Polyconductivity in polypyrrole: the correlated electron glass

p-toluensulfonate doped polypyrrole ~PPy!, undergoes an electric-field induced reversible transition from an insulating state to a highly conductive one. The spatially average field can be as small as 200 V/cm, when the temperature of the sample is below 20 K. The applied electric field leads to a sharp jump in the value of the current to a value which is nearly five orders of magnitude higher than before. When the applied electric field is reduced to below a critical value, the system switches back to a low conductive state. The effect is reversible, symmetric in voltage, and reproducible for different samples. The switching is, we believe, an electronic glass melting transition and it is due to the disordered, highly charged granular nature of PPy.

Highly textured Sr, Nb, co-doped BiFeO3 thin films grown on SrRuO3/Si substrates by rf-sputtering

In this study, (011)-highly oriented Sr, Nb co-doped BiFeO3 (BFO) thin films were successfully grown on SrRuO3/Si substrates by rf-magnetron sputtering. The presence of parasite magnetic phases was ruled out based on the high resolution x-ray diffraction data. BFO films exhibited a columnar-like grain growth with rms surface roughness values of 5.3 nm and average grain sizes of 65-70 nm for samples with different thicknesses. Remanent polarization values (2Pr) of 54 lC cm 2 at room temperature were found for the BFO films with a ferroelectric behavior characteristic of an asymmetric device structure. Analysis of the leakage mechanisms for this structure in negative bias suggests Schottky injection and a dominant Poole-Frenkel trap-limited conduction at room temperature. Oxygen vacancies and Fe3þ/Fe2þ trap centers are consistent with the surface chemical bonding states analysis from x-ray photoelectron spectroscopy data. The (011)-BFO/ SrRuO3/Si film structure exhibits a strong magnetic interaction at the interface between the multiferroic film and the substrate layer where an enhanced ferromagnetic response at 5 K was observed. Zero-field cooled (ZFC) and field cooled (FC) magnetization curves of this film system revealed a possible spin glass behavior at spin freezing temperatures below 30 K depending on the BFO film thickness.

Intensities of 4f-4f transitions in glass materials

In this article we review some of the basic aspects of rare earth spectroscopy applied to vitreous materials. The characteristics of the intra-atomic free ion and ligand field interactions, as well as the formalisms of the forced electric dipole and dynamic coupling mechanisms of 4f-4f intensities, are outlined. The contribution of the later mechanism to the 4f-4f intensities is critically discussed, a point that has been commonly overlooked in the literature of rare earth doped glasses. The observed correlation between the empirical intensity parameter W2 and the covalence of the ion first coordination shell is discussed accordingly to the theoretical predictions.

Development of porous glass-fiber reinforced composite for bone implants. Evaluation of antimicrobial effect and implant fixation

Cranial bone reconstructions are necessary for correcting large skull bone defects due to trauma, tumors, infections and craniotomies. Traditional synthetic implant materials include solid or mesh titanium, various plastics and ceramics. Recently, biostable glass-fiber reinforced composites (FRC), which are based on bifunctional methacrylate resin, were introduced as novel implant solution. FRCs were originally developed and clinically used in dental applications. As a result of further in vitro and in vivo testing, these composites were also approved for clinical use in cranial surgery. To date, reconstructions of large bone defects were performed in 35 patients. This thesis is dedicated to the development of a novel FRC-based implant for cranial reconstructions. The proposed multi-component implant consists of three main parts: (i) porous FRC structure; (ii) bioactive glass granules embedded between FRC layers and (iii) a silver-polysaccharide nanocomposite coating. The porosity of the FRC structure should allow bone ingrowth. Bioactive glass as an osteopromotive material is expected to stimulate the formation of new bone. The polysaccharide coating is expected to prevent bacterial colonization of the implant. The FRC implants developed in this study are based on the porous network of randomly-oriented E-glass fibers bound together by non-resorbable photopolymerizable methacrylate resin. These structures had a total porosity of 10–70 volume %, of which > 70% were open pores. The pore sizes > 100 μm were in the biologically-relevant range (50-400 μm), which is essential for vascularization and bone ingrowth. Bone ingrowth into these structures was simulated by imbedding of porous FRC specimens in gypsum. Results of push-out tests indicated the increase in the shear strength and fracture toughness of the interface with the increase in the total porosity of FRC specimens. The osteopromotive effect of bioactive glass is based on its dissolution in the physiological environment. Here, calcium and phosphate ions, released from the glass, precipitated on the glass surface and its proximity (the FRC) and formed bone-like apatite. The biomineralization of the FRC structure, due to the bioactive glass reactions, was studied in Simulated Body Fluid (SBF) in static and dynamic conditions. An antimicrobial, non-cytotoxic polysaccharide coating, containing silver nanoparticles, was obtained through strong electrostatic interactions with the surface of FRC. In in vitro conditions the lactose-modified chitosan (chitlac) coating showed no signs of degradation within seven days of exposure to lysozyme or one day to hydrogen peroxide (H2O2). The antimicrobial efficacy of the coating was tested against Staphylococcus aureus and Pseudomonas aeruginosa. The contact-active coating had an excellent short time antimicrobial effect. The coating neither affected the initial adhesion of microorganisms to the implant surface nor the biofilm formation after 24 h and 72 h of incubation. Silver ions released to the aqueous environment led to a reduction of bacterial growth in the culture medium.

Set-up and evaluation of a mid-infrared reflectometer and investigation of the optical properties of doped tin telluride

A system comprised of a Bomem interferometer and a LT3-110 Heli-Tran cryostat was set up to measure the reflectance of materials in the mid-infrared spectral region. Several tests were conducted to ensure the consistency and reliability of the system. Silicon and Chromium, two materials with well known optical properties were measured to test the accuracy of the system, and the results were found to be in good agreement with the literature. Reflectance measurements on pure SnTe and several Pb and Mn-doped alloys were carried out. These materials were chosen because they exhibit a strong plasma edge in the mid infrared region. The optical conductivity and several related optical parameters were calculated from the measured reflectance. Very low temperature measurements were carried out in the far-infrared on Sn9SMn2Te, and the results are indicative of a spin glass phase at 0.8 K. Resistivity measurements were made at room temperature. The resistivity values were found, as expected, to decrease with increasing carrier concentration and to increase with increasing manganese concentration.

The Effect of Glass Additives on the Microwave Dielectric Properties of Ba(Mg 1 /3Ta2/3)03 Ceramics

The effect of glass additives on the densification , phase evolution, microstructure and microwave dielectric properties of Ba(Mg1;3 Ta2i3)03 (BMT) was investigated . Different weight percentages of quenched glass such as B203 , Si02, B203-SiO2, ZnO-B203, 5ZnO-2B2O3, Al203-SiO2, Na20-2B203.10H20, BaO-B203-SiO2, MgO-B203-SiO2, PbO-B203-SiO2 , ZnO-B203-SiO2 and 2MgO-Al203-5SiO2 were added to calcined BMT precursor . The sintering temperature of the glass -added BMT samples were lowered down to 1300 °C compared to solid-state sintering where the temperature was 1650 °C. The formation of high temperature satellite phases such as Ba5Ta4O15 and Ba7Ta6O22 were found to be suppressed by the glass addition . Addition of glass systems such as B203, ZnO-B203, 5ZnO-2B203 and ZnO-B203-SiO2 improved the densification and microwave dielectric properties. Other glasses were found to react with BMT to form low-Q phases which prevented densification . The microwave dielectric properties of undoped BMT with a densification of 93 . 1 % of the theoretical density were Cr = 24 . 8, Tr = 8 ppm/°C and Q„ x f= 80,000 GHz. The BMT doped with 1.0 wt% of B203 has Q„ x f = 124,700GHz, Cr = 24.2, and T f = -1.3 ppm /°C. The unloaded Q factor of 0.2 wt% ZnO-B203-doped BMT was 136,500 GHz while that of 1.0 wt% of 5ZnO-2B203 added ceramic was Q„ x f= 141,800 GHz . The best microwave quality factor was observed for ZnO -B203-SiO2 (ZBS) glass-added ceramics which can act as a perfect liquid-phase medium for the sintering of BMT. The microwave dielectric properties of 0.2wt% ZBS-added BMT dielectric was Q„ x f= 152,800 GHz, F,= 25.5, and Tr = - 1.5 ppm/°C

Measurement of laser ablation threshold on doped BiSrCaCuO high temperature superconductors by the pulsed photothermal deflection technique

Laser‐induced damage and ablation thresholds of bulk superconducting samples of Bi2(SrCa)xCu3Oy(x=2, 2.2, 2.6, 2.8, 3) and Bi1.6 (Pb)xSr2Ca2Cu3 Oy (x=0, 0.1, 0.2, 0.3, 0.4) for irradiation with a 1.06 μm beam from a Nd‐YAG laser have been determined as a function of x by the pulsed photothermal deflection technique. The threshold values of power density for ablation as well as damage are found to increase with increasing values of x in both systems while in the Pb‐doped system the threshold values decrease above a specific value of x, coinciding with the point at which the Tc also begins to fall.  

Optical and thermal characterization of dye intercalated montmorillonites and rare earth doped materials

The advent of high optical quality transparent nano—structured glasses, the so-called transparent glass ceramics or vitroceramics disclosed the possibility of producing nano-sized photonic devices based on rare-earth doped up—converters. Transparent glass ceramics have been investigated as hosts for lanthanide ions envisioning the production of materials that are easy to shape and with high performance for photonic applications. Rare earth doped glasses have been extensively studied due to their potential applications in optical devices such as solid state lasers and optical fibers. Various photothermal and optical techniques have been successfully applied for the thermal and optical characterization of these rare earth doped materials. In the present thesis, the effective thermal parameters like thermal diffusivity and thermal effusivity of complex materials for various applications have been investigated using photothermal methods along with their optical characterization utilising the common optical absorption as well as fluorescence spectroscopic techniques. These sensitive optical procedures are also essential for exploiting these materials for further photonic applications.

Layer-by-layer deposition of praseodymium oxide on tin-doped indium oxide (ITO) surface

Praseodymium oxide as a thin film of controllable layer is known to display many unique physiochemical properties, which can be useful to ceramic, semiconductive and sensor industries. Here in this short paper, we describe a new chemical method of depositing praseodymium oxide on tin-doped indium oxide (ITO) surface using a layer-by-layer approach. The process is carried out by dipping the ITO in solutions of adsorbable polycationic chitosan and alkaline praseodymium hydroxide Pr(OH)(3) alternatively in order to build up the well-defined multi-layers. XRD suggests that the predominant form of the oxide is Pr6O11, obtained after heat treatment of the deposited ITO in static air at 500 degrees C. Microscopic studies including AFM, TEM and SEM indicate that the deposited oxide particles are uniform in size and shape (cylindrical), mesoporous and the thickness of the film can be controlled. AC impedance measurements of the deposited materials also reveal that the oxide layers display a high electrical conductivity hence suitable for sensor uses. (c) 2006 Elsevier B.V. All rights reserved.

A comparison of photoinduced poling and thermal poling of azo‐dye‐doped polymer films for second order nonlinear optical applications

Photoinduced poling (PIP) is a new technique which allows the room‐temperature preparation of guest/host polymer films exhibiting significant polar order for nonlinear optical applications. We report a comparison of this novel technique with the conventional electrode poling procedure performed at the glass transition temperature of the polymer using disperse red 1/poly(methylmethacrylate) films. In particular, in situ second harmonic generation measurements show that levels of polar order achieved using these two techniques are similar. In contrast, the stability of the polar order is reduced by up to 20 times in terms of the decay time constant in films prepared using PIP although the stability is very dependent upon the temperature at which the poling was performed.

Investigation of some dielectric properties of phosphate glasses doped with iron oxides, by a microwave technique

The effects of iron ions on dielectric properties of lithium sodium phosphate glasses were studied by non-usual, fast and non-destructive microwave techniques. The dielectric constant (epsilon`). insertion loss (L) and microwave absorption spectra (microwave response) of the selected glass system xFe(2)O(3)center dot(1 - x)(50P(2)O5 center dot 25Li(2)O center dot 25Na(2)O), being x = 0, 3, 6, ....,15 expressed in mol.%, were investigated. The dielectric constant of the samples was investigated at 9.00 GHz using the shorted-line method (SLM) giving the minimum value of epsilon` = 2.10 +/- 0.02 at room temperature, and increasing further with x, following a given law. It was observed a gradual increasing slope Of E in the temperature range of 25 <= t <= 330 degrees C, at the frequency of 9.00 GHz. Insertion loss (measured at 9.00 GHz) and measurements of microwave energy attenuation, at frequencies ranging from 8.00 to 12.00 GHz were also studied as a function of iron content in the glass samples. (C) 2009 Elsevier Ltd. All rights reserved.

Antiferromagnetic spherical spin-glass model

We study the thermodynamic properties and the phase diagrams of a multi-spin antiferromagnetic spherical spin-glass model using the replica method. It is a two-sublattice version of the ferromagnetic spherical p-spin glass model. We consider both the replica-symmetric and the one-step replica-symmetry-breaking solutions, the latter being the most general solution for this model. We find paramagnetic, spin-glass, antiferromagnetic and mixed or glassy antiferromagnetic phases. The phase transitions are always of second order in the thermodynamic sense, but the spin-glass order parameter may undergo a discontinuous change.

Thermoluminescent and optical absorption properties of neodymium doped yttrium aluminoborate and yttrium calcium borate glasses

Neodymium doped yttrium aluminoborate and yttrium calcium borate glasses were prepared by the conventional melting-quenching technique with neodymium concentration varying from 0.10 to 1.0 mol%. The obtained glasses present a wide transparency in the UV-visible region (till 240 nm). The thermoluminescent (TL) emission of beta-irradiated samples was measured, showing a broad peak at similar to 240 degrees C with intensities related to the Nd(3+) content, for both glasses. Calcium borate glass samples are about one order of magnitude less luminescent than the aluminoborate glasses. Probably the presence of Ca(2+), instead of Al(3+) and Y(3+) in the matrix, inhibits the production of the intrinsic hole centers. connected to boron and oxygen, known in the literature to act as luminescent centers in TL emission of borate glasses. We suggest that Nd(3+) ions act as electron trapping centers in both glass matrices, as they modify the temperature of emission and the light intensity. Also, the Nd:YAIB glass can be used as a dosimeter in various applications, including radiotherapy. but the sensitivity of this material to neutron should be checked. (C) 2008 Elsevier B.V. All rights reserved.

Structural Characterization of Rare-Earth Doped Yttrium Aluminoborate Laser Glasses Using Solid State NMR

The structure of laser glasses in the system (B(2)O(3))(0.6){(Al(2)O(3))(0.4-x)(Y(2)O(3))(x)} (0.1 <= x <= 0.25) has been investigated by means of (11)B, (27)Al, and (89)Y solid state NMR as well as Y-3d core-level X-ray photoelectron spectroscopy, (11)B magic-angle spinning (MAS) NMR spectra reveal that the majority of the boron atoms are three-coordinated, and a slight increase of four-coordinated boron content with increasing x can be noticed. (27)Al MAS NMR spectra show that the alumina species are present in the coordination states four, five and six. All of them are in intimate contact with both the three- and the four-coordinate boron species and vice versa, as indicated by (11)B/(27)Al rotational echo double resonance (REDOR) data. These results are consistent with the formation of a homogeneous, nonsegregated glass structure. For the first time, (89)Y solid state NMR has been used to probe the local environment of Y(3+) ions in a glass-forming system. The intrinsic sensitivity problem associated with (89)Y NMR has been overcome by combining the benefits of paramagnetic doping with those of signal accumulation via Carr-Purcell spin echo trains. Both the (89)Y chemical shifts and the Y-3d core level binding energies are found to be rather sensitive to the yttrium bonding state and reveal that the bonding properties of the yttrium atoms in these glasses are similar to those found in the model compounds YBO(3) and YAl(3)(BO(3))(4), Based on charge balance considerations as well as (11)B NMR line shape analyses, the dominant borate species are concluded to be meta- and pyroborate anions.

Solid state NMR as a new approach for the structural characterization of rare-earth doped lead lanthanum zirconate titanate laser ceramics

To facilitate the design of laser host materials with optimized emission properties, detailed structural information at the atomic level is essential, regarding the local bonding environment of the active ions (distribution over distinct lattice sites) and their extent of local clustering as well as their population distribution over separate micro- or nanophases. The present study explores the potential of solid state NMR spectroscopy to provide such understanding for rare-earth doped lead lanthanum zirconate titanate (PLZT) ceramics. As the NMR signals of the paramagnetic dopant species cannot be observed directly, two complementary approaches are utilized: (1) direct observation of diamagnetic mimics using Sc-45 NMR and (2) study of the paramagnetic interaction of the constituent host lattice nuclei with the rare-earth dopant, using Pb-207 NMR lineshape analysis. Sc-45 MAS NMR spectra of scandium-doped PLZT samples unambiguously reveal scandium to be six-coordinated, suggesting that this rare-earth ion substitutes in the B site. Static Pb-207 spin echo NMR spectra of a series of Tm-doped PLZT samples reveal a clear influence of paramagnetic rare-earth dopant concentration on the NMR lineshape. In the latter case high-fidelity spectra can be obtained by spin echo mapping under systematic incrementation of the excitation frequency, benefiting from the signal-to-noise enhancement afforded by spin echo train Fourier transforms. Consistent with XRD data, the Pb-207 NMR lineshape analysis suggests that statistical incorporation into the PLZT lattice occurs at dopant levels of up to 1 wt.% Tm3+, while at higher levels the solubility limit is reached. (C) 2008 Elsevier Masson SAS. All rights reserved.