High piezoelectric properties of BaTiO3-xLiF ceramics sintered at low temperatures

BaTiO₃-xLiF ceramics were prepared by a conventional sintering method using BaTiO₃ powder about 100 nm in diameter. The effects of LiF content (x) and sintering temperature on density, crystalline structure and electrical properties were investigated. A phase transition from tetragonal to orthorhombic symmetry appeared as sintering temperatures were raised from 1100 °C to 1200 °C or as LiF was added from 0 mol% to 3 mol%. BaTiO₃-6 mol% LiF ceramic sintered at 1000 °C exhibited a high relative density of 95.5%, which was comparable to that for pure BaTiO₃ sintered at 1250 °C. BaTiO₃-4 mol% LiF ceramic sintered at 1100 °C exhibited excellent properties with a piezoelectric constant d₃₃ = 270 pC/N and a planar electromechanical coupling coefficient k_p = 45%, because it is close to the phase transition point in addition to high density.     

Low electric field induced large electromechanical properties of BiFeO3-BaTiO3-based ceramics via phase composition modulation

The development of high-temperature lead-free piezoelectric ceramics with excellent electromechanical properties under low field remains a key challenge. A series of 0.995(xBiFeO₃-(1-x)BaTiO₃)-0.005Bi(Zn_0.5Hf_0.5)O₃ ceramics were designed via modulating phase composition. The excellent electromechanical properties of d₃₃* = 511 pm/V (45 kV/cm) at room temperature and S = 0.476 % (d₃₃* = 1190 pm/V, 40 kV/cm) at 120 ℃ were achieved in the x = 0.67 ceramic owing to the synergistic contribution of phase composition and domain evolution. The XRD results verify that the x = 0.67 ceramic is dominated by the pseudocubic phase. The PFM results in the x = 0.67 and 0.71 ceramics confirm that the domain structures consist of nanodomains with strong and weak piezoelectric responses. More importantly, the temperature and voltage-dependent domain evolution testify the nanodomains are easier to switch in the x = 0.67 ceramic. This work provides a strategy to optimize the electromechanical performance at the low field and a deeper understanding of BF-BT-based piezoceramics.     

Comparison of multi-valent manganese oxides (Mn4+, Mn3+, and Mn2+) doping in BiFeO3-BaTiO3 piezoelectric ceramics

Different manganese oxides-doping effects were compared in piezoceramic BiFeO₃-BaTiO₃ system. 0.67Bi_1.05(Fe_0.99Mn^x_0.01)O₃-0.33BaTiO₃ (valence state x = 4+, 3+, and 2+) ceramics were prepared via a solid-state reaction process followed by furnace-cooling (FC) or water-quenching (WQ) process. For the FC ceramics, the direct piezoelectric sensor coefficient (d₃₃) was almost independent of valence state of doped Mn, while d₃₃ depended on the fraction of Fe³⁺/Fe²⁺ in WQ ceramics. The d₃₃ value was highest for the donor Mn⁴⁺-doped ceramic, among the FC ceramics, with 175 pC/N. However, acceptor-doping with Mn²⁺ prevented the transition of Fe ion valence state from 3+ to 2+ in the WQ ceramics, the Mn²⁺-doped WQ ceramic showed the largest d₃₃ of 313 pC/N and converse piezoelectric actuator coefficient, d₃₃^* of 352 pm/V, with high Curie phase transition temperature (482 °C).     

Temperature-induced strain mediated magnetization changes in NiFe2O4/BaTiO3 heterostructure

Herein, we report the temperature-induced magnetization changes of NiFe₂O₄ thin film, which is coated over a ferroelectric BaTiO₃ ceramic substrate. The solid-state reaction method was adopted for the preparation of ferroelectric BaTiO₃ (BT) substrate, whereas NiFe₂O₄ (NFO) film was deposited by spin-coating method. Rietveld refinement revealed that BT substrate has a tetragonal (P4mm) crystal system along with a minor orthorhombic phase (Amm2) at room temperature. The GIXRD analysis confirms the phase purity of NFO/BT heterostructure. Polarization hysteresis with respect to electric field (P-E loop) and the temperature-dependent dielectric measurement of BT substrate demonstrate its typical ferroelectric and phase transition behavior, respectively. Magnetization hysteresis loops were recorded for the NFO/BT heterostructure at 150, 240 and 300?K. A significant increase in the remnant magnetization (M_R) and coercive field (H_C) of NFO film are noticed while cooling the heterostructure below 300?K. Variation in the magnetization of NFO film corresponds to the change in the structural phase transition (Amm2 at 240?K and R3c at 150?K) of BT while cooling below RT. The interfacial strain mediated coupling is the primary mechanism attributed to the temperature-induced changes in the magnetization of NFO/BT heterostructure.     

Polymorphic phase transition in BaTiO3 by Ni doping

We demonstrate a phase transition between BaTiO₃ polymorphs induced by Ni substitution experimentally. The structural evolution of tetragonal-to-hexagonal polymorph in Ni-doped BaTiO₃ ceramics is observed macroscopically and then, visualized in an atomic scale. Under this structural transition, the long-range ferroelectric ordering in the undoped BaTiO₃ with tetragonal symmetry is suppressed and eventually, vanishes in the heavily Ni-doped BaTiO₃ with hexagonal symmetry and dielectricity. An oxygen vacancy defect can be created at a local Ni doping site with a decrease in the charge valence state from Ti⁴⁺ (3d⁰) to Ti³⁺ (3d¹). With the reduction of the Ti⁴⁺ oxidation state, the polar Ti–O ionic displacement is degenerated in the tetragonal BaTiO₃ and thereby, the short-range Coulomb repulsion may be restored in the hexagonal BaTiO₃ resulting in a polymorphic phase transition. Our work is of potential interest for artificial realization of an exotic phase in complex oxide materials by doping.     

Influence of cosurfactant in microemulsion systems for color removal from textile wastewater

Microemulsion systems have proved very efficient in color removal from textile wastewater using n‐butyl alcohol as cosurfactant. The cosurfactant has a very important role in microemulsified systems, as it is responsible for their stability, mainly in systems formed by ionic surfactants. Although very efficient, n‐butyl alcohol is partially soluble in water, which would permit its passage to the effluent. In this work, isoamyl and octyl alcohols, due to their lower solubility in water, were used as cosurfactants to evaluate their influence in color removal. The colorimetry system used was the CIE L*a*b* (CIELAB) color space and CIE L*a*b* color difference (ΔE*_ab). The wastewater used in this study was the reactive exhausted dye liquor from a dye house (first discharge) containing Procion Yellow H‐E4R (CI Reactive Yellow 84), Procion Blue H‐ERD (CI Reactive Blue 160) and Procion Red H‐E3B (CI Reactive Red 120). The obtained results were modeled using an experimental planning (the Scheffé net) and evaluated through isoresponse diagrams by correlation graphs between experimental values and those obtained by the models with an error lower than 4%. All the optimized systems were very efficient and more than 94% of the dyes contained in the effluent were removed. The microemulsion load capacity was determined using a synthetic solution containing, the same dyes present in the reactive exhausted dyebath, but 200 times concentrated, and the dyes extraction was more than 99.6%. By comparing n‐butyl, isoamyl and octyl alcohols, it was observed that the system using isoamyl alcohol presented slightly better color removal and much higher load capacity than the n‐butyl and octyl alcohols. Copyright © 2004 Society of Chemical Industry     

The perception of static colored noise: Detection and masking described by CIE94

We present psychophysical data on the perception of static colored noise. In our experiments, we use the CIE94 color difference formula to quantify the noise strength and for describing our threshold data. In Experiment 1 we measure the visual detection thresholds for fixed pattern noise on a uniform background color. The noise was present in one of three perceptual color dimensions lightness (L*), chroma (C*), or hue (h). Results show that the average detection threshold for noise in L* is independent of hue angle and significantly lower than that for noise in C* or h. Thresholds for noise in C* and h depend on hue angle in an opponent fashion. The measured detection thresholds, expressed in terms of the components ΔL*/k_LS_L, ΔC*/k_CS_C, and ΔH*/k_HS_H that build up the CIE94 color difference formula are used to tune CIE94 to our experimental conditions by adjusting the parametric scaling factors k_L, k_C, and k_H. In Experiment 2, we measure thresholds for recognizing the orientation (left, right, up, down) of a test symbol that was incremental in L*, C*, or h, masked by supra‐threshold background noise levels in L*, C*, or h. On the basis of the CIE94 color difference formula we hypothesized (a) a constant ratio between recognition threshold and noise level when the test symbol and background noise are in the same perceptual dimension, and (b) a constant recognition threshold when in different dimensions. The first hypothesis was confirmed for each color dimension, the second however, was only confirmed for background noise in L*. The L*, C*, h recognition thresholds increase with increasing background noise in C* or h. On the basis of some 16,200 visual observations we conclude that the three perceptual dimensions L*, C*, and h require different scaling factors (hue dependent for C* and h) in the CIE94 color difference formula, to predict detection threshold data for color noise. In addition these dimensions are not independent for symbol recognition in color noise. © 2008 Wiley Periodicals, Inc. Col Res Appl, 33, 178–191, 2008     

Preparation of separative-phase fancy glaze derived from iron ore slag

The separative-phase fancy glaze was successfully prepared by using the iron ore residue as the ceramic colorant. A possible coloring mechanism was proposed to explain the variation of glaze colors and patterns with the increasing of firing temperature. Effects of the firing temperature on the chromaticity, precipitated phase and microstructure of separative-phase fancy glaze were investigated. The results indicated that with increasing the firing temperature, the content of whitlockite decreased while the size of phase separation droplets in glazes increased. The residual whitlockite weakened coloring of Fe₂O₃ and formed glaze patterns. In addition, the increased size of phase separation droplets weakened the structural color, which increased the L* and b* value of glazes. Therefore, the color of separative-phase fancy glaze got more yellow and brown gradually.     

Dielectric properties and relaxor behavior of 0.935(Na0.5Bi0.5)TiO3-0.065BaTiO3 lead free piezoelectric ceramic

Dielectric properties of 0.935(Na_0.5Bi_0.5)TiO₃-0.065BaTiO₃ lead free piezoelectric ceramic are studied. The study shows a diffuse phase transition (DPT) characterized by a frequency dispersion of permittivity which is related to cation disorder at A-site. Additionally to this dispersion, this solid solution exhibits relaxor behavior. The mechanism of relaxor behavior was discussed according to Debye, Vogel–Fulcher (V–F) and Power law models and the suitable model was predicted by means of goodness of parameter.     

Effect of Fe2O3 doping on color and mechanical properties of dental 3Y-TZP ceramics fabricated by stereolithography-based additive manufacturing

In this study, iron(III) oxide (Fe₂O₃)-doped zirconia (3Y-TZP) ceramics with desirable mechanical and color properties for dental restorations were fabricated by stereolithography-based additive manufacturing. Six zirconia ceramic paste specimens with high solid loading (58 vol%) and reasonably low viscosity were prepared according to doped content of Fe₂O₃ (0–0.14 wt%). Zirconia ceramics were fabricated using commercial stereolithography three-dimensional printer and sintered at 1500 °C for 4 h to obtain final dense parts with a relative density of above 99%. Effects of Fe₂O₃ doping on microstructure, mechanical properties, and color of 3Y-TZP ceramics were investigated. Results indicate that Fe₂O₃ exhibited little effect on the shrinkage and density of colored ceramics compared to uncolored ceramics. Average grain size of 3Y-TZP ceramics sintered at 1500 °C increased with increasing content of Fe₂O₃. X-ray diffraction analysis showed that tetragonal phase was dominant phase structure of white and colored 3Y-TZP ceramics, and monoclinic phase increased with increasing Fe₂O₃ content. Compared to uncolored specimens, Fe₂O₃ exhibited negative effects on three-point flexural strength (mean > 879.70 MPa), Vickers hardness (mean > 12.14 GPa), and indentation fracture toughness (mean > 4.23 MPa m^1/2) of the colored specimens. With the increase in the content of Fe₂O₃ from 0 to 0.14 wt%, L* (black–white index) value decreased from 83.39 to 79.54, a* (green–red index) value increased from −2.28 to −0.74, and b* (blue–yellow index) value increased from 1.15 to 17.94. Chromaticity (L*, a*, b*) fell within the range of natural tooth color, indicating that it is suitable for dental application because of its color compatibility with natural teeth. In addition, the transmittance slightly decreased with increasing Fe₂O₃ content. Thus, Fe₂O₃-doped 3Y-TZP ceramics can be used as potential candidates for aesthetic dental restoration materials.     

Dielectric,ferroelectric and magnetoelectric properties of in-situ synthesized CoFe2O4/BaTiO3 composite ceramics

Magnetoelectric composite materials have attracted more and more attention because of their coupling of ferroelectricity and ferromagnetism. It is a hotspot to realize the combination of ferromagnetic phase and ferroelectric phase. In this work, we used a new strategy to prepare CoFe₂O₄/BaTiO₃ composite ceramics: firstly, porous ferromagnetic CoFe₂O₄ phase was prepared by annealing of MOFs (metal organic frameworks) precursor Fe₃[Co(CN)₆]₂. And then, the ferroelectric BaTiO₃ phase in-situ grew in the pores of CoFe₂O₄ by a hydrothermal method. In the end, the CoFe₂O₄/BaTiO₃ composite ceramics sintered at different temperatures have been synthesized. The effects of sintering temperature on the structure, dielectric and ferroelectric properties have also been studied. Because the crystallinity and density increase with the increase of sintering temperature, the composite ceramic sintered at 1200 °C shows the best dielectric properties. It is found that sintering temperature has little effect on the ferroelectric and magnetic properties of ceramics. Taking the CoFe₂O₄/BaTiO₃ composite ceramic sintered at 1200 °C as an example, derived from the interaction between the ferromagnetic CoFe₂O₄ phase and ferroelectric BaTiO₃ phase, the applied magnetic field lead to the reduction of P_r and E_c.     

Formation of photo- and thermo-stable layered double hydroxide films with photo-responsive wettability by intercalation of functionalized azobenzenes

A hybrid film containing a substituted azobenzene, 7-[(trifluoromethoxyphenylazo)phenoxy]pentanoate anion (CF₃AZO^-), intercalated in a layered double hydroxide (LDH) film immobilized on a porous anodic alumina/aluminum (PAO/Al) substrate has been prepared by an anion-exchange reaction of a ZnAl-NO₃-LDH/PAO/Al precursor film with the sodium salt of CF₃AZO^- anions under mild conditions. The hybrid LDH film was characterized by scanning electron microscopy, powder X-ray diffraction and Fourier transform infrared spectroscopy. TG-DTA, UV-visible spectroscopy and CIE 1976 L*a*b* color difference (ΔE) tests indicated that the intercalated ZnAl-CF₃AZO-LDH showed enhanced thermo-stability and photo-stability compared to the pristine CF₃AZO salt. Irradiation with UV light led to a switch in wettability of the film from superhydrophobic to hydrophilic and this process could be reversed by subsequent irradiation with visible light.     

Thermal stability and local atomic structure of (Na0.5K0.5)NbO3 doped BaTiO3 ceramics

Dielectric properties of x(Na_0.5K_0.5)NbO₃–(1−x)BaTiO₃ (x=0.00 and 0.06) specimens were investigated in terms of changes in local atomic structure, according to the phase transition by elevating the overall temperature. A 0.06(Na_0.5K_0.5)NbO₃–0.94BaTiO₃ (NKN–BT) specimen exhibited enhanced temperature stability along with an increased dielectric constant. The degree of reduction in tetragonality (c/a) at the Curie temperature was smaller in NKN–BT compared to that in pure BaTiO₃, as calculated by Rietveld refinement. From a comparison of the pre-edge region in the Ti K-edge, it was determined that the off-center displacement of the Ti atom was also raised to 13.4% through NKN substitution, with a change in local orientation from the [001] to the [111] directions. The substitution by NKN, which has a different ionic radius and electrical charge compared with BaTiO₃, causes structural distortion of the TiO₆ octahedra in the NKN–BT lattice, resulting in local polarization. These structural changes lead to the temperature stability of the dielectric constant and an overall improvement in the electrical properties of BaTiO₃.     

CIELAB color space boundaries under theoretical spectra and 99 test color samples

A color space is a three-dimensional representation of all the possible color percepts. The CIE 1976 L*a*b* is one of the most widely used object color spaces. In CIELAB, lightness L* is limited between 0 and 100, while a* and b* coordinates have no fixed boundaries. The outer boundaries of CIELAB have been previously calculated using theoretical object spectral reflectance functions and the CIE 1931 and 1964 observers under the CIE standard illuminants D50 and D65. However, natural and manufactured objects reflect light smoothly as opposed to theoretical spectral reflectance functions. Here, data generated from a linear optimization method are analyzed to re-evaluate the outer boundaries of the CIELAB. The color appearance of 99 test color samples under theoretical test spectra has been calculated in the CIELAB using CIE 1931 standard observer. The lightness L* boundary ranged between 6 and 97, redness-greenness a* boundary ranged between −199 and 270, and yellowness-blueness b* boundary ranged between −74 and 161. The boundary in the direction of positive b* (yellowness) was close to the previous findings. While the positive a* (redness) boundary exceeded previously known limits, the negative a* (greenness) and b* (blueness) boundaries were lower than the previously calculated CIELAB boundaries. The boundaries found here are dependent on the color samples used here and the spectral shape of the test light sources. Irregular spectral shapes and more saturated color samples can result in extended boundaries at the expense of computational time and power.     

Characterization of MgxM2 − xP2O7 (M = Cu and Ni) solid solutions

In this study, Mg_xM_2 − xP₂O₇ (M = Cu, Ni; 0 ≤ x ≤ 2) and Mg_3 − yNi_y(PO₄)₂ (0 ≤ y ≤ 3) compositions were synthesized by the chemical coprecipitation method and characterized by X-ray diffraction, UV-vis-NIR spectroscopy and CIE L* a* b* (Commission Internationale de l’Eclairage L* a* b*) parameters measurements.Solid solutions with α-Cu₂P₂O₇ and α-Ni₂P₂O₇ structures and solid solutions with Ni₃(PO₄)₂ structure were obtained from diphosphate and orthophosphate compositions respectively. Isostructurality of α-Ni₂P₂O₇ and α-Mg₂P₂O₇ structures enlarges the compositional range of solid solution formation respect to the Mg_xCu_2 − xP₂O₇ solid solutions one.The CIE L* a* b* parameters in Mg_xNi_2 − xP₂O₇ samples were obtained comparable with these parameters in others yellow materials suitable for ceramic pigments. Mg_0.5Ni_1.5P₂O₇ composition fired at 800 °C or 1000 °C is the optimal composition to obtain yellow materials with α-diphosphate structure in conditions of this study.     

Sintering of ferrite-BaTiO3 bulk particulate composites

Particulate magnetoelectric ceramic composites (PMCC) have received much attention since the last decade. These composites have many technological applications and are usually composed by magnetostrictive and piezoelectric phases. Cobalt-based spinel ferrites are among the most studied magnetostrictive phases for ferrite-based PMCCs and BaTiO₃ is an interesting choice for the piezoelectric phase because it is a lead-free ceramic, unlike the traditional PZT. In this work, cobalt ferrite (FCO) and Ni–Co ferrite (FNICO) were produced by the ceramic method and mixed to BaTiO₃ (TB) in order to further obtain sintered ferrite-BaTiO₃ particulate ceramic composites with a composition of 15 mol% ferrite – 85 mol% BaTiO₃. The ferrites, the BaTiO₃, and the ferrite-BaTiO₃ mixtures were analyzed by dilatometry, thermogravimetry (TG), and calorimetry (DSC) in temperatures up to 1300–1400 °C, with the aim to analyze the sintering behavior and the interactions between both ferrites and the BaTiO₃ during sintering. Sintered TB-FNICO and TB-FCO composite samples were also produced and they were analyzed by scanning electron microscopy (SEM) and X-ray diffractometry (XRD). The dilatometry results evidenced that the densification of the ferrite-BaTiO₃ samples is impaired, when compared to the pure ferrite and BaTiO₃ samples. The DSC/TG results evidenced the occurrence of reactions between the ferrites and the BaTiO₃ when they are co-sintered in air or argon atmospheres. The XRD patterns of the sintered composite samples did not exhibit diffraction peaks attributed to a third phase, whilst the punctual EDS analysis showed evidence of diffusion between the ferrite and BaTiO₃ particles.     

Large electrostrain and structural evolution in (1-x)[0.94Bi0.5Na0.5TiO3-0.06BaTiO3]-xAgNbO3 ceramics

A lead-free system formulated as (1-x)[0.94Bi_0.5Na_0.5TiO₃-0.06BaTiO₃]-xAgNbO₃ exhibits an electrostrain of 0.50% at 80 kV/cm and a maximum d₃₃^* of 721 pm/V at 60 kV/cm for x=0.3. The incorporation of AgNbO₃ shifts the relaxor-ferroelectric phase transformation temperature (T_F-R) to room temperature and lowers the energy barrier of the field-induced phase transformation. Furthermore, the in-situ electric field dependent high-energy synchrotron X-ray diffraction (SXRD) technique reveals that the sample x=0.03 transforms from dominant P4bm phase to a phase mixture of R3c + P4mm at 55 kV/cm during the electric field loading, and returns to initial dominant P4bm phase at 15 kV/cm during the unloading cycle of the electric field. Furthermore, it can be demonstrated that the electric field induced-phase transition in NBTBT-3AN occurs in the whole sample, rather than in the single direction of electric field. Therefore, the electrocstrain in NBTBT-3AN is more uniform, which would be beneficial to its actuator applications.     

Determining the effects of BaTiO3 template alignment on template grain growth of Pb(Mg1/3Nb2/3)O3 –PbTiO3 and effects on piezoelectric properties

Crystallographic texturing of ferroelectric ceramics is an established method of inducing single crystal-like properties in a ceramic material via epitaxial grain growth according to the template used, otherwise known as Templated Grain Growth (TGG). The piezoelectric enhancement is dependent on the degree of TGG throughout the ceramic, which is closely linked to the tape casting parameters and sintering conditions. Pb(Mg1/3Nb2/3)O₃-PbTiO₃ (PMN-PT) perovskite ferroelectrics with morphotropic phase boundary compositions using 3 vol% BaTiO₃ templates were used for analysis. The blade gap and template size have the greatest impact on the overall grain alignment. The varying degrees of template alignment is related to the different enhancements of TGG and the correlating piezoelectric d₃₃ and d*₃₃. The highest piezoelectric property was demonstrated in PMN-31PT with Lotgering factor of 93% where d₃₃ = 1020 pC/N and d*₃₃ = 1420 pm/V were achieved.     

Giant electric field-induced strain at room temperature in LiNbO3-doped 0.94(Bi0.5Na0.5)TiO3-0.06BaTiO3

We report experimental investigation on the ferroelectricity and electric field-induced strain response in LiNbO₃-doped 0.94(Bi_0.5Na_0.5)TiO₃-0.06BaTiO₃ (BNT-BT) piezoelectric ceramics. At room temperature, a large strain of 0.6% (at 70 kV/cm) is achieved in the 2.5%-LiNbO₃-doped BNT-BT, higher than that of commercially-utilized Pb(Zr,Ti)O₃. The corresponding piezoelectric coefficient d^*₃₃ reaches 857 pm/V, which is high among these of BNT-based ceramics at room temperature. Further study indicates that the superior piezoelectric properties are realized at the ferroelectric-relaxor transition temperature T_F-R, which is pushed to room temperature with 2.5% LiNbO₃ doping. This indicates that large electromechanical response can be induced via delicate mixing of the ferroelectric rhombohedral phase and the polar nanoregions (PNRs) relaxor-ferroelectric tetragonal phase.     

Local structure study of phase transition behavior in Ba(Ti,Sn)O3 perovskite by X-ray absorption fine structure

In this work, BaTi_1−xSn_xO₃ (BST) powders (x=0–0.95) were synthesized by a conventional mixed-oxide method. The phase information was investigated by a combination of X-ray diffraction and X-ray absorption spectroscopy techniques. The XRD measurements indicated the global phase transition from tetragonal to cubic perovskite structure. From the synchrotron X-ray Absorption Near-Edge Structure (XANES) measurements at the Ti K-edge and Sn L₃-edge, it was seen that an increase of Sn content in BaTiO₃ affected the phase transition behavior and local structure of BST. In addition, the local structure of Ba(Ti,Sn)O₃ materials were experimentally determined and compared with that obtained from the simulation. The local structure obtained from the XANES technique provided additional structural information unavailable from XRD investigation. Finally, the phase transition behavior from relaxor ferroelectric to polar cluster in BST system was discussed and attributed mainly to the change in the local structure.