Enhanced depolarization temperature in 0.90NBT–0.05KBT–0.05BT ceramics induced by BT nanowires

The depolarization temperature (T_d) of piezoelectric materials is an important figure of merit for their application at elevated temperatures. This study focuses on the effect of BaTiO₃ (BT) nanowires on T_d and piezoelectric properties of morphotropic-phase-boundary 0.90NBT–0.05KBT–0.05BT ceramics. The results reveal that BaTiO₃ nanowires can pin the domain wall, leading to the increase of coercive field (E_c) from 21.06 kV/cm to 34.99 kV/cm. The T_d value of 0.90NBT–0.05KBT–0.05BT ceramics can be enhanced approximately 20 °C when using BT nanowires instead of BT solution as the raw material. Meanwhile, at the same polarization conditions, the piezoelectric constant of the ceramic added BT nanowires (172 pC/N) is decreased but still remains a larger value compared with those of other lead-free ceramics. The results imply that the addition of BT nanowires into NBT–KBT is a very effective route to improve T_d.     

Characterization and organic electric-double-layer-capacitor application of KOH activated coal-tar-pitch-based carbons: Effect of carbonization temperature

The present study reports the influence of pre-carbonization on the properties of KOH-activated coal tar pitch (CTP). The change of crystallinity and pore structure of pre-carbonized CTPs as well as their activated carbons (ACs) as function of pre-carbonization temperature are investigated. The crystallinity of pre-carbonized CTPs increases with increasing the carbonization temperature up to 600 °C, but a disorder occurs during the carbonization around 700 °C and an order happens gradually with increasing the carbonization temperatures in range of 800–1000 °C. The CTPs pre-carbonized at high temperatures are more difficult to be activated with KOH than those pre-carbonized at low temperatures due to the increase of micro-crystalline size and the decrease of surface functional groups. The micro-pores and meso-pores are well developed at around 1.0 nm and 2.4 nm, respectively, as the ACs are pre-carbonized at temperatures of 500–600 °C, exhibiting high specific capacitances as electrode materials for electric double layer capacitor (EDLC). Although the specific surface area (SSA) and pore volume of ACs pre-carbonized at temperatures of 900–1000 °C are extraordinary low (non-porous) as compared to those of AC pre-carbonized at 600 °C, their specific capacitances are comparable to each other. The large specific capacitances with low SSA ACs can be attributed to the structural change resulting from the electrochemical activation during the 1st charge above 2.0 V.     

1-(2′,2′,2′-Trifluoroethyl)-4-phosphopyrazoles: Synthese et Etude Spectroscopique ir et RMN 1H, 13C, 19F,et 31P

Seven new 1-fluorinated-4-phosphopyrazoles 2 have been prepared in 60–94% yield by cyclization of N-(2′,2′,2′-trifluoroethyl) phosphonyl β-hydrazones 1 with triethyl orthoformate in the presence of acetic acid. The IR data, the ¹H, ¹³C, ¹⁹F, ³¹P chemical shifts and coupling constants of the compounds 2 are reported.     

Studies on the Thermodynamic and Kinetic Properties of the Reactions of Ti+ with Sulfur Transfer Reagent SCO Along the C═S Bond Activation Branch at 200–1200K

Theoretical studies on the thermodynamic and kinetic properties of the reactions of Ti⁺ with sulfur transfer reagent SCO via the C═S bond activation pathway have been carried on using DFT/B3LYP method, general statistical thermodynamics, and Eyring transition state theory with Wigner correction. The relevant reactions include reaction 1 ⁴ Ti⁺+¹SCO → ⁴ IM ₁ → ⁴ TS ₁ → ⁴ IM ₂ → ⁴ TiS⁺+ ¹ CO, and reaction 2 ⁴Ti⁺+¹SCO →⁴IM₁→ CP →²IM₂→²TiS⁺+¹CO in which the spin multiplicity changes from the quartet state to the doublet state in the crossing region. It is concluded that the increase of the temperature is favored to the reaction 1 process, since the equilibrium constants (K) rises from 0.566 × 10[P]-9 at 200 K to 0.109 × 10⁰ at 1200 K, and the reaction rate constant (k) from 0.222 × 10⁰ s[P]-1 at 200 K to 0.540 × 10 ¹¹ s[P]-1 at 1200 K. Moreover, reaction 1 is endothermic, and non-spontaneous in the way the entropy increases, while reaction 2 is exothermic and spontaneous in the way their entropy decreases. The reaction path 2 is the energetically favorable channel, and its thermodynamic data change not largely with the rise of temperature.     

Synthesis and Reactivity of Fluoro(Organyl)Phosphanes

Abstract

A new method for producing fluoro(organyl) phosphanes is presented. They are prepared by Cl/F-exchange from the corresponding chloro compounds using Et₃N.nHF as a fluorinating agent. Phosphanyl fluorophospharanes, R₂P-PR₂F₂, are found to be intermediates of the disproportionation of Fluoro (diorganyl) phosphanes. R₂PF react with aldehydes to form phosphinito phosphoranes, R₂PF₂-CHR'-OPR₂. Oxaphospholenes are formed in their reaction with α, β- unsaturated aldehydes. Furthermore, the reactions with 1.2-diketones, carboxylic acid derivatives, and covalent azides are described.     

SYNTHESIS OF SOME SULFUR-CONTAINING SPIROINDOLE DERIVATIVES

Abstract

The synthesis of some new sulfur-containing spiroindole derivatives is reported. Fluorinated 3′-aryl-2′-phenylimino-spiro[3H-indole-3,6′[4,5′-pyrazolin][4,3-d]thiazolo]2(1H)-ones were prepared by the reaction of 5-(2-oxo-3-indolinylidene)-3-aryl-2-phenylimino-4-thiazolidinones with hydrazine hydrate. The compounds have been characterized on the basis of elemental and spectral studies.     

Fluorinated Porous Poly(spirobifluorene) Via Direct C‒H Arylation: Characterization,Porosity, and Gas Uptake

Considering intrinsic properties of conjugated polyfluorenes and special functions of porous polymers, synthesis of fluorinated porous poly(spirobifluorene) via direct C?H arylation polycondensation is explored. Owing to the contorted structure and cross-linking nature, the obtained polymer FPSBF shows permanent porosities with Brunauer–Emmett–Teller specific surface area up to 700 m² g^?1 and exhibits a narrow pore size distribution with the dominant pore size at about 0.63 nm, which is more suitable for adsorption of small gas molecules. Based on the measured gas physisorption isotherms with pressure up to 1.13 bar, the obtained polymer shows good uptaking capacities for hydrogen (1.30 wt% at 1.0 bar and 77 K) and methane (4.80 wt% 1.0 bar and 273 K). Moreover, FPSBF has significant adsorption selectivity for CH₄ against N₂ and the estimated ideal adsorption selectivity ratio is up to 30/1 at 1.0 bar and 273 K, which makes the material possess potential application in gas separation.     

Copolymerization of 4‐Propanoylphenyl Acrylate with Methyl Methacrylate: Synthesis,Characterization and Reactivity Ratios

The new acrylic monomer 4‐propanoylphenyl acrylate (PPA) was synthesized and copolymerized with methyl methacrylate (MMA) in methyl ethyl ketone at 70±1°C using benzoyl peroxide as a free radical initiator. The copolymers were characterized by FT‐IR, ¹H‐NMR and ¹³C‐NMR spectroscopic techniques. The compositions of the copolymers were determined by ¹H‐NMR analysis. The reactivity ratios of the monomers were determined using Fineman‐Ross (r₁=0.5535 and r₂=1.5428), Kelen‐Tüdös (r₁=0.5307 and r₂=1.4482), and Ext. Kelen‐Tüdös (r₁=0.5044 and r₂=1.4614), as well as by a nonlinear error‐in‐variables model (EVM) method using a computer program, RREVM (r₁=0.5314 and r₂=1.4530). The solubility of the polymers was tested in various polar and non‐polar solvents. The elemental analysis was determined by a Perkin‐Elmer C‐H analyzer. The molecular weights (M_w and M_n) of the copolymers were determined by gel permeation chromatography. Thermogravimetric analysis of the polymers reveals that the thermal stability of the copolymers increases with an increase in the mole fraction of MMA in the copolymers. Glass transition temperatures of the copolymers were found to increase with an increase in the mole fraction of MMA in the copolymers.     

Vinyl Polymerization. 436. Effect of Magnetic Field on Uncatalyzed Polymerization

The radical polymerization of vinyl monomers initiated with several kinds of hydrophilic macromolecule was carried out in a magnetic field. The magnetic field promoted the polymerization; the conversion of monomers and the molecular weight of the polymers obtained increased with increasing field strength in the range of 0–0.1 T. The dependence of the composition and tacticity of the mother polymer on the magnitude of the magnetic field was studied. Using graft or block copolymers, which consisted of hard and soft segments, the effect of a magnetic field was further investigated. The degree of hardness and tightness of the hydrophobic areas (reaction areas) formed by the mother polymer in the aqueous solution was found to affect the magnetic field effect on the uncatalyzed polymerization. The overall activation energy obtained in the magnetic field was almost equal to that obtained without a magnetic field.