Enhanced piezoelectric performance of donor La3+-doped BiFeO3–BaTiO3 lead-free piezoceramics

Lead-free 0.70Bi_1.03FeO₃-0.30Ba_(1-x)La_xTiO₃ piezoelectric ceramics (with x = 0.000, 0.005, 0.010, 0.015 and 0.035 abbreviated as 0.0BaLa, 0.5BaLa, 1.0BaLa, 1.5BaLa and 3.5BaLa) were prepared through the conventional solid-state reaction route followed by water quenching process. The X-ray diffraction profile shows that the substitution of Ba²⁺ = 1.61 Å with a donor ion, La³⁺ = 1.36 Å, has a profound impact on the crystal symmetry as results the crystal structure transform from dominant rhombohedral (R) to tetragonal (T) phase. A large remnant polarization (P_r = 30.3 μC/cm²) and an enhanced direct piezoelectric coefficient, (d₃₃ = 297 pC/N) together with a high Curie temperature (T_C = 530 °C) was obtained near to the morphotropic phase boundary (MPB) of the R and T phases. A maximum strain of (S_max = 0.188%) with corresponding converse piezoelectric coefficient (d₃₃* = 340 pm/V) and low strain hysteresis (≈20%) was found for 1.5BaLa ceramic. Additionally, the water quenching effect was more prominent for 1.0BaLa ceramic as observed from the high thermal hysteresis in heating/cooling results of the dielectric constant (ε_r), leading to the enhancement of ferroelectric switching behavior. Hence, a small amount of La³⁺-substitution for Ba²⁺-site is more effective for the enhancement of ferroelectric and piezoelectric properties, similarly to the donor La³⁺-doped Pb(Zr,Ti)O₃ ceramic.     

Study of Eu3+–Gd3+ co-doped Ba–Bi–B glasses for red-laser applications: Physical,structural, photoluminescence and time-resolved spectral characteristics

A series of Eu³⁺ and Eu³⁺/Gd³⁺ co-doped barium-bismuth-borate (Ba–Bi–B) glasses were prepared by melt-quench technique. And deliberated the physical, structural, and spectroscopic properties of all glasses and explored the energy transfer process from Gd³⁺ to Eu³⁺ ions. The density of glasses increased with increasing of Gd³⁺ concentration in co-doped glasses. Characteristics of steady-state and time-resolved photoluminescence (PL) of Eu-doped and Eu³⁺-Gd³⁺ co-doped glasses under different excitation wavelengths suggested the prospects of the investigated glass system for display device applications. PL spectrum displays a strong red emission peak centered at 612 nm due to the Eu³⁺: ⁵D₀→ ⁷F₂ transition. Less intense emissions centered at 577 nm (⁷F₀), 590 nm (⁷F₁), 651 nm (⁷F₃) and 700 nm (⁷F₄) are also observed from the radiative transitions of the excited state ⁵D₀ of Eu³⁺ions. The values of radiative parameters such as transition probability, branching ratios, and stimulated emission cross-sections were obtained from Judd–Ofelt theory analysis and indicated the aptness of the Ba–Bi–B glasses for optical devices. A 5-fold enhancement in the PL intensity was observed in 1.0 mol% Eu³⁺ and 3.0 mol% Gd³⁺ co-doped glass under λ_Exci. = 394 nm excitation. The calculated commission Internationale de l'eclairage color coordinates and correlated color temperature values show that the Ba–Bi–B glasses are useful for red-laser and display device applications.     

Structural,luminescence and NMR studies on Nd3+-doped sodium–calcium-borate glasses for lasing applications

In this work, Neodymium (Nd³⁺) -doped borate glasses were synthesised by melt-quenching method and their structural as well as optical properties were analysed through XRD, Raman, NMR, DSC, UV–Visible, luminescence and decay studies for the possible application as laser gain medium. DSC and XRD results revealed that the glasses have high transition temperature and are in amorphous nature, respectively. The vibrational characteristics of the host matrices as well as the effect of Nd³⁺ incorporation were analysed by using Raman spectra, which exhibit majorly borate groups as supported by NMR results. The band gap energy of the glasses decreases with an increase in Nd³⁺ concentration. Using Judd-Oflet theory the characteristic intensity parameters (Ω_λ, λ = 2, 4 and 6) were calculated and further used for calculating the various radiative parameters from the emission spectra. The emission cross-section (σ_em) was estimated as high as 1.15 × 10⁻²⁰ cm² from the Füchtbauer–Landenburg (FL) equation for the dominant ⁴F_3/2→⁴I_11/2 (1056 nm) transition. The effect of Nd³⁺ concentration on the lifetime of the ⁴F_3/2 luminescent level was analysed from the decay curve analyses. From which, the corresponding quantum efficiency (η) was estimated and found as high as 54%. The investigated result suggests the prepared glasses can be utilized as gain medium to generate laser at around 1.05 μm.     

1.53 µm luminescence properties of Er3+-doped K–Sr–Al phosphate glasses

Trivalent erbium (Er³⁺)-doped K–Sr–Al phosphate glasses were prepared and studied their spectroscopic properties as a function of Er₂O₃ concentration. Judd–Ofelt analysis has been carried out for 1.0 mol% Er₂O₃-doped phosphate glass and in turn radiative properties have been evaluated for the excited levels of Er³⁺ ion. The radiative lifetime for the ⁴I_13/2 level was found to be higher for the present glass when compared to other Er³⁺-doped glasses. The Er³⁺-doped glasses exhibit intense near infrared emission at 1.53 µm corresponds to ⁴I_13/2→⁴I_15/2 transition as well as green emission at 546 nm corresponding to ⁴S_3/2→⁴I_15/2 under 980 nm and 488 nm excitations, respectively. The emission cross-section spectrum for 1.0 mol% of Er₂O₃-doped glass has been evaluated using McCumber theory. The gain cross-section has been evaluated as a function of population inversion, which revealed that the lasing action would be achieved at 1.53 µm for a population inversion about 40%. Decay curves for the ⁴I_13/2 level were measured and lifetimes have been determined for the studied glasses. The results indicate that the present glasses could be useful for laser as well as optical amplifiers at 1.53 µm.     

Radiation response properties of Eu3+-doped K2O–Ta2O5–Ga2O3 glasses

Eu₂O₃-doped 40K₂O–20Ta₂O₅–40Ga₂O₃ gallate glasses were synthesized, and their radiation response characteristics were studied systematically. According to their photoluminescence spectra, they showed intense emissions with sharp peaks centered at around 580, 594, 613, 656, and 706 nm when irradiated by 380 nm light. The sharp peaks originate from the 4f-4f transitions of Eu³⁺. Moreover, these sharp peaks were also detected when excited by X-ray, and the 1.0% Eu₂O₃-doped gallate glasses showed the largest luminescence intensity under UV light and X-ray. Furthermore, the afterglow levels of the Eu₂O₃-doped 40K₂O–20Ta₂O₅–40Ga₂O₃ gallate glasses were determined to be approximately 300 ppm. These levels are close to the levels of TI-doped CsI single crystals.     

Enhanced dielectric energy storage performance of A-site Ca2+-doped Na0.5Bi0.5TiO3–BaTiO3–BiFeO3 Pb-free ceramics

(1-x) (0.98Na_0.5Bi_0.5TiO₃–0.01BaTiO₃–0.01BiFeO₃)–xCaTiO₃ (NBB-xCT) ceramics were produced using traditional solid-state synthesis methods. The surface morphology, domain structure, and electrical properties of the ceramic samples were systematically studied. In addition, the temperature and frequency stabilities of the NBB-15CT sample at 200 kV/cm were tested. Generally, NBB-xCT ceramics exhibit a typical single perovskite phase structure. The results indicate that the NBB-15CT ceramics showed a high energy density of 3.14 J/cm³ at 250 kV/cm. The piezoresponse force microscopy (PFM) results showed that the addition of CT broke the macrodomains of the 0.98Na_0.5Bi_0.5TiO₃-0.01BaTiO₃-0.01BiFeO₃ ceramic and helped to form nanodomains, leading to an improved energy storage performance. The above performance indicates that the specimens possess very good temperature-and frequency-dependent energy storage performances at 30–150 °C and 1–100 Hz. Moreover, the electric energy storage and release in the NBB-15CT ceramic indicated that the power density could reach 55.30 MV/cm³ at 180 kV/cm. Therefore, the NBB-15CT ceramic is a promising material for electrical capacitors.     

Effect of Mg2+ and fluorine on the network and highly efficient photoluminescence of Eu3+ ion in MgF2–BaO–B2O3 glasses

The glass structure and photoluminescence of new oxyfluoride glasses with the composition of xMgF₂–(66.7−2x/3)BaO–(33.3−x/3)B₂O₃ (x = 10-50 mol%) were investigated in this work. The structure of the glasses was investigated by magic-angle spinning NMR, XAS, and Raman scattering spectroscopies. It was revealed that the glasses are mainly composed of BO₃ units with a disconnected borate network consisting mainly of ortho- and pyro-borate units, and ortho-borate increases with the addition of MgF₂. The fluorine atoms are surrounded by Mg²⁺ and Ba²⁺ ions. The photoluminescence of Eu³⁺-doped samples were investigated. It was indicated that asymmetry of the Eu³⁺ site increased with the addition of MgF₂. The photoluminescence quantum yield (η) of the glasses are very high and increased with MgF₂ addition; red photoluminescence is observed with η = 82% for 10MgF₂ and η = 98% for 50MgF₂ for excitation at 393 nm.     

Tunable photoluminescence properties of Pr3+/Er3+-doped 0.93Bi0.5Na0.5TiO3–0.07BaTiO3 low-temperature sintered multifunctional ceramics

Pr³⁺/Er³⁺-doped 0.93Bi_0.5Na_0.5TiO₃–0.07BaTiO₃ ceramics have been fabricated at a low sintering temperature of 960°C using a sintering aid of Li₂CO₃. The effects of energy transfer between Pr³⁺and Er³⁺on their photoluminescence properties have been investigated. Our results reveal that the down-conversion emissions of Pr³⁺are weakened and the lifetimes are shortened by the co-doping of Er³⁺. As a result, when both Pr³⁺and Er³⁺are excited simultaneously, with increasing the concentration of Er³⁺, the green emissions from Er³⁺increase but the red emissions from Pr³⁺decrease. Moreover, the emission color of the ceramics can be reversibly changed between red, yellow and yellowish green by using excitation sources of different wavelengths. Strong up-conversion green emissions with short lifetimes arisen from Er³⁺have also been observed for the ceramics under the excitation of 980 nm. Owing to the Li₂CO₃ sintering aid, the low-temperature sintered ceramics also exhibit reasonably good ferroelectric and piezoelectric properties, and hence should be promising for multifunctional applications such as electro-optical coupling devices.     

Structure and photoluminescence properties of Ca0.99−xSrxAlSiN3:0.01Ce3+ solid solutions

Nitride phosphors of Ca_0.99−xSr_xAl_1.01Si_0.99N₃:0.01Ce³⁺ (0 ≤ x ≤ 0.9) were synthesized by conventional solid-state method. XRD data analysis shows that all samples are single phase with CaAlSiN₃-type structure. Under blue or near-ultraviolet (~400 nm) light excitation, the emission peak can be tuned largely from 615 to 568 nm by increasing Sr content, and the emission intensity is maximal at x = 0.8. With the Sr content increase, the emission band blue-shifts due to the decreased crystal field splitting and the reduced centroid shift; while the thermal luminescence quenching resistance is almost unchanged. The quenching temperature (T₅₀) is well above 500 K for all samples, which satisfies the requirement of commercial application. The quenching process is mainly attributed to the radiationless transitions by thermally activated crossover from the 5d excited state to 4f ground state in the configurational coordinate diagram. The luminescence properties show that the (Ca,Sr)AlSiN₃:Ce³⁺ phosphors are very promising for use in blue and near-ultraviolet light excited white-light-emitting diodes.     

Preparation,structural and thermo-mechanical properties of lithium aluminum silicate glass–ceramics

Lithium aluminum silicate glasses of composition (wt%) 12.6Li₂O–71.7SiO₂–5.1Al₂O₃–4.9K₂O–3.2B₂O₃–2.5P₂O₅ were prepared by the melt quench technique. These glasses were converted to glass–ceramics based on DTA data. X-ray diffraction (XRD) and Fourier transform infra-red spectroscopy (FTIR) were used to discern the phases evolved in the glass–ceramics. Phase morphology was studied using scanning electron microscopy (SEM). Thermal expansion coefficient (TEC) and glass transition temperature (T_g) of all samples were measured using thermo-mechanical analyzer (TMA). It was found that 3 h dwell time at crystallization temperature yielded samples with good crystallinity with a TEC of 9.461 × 10⁻⁶ °C⁻¹. Glass–ceramic-to-metal compressive seal with SS-304 was fabricated using LAS glass–ceramic. The presence of metal housing and compressive stresses at the glass–ceramic-to-metal interface reduced average grain size and changed the overall microstructure.     

Mechanical properties and calcium–magnesium–alumino–silicate corrosion behaviour of Ce/Gd co-doped SrZrO3 ceramics

Sr(Zr_1-2xCe_xGd_x)O_3-0.5x (x = 0, 0.05, 0.1 and 0.15) ceramics were prepared by pressureless sintering using powders that were synthesized by solid-state reaction. The mechanical properties and calcium–magnesium–alumino–silicate (CMAS) early corrosion behaviour of the prepared ceramics were reported. The mechanical properties of rare-earth-doped SrZrO₃ improved significantly. The reaction products of the Sr(Zr_1-2xCe_xGd_x)O_3-0.5x ceramics after CMAS corrosion were similar: zirconia, SrAl₂O₄, akermanite, and anorthite. The mechanism of CMAS corrosion resistance is summarized as follows: elemental Sr easily enters the CMAS melt, because of its high diffusivity, and promotes crystallization. Rare-earth elements can prevent melt infiltration because of their low diffusivity.     

Dy3+ doped LiCl–CaO–Bi2O3–B2O3 glasses for WLED applications

Dy³⁺ doped calcium bismuth borate glasses were synthesized in the composition range of xLiCl-(30 − x)CaO-20Bi₂O₃-50B₂O₃ + 1 mol% Dy₂O₃ (x = 0, 2, 5, 7, 10 and 15 mol%, LC0, LC2, LC5, LC7, LC10 and LC15 respectively) using conventional melt-quench technique. Broad XRD profiles confirmed non-crystalline nature of synthesized compositions. The compositional dependencies of structural changes (using FTIR spectra), thermal behavior (using DSC thermographs) and optical band gap (using UV–Vis–NIR spectra) were discussed. Photoluminescence (PL) excitation spectra recorded at 577 nm yielded six different excitation peaks belonging to Dy³⁺ ions. The PL emission spectra recorded at 451 nm were analyzed to extract different light emission parameters viz. Y/B ratio, color coordinates, correlated color temperature (CCT) following CIE 1931 chromaticity diagram. The emission colors were found to lie in white light region and lies very close to standard white light emission. The CCT of sample LC10 (5335 K) is closest to CCT of standard white light (5615 K) which depicted the optimized concentration of LiCl for application of these glasses in WLED application.     

Structure,Judd-Ofelt analysis and spectra studies of Sm3+-doped MO-ZnO-B2O3–P2O5 (M = Mg,Ca, Sr,Ba) glasses for reddish-orange light application

In the present work, a series of Sm³⁺-doped MO-ZnO-B₂O₃–P₂O₅ (M = Mg, Ca, Sr, Ba) glasses were prepared. The glass structure and luminescence properties were investigated by XRD, DSC, IR, absorption spectroscopy, Judd-Ofelt theory and photoluminescence spectra. The J-O parameters of Sm³⁺-doped glasses follow the trend of Ω₄＞Ω₆＞Ω₂. Under the excitation of 401 nm Xenon lamp, Sm³⁺-doped glasses exhibited four emissions from the transitions of ⁴G_5/2→⁶H_J/2 (J = 5, 7, 9, 11) in the visible spectra. The luminous intensity of Sm³⁺ increases with the asymmetry in local environments and decreases with the increasing radius of the alkaline-earth cation. Among the as-prepared glass, the Sm³⁺-doped glass containing magnesium oxide exhibits higher values of stimulated emission cross-section (2.18 × 10⁻²¹ cm²), gain bandwidth (1.40 × 10⁻²⁷ cm³), and optical gain (3.83 × 10⁻²⁴ cm²). All the Sm³⁺-doped glasses show intense orange light in the CIE 1931 chromaticity diagram with a high color purity exceeding 99%. In addition, the time-resolved emission spectra reveal the decay process of the Sm³⁺ ions for the transitions ⁴G_5/2 → ⁶H_7/2 and ⁴G_5/2 → ⁶H_9/2 in the glass containing magnesium oxide. It suggests that Sm³⁺-doped alkaline-earth zinc borophosphate glasses could be a potential candidate for reddish-orange light-conversion fluorescent materials based on the ultraviolet light-emitting diode.     

Advanced chrome-free organic–inorganic hybrid pretreatments for aerospace aluminum alloy 2024-T3—application of novel bis-ureasil sol–gel precursors

Effective pretreatment of aluminum alloys is very critical to success of protective coating systems for aerospace applications. While chromate-based pretreatments have been very successful for corrosion protection, they have been a target for replacement due to the increasingly stricter regulatory requirements arising from toxicity and carcinogenic nature of Cr(VI) used in such pretreatments. Among many approaches to develop alternative systems, the organic–inorganic hybrid (OIH) coatings based on sol–gel technology has advanced rapidly. We have successfully developed OIH coating systems by using suitably tailored organosilane precursors and sol–gel processing conditions. A series of novel bis-ureasil precursors have been developed and employed as organic precursor of OIH systems. Statistical design of experimental methodology (DoE) has been used to study and optimize compositional and process parameters using multifactor analysis of variance (ANOVA) analysis method. The corrosion resistance study (Potentiodynamic polarization, salt-spray corrosion test) shows that by proper choice of sol–gel precursors, cross-linkers, and reaction conditions, very dense, adherent and protective hybrid coatings, comparable in performance to chromate-based ones, can be obtained for aerospace aluminum alloy 2024-T3. This paper was awarded the Southern Society A.L. Hendry Award for best student paper. The paper was presented at FutureCoat! 2008, sponsored by Federation of Societies for Coatings Technology, held October 14–16, 2008, in Chicago, IL.     

Compositions of MgTiO3–CaTiO3 ceramic with two borosilicate glasses for LTCC technology

Mixtures of ZnO–SiO₂–B₂O₃/MgTiO₃–CaTiO₃ (ZSB/MMT-20) and BaO–SiO₂–B₂O₃/MgTiO₃–CaTiO₃ (BSB/MMT-20) have been investigated as new candidates for LTCC dielectric materials. Two-stage sintering behaviour was observed in both materials, starting at around 600 and 850°C. Nearly full density (97%) was achieved in ZSB/MMT-20 after sintering at 900°C, while a high porosity of 23% was measured in BSB/MMT-20 after firing at 875°C followed by partial melting of samples during sintering at 900°C. After firing, fully crystalline structure with phases of ZnTiO₃, Zn₂SiO₄, Mg_4/3Zn_2/3B₂O₅ and TiO₂ were found in ZSB/MMT-20, while the structure of BSB/MMT-20 consisted of crystalline TiO₂ and BaTi(BO₃)₂ and amorphous SiBa(BO₃)₂ and SiB₂O₅. ZSB/MMT-20 fired at 900^oC showed promising microwave properties having the dissipation factor of 0.001 and a permittivity of 10.6 at 7 GHz. The corresponding values for BSB/MMT-20 fired at 875°C were 0.002 and 8.2, respectively.     

Intense broadband 3.1 μm emission in Er3+-doped fluoroaluminate-tellurite glass for mid-infrared laser application

Er³⁺ single doped fluoroaluminate-tellurite glasses were made by employing a conventional melt-quenching technique. A strong fluorescence around 3.1 μm was achieved from Er³⁺-doped fluoride glasses, under a 980 nm laser diode pump, which was assigned to the Er³⁺: ⁴S_3/2 → ⁴F_9/2 radiation transition process. The up-conversion and mid-infrared spectra of emission for fluoroaluminate-tellurite glasses with various concentrations of Er³⁺ ions dopant was researched. In addition, the calculated fluorescence lifetime value about 3.1 μm reaches 0.48 ms. The findings indicate that fluoroaluminate-tellurite glasses doped with Er³⁺ have prospects of being developed into 3.1 μm mid-infrared fiber and laser materials.     

Outstanding optical temperature sensitivity and dual-mode temperature-dependent photoluminescence in Ho3+-doped (K,Na)NbO3–SrTiO3 transparent ceramics

High optical temperature sensing properties based on rare-earth-doped (K,Na)NbO₃-based ferro-/piezoelectrics have attracted much attention due to their potential application in novel optoelectronic devices. Here, we fabricated Ho³⁺-doped (K_0.5Na_0.5)NbO₃–SrTiO₃ transparent ceramics by conventional pressureless sintering. Their microstructures, transmittances, up-conversion photoluminescence, and optical temperature sensing properties have been characterized in details. Because of the cubic-like phase, dense, and fine-grained structure as well as relaxor-like feature, the ceramics exhibit high transmittance (~70%) in the near-infrared region. Owing to Ho³⁺, green and red up-conversion emissions have been observed, which can be easily modulated by temperature. The ceramics have stable emission colors (<200°C) and superior temperature-modulating emission color-tunable performance (>200°C). Furthermore, the temperature sensing behavior based on the thermally coupled levels (⁵F₄, ⁵S₂) of Ho³⁺ has been analyzed by a fluorescence intensity ratio technique. The transparent ceramics possess outstanding optical temperature sensitivity (~0.0096/K at 550 K), higher than most rare-earth-doped materials (e.g., ceramics, glasses, and phosphors).     

Molybdenum carbonyl grafted onto silicate intercalated cobalt–aluminum hydrotalcite: A new potential catalyst for the hydroformylation of octene

We present the first example of molybdenum carbonyl grafted on diaminosiloxane-functionalized cobalt–aluminum hydrotalcite (CA–HTSi–DA–Mo) as a promising catalyst for the hydroformylation of olefins. The catalyst showed 80% conversion with selective formation of branched aldehyde. About 70% of the catalytic activity retains even after three cycles.