Preparation and properties of uniform praseodymium-doped ceria colloidal particles

 A procedure to prepare submicrometre spherical particles of Pr(III), Ce(III) or Pr(III)-doped C(III) hydroxycarbonates with narrow size distribution is reported. The particles were obtained by aging aqueous solutions of Pr(III) chloride and/or Ce(III) nitrate in the presence of urea at 100 °C for 2 h. The effect of Pr and/or Ce salt concentrations in the starting solutions on the size, shape and composition of the precipitated particles is reported. The thermal behaviour of the basic carbonates up to decomposition into the metal oxides was followed by differential thermal and thermogravimetric analyses, X-ray diffraction, IR spectroscopy and transmission electron microscopy. All the systems were also characterized by their electrokinetic behaviour (determination of isoelectric point) and specific surface areas. The colour of the powders was also evaluated as a function of the Pr content and temperature and was compared with previous results on red pigments of similar composition. Received: 30 May 2001 Revised: 17 September 2001 Accepted: 20 September 2001     

Role of yttrium loading in the physico-chemical properties and soot combustion activity of ceria and ceria–zirconia catalysts

Ce_1−xY_xO₂ and Ce_0.85−xZr_0.15Y_xO₂ mixed oxides have been prepared by 1000 °C-nitrates calcination to ensure thermally stable catalysts. The physico-chemical properties of the mixed oxides have been studied by N₂ adsorption at −196 °C, XPS, XRD, Raman spectroscopy and H₂-TPR, and the catalytic activity for soot oxidation in air has been studied by TG in the loose and tight contact modes. Yttrium is accumulated at the surface of Ce_1−xY_xO₂ and Ce_0.85−xZr_0.15Y_xO₂, and this accumulation is more pronounced for the former formulation than for the latter, because the deformation of the lattice due to zirconium doping favours yttrium incorporation. Yttrium and zirconium exhibit opposite effects on the surface concentration of cerium; while zirconium promotes the formation of cerium-rich surfaces, yttrium hinders the accumulation of cerium on the surface. For experiments in tight contact between soot and catalyst, all the Ce_1−xY_xO₂ catalysts are more active than bare CeO₂, and Ce_0.99Y_0.01O₂ is the most active catalyst. The benefit of yttrium doping in catalytic activity of ceria can be related to two facts: (i) the Y³⁺ surface enrichment hinders crystallite growth; (ii) the surface segregation of Y³⁺ promotes oxygen vacancies creation. High yttrium loading (x = 0.12) is less effective than low dosage (x = 0.01) because yttrium is mainly accumulated at the surface of the particles and hinders the participation of cerium in the soot oxidation reaction, which is the active component. For the mixed oxides with formulation Ce_0.85−xZr_0.15Y_xO₂ (operating in tight contact) the effect of zirconium on the catalytic activity prevails with respect to that of yttrium. For experiments in loose contact between soot and catalyst, the catalytic activity depends on their BET surface area, and the catalysts Ce_0.85−xZr_0.15Y_xO₂ (BET = 10–13 m²/g) are more active than the catalysts Ce_1−xY_xO₂ (BET = 2–3 m²/g). In the loose contact mode, the yttrium doping and loading have a minor or null affect on the activity, and the stabilising effect of the BET area due to zirconium doping prevails.     

Evaluation of the structural,optical and electrical properties of AZO thin films prepared by chemical bath deposition for optoelectronics

Aluminum doped zinc oxide (AZO) thin films for electrode applications were deposited on glass substrates using chemical bath deposition (CBD) method. The influence of deposition time on the structural, morphological, and opto-electrical properties of AZO films were investigated. Structural studies confirmed that all the deposited films were hexagonal wurtzite structure with polycrystalline nature and exhibited (002) preferential orientation. There is no other impurity phases were detected for different deposition time. Surface morphological images shows the spherically shaped grains are uniformly arranged on to the entire film surface. The EDS spectrum confirms the presence of Zn, O and Al elements in deposited AZO film. The observed optical transmittance is high (87%) in the visible region, and the calculated band gap value is 3.27 eV. In this study, the transmittance value is decreased with increasing deposition time. The room temperature PL spectrum exposed that AZO thin film deposited at (60 min) has good optical quality with less defect density. The minimum electrical resistivity and maximum carrier concentration values were observed as 8.53 × 10⁻³(Ω cm) and 3.53 × 10¹⁸ cm⁻³ for 60 min deposited film, respectively. The obtained figure of merit (ϕ) value 3.05 × 10⁻³(Ω/sq)^{- 1} is suggested for an optoelectronic device.     

Synergistic effect of dealumination and ceria impregnation to the catalytic properties of MOR zeolite

MOR zeolite has been extensively employed as a catalyst in industries. However, high Brønsted acidity in MOR leads to rapid deactivation due to coke deposition on the pore mouths; thus, the surface acidity of MOR needs to be moderated. Herein, we report a modification of MOR chemical composition via acid treatment and deposition of ceria nanoparticles using a wet impregnation method. The acid treatment successfully increases the Si/Al ratio of MOR from 8.39 to 11.58 and reduces the total acid site concentration of MOR from 990 μmol/g to 752 μmol/g. The acidity of MOR is decreased when the Si/Al ratio is increased since the quantity of Brønsted acid sites is proportional to the number of Al framework. In addition, the acid treatment also improves the external surface area of MOR. Furthermore, ceria particles were successfully deposited on the MOR surface using wet impregnation method. The ceria content of parent MOR sample is lower compared to that of preceded by the acid treatment, which may be attributed to the formation of more terminal silanol groups. Finally, catalytic test on Friedel–Crafts alkylation of toluene with benzyl alcohol shows that the synergy between dealumination and the impregnation of ceria significantly improves the activity of MOR zeolite.     

Effect of temperature and dopant concentration on the conductivity of samaria-doped ceria electrolyte

The conductivity, σ, of a samaria-doped ceria electrolyte is studied as a function of temperature and dopant concentration, x, which was from 5 to 30 mol%. It is shown that a maximum in σ versus x corresponds to a minimum in activation energy. It is found that the conductivity is completely due to oxygen vacancy conduction. The conductivity increases with increasing samaria doping and reaches a maximum for (CeO₂)_0.8(SmO_1.5)_0.2, which has a conductivity of 5.6×10^–1 S/cm at 800 °C. A curvature at T=T _c, the critical temperature, has been observed in the Arrhenius plot. This phenomenon may be explained by a model which proposed that, below T _c, nucleation of mobile oxygen vacancies into ordered clusters occurs, and, above T _c, all oxygen vacancies appear to be mobile without interaction with dopant cation. In addition, the composition dependences of both the critical temperature and the trapping energy are consistent with that of the activation energy. Electronic Publication     

The effects of the spinodal microstructure on the electrical properties of TiO2-SnO2 ceramics

The electrical properties of ceramics within the TiO₂-SnO₂ system which exhibit spinodal decomposition were investigated under different annealing conditions. Changes in the lattice parameter and the phase evolution of the spinodal decomposition, measured in terms of the volume fraction transformed X(t), were examined as a function of annealing time using X-ray diffraction. The room temperature dielectric properties were measured and compared to dielectric mixing rules. Doping with pentavalent Nb was found to slow the decomposition kinetics and a high permittivity (ε_r>1000) was induced. The origin of the high permittivity is linked to the formation of an electrically heterogeneous structure which is derived from the spinodal microstructure. Lastly, it was observed that Nb-doped TiO₂-SnO₂ ceramics exhibited non-linear current-voltage behavior which can be attributed to the negative temperature coefficient of resistance effect.     

Effects of different compositions from magnetic and nonmagnetic dopants on structural and electrical properties of ZnO nanoparticles-based varistor ceramics

In the current study, 20 nm zinc oxide (ZnO) nanoparticles were used to manufacture high-density ZnO discs doped with Mn and Sn via the conventional ceramic processing method, and their properties were characterized. Results show that the dopants were found to have significant effects on the ZnO varistors, especially on the shape and size of grains, which are significantly different for both dopants. The strong solid-state reaction in the varistor from the 20 nm ZnO powder during the sintering process may be attributed to the high surface area of the 20 nm ZnO nanoparticles. Although Mn and Sn do not affect the well-known peaks related to the wurtzite structure of ZnO ceramics, a few of the additional peaks could be formed at high doping content (≥2.0) due to the formation of other unknown phases during the sintering process. Both additives also significantly affect the electrical properties of the varistor, with a marked changed in the breakdown voltage from 415 V to 460 V for Sn and from 400 V to 950 V for Mn. Interestingly, the electrical behaviors of the varistors, such as breakdown voltage, nonlinear coefficient, and barrier height, are higher for Mn- than Sn-doping samples, and the opposite behaviors hold for hardness, leakage currents, and electrical conductivities. Results show that the magnetic moment and valence state of the two additive dopants are responsible for all demonstrated differences in the electrical characteristics between the two dopants.     

An enhancement on electrical properties of carboxymethyl cellulose-NH4Br based biopolymer electrolytes through impedance characterization

In this work, the formulation of biopolymer electrolytes (BEs) system has been accomplished by incorporating various plasticizers with carboxymethyl cellulose–NH₄Br through solution casting technique. The ionic conductivity at room temperature of BEs system was achieved at ～10^?4 S cm^?1 with addition of 25?wt% NH₄Br and enhanced to ～10^?3 S cm^?1 when plasticizers were added. The temperature-dependence of the BEs system exhibits Arrhenius behavior. Jonschers power law was used to study the electrical properties and shows that the highest conducting BEs system can be represented by overlapping overlapping a large polaron tunneling model for poly(ethylene glycol) system a, small polaron hopping model for glycerol system, and a quantum mechanical tunneling model for ethylene carbonate system.     

Effects of gamma irradiation and accelerated aging on GO/UHMWPE nanocomposites

This article investigates irradiated and accelerated aged graphene oxide (GO)/ultrahigh molecular weight polyethylene (UHMWPE) nanocomposites. The prepared GO/UHMWPE nanocomposites are gamma-irradiated at a high irradiation dose in a vacuum and then accelerated aging procedure is performed at 80°C in an air oven for 21 days. Irradiated and aged samples are characterized by Raman spectrum, Fourier transform infrared (FT-IR) spectrum, differential scanning calorimetry, contact angle, and gel content. Filling GO reduces the intensity of Raman spectrum of UHMWPE and irradiation or aging cannot affect vibrational modes of UHMWPE and GO/UHMWPE. The result of the FT-IR spectrum shows that UHMWPE and GO/UHMWPE basically have the same oxidation index values, whether with irradiation or accelerated aging. Irradiation or aging can slightly increase the melting temperature. GO, irradiation, or aging can significantly increase the crystallinity and improve wetting properties. In irradiated GO/UHMWPE, GO is able to maintain the efficiency of the cross-linking. However, after aging, the cross-linking density of GO/UHMWPE is reduced significantly. According to the above results, it is proposed that GO shows a very weak scavenging free radicals capacity in GO/UHMWPE composites and cannot display antioxidant capacity.     

Tunable electrical properties of self-organized zirconia nanotubes

Structural and electrical properties of self-organized zirconia nanotube layers can be tuned by a simple thermal treatment. The effect of F on the electrical conductivity of the MO_x nanotubes grown by anodization in fluoride-containing electrolytes is demonstrated.     

Hydrothermal synthesis of WO3·1/3H2O nanorods and study of their electrical properties

Crystalline tungsten oxide hydrate (WO₃·1/3H₂O) nanorods have been prepared by a hydrothermal process using Na₂WO₄·2H₂O and 4-phenylbutylamine as a structure-directing agent. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray analysis (EDX), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy and thermal analysis techniques have been used to characterize the structure, morphology and composition of the nanorods. The WO₃·1/3H₂O nanorods are up to several hundred nanometers in length, and the widths and thicknesses are 40 and 8 nm, respectively. A study of the electric properties in the temperature range 170–730 °C and frequency range 5–13 MHz is reported. The obtained results show that the activation energies are about 0.07, 0.63 and 2.46 eV for o-WO₃·1/3H₂O, h-WO₃ and m-WO₃, respectively. The as-synthesized materials are promising for chemical and energy-related applications such as catalysts and electrochemical devices, and may be applied in rechargeable lithium-ion batteries.     

Changes in the acid-base properties of hydrogels of metal oxide hydroxides induced by aging in solutions of electrolytes

Changes in the acid-base properties of titanium(IV), zirconium(IV), iron(III), chromium(III), and indium(III) hydrogels of oxide hydroxides induced by aging in sodium chloride and sulfate solutions were studied by the point of zero charge method. On aging in a solution of the sulfate electrolyte the hydrogels loose their basic properties much more rapidly than in the chloride solution. The most changes were observed in the region of high pH of the point of zero charge of the hydrogels. The changes in the acid-base properties can be explained by a decrease in the content of surface OH groups with are displaced by the supporting electrolyte ions, and due to the oxolation of the hydrogels. Published inIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1329–1332, August, 2000.     

Investigation of the electrical properties of XLPE/SiC nanocomposites

The interface between nanoparticles and the polymer matrix, which dominates the electrical properties of nanocomposites, can effectively improve the DC breakdown and suppress space charge accumulation in nanocomposites. To research the interface characteristics, XLPE/SiC nanocomposites with concentrations of 1 wt%, 3 wt% and 5 wt% were prepared. The DC breakdown, dielectric properties and space charge behavior were examined using pulsed electro-acoustic (PEA) equipment and a dielectric analyzer. The test results show that the nanocomposites with concentrations of 1 wt% and 3 wt% have higher DC breakdown field strength than neat XLPE. In contrast, there is a lower DC breakdown strength at a concentration of 5 wt%, possibly due to the agglomeration of nanoparticles. Nanoparticle doping increases the real and imaginary permittivities over those of neat XLPE. Furthermore, with increasing concentration, a larger increase in the permittivity amplitude was observed. Based on the space charge behavior, all nanocomposites could suppress space charge accumulation, but the nanocomposite with a concentration of 1 wt% exhibited the best effect. Meanwhile, heterocharge accumulation near electrodes was observed in neat XLPE and the nanocomposite with a concentration of 5 wt%. In contrast, homocharge accumulation near electrodes was observed in the nanocomposite with a concentration of 3 wt%. This phenomenon may be due to different amounts of shallow traps in nanocomposites with different concentrations, which might lead to differing electron or hole mobility.     

Effect of tin concentration on the electrical properties of ceramic membranes used as separators in electrochemical reactors

This paper deals with the study of different microporous ceramic membranes used as separators in electrochemical reactors to treat the activating solutions coming from the electroless plating of polymers. The main component of these solutions is Sn(IV) in HCl as diluting agent, then, the effect of the complex species formed between Sn⁴⁺ and Cl⁻ ions on the electrical properties of the membranes has been studied.     

Effect of carboxyl end groups content on the thermal and electrical properties of poly(propylene terephthalate)

Poly(propylene terephthalate) (PPT) samples with different carboxyl terminal groups content were synthesized in bulk and characterized in terms of chemical structure and molecular weight. The thermal behavior was examined by thermogravimetric analysis and differential scanning calorimetry. All the polymers under investigation show a good thermal stability, however decreasing with increasing carboxyl terminal groups content. No significant change of the glass transition temperature as well as melting temperature values was found in the samples under investigation; on the contrary, the crystallization rate of PPT was found to be affected by carboxyl terminal groups content, regularly decreasing as the amount of -COOH terminal groups is increased. This trend was interpreted on the basis of the interactions among the terminal groups of the polymeric chains, which determine a decrease in the chain mobility. Direct current (dc) electrical behavior was also investigated. The dc charging/discharging currents and electrical conductivity are studied as a function of temperature, time of applied voltage and amount of -COOH terminal groups. The conductivity values were found to increase as the content of -COOH end groups was increased, due to an increment of amount of ionic charge carriers.     

Synthesis,characterization, optical,thermal and electrical properties of polybenzimidazoles

The variation of dielectric constant and dielectric loss of two novel polybenzimidazole (PBI) were studied at constant temperature with variable frequency. The polymers have shown maximum dielectric constant at low applied frequency 50 Hz at 393 K due to the space charge polarization. The AC conductivity and activation energy of polymers were arrived from dielectric constant and dielectric loss values. PBIs were synthesized by the oxidative polycondensation of benzimidazole monomers, 2-(1H-benzo [d] imidazole-2-yl)-4-bromophenol (BIBP), and 2-(1H-benzo [d] imidazole-2-yl)-6-methoxyphenol (BIMP) in an aqueous alkaline medium using NaOCl as oxidant. The monomers and polymers were characterized by various spectroscopic techniques. Fluorescence spectra of monomers and polymers showed their λ _max emission in the region of 472–479 and 463–472 nm respectively. The electrical conductivities of iodine doped polybenzimidazoles were measured by four-point probe technique and it increases with increase in iodine vapour contact time. The electrical conductivity values were correlated with the charge density on imidazole nitrogen obtained from Huckel calculation method. Both the PBI are having reasonably good thermal stability and are shown by high carbines residues of around 40% at 500°C in thermogravimetric analysis.     

Electrical and magnetic properties of ion-exchangeable layered ruthenates

An ion-exchangeable ruthenate with a layered structure, K_0.2RuO_2.1, was prepared by solid-state reactions. The interlayer cation was exchanged with H⁺, C₂H₅NH₃⁺, and ((C₄H₉)₄N⁺) through proton-exchange, ion-exchange, and guest-exchange reactions. The electrical and magnetic properties of the products were characterized by DC resistivity and susceptibility measurements. Layered K_0.2RuO_2.1 exhibited metallic conduction between 300 and 13 K. The products exhibited similar magnetic behavior despite the differences in the type of interlayer cation, suggesting that the ruthenate sheet in the protonated form and the intercalation compounds possesses metallic nature.     

Changes of mechanical properties in cold-crystallized syndiotactic polypropylene during aging

Many semicrystalline polymers undergo a process of aging when they are stored at temperatures higher than their glass-transition temperature (T _g). Syndiotactic polypropylene was quenched from the melt to −40 °C, crystallized from the glassy state at 20 or 40 °C and stored at the respective temperature for different aging times up to 7200 h. A significant increase in the tensile modulus and stress at yield and a decrease in strain at yield were observed for both aging temperatures. Differential scanning calorimetry (DSC) scans of aged material showed an endothermic annealing peak 15–30 °C above the previous aging temperature, the maximum temperature and enthalpic content of which increased with aging time. The position and the shape of the melting peak were not affected by aging. Scans of the storage modulus obtained from dynamic mechanical analyser measurements indicated a softening process starting at about 20 °C above the aging temperature and correlating with the annealing peak detected by DSC. Density measurements and wide-angle X-ray scattering investigations revealed that neither the crystallinity increased significantly nor did the crystal structure change. So the observed property changes induced by aging are attributed to microstructural changes within the amorphous phase. Furthermore, it could be shown by annealing experiments carried out at 60 °C, that aging above T _g is, analogous to aging below T _g (physical aging), a thermoreversible process. Received: 18 September 2000 Accepted: 2 January 2001     

Absolute determination of the conductivity of electrolytes. Double differential cell with adjustable constant

Existing methods for the determination of the electrical conductivity of electrolytes require a cell calibration by an indirect method and the determination of their electrical resistance. A new conductivity cell is described which is a double differential cell with an adjustable constant. Using this cell, absolute determination of the conductivity of electrolytic solutions can be obtained over a wide temperature range. The influence of the frequency is either eliminated or greatly reduced in all other cases. The accuracy is at least as good as that obtained by indirect methods.This paper is part of a Ph.D. dissertation by the author.     

Decreasing the shell ratio of core-shell type nanoparticles with a ceria core and polymer shell by acid treatment

Core-shell type nanoparticles with a ceria core and polymer shell have good dispersibility. Some applications, such as fillers for increasing the refractive index and/or protecting resin films from ultraviolet (UV) light, i.e., UV cutting, require a smaller shell. Previous studies have decreased the shell weight by heat treatment in gas; however, the dispersibility of the treated nanoparticles was poor in water or alcohol. In this study, we investigated the efficacy of acid treatment for decreasing the shell weight and also evaluated the dispersibility of acid-treated nanoparticles. The thus-formed nanoparticles treated by acetic acid and formic acid show not only good dispersibility but also a well decreased shell thickness. The structure of the shell after acetic acid treatment was found to be the same as that of the untreated core-shell nanoparticles; moreover, acetic acid was present in the shell. Furthermore, by using the acetic-acid-treated nanoparticles, a transparent resin film without nanoparticle aggregation could be obtained.