Bimodal-Structured 0.9KNbO3-0.1BaTiO3 Solid Solutions with Highly Enhanced Electrocaloric Effect at Room Temperature.

0.9KNbO3-0.1BaTiO3 ceramics, with a bimodal grain size distribution and typical tetragonal perovskite structure at room temperature, were prepared by using an induced abnormal grain growth (IAGG) method at a relatively low sintering temperature. In this bimodal grain size distribution structure, the extra-large grains (~10-50 µm) were evolved from the micron-sized filler powders, and the fine grains (~0.05-0.35 µm) were derived from the sol precursor matrix. The 0.9KNbO3-0.1BaTiO3 ceramics exhibit relaxor-like behavior with a diffused phase transition near room temperature, as confirmed by the presence of the polar nanodomain regions revealed through high resolution transmission electron microscope analyses. A large room-temperature electrocaloric effect (ECE) was observed, with an adiabatic temperature drop (ΔT) of 1.5 K, an isothermal entropy change (ΔS) of 2.48 J·kg-1·K-1, and high ECE strengths of |ΔT/ΔE| = 1.50 × 10-6 K·m·V-1 and ΔS/ΔE = 2.48 × 10-6 J·m·kg-1·K-1·V-1 (directly measured at E = 1.0 MV·m-1). These greatly enhanced ECEs demonstrate that our simple IAGG method is highly appreciated for synthesizing high-performance electrocaloric materials for efficient cooling devices.

Enhanced Electrocaloric Effect in Sr2+-Modified Lead-Free BaZr xTi1- xO3 Ceramics.

Barium strontium zirconate titanate ceramics ((BaSr)(ZrTi)O3-BSZT) with Zr4+ ionic contents of 15 and 20 mol % and Sr2+ ionic contents of 15, 20, 25, and 30 mol % were prepared using a solid-state reaction approach. X-ray diffraction and scanning electron microscopy were used to characterize the lattice structure and morphologies of the ceramics. Permittivity and polarization as a function of temperature were characterized using an impedance analyzer and a Tower-Sawyer circuit. The electrocaloric effect was measured directly and calculated using the Maxwell relation (indirectly). The results indicated that the BSZT ceramics change from a normal ferroelectric to a relaxor ferroelectric with increasing Zr4+ ionic content, which can be further modified by the addition of Sr2+ ionic content. The optimized adiabatic temperature change Δ T obtained is 2.43 K in (Ba0.85Sr0.15)(Zr0.15Ti0.75)O3 ceramics, and Δ T >1.6 K over a wide temperature span of 120 °C was obtained.

Direct Measurement of Large Electrocaloric Effect in Ba(ZrxTi1-x)O3 Ceramics.

Barium zirconate titanate (BZT) (Ba(ZrxTi1-x)O3) ceramics with Zr4+ contents of x = 5, 10, 15, 20, 25, and 30 mol % were prepared using a solid-state reaction approach. The microstructures, morphologies, and electric properties were characterized using X-ray diffraction, scanning electron microscopy, and impedance analysis methods, respectively. The dielectric analyses indicate that the BZT bulk ceramics show characteristics of phase transition from a normal ferroelectric to a relaxor ferroelectric with the increasing Zr4+ ionic content. The electrocaloric effect adiabatic temperature change decreases with the increasing Zr4+ content. The highest adiabatic temperature change obtained is 2.4 K for BZT ceramics with a 5 mol % of Zr4+ ionic content.

Enhanced electrocaloric analysis and energy-storage performance of lanthanum modified lead titanate ceramics for potential solid-state refrigeration applications.

The unique properties and great variety of relaxer ferroelectrics make them highly attractive in energy-storage and solid-state refrigeration technologies. In this work, lanthanum modified lead titanate ceramics are prepared and studied. The giant electrocaloric effect in lanthanum modified lead titanate ceramics is revealed for the first time. Large refrigeration efficiency (27.4) and high adiabatic temperature change (1.67 K) are achieved by indirect analysis. Direct measurements of electrocaloric effect show that reversible adiabatic temperature change is also about 1.67 K, which exceeds many electrocaloric effect values in current direct measured electrocaloric studies. Both theoretical calculated and direct measured electrocaloric effects are in good agreements in high temperatures. Temperature and electric field related energy storage properties are also analyzed, maximum energy-storage density and energy-storage efficiency are about 0.31 J/cm3 and 91.2%, respectively.

Large Electrocaloric Effect in Relaxor Ferroelectric and Antiferroelectric Lanthanum Doped Lead Zirconate Titanate Ceramics.

Both relaxor ferroelectric and antiferroelectric materials can individually demonstrate large electrocaloric effects (ECE). However, in order to further enhance the ECE it is crucial to find a material system, which can exhibit simultaneously both relaxor ferroelectric and antiferroelectric properties, or easily convert from one into another in terms of the compositional tailoring. Here we report on a system, in which the structure can readily change from antiferroelectric into relaxor ferroelectric and vice versa. To this end relaxor ferroelectric Pb0.89La0.11(Zr0.7Ti0.3)0.9725O3 and antiferroelectric Pb0.93La0.07(Zr0.82Ti0.18)0.9825O3 ceramics were designed near the antiferroelectric-ferroelectric phase boundary line in the La2O3-PbZrO3-PbTiO3 phase diagram. Conventional solid state reaction processing was used to prepare the two compositions. The ECE properties were deduced from Maxwell relations and Landau-Ginzburg-Devonshire (LGD) phenomenological theory, respectively, and also directly controlled by a computer and measured by thermometry. Large electrocaloric efficiencies were obtained and comparable with the results calculated via the phenomenological theory. Results show great potential in achieving large cooling power as refrigerants.

Electromechanical properties of relaxor ferroelectric P(VDF-TrFE-CFE)-P(VDF-CTFE) blends.

Electromechanical properties of the relaxor ferroelectric poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) [P(VDF-TrFE-CFE)] terpolymer blended with a small amount of poly(vinylidene fluoride-chlorotrifluoroethylene) [P(VDF-CTFE)] copolymer, which possesses a much higher elastic modulus than that of the neat terpolymer, were investigated. It was observed that the presence of small amount of P(VDF-CTFE) does not affect the microstructure of the crystalline phase. However, the uniaxially stretched blended films show a slight increase in the crystallinity and increased or similar induced polarization at high electric fields compared with the neat terpolymer, likely caused by the interface effect. Consequently, for blends with P(VDF-CTFE) less than 5 wt%, the transverse strains S1 along the stretching direction for uniaxially stretched blended films are nearly the same as those of neat P(VDF-TrFE-CFE), whereas the elastic modulus along the S1-direction increases with the P(VDF-CTFE) content. As a result, the blended films exhibit a higher elastic energy density and electromechanical coupling factor k31 compared with the neat terpolymer.

Core-free rolled actuators for Braille displays using P(VDF-TrFE-CFE).

Refreshable Braille displays require many small diameter actuators to move the pins. The electrostrictive P(VDF-TrFE-CFE) terpolymer can provide the high strain and actuation force under modest electric fields that are required for this application. In this paper, we develop core-free tubular actuators and integrate them into a 3 × 2 Braille cell. The terpolymer films are solution cast, stretched to 6 µm thick, electroded, laminated into a bilayer, rolled into a 2 mm diameter tube, bonded, and provided with top and bottom contacts. Experimental testing of 17 actuators demonstrates significant strains (up to 4%) and blocking forces (1 N) at moderate electric fields (100 MV m-1). A novel Braille cell is designed and fabricated using six of these actuators.

Enhanced reducing equivalent generation for 1,3-propanediol production through cofermentation of glycerol and xylose by Klebsiella pneumoniae.

1,3-Propanediol (1,3-PD) biosynthesis plays a key role in NADH consumption to regulate the intracellular reducing equivalent balance of Klebsiella pneumoniae. This study aimed to increase reducing equivalent for enhancing 1,3-PD production through cofermentation of glycerol and xylose. Adding xylose as cosubstrate resulted in more reducing equivalent generation and higher cell growth. In batch fermentation under microaerobic condition, the 1,3-PD concentration, conversion from glycerol, and biomass (OD(600)) relative to cofermentation were increased significantly by 9.1%, 20%, and 15.8%, respectively. The reducing equivalent (NADH) was increased by 1-3 mg/g (cell dry weight) compared with that from glycerol alone. Furthermore, 2,3-butannediol was also doubly produced as major byproduct. In fed-batch fermentation with xylose as cosubstrate, the final 1,3-PD concentration, conversion from glycerol, and productivity were improved evidently from 60.78 to 67.21 g/l, 0.52 to 0.63 mol/mol, and 1.64 to 1.82 g/l/h, respectively.

Improved 1,3-propanediol production with hemicellulosic hydrolysates (corn straw) as cosubstrate: Impact of degradation products on Klebsiella pneumoniae growth and 1,3-propanediol fermentation.

To improve 1,3-propanediol (1,3-PD) production by an economic and efficient approach, hemicellulosic hydrolysates (HH) used as cosubstrate resulted in more biomass and higher reducing power for 1,3-PD production. The effects of primary degradation products such as individual sugars (xylose, glucose, mannose, arabinose and galactose) and major inhibitors (furfural, acetate and formate) on the Klebsiella pneumoiae growth and 1,3-PD production were investigated in this study. Xylose and mannose could efficiently promote the 1,3-PD production and cell growth. Furfural (0.28 g/l) and sodium acetate (1.46 g/l) in low concentration were not inhibitory to Klebsiella pneumoniae, rather they have stimulatory effect on the growth and 1,3-PD biosynthesis, especially the acetate. In fed-batch fermentation with HH as cosubstrate, the final 1,3-PD production, conversion from glycerol and productivity were 71.58 g/l, 0.65 mol/mol and 1.93 g/l/h, respectively, which were 17.8%, 25.0% and 17.7% higher than that from glycerol alone.

Multiferroic polymer composites with greatly enhanced magnetoelectric effect under a low magnetic bias.

Multiferroic laminate composites consisting of chain-end cross-linked ferroelectric polymers and magnetostrictive Metglas are reported. The composites exhibit a greatly enhanced multiferroic voltage coefficient and sensitivity relative to analogous composites. These remarkable properties are attributed to high piezoelectric and electromechanical coupling coefficients, because of the formation of larger crystalline sizes and concurrent improvement in the polarization ordering in the cross-linked polymers.

Dielectric relaxation of relaxor ferroelectric P(VDF-TrFE-CFE) terpolymer over broad frequency range.

Dielectric properties of a relaxor ferroelectric polymer, poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) [P(VDF-TrFE-CFE)] terpolymer, were investigated over a broad range of frequency (from 0.1 kHz to 1 GHz) and a broad range of temperature (-20 degrees C to 76 degrees C). Time-temperature superposition was used to extrapolate the dielectric constant to high frequencies (approximately 1 GHz) from low frequency data (1 MHz). The consistency between the directly measured and the extrapolated data indicate that the time-temperature superposition can be applied at temperature ranging from the glass transition to the broad ferroelectric-paraelectric transition peak of relaxor, indicating that the glass transition is still the dominating relaxation process at room temperature for the ferroelectric relaxor. Compared with the dielectric properties of poly(vinylidene fluoride-trifluoroethylene) [P(VDF-TrFE] copolymer, the terpolymer shows a higher dielectric constant even at 1 GHz, which is considered to originate from the random defects modification converting the long-chain polar-molecular conformation to short-range molecular microstructures and enhancing the molecular motions in both polar and nonpolar nanodomains.

Large electrocaloric effect in ferroelectric polymers near room temperature.

Applying an electrical field to a polar polymer may induce a large change in the dipolar ordering, and if the associated entropy changes are large, they can be explored in cooling applications. With the use of the Maxwell relation between the pyroelectric coefficient and the electrocaloric effect (ECE), it was determined that a large ECE can be realized in the ferroelectric poly(vinylidene fluoride-trifluoroethylene) [P(VDF-TrFE)] copolymer at temperatures above the ferroelectric-paraelectric transition (above 70 degrees C), where an isothermal entropy change of more than 55 joules per kilogram per kelvin degree and adiabatic temperature change of more than 12 degrees C were observed. We further showed that a similar level of ECE near room temperature can be achieved by working with the relaxor ferroelectric polymer of P(VDF-TrFE-chlorofluoroethylene).