Preparation and magnetic properties of La–Mn and La–Co doped barium hexaferrites prepared via an improved co-precipitation/molten salt method

LaMn and LaCo doped barium hexaferrites of formula Ba(1-x)LaxFe(12-x)MxO19 (M=Mn, Co) (x=0.05 to 0.40) were prepared with an improved co-precipitation/molten salt method. For the synthesis, aqueous solutions of the appropriate metal chlorides were prepared in the ratio required except that the initial mole ratio of Fe and dopants to Ba was chosen to be 11:1, and then mixed with excess Na2CO3. The solutions were then cooled, filtered off, dried, then mixed with KCl flux, and heated at 450 degrees C and for 2 h. The temperature was then raised to 950 degrees C and kept for 4 h, then cooled. This new synthesis method, which employs a lower temperature and shorter reaction time, gives products with improved crystallinity and purity while the saturation magnetization and coercivity values are comparable with those synthesized via the high temperature method.

Efficiency and purity control in the preparation of pure and/or aluminum-doped barium ferrites by hydrothermal methods using ferrous ions as reactants

The synthesis of hexagonal barium ferrite (BaFe12O19) was studied under hydrothermal conditions by a method in which a significant amount of ferrous chloride was introduced along side ferric chloride among the starting materials. Though all of the Fe2+ ions in the starting material were converted to Fe3+ ions in the final product, Fe2+ was confirmed to participate differently from the Fe3+ used in the conventional method in the mechanism of forming barium ferrite. Indeed the efficiency of the synthesis and the quality of the product and the lack of impurities such as Fe2O3 and BaFe2O4 were improved when Fe2+ was included. However, the amount of ferrous ions that could be included to obtain the desired product was limited with an optimum ratio of 2:8 for FeCl2/FeCl3 when only 2h of reaction time were needed. It was also found that the role of trivalent Fe3+ could be successfully replaced by Al3+. Up to 50% of their on could be replaced by Al3+ in the reactants to produce Al- doped products. It was also found that the ratio of Fe2+/M3+ could be increased in the presence of Al3+ to produce high quality barium ferrite.

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.

Photo-induced phase transitions in azobenzene-doped liquid crystals

The effect of irradiation (UV-visible light) on a nematic liquid crystal doped with a photoactive azobenzene derivative was investigated. The selective irradiation results in either an E implies Z or Z implies E isomerization of the azobenzene unit. The effect of the isomerization is to cause a reversible depression of the liquid crystal to isotropic (LC implies l) phase transition temperature of the doped mixture, which can be monitored optically as an isothermal phase transition. This depression also results in a biphasic liquid crystal+isotropic region which is discussed. The authors investigate the cause and magnitude of the phase depression as a function of the amount of doped 4-butyl-4'-methoxyazobenzene (photoactive unit) in 4-cyano-4'-n-pentylbiphenyl (liquid crystal unit), and as a function of the percentage conversion of E implies Z (caused by isomerization) in the azobenzene. The photostationary state of the doped mixtures achieved by Z implies E isomerization is considered and its effect upon the transition temperature of the mixture and response time of the system is discussed. They discuss the implications of the photostationary state with regards to the reversibility of the photo-induced phase transition and hence potential applications.

Temperature optimization of optical-phase conjugation in dye doped polymer-films

Experimental results of the temperature dependence of the nonlinear optical response of methyl red doped polymethylmethacrylate films in the range 20°C to 170°C are reported. It is found that the intensity of the phase conjugate signal resulting from degenerate four-wave mixing using pump and probe beams with parallel polarisation states increases dramatically on heating by a factor of ∼ 10, reaching a maximum at ∼ 100°C. The intensity of the phase conjugate signal for the case with crossed polarisation states of the pump and probe beams drops monotonically with increasing temperature. For both configurations the response time shortens with increasing temperature. The particular role of the polymer matrix in this temperature variation of the nonlinear optical response is discussed.

Ternary erbium chromium sulfides : structural relationships and magnetic properties

Single crystals of four erbium-chromium sulfides have been grown by chemical vapor transport using iodine as the transporting agent. Single-crystal X-ray diffraction reveals that in Er(3)CrS(6) octahedral sites are occupied exclusively by Cr(3+) cations, leading to one-dimensional CrS(4)(5-) chains of edge-sharing octahedra, while in Er(2)CrS(4), Er(3+), and Cr(2+) cations occupy the available octahedral sites in an ordered manner. By contrast, in Er(6)Cr(2)S(11) and Er(4)CrS(7), Er(3+) and Cr(2+) ions are disordered over the octahedral sites. In Er(2)CrS(4), Er(6)Cr(2)S(11), and Er(4)CrS(7), the network of octahedra generates an anionic framework constructed from M(2)S(5) slabs of varying thickness, linked by one-dimensional octahedral chains. This suggests that these three phases belong to a series in which the anionic framework may be described by the general formula [M(2n+1)S(4n+3)](x-), with charge balancing provided by Er(3+) cations located in sites of high-coordination number within one-dimensional channels defined by the framework. Er(4)CrS(7), Er(6)Cr(2)S(11), and Er(2)CrS(4) may thus be considered as the n = 1, 2, and infinity members of this series. While Er(4)CrS(7) is paramagnetic, successive magnetic transitions associated with ordering of the chromium and erbium sub-lattices are observed on cooling Er(3)CrS(6) (T(C)(Cr) = 30 K; T(C)(Er) = 11 K) and Er(2)CrS(4) (T(N)(Cr) = 42 K, T(N)(Er) = 10 K) whereas Er(6)Cr(2)S(11) exhibits ordering of the chromium sub-lattice only (T(N) = 11.4 K).

Dopant-vacancy binding effects in Li-doped magnesium hydride

We use a combination of ab initio calculations and statistical mechanics to investigate the substitution of Li+ for Mg2+ in magnesium hydride (MgH2) accompanied by the formation of hydrogen vacancies with positive charge (with respect to the original ion at the site). We show that the binding energy between dopants and vacancy defects leads to a significant fraction of trapped vacancies and therefore a dramatic reduction in the number of free vacancies available for diffusion. The concentration of free vacancies initially increases with dopant concentration but reaches a maximum at around 1 mol % Li doping and slowly decreases with further doping. At the optimal level of doping, the corresponding concentration of free vacancies is much higher than the equilibrium concentrations of charged and neutral vacancies in pure MgH2 at typical hydrogen storage conditions. We also show that Li-doped MgH2 is thermodynamically metastable with respect to phase separation into pure magnesium and lithium hydrides at any significant Li concentration, even after considering the stabilization provided by dopant-vacancy interactions and configurational entropic effects. Our results suggest that lithium doping may enhance hydrogen diffusion hydride but only to a limited extent determined by an optimal dopant concentration and conditioned to the stability of the doped phase.

Ball milling as an effective route for the preparation of doped bornite: synthesis, stability and thermoelectric properties

Bornite, Cu5FeS4, is a naturally-occuring mineral with an ultralow thermal conductivity and potential for thermoelectric power generation. We describe here a new, easy and scalable route to synthesise bornite, together with the thermoelectric behaviour of manganese-substituted derivatives, Cu5Fe1-xMnxS4 (0 ≤ x ≤ 0.10). The electrical and thermal transport properties of Cu5Fe1-xMnxS4 (0 ≤ x ≤ 0.10), which are p-type semiconductors, were measured from room temperature to 573 K. The stability of bornite was investigated by thermogravimetric analysis under inert and oxidising atmospheres. Repeated measurements of the electrical transport properties confirm that bornite is stable up to 580 K under an inert atmosphere, while heating to 890 K results in rapid degradation. Ball milling leads to a substantial improvement in the thermoelectric figure of merit of unsusbtituted bornite (ZT = 0.55 at 543 K), when compared to bornite prepared by conventional high-temperature synthesis (ZT < 0.3 at 543 K). Manganese-substituted samples have a ZT comparable to that of unsubstituted bornite.

Bond durability in erbium:yttrium-aluminum-garnet laser-irradiated enamel

This study sought to evaluate the influence of thermocycling and water storage on the microtensile bond strength of composite resin bonded to erbium:yttrium-aluminum-garnet (Er:YAG)-irradiated and bur-prepared enamel. Eighty bovine incisors were selected and sectioned. Specimens were ground to produce a flat enamel surface. Samples were randomly assigned according to cavity preparation device: (I) Er:YAG laser and (II) high-speed turbine, and were subsequently restored with composite resin. They were subdivided according to the duration of water storage (WS)/number of thermocycles (TCs): 24 h WS/no TCs; 7 days WS/500 TCs; 1 month WS/2,000 TCs; 6 months WS/12,000 TCs. The teeth were sectioned into 1.0 mm(2)-thick slabs and subjected to tensile stress in a universal testing machine. Data were submitted to two-way analysis of variance (ANOVA) and Tukey`s test at a 0.05 significance level. The different periods of water storage and thermocycling did not influence the microtensile bond strength (A mu TBS) values in the Er:YAG laser-prepared groups. In bur-prepared enamel, the group submitted to 12,000 TCs/6 months` WS (IID) showed a significant decrease in bond strength values when compared to the group stored in water for 24 h and not submitted to thermocycling (IIA), but values were statistically similar to those obtained in all Er:YAG laser groups and in the bur- prepared groups degraded with 500 TCs/1 week WS (IIB) or 2,000 TCs/1 month WS (IIC). It may be concluded that adhesion of an etch-and-rinse adhesive to Er:YAG laser-irradiated enamel was not affected by the methods used to simulate degradation of the adhesive interface and was similar to adhesion in the bur-prepared groups in all periods of water storage and thermocycling.

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.

Retention at room temperature of the tetragonal t ``-form in Sc(2)O(3)-doped ZrO(2) nanopowders

Synchrotron X-ray powder diffraction was applied to the study of the effect of crystallite size on the crystal structure of ZrO(2)-10 mol% Sc(2)O(3) nanopowders synthesized by a nitrate-lysine gel-combustion route Nanopowders with different average crystallite sizes were obtained by calcination at several temperatures, ranging from 650 to 1200 degrees C The metastable t""-form of the tetragonal phase, exhibiting a cubic unit cell and tetragonal P4(2)/nmc spatial symmetry, was retained at room temperature in fine nanocrystalline powders, completely avoiding the presence of the stable rhombohedral beta phase. Differently, this phase was identified in samples calcined at high temperatures and its content increased with increasing crystallite size The critical maximum crystallite size for the retention of the mestastable t""-form resulted of about 35 nm (C) 2009 Elsevier B.V All rights reserved

Photoluminescence behavior of Eu(3+) ion doped into gamma- and alpha-alumina systems prepared by combustion, ceramic and Pechini methods

Al(2)O(3):Eu(3+)(1%) samples were prepared by combustion, ceramic, and Pechini methods annealed from 400 to 1400 degrees C. XRD patterns indicate that samples heated up to 1000 degrees C present disordered character of activated alumina (gamma-Al(2)O(3)). However, alpha-Al(2)O(3) phase showed high crystallinity and thermostability at 1200-1400 degrees C. The sample characterizations were also carried out by means of infrared spectroscopy (IR), scanning electron microscopy (SEM) and specific surface areas analysis (BET method). Excitation spectra of Al(2)O(3):Eu(3+) samples present broaden bands attributed to defects of Al(2)O(3) matrices and to LMCT state of O -> Eu(3+), however, the narrow bands are assigned to (7)F(0) -> (5)D(J),(5)H(J) and (5)L(J) transitions of Eu(3+) ion. Emission spectra of samples calcined up to 1000 degrees C show broaden bands for (5)D(0) -> (7)F(J) transitions of Eu(3+) ion suggesting that the rare earth ion is in different symmetry sites showed by inhomogeneous line broadening of bands, confirming the predominance of the gamma-alumina phase. For all samples heated from 1200 to 1400 degrees C the spectra exhibit narrow (5)D(0) -> (7)F(J) transitions of Eu(3+) ion indicating the conversion of gamma to alpha-Al(2)O(3) phases, a high intensity narrow peak around 695 nm assigned to R lines of Cr(3+) ion is shown. Al(2)O(3):Eu(3+) heated up to 1100 degrees C presents an increase in the Omega(2) intensity parameter with the increase of temperatures enhancing the covalent character of metal-donor interaction. The disordered structural systems present the highest values of emission quantum efficiencies (eta). CIE coordinates of Al(2)O(3):Eu(3+) are also discussed. (C) 2007 Elsevier Inc. All rights reserved.

Magnetic and structural properties of NiFe(2)O(4) ferrite nanopowder doped with Zn(2+)

This work involved an investigation to ascertain how the substitution of nickel ions for zinc ions affects the structural, morphological and magnetic properties of NiFe(2)O(4) ferrite samples. Ni(1-x)Zn(x)Fe(2)O(4) (x = 0.0, 0.3 0.5, 0.7) powders were prepared by combustion reaction and characterized structurally by X-ray diffraction. The specific surface area of the powders was determined by the nitrogen adsorption method (BET). Magnetization measurements were taken using an alternative gradient magnetometer (AGM), which revealed that the powders prepared by combustion reaction resulted in nanosized particles with a particle size of 18-27 nm. The crystallite size and lattice parameter increased as the concentration of Zn increased. Moreover, augmenting the Zn content in the NiFe(2)O(4) ferrite increased the saturation magnetization and coercive field. (C) 2008 Elsevier B.V. All rights reserved.