Strategies for low-temperature sintering of BST ceramics with attractive dielectric properties

In this study, the powders of the Ba_0.75Sr_0.25TiO₃ (BST) nanoparticles were directly synthesized by milling of Ba(OH)₂·8H₂O, Sr(OH)₂·8H₂O, and Ti(BuO)₄ in ethanol at room temperature. They have homogenous grains of?~?15 nm and high sintering activity. The dense ceramics with the density?>?90% can be obtained at a sintering temperature of?≤?950 °C by adding 3 wt% sintering aids of Bi₂O₃ and Li₂CO₃. Several Bi-related intermediate compounds act as perovskite-structured templates to sintering the ceramics at a different temperature. They enhance the mass transfer and promote the sintering densification. These compounds such as Ba₂BiO₄ and SrBiO₄ appear at 800 °C, LiBa₄Bi₃O₁₁ and Sr_1.2Bi_0.8O₃ appear over 830 °C, and Bi_8.11Ba_0.89O_13.05 appears at 950 °C. The cation Bi in them can have mixture valences of 3+ and 5+. It makes the ceramics as semiconducting state with the dark gray color and decreases the ceramic resistivities. With the sintering temperature increase, especially at 950 °C, the cation Bi tends back to single valence of +3 in the ceramics. The most of alkaline earth cations in Bi-related compounds will release and resorb into the lattice of BST and drive the sintering densification. The BST ceramics can have a peak dielectric constant?>?6500 (at 53 °C) with loss?<?0.025 at 10 kHz, and resistivity?>?10¹² Ω cm when sintered at a temperature of?≥?900 °C with 3 wt% sintering aids. They have a potential application for multiple layer ceramic capacitors (MLCC) with silver inner electrodes.

     

Electrochemical Behaviour of Ce0.9Gd0.1O2−δ SOFC‐Anodes

In order to compare the electrochemical performance of Ce_0.9Gd_0.1O_2−δ (CGO) in various fuels, impedance spectroscopy measurements were carried out in the atmospheres containing H₂, CO, CO₂, CH₄, N₂ at various compositions, in the temperature range 650°C to 850°C. Ohmic loss and polarization resistance were derived from impedance spectroscopy measurements. The stability at different temperatures of the anode was also investigated in 9%H₂/91%N₂ humidified with 3% H₂O. The microstructure of the anode before and after degradation test was analysed by SEM. These investigations indicated similarities in the impedance and the activation enthalpies in hydrogen/water, methane/water and CO/CO₂ atmospheres. No indications of methane cracking leading to carbon formation were found.     

Current–voltage nonlinear and dielectric properties of CaCu3Ti4O12 ceramics prepared by a simple thermal decomposition method

In this work, pure-CaCu₃Ti₄O₁₂ was successfully prepared by a simple thermal decomposition method. This can easily be achieved by direct firing of starting raw materials dissolved in an aqueous citric acid solution at 800 °C for 6 h. The results show that sintering conditions have a remarkable influence on the microstructure of the CaCu₃Ti₄O₁₂ ceramics. Interestingly, dense CaCu₃Ti₄O₁₂ ceramic sintered at 1,050 °C for 2 h exhibits a high dielectric constant of ~5.1 × 10³ with low loss tangent of ~0.048 at 30 °C and 1 kHz. The dielectric properties, electrical response of grain boundaries, and related nonlinear current–voltage behavior are found to be associated with the microstructure of CaCu₃Ti₄O₁₂ ceramics.     

Facile synthesis of Gd2O2SO4:Tb and Gd2O2S:Tb green phosphor nanopowders of unimodal size distribution and photoluminescence

Suppressing the crystallization and plate-like crystallite growth of RE₂(OH)₄SO₄·2H₂O compound by low-temperature (~4 °C) precipitation produced an amorphous RE₂(OH)_3.3(CO₃)_0.35SO₄·2H₂O precursor (RE = Gd_1-xTb_x) that can be decomposed to Gd₂O₂SO₄:Tb and Gd₂O₂S:Tb green phosphor nanopowders of unimodal size distributions upon calcination in air at 1000 °C (average particle size ~156.9 nm) and in hydrogen at 800 °C (average particle size ~130.2 nm), respectively. The optimal RE³⁺ concentration for precursor synthesis was determined to be ~0.10 mol/L. Through detailed characterization by XRD, FTIR, DTA/TG, FE-SEM, TEM and particle sizing, the courses of phase/morphology evolution were clarified. Photoluminescence study found that the (Gd_0.99Tb_0.01)₂O₂SO₄ and (Gd_0.98Tb_0.02)₂O₂S representative phosphors have quantum efficiencies of ~16.8% (λ_ex = 275 nm) and 38.5% (λ_ex = 286 nm), fluorescence lifetimes of ~3.70 and 1.75 ms and activation energies for thermal quenching of ~0.552 and 0.385 eV, respectively. The values are remarkably larger than those reported for Gd₂O₂S:Tb, which are considered to be due to higher purity, better crystallization and fewer luminescence-quenching defects of the product. Particularly, the (Gd_0.99Tb_0.01)₂O₂SO₄ phosphor has negative thermal quenching up to ~150 °C and can retain over 85% of its room temperature emission intensity at 250 °C, which may enlighten its application in high-power LEDs.     

X-ray photoelectron study on Ba0.5Sr0.5CoxFe1?xO3?δ (BSCF: x?=?0.2 and 0.8) ceramics annealed at different temperature and pO2

X-ray diffraction (XRD) and the X-ray photoelectron spectroscopy (XPS) were measured for the sintered BSCF ceramics (Ba_0.5Sr_0.5Co _x Fe_1−x O_3−δ, x = 0.2 and 0.8: BSCF5528 and BSCF5582, respectively), which were annealed at different temperatures (700 and 950 °C) and gases (O₂ and Ar). The unit cell of the annealed BSCF5528 at 950 °C under Ar expanded by 0.8%, while contracting by 0.45% under O₂. The cubic and rhombohedral phases coexist in the BSCF5582 annealed at 700 °C under O₂. The XPS peak areas of lattice oxygen (O²⁻) in O_1s , ~528 eV, and the shoulder peak of Co_2p /Ba_3d in BSCF5582 (~778 eV) increased significantly after being annealed in O₂. The areas of the peaks for BaCO₃ (87.9/90.2 eV) in Ba_4d preferentially were shown to decrease in Ar and increase in O₂.     

Sol–gel derived solid chiral materials and their optical activity

The chiral organic molecules glucose (C₆H₁₂O₆) and griseofulvin (C₁₇H₁₇ClO₆) were first uniformly incorporated in sol–gel derived materials. The polarity response, absorption spectra and thermal stability were measured and discussed. The DTA results indicated that the C₆H₁₂O₆ and C₁₇H₁₇ClO₆ in gels were stable in air at the temperature lower than 210 and 350 °C, respectively. An absorption band at about 1.4 μm due to OH⁻ existed in the infrared absorption spectra of the gels. The similar behaviors of optical activity for the organic chiral molecules in solutions were hold in solid gels. The specific rotations for C₆H₁₂O₆ and C₁₇H₁₇ClO₆ in gels were −0.95 and −1.45°/cm, corresponding to the chiral parameter 1.55 × 10⁻⁷ and 2.37 × 10⁻⁷, respectively.     

Thermal and dielectric properties of the LTCC composites based on the eutectic system BaO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript>–B<Subscript>2</Subscript>O<Subscript>3</Subscript>

The low-temperature co-fired ceramic (LTCC) composites containing quartz based on the eutectic system BaO–Al₂O₃–SiO₂–B₂O₃ are fabricated at the sintering temperature below 980 °C. Preparation process and sintering mechanism were described and discussed, respectively. The results indicated that the addition of quartz to the eutectic system can availably improve dielectric properties of the LTCC composites. In addition, The LTCC composites with optimum compositions, which were obtained by the regulation of an Al₂O₃ content in the composite, can express excellent dielectric properties (permittivity: 5.94, 5.48; loss: 7 × 10⁻⁴, 5 × 10⁻⁴), considerable CTE values (11.7 ppm. °C⁻¹, 10.6 ppm. °C⁻¹) and good mechanical properties (128 MPa,133 MPa).     

Nanocrystalline LaFeO3 preparation and thermal process of precursor

Nanocrystalline LaFeO₃ was synthesized by calcining precursor La₂(CO₃)₂(OH)₂–Fe₂O₃?1.5H₂O in air. XRD analysis showed that precursor dried at 80 °C was a mixture containing orthorhombic La₂(CO₃)₂(OH)₂ and amorphous Fe₂O₃?1.5H₂O. Orthorhombic LaFeO₃ with highly crystallization was obtained when La₂(CO₃)₂(OH)₂–Fe₂O₃?1.5H₂O was calcined at 900 °C in air for 2 h. Magnetic characterization indicated that the calcined product at 900 °C behaved weak magnetic behavior at room temperature. The thermal process of La₂(CO₃)₂(OH)₂–Fe₂O₃?1.5H₂O experienced five steps, which involves, at first, dehydration of 0.8 absorption water, then dehydration of 0.7 crystal water, decomposition of orthorhombic La₂(CO₃)₂(OH)₂ into orthorhombic LaCO₃OH, reaction of two LaCO₃OH into hexagonal La₂O₂CO₃ and crystallization of tetragonal Fe₂O₃, at last, reaction of hexagonal La₂O₂CO₃ with tetragonal Fe₂O₃ into orthorhombic LaFeO₃. In the DTG curve, four DTG peaks indicated the precursor experienced mass loss of four steps.     

Density and Volume Fraction of Supercritical CO<Subscript>2</Subscript> in Pores of Native and Oxidized Aerogels

The density and volume fraction of an adsorbed phase of carbon dioxide (CO₂) in aerogels was investigated using a formalism based on independent measurements of neutron transmission and small-angle neutron scattering from fluid-saturated absorbers (Rother et al. J. Phys. Chem. C 111, 15736 (2007)). The range of excess fluid pressures (0 <  P <  8 MPa) and temperatures (T = 35°C and 80°C) corresponded to the supercritical regime above the critical temperature T _C = 31.1°C and critical density ρ _C = 0.468 g · cm⁻³ of the bulk fluid. The results demonstrate that a porous aerogel matrix works to create an adsorbed phase with liquid-like fluid densities reaching ~1.1 g · cm⁻³ and ~0.8 g · cm⁻³ at T = 35°C and 80°C, respectively. Thus, despite the fact that the density and volume fraction of the adsorbed fluid both decrease with temperature, the dense adsorbed phase is still present in the aerogel at temperatures far exceeding the T _C. Heat treatment (“oxidation”) of the aerogel at 500°C for 2 h, which removes a significant fraction of the alkyl groups from the aerogel surface, has little effect on the adsorption properties. The observed reduction of the density and volume fraction of the adsorbed CO₂ with temperature and its minor dependence on the surface modification are consistent with predictions of the pore-filling model.     

A study on the synthesis of nanostructured WC–10 wt% Co particles from WO<Subscript>3</Subscript>, Co<Subscript>3</Subscript>O<Subscript>4</Subscript>, and graphite

The formation of the nanostructured WC–10 wt% Co powder from WO₃, Co₃O₄, and graphite is studied. The effects of the processing parameters of high-energy ball milling, reduction in H₂ atmosphere, and carburization in Ar/CO atmosphere are investigated. The crystallite size of the as-synthesized WC is 30–40 and 40–50 nm for 900 and 1000 °C carburized powders, respectively. The powder is agglomerated with the size of the primary particles ranging from 50 to 700 nm. High-energy ball milling of WO₃–Co₃O₄–C powder mixtures leads to finer particle and crystallite sizes with larger surface area. Such milled powders can be reduced to nanostructured W at 570 °C and carburized to form WC at temperatures as low as 900 °C. Crystal growth has taken place during carburization, particularly at 1000 °C, which results in the formation of truncated triangular prisms and nanoplates of WC at 1000 °C.     

Hydrothermal synthesis of Sr–Ce–Sn–Mn–O mixed oxidic/stannate pyrochlore and its catalytic performance for NO reduction

Mixed oxides and pyrochlore-type materials based on the Sr, Ce, Sn, and Mn elements have been prepared by hydrothermal method using a mixture of nitrate salts at 200 °C for 40 h under N₂ atmosphere. Two groups of solids were synthesized: (i) (Sr_xCe_1?x)₂Sn₂O_7±δ (0.345 ≤ x ≤ 0.365) and (ii) (Sr_xCe_1?x)₂(Sn_yMn_1?y)₂O_7±δ (0.345 ≤ x ≤ 0.365, 0.385 ≤ y ≤ 0.395). The structure of the solids were studied by X-ray diffraction and the main crystal phases determined were SnO₂, (SrCe)₂Sn₂O₇ and a trace amount of CeO₂ in group (i) and only SnO₂ and CeO₂ were detected in group (ii). The mixed oxides/stannate pyrochlore have been tested as catalyst for NO reduction with hydrocarbons (CH₄, C₂H₄, and C₃H₆) in the presence of O₂. The CeO₂ containing stannate Sr_2xCe_2?2xSn₂O_7±δ pyrochlore coexist with SnO₂ (group (i)) was found to be the best for NO + C₃H₆ reaction giving very high N₂ production at 350 °C in the presence of O₂ and water vapor. SnO₂ as well as CeO₂ alone were also synthesized by the hydrothermal method and their NO reduction properties have been compared with those of the groups (i) and (ii).     

Growth of ZnO thin films at low temperature by plasma-enhanced atomic layer deposition using H2O and O2 plasma oxidants

Zinc oxide (ZnO) thin films were grown at 70 °C by plasma-enhanced atomic layer deposition using H₂O and O₂ plasmas. Plasma oxidants were used in order to improve the ZnO crystallinity and optoelectronic properties, avoiding high-temperature synthesis. The deposition parameters were optimized to achieve saturation in each reaction step. X-ray photoelectron spectroscopy (XPS) reveals high purity of the obtained ZnO films. X-ray diffraction (XRD) measurements indicate that the grown layers are polycrystalline and that the H₂O plasma synthesis leads to better crystallinity than the O₂ plasma as inferred from the intensity of the (100) and (002) peaks. The films are with high optical transmission, ~90%, as inferred from UV–visible (UV–Vis) transmittance measurements, and optical band gaps of 3.22 and 3.23 eV for H₂O and O₂ plasma, respectively. Atomic force microscopy (AFM) indicates that the films are smooth, with an average roughness of ~?0.22 nm. The growth rate was found to be in the range of 1.2–1.4 Å/cycle. The XPS, XRD, UV–Vis, and AFM results prove the possibility to obtain high-quality ZnO films by O₂ and H₂O plasma processes at 70 °C with chemical, structural, and optical properties promising for flexible electronics. ZnO films were successfully deposited on polyethylene terephthalate substrates using the optimal conditions for H₂O plasma process. No damage of the film surface or substrate was observed.

     

A sol–gel-derived α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> crystal interlayer modified 316L porous stainless steel to support TiO<Subscript>2</Subscript>, SiO<Subscript>2</Subscript>, and TiO<Subscript>2</Subscript>–SiO<Subscript>2</Subscript> hybrid membranes

A homogeneous α-Al₂O₃ crystal membrane was fabricated by the sol–gel technique on 316L porous stainless steel (PSS) substrate with an average pore size of 1.0 μm. The preparation process was optimized by carefully choosing the binder, the concentrations of the casting solutions and the sintering temperatures of the membranes. Compared to methylcellulose and polyethylene glycol 20000, polyvinyl alcohol 1750 was found to be the most effective binder to fabricate a homogeneously structured Al₂O₃ membrane without defects. The concentration to prepare an uniform coverage membrane with a thickness of ~10 μm was 0.032 mol/L. When sintered at 1000 °C, γ-Al₂O₃ membrane with ~3 μm grains was obtained. When sintered at 1200 °C, γ-Al₂O₃ completely transformed into α-Al₂O₃ and the grains grew to ~5 μm. Accordingly, the process was applied to a bigger pore-sized PSS with an average pore size of 1.5 μm to fabricate an α-Al₂O₃ intermediate layer to initially modify its surface. A single α-Al₂O₃ crystal layer with a thickness of ~5 μm and an average pore size of 0.7 μm was achieved. Subsequently, TiO₂, SiO₂, and TiO₂–SiO₂ hybrid membranes were tried on the modified PSS. Defect-free microfiltration membranes with average pore sizes of ~0.3 μm were readily fabricated. The results indicate that the sol–gel method is promising to initially modify the PSS substrates and the sol–gel-derived α-Al₂O₃ crystal layer is an appropriate intermediate layer to modify the PSS and to support smaller grain-sized top membranes.     

Nanocrystalline LaMnO3 preparation and kinetics of crystallization process

Precursor of nanocrystalline LaMnO₃ was synthesized by solid-state reaction at low heat using La(NO₃)₃·6H₂O, MnSO₄·H₂O, and Na₂CO₃·10H₂O as raw materials. XRD analysis showed that precursor was a mixture containing orthorhombic La₂(CO₃)₃·8H₂O and rhombohedral MnCO₃. When the precursor was calcined at 800 ^°C for 2 h, pure phase LaMnO₃ with rhombohedral structure was obtained. Magnetic characterization indicated that rhombohedral LaMnO₃ behaved weak magnetic properties. The thermal process of the precursor experienced four steps, which involved the dehydration of crystallization water at first, and then decomposition of manganese carbonate into MnO₂, and decomposition of La₂(CO₃)₃ and MnO₂ together into La₂O₂CO₃ and Mn₂O₃, and lastly reaction of monoclinic La₂O₂CO₃ with Mn₂O₃ and formation of rhombohedral LaMnO₃. Based on the Kissinger equation, the value of the activation energy associated with the formation of rhombohedral LaMnO₃ was determined to be 260 kJ mol^?1. The value of the Avrami exponent, n, was equal to 1.68, which suggested that crystallization process of LaMnO₃ was the random nucleation and growth of nuclei reaction.     

Preparation of nano-sized ABi2Nb2O9 (A?=?Ca2+, Sr2+, Ba2+) ferroelectric ceramics by soluble Nb(V) tartarate precursor and their dielectric characteristics after sintering

ABi₂Nb₂O₉ (A = Ca²⁺, Sr²⁺, Ba²⁺) were prepared by using an aqueous solution method from the mixture of water-soluble M-EDTA (M = Ca²⁺, Sr²⁺, Ba²⁺), Bi-EDTA, Nb-tartarate and TEA as the starting materials. A black fluffy mass resulted on heating the solution mixture at ∼200 °C. X-ray powder diffraction (XRD) showed that a single phase with the layered perovskite structure was formed after calcining the black fluffy mass at 600 °C. No intermediate phase was found during heat treatment at and above 600 °C. The particle size obtained from TEM lay between 20 and 30 nm. Structural electron microscopy (SEM) revealed that the average grain size after sintering at 900 °C for 4 h ranges from 1.2 to 1.67 μm with a relative compact density of ≥90%. A comparative study on dielectric constant and corresponding tangent loss were carried out at 1 kHz, 100 kHz, 1 MHz, and 5 MHz from which the Curie temperature (T _c) was found to be at 935, 450, and 170 °C with peak dielectric constants at 930, 595, and 545, respectively, for CBN (CaBi₂Nb₂O₉), SBN (SrBi₂Nb₂O₉), and BBN (BaBi₂Nb₂O₉) measured at frequency 100 kHz with very low tangent loss.     

Low temperature preparation of the Zn<Subscript>2</Subscript>SiO<Subscript>4</Subscript> ceramics with the addition of BaO and B<Subscript>2</Subscript>O<Subscript>3</Subscript>

The Zn₂SiO₄ ceramics with the addition of BaO and B₂O₃ are fabricated by traditional solid-state preparation process at a sintering temperature of 900 °C. The introduction of BaO and B₂O₃ to the binary system ZnO-SiO₂ is achieved by adding 10 and 20 wt. % flux BB to the mixed ZnO-SiO₂ ceramic powders pre-sintered at 1,100 °C, respectively. The chemical composition of the flux BB (50 wt.%BaO-50 wt.% B₂O₃) is located at a liquid phase zone with a temperature range of about 869–900 °C in the binary diagram BaO-B₂O₃. In addition, the introduction of BaO and B₂O₃ to the binary system ZnO-SiO₂ is also achieved by the means of a chemical combination of H₂SiO₃, H₃BO₃, ZnO and Ba(OH)₂·8H₂O, which can result in the formation of the hydrated barium borates with low melting characteristics. In turn, by the liquid sintering aid of the barium borate melts, the preparation process of the Zn₂SiO₄ ceramics can be further simplified. In the two preparation methods, the Zn₂SiO₄ ceramics with the 1.5–2.0 ZnO/SiO₂ molar ratios and the addition of a 10 wt. % flux BB can show good dielectric properties whereas the bending strength mainly depends on the microstructure of the Zn₂SiO₄ ceramics and SiO₂ content in the composition of the specimen.     

Effect of ZrO2-doping of nanosized Fe2O3/MgO system on its structural,surface and catalytic properties

Fe₂O₃/MgO system was prepared by wet impregnation method followed by treatment with different amounts of Zr-dopant salt then heating at 500 and 700 °C. The dopant concentrations were 0.48, 0.95 and 1.4 mol% ZrO₂. Pure and variously doped solids were characterized using XRD, N₂-adsorption isotherms carried out at ?196 °C and catalytic decomposition of H₂O₂ in aqueous solution at 25–35 °C. The results revealed that the nanosized MgO phase was only detected in the diffractograms of pure and doped solids calcined at 500 °C. Heating pure and doped solids at 700 °C produced nanosized MgFe₂O₄ phase together with MgO phase. Pure and ZrO₂-doped solids calcined at 500 and 700 °C are mesoporous adsorbents. The doping process brought about a measurable decrease in the S_BET of Fe₂O₃/MgO system with subsequent increase in its catalytic activity. The catalytic activity of the investigated system toward H₂O₂ decomposition, expressed as reaction rate constant per unit surface area was found to increase as a function of dopant concentration. The maximum increase in the reaction rate constant per unit surface area measured for the reaction carried out at 30 °C attained 125% for the heavily doped samples. This significant increase was based on the catalytic activity of pure catalyst sample measured under the same conditions.     

Facile synthesis,phase transition,optical switching and oxidation resistance properties of belt-like VO2(A) and VO2(M) with a rectangular cross section

Belt-like VO₂(A) with a rectangular cross section (VA-RCS) was successfully synthesized using V₂O₅, H₂C₂O₄·2H₂O and H₂O as the starting materials by a facile hydrothermal approach. Some synthetic parameters, such as, the reaction time, reaction temperature and concentration of H₂C₂O₄·2H₂O, were systematically investigated to control the fabrication of belt-like VA-RCS. The formation mechanism of belt-like VA-RCS was proposed. Subsequently, belt-like VO₂(M) with a rectangular cross section (VM-RCS) was prepared by the irreversible transformation of VA-RCS at 700 °C for 2 h under the inert atmosphere. The phase transition temperature (T_c) of VA-RCS and VM-RCS was evaluated by DSC test. The optical switching properties of VA-RCS and VM-RCS were studied by the variable-temperature infrared spectra, and it was found that the as-obtained VA-RCS and VM-RCS could be used as the optical switching materials. Furthermore, the oxidation resistance properties of VA-RCS and VM-RCS were investigated by TGA, indicating that they have good thermal stability and oxidation resistance below 400 °C in air.     

A Robust Molecular Porous Material for C2H2/CO2 Separation

A molecular porous material, MPM-2, comprised of cationic [Ni₂(AlF₆)(pzH)₈(H₂O)₂] and anionic [Ni₂Al₂F₁₁(pzH)₈(H₂O)₂] complexes that generate a charge-assisted hydrogen-bonded network with pcu topology is reported. The packing in MPM-2 is sustained by multiple interionic hydrogen bonding interactions that afford ultramicroporous channels between dense layers of anionic units. MPM-2 is found to exhibit excellent stability in water (>1 year). Unlike most hydrogen-bonded organic frameworks which typically show poor stability in organic solvents, MPM-2 exhibited excellent stability with respect to various organic solvents for at least two days. MPM-2 is found to be permanently porous with gas sorption isotherms at 298 K revealing a strong affinity for C₂H₂ over CO₂ thanks to a high (ΔQ_st)_AC [Q_st (C₂H₂) − Q_st (CO₂)] of 13.7 kJ mol⁻¹ at low coverage. Dynamic column breakthrough experiments on MPM-2 demonstrated the separation of C₂H₂ from a 1:1 C₂H₂/CO₂ mixture at 298 K with effluent CO₂ purity of 99.995% and C₂H₂ purity of >95% after temperature-programmed desorption. C-H···F interactions between C₂H₂ molecules and F atoms of AlF₆³⁻ are found to enable high selectivity toward C₂H₂, as determined by density functional theory simulations.     

Quantitative investigation in the influence of oxalic impurities on photoluminescence properties of porous AAOs

Anodic alumina oxides (AAOs) prepared in oxalic acid (H₂C₂O₄) solution at a constant voltage of 40 V were investigated by the techniques of temperature programmed desorption combined mass spectrograph (TPD-MS), thermogravimetric analysis (TGA), differential thermal analysis (DTA) and photoluminescence (PL). The results indicate that the desorption of H₂O, CO and CO₂ and the decomposition of H₂C₂O₄ which led to the weight loss of AAOs samples occurred below 400 °C, while the water desorption was the main reason for weight loss. In the temperature range of 400–900 °C, a small quantity of aluminum oxalate (Al₂(C₂O₄)₃) decomposed and gave birth to CO and CO₂, during this process CO became the major product. The drastic decompositions of aluminum carbonate (Al₂(CO₃)₃) and Al₂(C₂O₄)₃ took place near 930 °C, which produced a large amount of CO₂. The amount of (C₂O₄)²⁻ embedded in bulk AAOs was calculated versus the total weight of AAOs film, and the PL intensity of AAOs was correlated to the doping of oxalic acid radical. The above results may have great significance in the better application of AAOs as matrix of photonic crystals.