Electrochemical deposition of praseodymium oxide on tin-doped indium oxide as a thin sensing film

Fabrication of a thin praseodymium oxide film is of great technological interest in sensor, semiconducting, and ceramic industries. It is shown for the first time that an ultrathin layer of praseodymium oxide can be deposited on tin-doped indium oxide surface (ITO) by applying a negative sweeping voltage (cathodic electrodeposition) to the aqueous solution containing Pr(NO3)(3) and H2O2 using cyclic voltammetry, followed by annealing the film at 500 S C for 1 h. X-ray diffraction suggested that the predominant phase of the film is Pr6O11 and atomic force microscopy and scanning electron microscopy characterizations indicated that this film is assembled with a monolayer coverage of spherical praseodymium oxide nanoparticles packed closely on the ITO surface. AC impedance measurements of the thin Pr6O11 film on ITO also revealed that the composite material displays a much higher electrical conductivity compared to the pure ITO. As a result, the material could suitably be used as a new chemical sensor. (c) 2006 The Electrochemical Society.

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.

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.

Secondary uranium mineralization in southern Finland and its relationship to recent glacial events

Uranium series dating has been carried out on secondary uranyl silicate minerals formed during sub-glacial and post-glacial weathering of Proterozoic uraninite ores in south west Finland. The samples were obtained from two sites adjacent to the Salpauselkä III ice marginal formation and cover a range of depths, from the surface to more than 60 m. Measured ages fall into three distinct groups, 70–100 ka, 28–36 ka and < 2500 yr. The youngest set is associated with surface exposures and the crystals display clear evidence of re-working. The most likely trigger for uranium release at depths below the surface weathering zone is intrusion of oxidising glacial melt water. The latter is often characterised by very high discharge rates along channels, which close once the overpressure generated at the ice margin is released. There is excellent correspondence between the two Finnish sites and published data for similar deposits over a large area of southern and central Sweden. None of the seventy samples analysed gave a U–Th age between 40 and 70 ka; a second hiatus is apparent at 20 ka, coinciding with the Last Glacial Maximum. Thus, the process responsible for uranyl silicate formation was halted for significant periods, owing to a change in geochemical conditions or the hydrogeological regime. These data support the presence of interstadial conditions during the Early and Middle Weichselian since in the absence of major climatic perturbations the uranium phases at depth are stable. When viewed in conjunction with proxy data from mammoth remains it would appear that the region was ice-free prior to the Last Glacial Maximum.

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.

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.

The effect of adding stinging nettle (Urtica dioica) haylage to a total mixed ration on performance and rumen function of lactating dairy cows

In vitro studies found that inclusion of dried stinging nettle (Urtica dioica) at 100 mg/g dry matter (DM) increased the pH of a rumen fluid inoculated fermentation buffer by 30% and the effect was persistent for 7 days. Our objective was to evaluate the effects of adding stinging nettle haylage to a total mixed ration on feed intake, eating and rumination activity, rumen pH, milk yield, and milk composition of lactating dairy cows. Six lactating Holstein-Friesian cows were used in a replicated 3 × 3 Latin Square design experiment with 3 treatments and 3 week periods. Treatments were a control (C) high-starch (311 g/kg DM) total mixed ration diet and two treatment diets containing 50 (N5) and 100 (N10) g nettle haylage (DM/kg) as a replacement for ryegrass silage (Lolium perenne). There was an increase (linear, P < 0.010) in the proportion of large particles and a reduction in medium (linear, P = 0.045) and fine particles (linear, P = 0.026) in the diet offered with increasing nettle inclusion. A numerical decrease (linear, P = 0.106) in DM intake (DMI) was observed as nettle inclusion in the diet increased. Milk yield averaged 20.3 kg/day and was not affected by diet. There was a decrease (quadratic, P = 0.01) in the time animals spent ruminating as nettle inclusion in the diet increased, in spite of an increase in the number of boli produced daily for the N5 diet (quadratic, P = 0.031). Animals fed the N10 diet spent less time with a rumen pH below 5.5 (P < 0.05) than cows fed the N5 diet. Averaged over an 8.5 h sampling period, there were no changes in the concentration or proportions of acetate or propionate in the rumen, but feeding nettle haylage reduced the concentrations of n-butyrate (quadratic, P < 0.001), i-butyrate (linear, P < 0.009) and n-caproate (linear, P < 0.003). Milk and fat and protein corrected milk yield were not affected when nettles replaced ryegrass silage in the diet of lactating dairy cows, despite a numerical reduction in feed intake. Rumination activity was reduced by the addition of nettle haylage to the diet, which may reflect differences in fibre structure between the nettle haylage and ryegrass silage fed. Changes observed in rumen pH suggest potential benefits of feeding nettle haylage for reducing rumen acidosis. However, the extent to which these effects were due to the fermentability and structure of the nettle haylage compared to the ryegrass silage fed, or a bioactive component of the nettles, is not certain