crystal and electronic structure of the nondoped as well as Eu²⁺, R^2+/3+ and other defect containing materials were studied using DFT calculations. The experimental trap depths were obtained using thermoluminescence (TL) spectroscopy. The emission and excitation of Sr₂MgSi₂O₇:Eu²+,Dy³⁺ were also studied. Significant modifications in the local crystal structure due to the Eu²⁺ ion and lattice defects were found by the experimental and DFT methods. The charge compensation effects induced by the R³⁺ co-doping further increased the number of defects and distortions in the host lattice. As for the electronic structure of Sr₂MgSi₂O₇ and SrAl₂O₄, the experimental band gap energy of the host materials was well reproduced by the calculations. The DFT calculated Eu²⁺ and R^2+/3+ 4fn as well as 4f^n-15d¹ ground states in the Sr₂MgSi₂O₇ band structure provide an independent verification for an empirical model which is constructed using rather sparse experimental data for the R³⁺ and especially the R²⁺ ions. The intrinsic and defect induced electron traps were found to act together as energy storage sites contributing to the materials’ efficient persistent luminescence. The calculated trap energy range agreed with the trap structure of Sr₂MgSi₂O₇ obtained using TL measurements. More experimental studies should be carried out for SrAl₂O₄ to compare with the DFT calculations. The calculated and experimental results show that the electron traps created by both the rare earth ions and vacancies are modified due to the defect aggregation and charge compensation effects. The relationships between this modification and the energy storage properties of the solid state materials are discussed.