Synthesis and CO2 capture property of high aspect-ratio Li2ZrO3 nanotubes arrays

High aspect-ratio Li₂ZrO₃ nanotubes were prepared by hydrothermal method using ZrO₂ nanotubes layers as templates. Characterizations of SEM, XRD, TEM and CO₂ adsorption were performed. The results showed that tetragonal Li₂ZrO₃ nanotubes arrays containing a little monoclinic ZrO₂ can be obtained using this simple method. The mean diameter of the nanotubes is approximately 150 nm and the corresponding specific surface area is 57.9 m² g⁻¹. Moreover, the obtained Li₂ZrO₃ nanotubes were thermally analyzed under a CO₂ flow to evaluate their CO₂ capture property. It was found that the as-prepared Li₂ZrO₃ nanotubes arrays would be an effective acceptor for CO₂ at high temperature.     

Evidence of the surface layer in tungstated zirconia

We characterized the structure of tungstated zirconia (WO_x–ZrO₂) by combining X-ray diffraction, Raman spectroscopy and High Resolution Electron Microscopy (HREM) together with molecular simulations. Our results indicate that the structure of this material consists of metastable tetragonal ZrO₂ nanoparticles (<20 nm in diameter) covered by a few-nanometers thick low-crystallinity surface layer formed by tungsten oxospecies (WO_x). Although the X-ray diffraction pattern matched the spectra of the tetragonal ZrO₂ bulk phase the lattice fringes of the ZrO₂ nanoparticles observed by HREM were locally distorted, presumably as a result of the interaction with the surface WO_x layer. The local interplanar distances of the surface layer were close to those present in different bulk tungsten oxocompounds, and its variability was also an indication of the WO_x–ZrO₂ interaction. Molecular simulations corroborated our structural assignment. The results presented here are a direct evidence for the presence of a surface WO_x layer in the case of WO_x–ZrO₂. PACS 68.35.Bs; 81.05.Ys; 82.65.Dp     

The transverse laser induced thermoelectric voltages in step flow growth （1-x）Pb(Mg1/3Nb2/3)O3-xPbTiO3 thin films

This paper reports that the transverse laser induced thermoelectric voltages (LITV) are observed for the first time in the step flow growth (1-x)Pb(Mg1/3Nb2/3)O3-xPbTiO3 (PMN-PT,x = 0.20, 0.33, 0.50) thin films deposited on vicinal-cut strontium titanate single crystal substrates. Because lead magnesium niobate-lead titanate is a solid solution of lead magnesium niobate (PMN) and lead titanate (PT), there are two types of signals. One is wide with a time response of a microsecond, and the other superimposed with the wide signal is narrow with a time response of a nanosecond. The transverse LITV signals depend on the ratio of PMN to PT drastically. Under the irradiation of 28-ns pulsed KrF excimer laser with the 248-nm wavelength,the largest induced voltage is observed in the 0.50Pb(Mg1/Nb2/3)O3-0.50PbTiO3 films. Moreover, the effects of film thickness, substrates, and tilt angles of substrates are also investigated.     

Stable colloidal suspensions of nanostructured zirconium oxide synthesized by hydrothermal process

Nanocrystalline zirconium oxide was synthesized by hydrothermal treatment of ZrO(NO₃)₂ and ZrOCl₂ aqueous solutions at different temperatures and time in presence of hydrogen peroxide. Hydrothermal treatment of zirconium salts (0.25 and 0.50 mol L^?1) produced nanocrystalline monoclinic ZrO₂ powders with narrow size distribution, which were formed by the attachment of the smaller particles with crystallites size of 3.5 nm, estimated by means of the Scherrer’s equation and confirmed by transmission electronic microscopy. Typical monoclinic zirconium oxide X-ray powder diffraction patterns and Raman spectra were obtained for all the crystalline powders. It was observed that the crystallization depends strongly on the temperature, resulting in amorphous material when the synthesis was realized at 100 °C, and crystalline with monoclinic phase when synthesized at 110 °C, independently of the salt used. Zirconium oxide colloidal nanoparticles were formed only at hydrothermal treatments longer than 24 h. The stability of the colloids was successfully characterized of zeta potential, showing an initial value of + 59.2 mV in acid media and isoelectric point at pH = 5.2, in good agreement with previous studies.     

Synthesis, characterization and low field emission of CNx nanotubes

Aligned CN_x nanotubes were fabricated by pyrolyzing ethylenediamine on p-type Si(1 1 1) substrates using iron as the catalyst. Scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectrum (XPS) and Raman spectroscopy were used to characterize the CN_x nanotubes. The CN_x nanotubes with the average length of 20 μm and diameters in the range of 50–100 nm have the “bamboo-like” structure and worse crystalline order. The low-field emission measurements of the CN_x nanotubes indicated that 20 μA/cm² current densities were observed at an electric field of 1.4 V/μm and 1.280 mA/cm² were obtained at 2.54 V/μm. The CN_x nanotubes exhibit better field emission properties than the carbon nanotubes and the BCN nanotubes. The emission mechanism of CN_x nanotubes is also discussed.     

The structural and magnetic properties of Co-doped titanate nanotubes synthesized under hydrothermal conditions

Co-doped titanate nanotubes were prepared from hydrothermal treatment on Co-doped anatase TiO₂ powders in a concentrated NaOH aqueous solution and characterized by a variety of techniques. We mainly investigated the structural and magnetic properties of these nanotubes. It was found that the obtained nanotubes might possibly be constructed from H₂Ti₃O₇, their undoped counterpart. The result from Raman spectra showed that Ti–OH bonds existed in the tubular structure. The electron paramagnetic resonance and X-ray photoelectron spectroscopy studies clearly showed that the Co was incorporated into the titanate lattice as Co²⁺ and substituted for Ti cations sites. Also, from the photoluminescence measurement, the presence of oxygen vacancies was detected in the nanotubes. The vibrating sample magnetometer measurement revealed a clear paramagnetic behavior with weakly ferromagnetic ordering at room temperature. The results suggested that ferromagnetism of the nanotubes was related to the oxygen vacancies and could be suppressed by their quantum size. PACS 81.07.De; 75.75.+a; 75.50.Pp     

Solid state reaction crystallization and amorphization on thin film Fe-Zr multilayers

We study in this paper the thin multilayered film of the system Fe _x Zr_1-x using conversion electron Mössbauer spectroscopy (CEMS) as well as Rutherford backscattering spectroscopy (RBS). The solid state reaction (SSR) at 500°C for thex=0.33 andx=0.67 concentrations produces crystalline and amorphous phases. For the concentrationx=0.50 only an amorphous phase is obtained. For reactions at 700°C, besides Fe-Zr phases, another one is observed in the CEMS spectrum. This phase may be associated with some FeSi compound since the RBS profile shows the presence of Si at the surface.This work was supported by CNPq, FINEP and FAPERGS.     

Highlighting the mechanisms of the titanate nanotubes to titanate nanoribbons transformation

Titanate nanorods, nanoribbons, and nanofibers synthesized by hydrothermal treatment are being investigated by several groups. Similar to titanate nanotubes, with average diameter of 9 nm, there is a strong controversy regarding the composition and microscopic formation mechanism of these non-hollow nanostructures (nanoribbons). In this article, we report the synthesis and characterization of the titanate nanostructures by exploiting some aspects that were not exploited so far. By using X-ray diffraction, FT-infrared and Raman spectroscopies and electron microscopy, we have studied the intermediate structure and morphology between nanotubes and the non-hollow nanostructures. Our findings give further evidence that the transformation of nanotubes into non-hollow nanostructures is induced by a sequence of both oriented attachment and Ostwald rippening cooperative mechanisms.     

Formation and characterization of boride coatings thermochemically grown on the Fe64Ni36 alloy

Zirconium oxide (zirconia) exists in three crystalline forms of monoclinic, tetragonal and cubic structures at atmospheric pressures. The cubic form of zirconia is well known for its mechanical, electrochemical and optical applications. Fe-doped cubic zirconia (high temperature phase) compositions are synthesized by microwave combustion method. Here, we present a Mössbauer investigation of Zr_1???x Fe _x O₂ composition within a range of Fe (0.03 < x < 0.09). ⁵⁷Fe Mössbauer spectra were recorded at room temperature and at low temperature (77 K) for all samples. 3% Fe-doped ZrO₂ shows doublet and the corresponding 6% and 9% Fe-doped ZrO₂ samples show superimposed sextet and doublets. The isomer shift and quadrupole moment indicate, Iron to be in III oxidation state and to occupy different octahedral sites, associated with some amount of disorder. X-ray powder diffraction pattern of Fe-doped ZrO₂ samples appear as very well crystalline. The Miller indices refer to the cubic fluorite-type ZrO₂ structure. The magnetic behavior shows increase in moment and decrease in coercivity, with increase in Fe concentration. The M vs. H plots of the as-prepared Zr_1-x Fe _x O₂ essentially show typical hysteresis loops, indicating room temperature ferromagnetism. Thus, the introduced microwave combustion route is an effective process to achieve multifunctional Fe-doped Zirconia with coexistent magnetic properties.     

Recovery properties of hydrogen gas sensor with Pd/titanate and Pt/titanate nanotubes photo-catalyst by UV radiation from catalytic poisoning of H2S

Recovery properties after H₂S catalytic poisoning of catalytic-type gas sensor with photo-catalysts and UV radiation have been examined. Each sensing material of the sensor consists of Pd, Pt supported on γ-Al₂O₃ and Pd/titanate, Pt/titanate nanotubes or TiO₂ particles. Pd/titanate and Pt/titanate nanotubes photo-catalyst were synthesized by hydrothermal synthesis method. All the sensors were deactivated after 500 ppm H₂S exposure for 20 h. The sensors with Pd/titanate or Pt/titanate nanotubes showed regenerated voltage response under UV radiation. However the sensor with TiO₂ particles showed negligible regenerated voltage response. Regenerated voltage response with Pd/titanate or Pt/titanate nanotubes may stem from location of Pd or Pt catalyst on the titanate nanotube photo-catalyst.     

Effect of HPC and Water Concentration on the Evolution of Size,Aggregation and Crystallization of Sol-gel Nano Zirconia

Nano-sized zirconia (ZrO₂) powder is synthesized using sol-gel technique involving hydrolysis and condensation of zirconium(IV) n-propoxide in an alcohol solution, utilizing hydroxypropyl cellulose (HPC) polymer as a steric stabilizer. It is demonstrated that ZrO₂ nanoparticle size can be reduced using high R-value (defined as the ratio of molar concentrations of water and alkoxide). It is also shown that ZrO₂ nanoparticle size can be reduced further by synthesizing these particles in the presence of HPC polymer. The agglomeration tendency of ZrO₂ nanoparticles is demonstrated to decrease due to the steric hindrance created by the adsorbed polymer. The nanocrystallite size and their 'hard-aggregates' formation tendency are observed to affect the high temperature metastable tetragonal phase stabilization at room temperature within ZrO₂ particles.     

Effect of Ca substitution on structural,magnetic and dielectric properties of BiFeO3

Bi_1-xCa_xFeO₃ (x = 0.40, 0.50) compounds are synthesized by conventional solid-state reaction method. The effect of Ca²⁺ substitution is investigated on structural, dielectric and magnetic properties. Rietveld refinement confirms that crystal structures of both the samples are tetragonal with P4mm symmetry. The highest values of remnant magnetization (M_r ) and coercive field (H_c ) are 0.002 emu/g and 0.23 kOe, respectively, for x = 0.50. The electric modulus formalism is used to distinguish and separate out the relaxation process which is dominated by the transport phenomenon. The relaxation process has activation energy ～0.32 eV which is found to be related to both the hopping mechanisms, i.e. electronic and oxide ions.     

Zeeman splitting factor of the Er3+ ion in a crystal field

Numerical computations are presented on the energy levels of the Er³⁺ ion in crystalline fields of cubic, trigonal, tetragonal and orthorhombic symmetry. Zeeman splitting factors were obtained from the level splitting in an additional magnetic field. For the quartet Γ₈ states in cubic symmetry the Zeeman effect is described by an effective Hamiltonian ℋ= gμ_BBJ+ uμ_BBJ³ with the parametersg andu calculated for mixed fourth- and sixth-order potentials. For the eight doublets in the lower symmetry of an axial trigonal or tetragonal crystal field the principalg tensor components g_∥ and g_⊥ were calculated. The results of such calculations for a ground-state doublet can exactly account for the experimental data obtained on around 70 erbium centers in various crystalline hosts. However, sometimes different sets of parameters give comparably good results. An empirical rule of constant trace g_∥ + 2g_⊥ is supported by the calculations. In contrast to analytical treatments the effect of the crystalline field can be followed over a continuous range of the crystal field parameters. This allows one to establish relations on the relative signs of tensor components. It is found that the measured trace of tensors |g_∥| + 2|g_⊥| is not always equal to their real trace g_∥ + 2g_⊥. In an exploratory calculation a nonaxial center was simulated in an orthorhombic field, with calculation of the three principal values g_x, g_y and g_z. A good agreement is obtained for the recently reportedg values of an erbium center in silicon.     

Phase transformation of ZrO2 nanoparticles produced from zircon

This article focuses on the phase transformation of zirconia (ZrO₂) nanoparticles produced from zircon using a bottom-up approach. The influence of mechanical milling and thermal annealing on crystalline phase transformation of ZrO₂ nanoparticles was explored. It was found that the iron oxide, as an inherent impurity present in ZrO₂ nanoparticles, produced from zircon stabilises the cubic phase after calcination at 600°C. The stabilised cubic phase of ZrO₂ nanoparticles was disappeared and transformed into partial tetragonal and monoclinic phases after mechanical milling. The phase transformation occurred on account of the crystal defect induced by high-energy mechanical milling. The destabilisation of cubic phase into monoclinic phase was observed after the thermal annealing of ZrO₂ nanoparticles at 1000°C. The phase transitions observed are correlated to the exclusion of iron oxide from the zirconia crystal structure.     

Urchin-like CdS/ZrO2 nanocomposite prepared by microwave-assisted hydrothermal combined with ion-exchange and its multimode photocatalytic activity

A series of urchin-like CdS/ZrO₂ nanocomposites with different mole ratios of Cd/Zr were prepared by a two-step method combining the microwave-assisted hydrothermal and ion exchange methods. The products were characterized by X-ray diffraction, ultraviolet–visible diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, and N₂ adsorption–desorption measurements. The results of the study revealed that the CdS/ZrO₂ nanocomposites had mixed phases of tetragonal ZrO₂ and hexagonal CdS. Moreover, the samples prepared by the microwave-assisted hydrothermal method possessed the urchin-like structure with a surface composed of protrude-like nanoparticles in large quantities. The absorption in the visible region changed slightly with increasing mole ratio of Cd/Zr. Moreover, compared to the nanocomposites prepared by the conventional heating, the nanocomposites prepared by the microwave-assisted hydrothermal synthesis showed significantly different Brunauer–Emmett–Teller values, and the urchin-like CdS/ZrO₂ structures were obtained. The photocatalytic degradation of methyl orange under ultraviolet (UV) light irradiation indicated that the photocatalytic activity of the CdS/ZrO₂ nanocomposite with CdS/ZrO₂ molar ratio of 30 % was higher than those of CdS, ZrO₂, and other different ratios of CdS/ZrO₂ nanocomposites. Moreover, under UV light, visible light, and microwave-assisted multimode photocatalytic degradation, the urchin-like CdS/ZrO₂ nanocomposites significantly affected the photodegradation of various dyes. To understand the possible reaction mechanism of the photocatalysis by the CdS/ZrO₂ nanocomposites, a series of controlled experiments were performed, and the stability and reusability of the CdS/ZrO₂ nanocomposites were further investigated by the photocatalytic reaction.     

Sinterability of 8Y–ZrO2 powders hydrothermally synthesized at low temperature

Nanometric yttria (8 mol%)-stabilized zirconia powders were hydrothermally synthesized at 110 °C for 7 days in the presence of dilute (0.20 M) or concentrated (2.0 M) solutions of (KOH+K₂CO₃) mineralizer. Zirconia xerogel, crystalline Y(OH)₃, crystalline Y₂O₃ and a xerogel of coprecipitated (Y–Zr) hydroxide were used as starting materials. Setting the content of yttria constant and equal to 8 mol%, three types of mixtures were tested. Zirconia xerogel in mixture with crystalline Y₂O₃, zirconia xerogel in mixture with crystalline Y(OH)₃ and, finally, a xerogel of coprecipitated (Y–Zr) hydroxide were hydrothermally treated.The different characteristics of the resulting powders are discussed in terms of both the mineralizer concentration and the type of Y-based precursor used in the hydrothermal treatments, respectively.Weakly agglomerated cubic ZrO₂ powders with primary particles bigger in size and without any preliminary treatment show better performances when they are directly sintered at 1500 °C.     

Influence of Ba-substitution on the structural and ferroelectric properties of Pb1− x Ba x Zr0.40Ti0.60O3 ceramic materials

This work presents a comprehensive study about the influence of Ba-substitution on the structural and ferroelectric properties of Pb_1?x Ba _x Zr_0.40Ti_0.60O₃ (PBZT) ceramic system. Pb_1?x Ba _x Zr_0.40Ti_0.60O₃ ceramic samples were then prepared by solid state reaction method and characterized as a function of composition and temperature by X-ray diffraction (XRD) and impedance spectroscopy techniques. The dielectric measurements show that the substitution of Pb²⁺ for Ba²⁺ ions leads to a diffuse behavior of the dielectric permittivity curves for all samples and that only the x?=?0.50 sample presents a typical relaxor behavior. In good agreement with dielectric measurements, the structural phase transition study showed a phase transition from a tetragonal structure with P4mm space group to a cubic structure with Pm-3m space group for all samples, except for the x?=?0.50 sample were a cubic structure was observed in the complete temperature interval measured.     

Crystalline structural phase boundaries in (K,Na,Li)NbO 3 ceramics

Lead-free (K_xNa_1−x)_1−yLi_yNbO₃ ceramics (with x=0.50, y=0–0.08 and x=0.30–0.70, y=0.06, respectively) were synthesized using the conventional solid-state reaction technique. Compositional influences of K, Na and Li constituents on microstructures, crystalline structures, dielectric and piezoelectric properties were investigated. It has been known that microstructures change largely with the alkali constituents and that there exist three orthorhombic-tetragonal phase boundaries at room temperature. One occurs in (K_0.50Na_0.50)_1−yLi_yNbO₃ ceramics at y=0.05–0.06, which corresponds to the previously reported morphotropic phase boundary (MPB). The other two appear in (K_xNa_1−x)_0.94Li_0.06NbO₃ ceramics near x=0.40 and x=0.60, respectively. (K_0.50Na_0.50)_0.935Li_0.065NbO₃ and (K_0.45Na_0.55)_0.94Li_0.06NbO₃ ceramics show high piezoelectric properties with the d₃₃ values over 200 pC/N and the k_p values around 45% at room temperature. It is thought that the observed high piezoelectric properties are largely affected by the temperature-driven orthorhombic-tetragonal phase transition.     

Radiation-induced synthesis of ZrO2 nanoparticles by thermal decomposition of zirconium acetylacetonate

ZrO₂ nanoparticles were obtained by the thermal decomposition of un-irradiated and γ-irradiated zirconium acetylacetonate (ZrAcAc) precursors. Several influencing factors, including absorbed dose, calcination times, calcination temperatures and addition of surfactants, were thoroughly investigated. The results showed that the best conditions for the preparation of ZrO₂ nanoparticles were achieved by calcinations of ZrAcAc for 5 h at 600°C in the presence of 1 mL of benzyl alcohol as the surfactant. Different phases, morphologies and sizes for the as-prepared ZrO₂ nanoparticles were obtained by varying the dose of γ-ray absorbed. ZrO₂ nanoparticles obtained by thermal decomposition of un-irradiated ZrAcAc have mixture of monoclinic and tetragonal crystal systems, the particles are monodispersed with an irregular shape. In the case of γ-irradiated ZrAcAc with 10, 10² and 10³ KGy, ZrO₂ nanoparticles have only a tetragonal system with different morphologies depending on the γ-ray dose absorbed. Thermal stability of ZrO₂ nanoparticles was studied using thermogravimetric/differential thermal analyzer techniques. Thermodynamic and kinetic parameters were evaluated and discussed.     

Solvent and surfactant effect on the self-assembly and luminescence properties of ZrO2:Eu3+ nanoparticles

ZrO₂:Eu³⁺ nanocrystals ranging from 17 to 43 nm were prepared by the facile precipitation method with a hydrothermal process. The crystallite size was strongly influenced by the solvent composition and enhanced with the presence of surfactant. The use of ethanol combined with surfactant stabilizes 50 wt% of the monoclinic phase, while the use of water only results in 100 wt% tetragonal phase. 80% of nanobelts were obtained preparing the sample with ethanol and surfactant as a results of the self-assembly of nanoparticles. The photoluminescence emission peak centered at 606 nm dominates the emission band for nanobelts, while for nanoparticles it is dominated by a peak centered at 612 nm. Such differences were explained in terms of the site symmetry occupying Eu³⁺ in the host that in turn depends on the crystalline phase. Changes in the intensity ratio I(612 nm)/I(606 nm) is proposed as a tool to analyzing changes in the monoclinic/tetragonal phase composition. The calculated asymmetry ratio R=⁷F₂/⁷F₁～1.2 suggest a high degree of crystallinity of the prepared samples.