Hardening behavior and highly enhanced mechanical quality factor in (K0.5Na0.5)NbO3–based ceramics

This paper relates the microstructure, crystallographic structure, ferroelectric, and piezoelectric properties of (K_0.5Na_0.5)NbO₃ (KNN) ceramics modified with 0.38 mol% K_5.4Cu_1.3Ta₁₀O₂₉ (KCT) and different amounts of CuO. Results revealed that the addition of KCT and CuO were effective in enhancing the sinterability of KNN. The internal bias field (E_ib) increased from 0.3 kV/mm to 0.58 kV/mm at 0.5 mol% CuO–added KNN+KCT ceramics. The increase of E_ib corresponds very well with the observed increase of the mechanical quality factor (Q_m) from 112 to 2665 for 0.5 mol% CuO. Besides, addition of 0.5 mol% CuO to KNN+KCT resulted in a large increase of the EPR signal, which is related to the increased amount Cu²⁺ and a corresponding increase of the concentration of defect dipoles. This result is in good agreement with the increased E_ib and the resulting hardening behavior.     

Mesoporous CuO/TixZr1 − xO2 catalysts for low-temperature CO oxidation

Mesoporous CuO/Ti_xZr_1 − xO₂ catalysts were prepared by a surfactant-assisted method, and characterized by N₂ adsorption/desorption, TEM, XPS, in-situ FTIR and H₂-TPR. The catalysts exhibited high specific surface area (S_BET = 241 m²/g) and uniform pore size distribution. XPS and in-situ FTIR displayed that Cu⁺ and Cu²⁺ species coexisted in the catalysts. The CuO/Ti_xZr_1 − xO₂ catalysts presented obviously higher activity in CO oxidation reaction than the CuO/TiO₂ and CuO/ZrO₂ catalysts. Effect of molar ratios of Ti to Zr and calcination temperature on catalytic activity was investigated. The CuO/Ti_0.6Zr_0.4O₂ catalyst calcined at 400 °C exhibited excellent activity with 100% CO conversion at 140 °C.     

Investigations on electrical characteristics of (PbO)30(CuO)x(As2O3)(70-x) glass ceramics

This study is mainly focused on dielectric properties of lead arsenate glasses crystallized with different concentrations of CuO over continuous ranges of frequency (3 Hz −100 kHz) and temperature (300–633 K). The glasses were prepared by melt quenching technique and were heat treated for prolonged time for ceramization. Prepared samples were characterized by XRD, SEM and DSC techniques. SEM studies indicated that the samples are composed of small crystal grains of the size varying from 0.2 to 1.0 µm cemented with the residual glass phase. XRD studies indicated CuAs₂O₄, Pb₂Cu₇(AsO₄)₆ and Cu₂O are the main crystal phases developed during the crystallization. Optical absorption studies confirmed the presence of copper ions in Cu⁺ valence state in addition to Cu²⁺ state and the fraction of Cu⁺ ions is found to increase with the content of CuO. The optical band gap exhibited increasing trend with CuO content. IR spectral studies indicated an increase of degree of polymerization of the glass network with the CuO content. The observed variations of dielectric parameters with frequency, temperature and CuO content are discussed using different polarization mechanisms. The dielectric relaxation effects exhibited by the loss tangent and the electric moduli are analyzed using graphical method and observed relaxation effects are attributed to the complexes of divalent copper ions with oxygens. The impedance diagrams indicated increase of bulk resistance of the samples with increase of CuO content. The ac conductivity exhibited a decreasing trend with increase of CuO content. The conduction phenomenon is explained using polaron hopping between Cu⁺ and Cu²⁺ ions. The temperature independent part of the conductivity is explained using quantum mechanical tunneling (QMT) model. Finally, it is concluded that the insulating strength of the material increased with CuO content and such materials may be useful as electrical insulators in the low temperature region     

Development of solid oxide cells by co-sintering of GDC diffusion barriers with LSCF air electrode

The effects of a Cu-based additive and nano-Gd-doped ceria (GDC) sol on the sintering temperature for the construction of solid oxide cells (SOCs) were investigated. A GDC buffer layer with 0.25–2 mol% CuO as a sintering aid was prepared by reacting GDC powder and a CuN₂O₆ solution, followed by heating at 600 °C. The sintering of the CuO-added GDC powder was optimized by investigating linear shrinkage, microstructure, grain size, ionic conductivity, and activation energy at temperatures ranging from 1000 to 1400 °C. The sintering temperature of the CuO–GDC buffer layer was decreased from 1400 °C to 1100 °C by adding the CuO sintering aid at levels exceeding 0.25 mol%. The ionic conductivity of the CuO–GDC electrolyte was maximized at 0.5 mol% CuO. However, the addition of CuO did not significantly affect the activation energy of the GDC buffer layer. Buffer layers with CuO-added GDC or nano-GDC sol-infiltrated GDC were fabricated and tested in co-sintering (1050 °C, air) with La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ (LSCF). In addition, SOC tests were performed using button cells (active area: 1 cm²) and five-cell (active area: 30 cm²/cell) stacks. The button cell exhibited the maximum power density of 0.89 W cm⁻² in solid oxide fuel cell (SOFC) mode. The stack demonstrated more than 1000 h of operation stability in solid oxide electrolysis cell (SOEC) mode (decay rate: 0.004%/kh).     

Stability of the δ-TeO2 phase in the binary and ternary TeO2 glasses

The stability of δ-TeO₂ phase was studied in binary TeO₂–WO₃, TeO₂–CdO and ternary TeO₂–WO₃–CdO glasses. The samples were prepared by heating high purity powder mixtures of TeO₂, WO₃ and/or CdO to 800 °C in a platinum crucible with a closed lid, holding for 30 min and quenching in water bath. Differential thermal analysis (DTA), X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques were used to characterize the thermal, phase and microstructural properties of the δ-TeO₂ phase. The addition of CdO into the tellurite glasses increased the stability range of the δ-TeO₂ phase up to higher temperature values and expanded the compositional δ-TeO₂ formation range. The formation of δ-TeO₂ phase in the binary systems was observed for samples containing 5–10 mol% WO₃ and 5–15 mol% CdO. However, for the ternary TeO₂–WO₃–CdO system the formation of δ-TeO₂ phase was determined in a wider compositional range.     

Effect of CuO addition on magnetic and electrical properties of Sr2Bi4Ti5O18 lead-free ferroelectric ceramics

The effect of CuO addition on magnetic and electrical properties of Sr₂Bi₄Ti₅O₁₈ (SBT) lead-free bismuth layered structure ferroelectric ceramics have been studied and reported. Interestingly, the prepared samples exhibit multiferroic behavior with the coexistence of magnetic and ferroelectric phase transition temperature. Magnetic phase transition with Neel׳s temperature (T_N) of 657 K is observed at 0.75 mol% of CuO added SBT ceramics, which is higher than the well known multiferroic BiFeO₃ (643 K) and the ferroelectric phase transition with Curie temperature (T_C) of 587 K is observed at 1 mol% of CuO added SBT ceramics, which is relatively higher than the reported pure SBT ceramics (558 K). Further, the electrical properties such as dielectric, ferroelectric, piezoelectric, leakage current density characteristics and optical properties were investigated as a function of x (x=0, 0.25, 0.5, 0.75 and 1 mol%). Presence of strong magnetic super-exchange interactions in CuO and the creation of oxygen vacancies play a vital role in the enhancement of magnetic and electrical properties of CuO doped SBT ceramics. Moreover, the present results indicate that, small amount (0.25 mol%) of CuO addition in SBT ceramics enhances the electrical properties significantly and vice versa, large amount (0.75 mol%) of CuO addition enhances the magnetic properties. Thus, the presence of magneto-electric coupling effect was observed in CuO doped Sr₂Bi₄Ti₅O₁₈ ferroelectric ceramics.     

Optical and electrical studies of borosilicate glass containing vanadium and cobalt ions for smart windows applications

Borosilicate glass with different concentrations of vanadium and cobalt of the composition (mol%) 40 Na₂B₄O₇- 40 SiO₂- (20–x) V₂O₅- x Co₂O_3, with x=0, 1, 3 and 5 mol% were prepared by melt quenching technique at 1373 K and investigated by X-ray diffraction (XRD) and FTIR spectroscopy. Optical properties of the obtained borosilicate glasses in the UV–vis range were also investigated. Urbach theory has been used to analyze the optical data. The dc electrical conductivity was investigated for all samples in the temperature range from 298 K to 700 K. The ac electrical conductivity was measured in the frequency range from 50 Hz to 2 MHz from 298 to 523 K. Guntini's theory has been used to analyze the electrical data. It was found that Urbach energy decreases with the increase of vanadium content, the sample with x=0 shows the highest absorption in the visible and IR region and an electrical conductivity in the order of 10⁻² Scm⁻¹. The frequency exponent was calculated. A semiconducting behavior has been assessed for the studied glasses. The sample with x=0 has the highest IR absorption, the highest conductivity, at 323 K at different frequencies, and the lowest activation energy; these features are promising for smart windows applications.     

Tin–Zinc oxide composite ceramics for selective CO sensing

Composite metal oxide gas sensors were intensely studied over the past years having superior performance over their individual oxide components in detecting hazardous gases. A series of pellets with variable amounts of SnO₂ (0–50 mol%) was prepared using wet homogenization of the component oxides leading to the composite tin-zinc ceramic system formation. The annealing temperature was set to 1100 °C. The samples containing 2.5 mol% SnO₂ and 50 mol% SnO₂ were annealed also at 1300 °C, in order to observe/to investigate the influence of the sintering behaviour on CO detection. The sensor materials were morphologically characterized by scanning electron microscopy (SEM). The increase in the SnO₂ amount in the composite ceramic system leads to higher sample porosity and an improved sensitivity to CO. It was found that SnO₂ (50 mol%) - ZnO (50 mol%) sample exhibits excellent sensing response, at a working temperature of 500 °C, for 5 ppm of CO, with a fast response time of approximately 60 s and an average recovery time of 15 min. Sensor selectivity was tested using cross-response to CO, methane and propane. The results indicated that the SnO₂ (50 mol%)-ZnO (50 mol%) ceramic compound may be used for selective CO sensing applications.     

Sintering and cooling atmosphere effects on the microstructure,magnetic properties and DC superposition behavior of NiCuZn ferrites

This study investigated the sintering and cooling atmosphere effects on the microstructure and magnetic properties of NiCuZn ferrites. The copper-rich phase segregated during sintering near the grain boundaries. The sample sintered in N₂ and cooled in air (N₂-Air) exhibited the highest amount of segregated copper-rich second phase, followed by the sample sintered and cooled both in air (Air-Air). However, no precipitate was observed for the sample sintered and cooled both in N₂ (N₂-N₂). This can be explained by the fact that Cu²⁺ was reduced into Cu⁺, promoting Cu₂O phase precipitation and then reacting with CuO to form a liquid phase. The Air-Air sample exhibited the highest initial permeability (μ_i ≈ 250) and saturation magnetization (B_s ≈ 88 emu/g), followed by N₂-N₂ (μ_i ≈ 180, B_s ≈ 82) and N₂-Air (μ_i ≈ 150, B_s ≈ 80). The highest DC superposition behavior was obtained for N₂-Air sample due to the highest nonmagnetic copper-rich precipitate thickness at the grain boundaries.     

Photocatalytic hydrogen production from methanol aqueous solution under visible-light using Cu/S–TiO2 prepared by electroless plating method

Cu was loaded on the S-doped TiO₂ by electroless plating method. The prepared Cu/S–TiO₂ exhibited high photocatalytic activity for hydrogen generation, and the yield is up to 7.5 mmol h^− 1 g^− 1cat in methanol solution. Their physical structure and chemical properties were characterized by UV–Vis, XRD, XPS and EXAFS. The copper species were CuO and Cu₂O, and the sample showed excellent visible light absorption ability. Comparing with the sample prepared by chemical reducing method, the electroless plated copper on S–TiO₂ was highly dispersed, which could facilitate photo-generated charges capture, transfer and separation.     

Thermal conversion synthesis of Cu2O photocathode and the promoting effects of carbon coating

Simplifying the synthesis of cuprous oxide (Cu₂O) photocathode has turned out to be critical for scalable application. Herein, we present a novel thermal conversion approach to synthesize a shell/core structured Cu₂O/Cu photocathode. In this method a shell comprising a mixture of CuO and Cu₂O is obtained by heating Cu mesh at 500 °C in air beforehand, and subsequent annealing in N₂ atmosphere converts the unwanted CuO into Cu₂O gradually, which results in the desired Cu₂O/Cu structure. A slightly viscous starch sol coats the Cu₂O shell as carbon source, after carbonizing under N₂ atmosphere, the Cu₂O/Cu is covered with compact carbon films, i.e. C/Cu₂O/Cu. Photoelectrochemical experiments reveal that the introduction of carbon layers on Cu₂O enhances the photocurrent density from − 1.5 to − 2.75 mA·cm^− 2 at 0 V vs. reversible hydrogen electrode (RHE). Moreover, the deposition of carbon films on Cu₂O in this work has little effect on improving the stability.     

Porous acicular mullite ceramics fabricated with in situ formed soot oxidation catalyst obtained from waste MoSi2

Porous acicular mullite (3Al₂O₃·2SiO₂) ceramics containing Cu₃Mo₂O₉ as a soot oxidation catalyst was fabricated by a novel approach using commercial powders of Al₂O₃ and CuO, and powder obtained by controlled oxidation of ground waste MoSi₂. The obtained material consisted of elongated mullite grains which are known to be effective in carbon soot removal from diesel engine exhaust. The presence of in situ created Cu₃Mo₂O₉ was found to catalyze the carbon burnout which is an extremely important feature when it comes to filter regeneration, i.e., the captured soot removal. The carbon burnout temperature in the sample containing 12 wt% CuO was by 90 °C lower than that in the sample without CuO. Effect of sintering temperature as well as the effect of amount of CuO additive on mullite properties were studied. It was found that the increase in amount of CuO in samples sintered at 1300 °C decreased porosity and increased compressive strength of the porous mullite ceramics. The addition of 12 wt% CuO increased the strength of the porous mullite ceramics up to 70 MPa, whereas the porosity was reduced from 62% in the mullite without CuO to 44% in the mullite ceramics containing 12 wt% CuO. Although affected by the amount of CuO, the microstructure still consisted of elongated mullite grains.     

Effect of sintering atmospheres on the densification behavior of CuO ceramics

In this study, the effect of oxygen partial pressure on the densification and the resultant microstructure change of CuO were examined. When CuO green bodies were heated up to 1100 °C for sintering in air, denser CuO samples were obtained than the samples sintered in oxygen. When the samples were kept at 1100 °C for a prolonged period of time, however, the densification of the sample in oxygen was accelerated whereas that of the sample in air was hindered. This is attributed to the phase transformation from CuO to Cu₂O which accompanies oxygen release during sintering in air. On the basis of the results, dense CuO samples could be obtained by switching the sintering atmosphere from air to oxygen at the suitable stage so that oxygen release by reduction could be suppressed.     

Luminescence and structural properties of Gd2SiO5:Eu3+ phosphors synthesized from the modified solid state method

This paper reports the preparation of Eu³⁺ doped Gadolinium oxyorthosilicate (Gd₂SiO₅:Eu³⁺) phosphor with different concentration of Eu³⁺(0.1–2.5 mol%) using the modified solid state reaction method. The synthesis procedure of the Gd₂SiO₅:Eu³⁺phosphor using inorganic materials such as Gd₂O₃, silicon dioxide (SiO₂), europium oxide (Eu₂O₃) and boric acid (H₃BO₃) as flux is discussed in detail. The prepared phosphor samples were characterized by using X-Ray Diffraction (XRD), Field Emission Gun Scanning Electron Microscopy (FEGSEM), Transmission Electron Microscopy (TEM), Fourier Transform Infrared Spectroscopy (FTIR), Photoluminescence (PL) and Thermoluminescence (TL). The Commission Internationale de l′Eclairage(CIE) coordinates were also calculated. The PL emission was observed in the 350–630 nm range for the Gd₂SiO₅:Eu³⁺ phosphor. PL excitation peaks were observed at 266, 275, 312 and 395 nm while the emission peaks were observed at 380, 416, 437, 545, 579, 589, 607, 615 and 628 nm. The emission peak at 615 nm was the most intense peak for all the different Eu³⁺ concentration samples. From the XRD data, using the Scherrer's formula, the average crystallite size of the Gd₂SiO₅:Eu³⁺ phosphor was calculated to be 33 nm. TL was carried out for the phosphor after both UV and gamma irradiation. The TL response of the Gd₂SiO₅:Eu³⁺ phosphor for the two different radiations was compared and studied in detail. It was found that the present phosphor can acts as a single host for red emission (1.5 mol%) for display devices and light emitting diode (LED) and white light emission for Eu³⁺(0.1 mol%) and it might be used as a TL dosimetric material for gamma dose detection.     

Effect of excess lead on the structural and electrical characteristics of sol-gel synthesized RuO2/Pb(ZrxTi1−x)O3/RuO2

In this study, we investigated the effect of excess lead on the structural and electrical characteristics of lead zirconate titanate [Pb(Zr_xTi_1−x)O₃, PZT] thin films using the sol-gel spin coating method. X-ray diffraction, atomic force microscopy, X-ray photoelectron spectroscopy, and field-emission transmission electron microscopy were used to study the structural, morphological, chemical, and microstructural features, respectively, of these films as functions of the growth conditions (excess lead concentrations of 10, 20, and 25 mol%). The PZT thin film prepared at the 20 mol% condition exhibited the best electrical characteristics including a lower leakage current of 6×10⁻⁷ A/cm² at an electric field of 50 kV/cm, a larger capacitance value of 1.92 μF/cm² at a frequency of 1 kHz, and a higher remanent polarization of 20.1 μC/cm² at a frequency of 5 kHz. We attribute this behavior to the optimal amount of excess lead in this PZT film forming a perovskite structure and suppressing the reaction of PZT film with RuO₂ electrode.     

Green sonochemical synthesis of cupric and cuprous oxides nanoparticles and their optical properties

Nanoparticles of cupric oxide (CuO) and cuprous oxide (Cu₂O) with various morphologies were synthesized by a green sonochemical process without any surfactants and templates. The Cu₂O nanoparticles with the truncated cubic, cubic octahedral and octahedral morphologies were prepared via the deoxidation of the CuO nanoparticles. The Cu₂O and CuO samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and ultraviolet visible absorption spectroscopy (UV–vis). The experimental results indicate that the molar ratio of sodium hydroxide to copper sulfate affects the morphology and size of the CuO and Cu₂O nanoparticles produced by the sonication. The band gap energy of CuO nanoparticles was 1.45–1.75 eV, the morphology had a great effect on the optical properties of CuO. The Cu₂O nanoparticles had broad emission peaks at the visible region, and the band gap energy was estimated to be 1.95–2.09 eV. The growth mechanisms of the CuO and Cu₂O nanoparticles are discussed.     

The effect of Er3+ doping on the structure and thermoelectric properties of CdO ceramics

The effect of Er³⁺ doping on the structure and thermoelectric transport properties of CdO ceramics was investigated. The solubility limit of Er³⁺ in CdO was very small and that additions of more than about 0.5 at% Er³⁺ resulted in the presence of Er₂O₃. With the addition of Er³⁺, the average grain size of Cd_1?xEr_xO (0 ≤ x ≤ 0.015) decreased and the carrier concentration as well as mobility increased at room temperature. A small amount of Er³⁺ doping resulted in a marked increase of electric conductivity and a moderate decrease of Seebeck coefficient. Although Er³⁺ doping also leaded to an increase in thermal conductivity, a large ZT of 0.2 was achieved in x = 0.005 sample at 723 K due to the obvious improvement of power factor. The results demonstrate that CdO:Er is a new promising n-type thermoelectric material.     

Impact of Sr-doping on structural and electrical properties of Pb(Zr0.52Ti0.48)O3 thin films on RuO2 electrodes

In this paper, we investigated the impact of Sr-doping on the structural properties and electrical characteristics of lead zirconate titanate [Pb(Zr_0.52Ti_0.48)O₃, PZT] thin films deposited on RuO₂ electrodes by a sol-gel process and spin-coating technique. We used X-ray diffraction, atomic force microscopy, X-ray photoelectron spectroscopy, and field-emission transmission electron microscopy to explore the structural, morphological, chemical, and microstructural features, respectively, of these films as a function of the growth condition (strontium doping concentrations varied from 1, 3, and 5 mol%). The PZT thin film processed at the 3 mol% Sr exhibited the best electrical characteristics, including a low leakage current of 2.27×10⁻⁷ A/cm² at an electric field of 50 kV/cm, a large capacitance value of 2.74 μF/cm² at a frequency of 10 kHz, and a high remanent polarization of 37.95 μC/cm² at a frequency of 5 kHz. We attribute this behavior to the optimal amount of strontium in the PZT film forming a perovskite structure and a thicker interfacial layer at the PSZT film-RuO₂ electrode interface.     

Warm with high color rendering index white light from hybridization of Ca2BO3Cl:Eu2+ yellow phosphor and CdSe/ZnS nanocrystals

Yellow emitting Ca₂BO₃Cl:Eu²⁺ phosphor was prepared by solid state reaction at 900 °C. The particle was monoclinic crystal structure, and showed broad band emission at around 540–590 nm due to the 5d–4f transition. Single Ca₂BO₃Cl:Eu²⁺ phosphor converted white LED exhibited the CIE coordinates of (0.3441, 0.2675) with low CRI of 67.4. Hybridization of Ca₂BO₃Cl:Eu²⁺ with 535 and 610 nm emitting CdSe/ZnS nanocrystals contributed to increasing white spectrum and generated the warm color temperature (4055 K) with high CRI (83.9) of white light. The acceptable color stability was also observed from (0.3687, 0.3051) at 20 mA to (0.3645, 0.3101) at 80 mA.     

Melt synthesis of Eu-doped oxide phosphors using arc-imaging furnace

To synthesize various complex oxide materials and their solid solutions, we applied a novel “melt-synthesis technique” rather than conventional solid-state reaction techniques. Rapid synthesis methods to develop those double oxides have been strongly anticipated. During melt synthesis, the mixture of oxides or their precursors is melted rapidly (1–60 s) in an arc-imaging furnace using strong light radiation. A spherical molten sample with multiple homogeneously mixed cations was solidified directly on a copper hearth with rapid cooling of ca. 10² °C/s.We studied the synthesis of A₂BO₄ type double oxides (AA′)₂BO₄ (A = Sr²⁺, Ca²⁺, A′ = La³⁺, Gd³⁺, Y³⁺, Eu³⁺, B = Al) using this method. Homogeneous samples with Eu³⁺ dopants were synthesized using liquid phase mixing in a few seconds, which is much faster than diffusions of ions in solid phase. Red fluorescence under the irradiation of ultraviolet light (254 and 365 nm) was observed. The excitation band shifted.