Temperature Dependence of Domain Contributions as a Function of Aging in Soft and Hard Lead Zirconate Titanate Piezoelectric Ceramics.

The stress and temperature dependence of three different lead zirconate titanate ceramics have been measured at 48 h and 1 month after poling. The data were fit to a modified Rayleigh law in which a negative quadratic stress term accounts for a saturation of the domain wall contributions at higher stress. The relative changes to the fitting parameters can be explained by the materials possessing differences in the concentration of orientable defect dipoles, but with similar distributions of relaxation time constants.

Combinatorial microfluidic droplet engineering for biomimetic material synthesis.

Although droplet-based systems are used in a wide range of technologies, opportunities for systematically customizing their interface chemistries remain relatively unexplored. This article describes a new microfluidic strategy for rapidly tailoring emulsion droplet compositions and properties. The approach uses a simple platform for screening arrays of droplet-based microfluidic devices and couples this with combinatorial selection of the droplet compositions. Through the application of genetic algorithms over multiple screening rounds, droplets with target properties can be rapidly generated. The potential of this method is demonstrated by creating droplets with enhanced stability, where this is achieved by selecting carrier fluid chemistries that promote titanium dioxide formation at the droplet interfaces. The interface is a mixture of amorphous and crystalline phases, and the resulting composite droplets are biocompatible, supporting in vitro protein expression in their interiors. This general strategy will find widespread application in advancing emulsion properties for use in chemistry, biology, materials, and medicine.

Unexpected Spin-Crossover and a Low-Pressure Phase Change in an Iron(II)/Dipyrazolylpyridine Complex Exhibiting a High-Spin Jahn- Teller Distortion.

The synthesis of 4-methyl-2,6-di(pyrazol-1-yl)pyridine (L) and four salts of [FeL2]X2 (X­ = BF(4)(­), 1; X­ = ClO(4)(­), 2; X­ = PF(6)(­), 3; X­ = CF3SO(3)(­), 4) are reported. Powder samples of 1 and 2 both exhibit abrupt, hysteretic spin-state transitions on cooling, with T(1/2)↓ = 204 and T(1/2)↑ = 209 K (1), and T(1/2)↓ = 175 and T(1/2)↑ = 193 K (2). The 18 K thermal hysteresis loop for 2 is unusually wide for a complex of this type. Single crystal structures of 2 show it to exhibit a Jahn­Teller-distorted six-coordinate geometry in its high-spin state, which would normally inhibit spin-crossover. Bulk samples of 1 and 2 are isostructural by X-ray powder diffraction, and undergo a crystallographic phase change during their spin-transitions. At temperatures below T(1/2), exposing both compounds to 10(­5) Torr pressure inside the powder diffractometer causes a reversible transformation back to the high-temperature crystal phase. Consideration of thermodynamic data implies this cannot be accompanied by a low → high spin-state change, however. Both compounds also exhibit the LIESST effect, with 2 exhibiting an unusually high T(LIESST) of 112 K. The salts 3 and 4 are respectively high-spin and low-spin between 3 and 300 K, with crystalline 3 exhibiting a more pronounced version of the same Jahn­Teller distortion.

Unexpected Spin-Crossover and a Low-Pressure Phase Change in an Iron(II)/Dipyrazolylpyridine Complex Exhibiting a High-Spin Jahn-Teller Distortion.

The synthesis of 4-methyl-2,6-di(pyrazol-1-yl)pyridine (L) and four salts of [FeL2]X2 (X(-) = BF4(-), 1; X(-) = ClO4(-), 2; X(-) = PF6(-), 3; X(-) = CF3SO3(-), 4) are reported. Powder samples of 1 and 2 both exhibit abrupt, hysteretic spin-state transitions on cooling, with T1/2↓ = 204 and T1/2↑ = 209 K (1), and T1/2↓ = 175 and T1/2↑ = 193 K (2). The 18 K thermal hysteresis loop for 2 is unusually wide for a complex of this type. Single crystal structures of 2 show it to exhibit a Jahn-Teller-distorted six-coordinate geometry in its high-spin state, which would normally inhibit spin-crossover. Bulk samples of 1 and 2 are isostructural by X-ray powder diffraction, and undergo a crystallographic phase change during their spin-transitions. At temperatures below T1/2, exposing both compounds to 10(-5) Torr pressure inside the powder diffractometer causes a reversible transformation back to the high-temperature crystal phase. Consideration of thermodynamic data implies this cannot be accompanied by a low → high spin-state change, however. Both compounds also exhibit the LIESST effect, with 2 exhibiting an unusually high T(LIESST) of 112 K. The salts 3 and 4 are respectively high-spin and low-spin between 3 and 300 K, with crystalline 3 exhibiting a more pronounced version of the same Jahn-Teller distortion.

Decoupled spin crossover and structural phase transition in a molecular iron(II) complex.

Crystalline [Fe(bppSMe)2][BF4]2 (1; bppSMe = 4-(methylsulfanyl)-2,6-di(pyrazol-1-yl)pyridine) undergoes an abrupt spin-crossover (SCO) event at 265±5 K. The crystals also undergo a separate phase transition near 205 K, involving a contraction of the unit-cell a axis to one-third of its original value (high-temperature phase 1; Pbcn, Z = 12; low-temperature phase 2; Pbcn, Z = 4). The SCO-active phase 1 contains two unique molecular environments, one of which appears to undergo SCO more gradually than the other. In contrast, powder samples of 1 retain phase 1 between 140-300 K, although their SCO behaviour is essentially identical to the single crystals. The compounds [Fe(bppBr)2][BF4]2 (2; bppBr = 4-bromo-2,6-di(pyrazol-1-yl)pyridine) and [Fe(bppI)2][BF4]2 (3; bppI = 4-iodo-2,6-di(pyrazol-1-yl)-pyridine) exhibit more gradual SCO near room temperature, and adopt phase 2 in both spin states. Comparison of 1-3 reveals that the more cooperative spin transition in 1, and its separate crystallographic phase transition, can both be attributed to an intermolecular steric interaction involving the methylsulfanyl substituents. All three compounds exhibit the light-induced excited-spin-state trapping (LIESST) effect with T(LIESST = 70-80 K), but show complicated LIESST relaxation kinetics involving both weakly cooperative (exponential) and strongly cooperative (sigmoidal) components.

Complex thermal expansion properties in a molecular honeycomb lattice.

[FeL3][BF4]2·xH2O (L = 3-(pyrazinyl)-1H-pyrazole) shows negative thermal expansion between 150-240 K but positive thermal expansion at 240-300 K, linked to rearrangement of anions and water molecules within pores in the lattice.

Active glass-polymer superlattice structure for photonic integration.

We propose an all-laser processing approach allowing controlled growth of organic-inorganic superlattice structures of rare-earth ion doped tellurium-oxide-based glass and optically transparent polydimethyl siloxane (PDMS) polymer; the purpose of which is to illustrate the structural and thermal compatibility of chemically dissimilar materials at the nanometer scale. Superlattice films with interlayer thicknesses as low as 2 nm were grown using pulsed laser deposition (PLD) at low temperatures (100 °C). Planar waveguides were successfully patterned by femtosecond-laser micro-machining for light propagation and efficient Er(3+)-ion amplified spontaneous emission (ASE). The proposed approach to achieve polymer-glass integration will allow the fabrication of efficient and durable polymer optical amplifiers and lossless photonic devices. The all-laser processing approach, discussed further in this paper, permits the growth of films of a multitude of chemically complex and dissimilar materials for a range of optical, thermal, mechanical and biological functions, which otherwise are impossible to integrate via conventional materials processing techniques.

Dielectric and piezoelectric properties in the lead-free system Na0.5K0.5NbO3-BiScO3-LiTaO3.

Phase relations, dielectric and piezoelectric properties are reported for the ternary system 98%[(1 - x) (Na(0.5)K(0.5)NbO(3))-x(LiTaO(3))]-2%[BiScO(3)] for compositions x ≤ 10 mol% LiTaO(3). The phase content at room-temperature changed from mixed phase, monoclinic + tetragonal, for unmodified 98%(Na(0.5)K(0.5)NbO(3))-2%(BiScO(3)), to tetragonal phase for compositions >2 mol% LiTaO(3). Curie peaks at 360 to 370°C were observed for all compositions, but peaks became diffuse at x ≥ 3 mol%, and two dielectric peaks, at 370 and 470°C, were observed for 5 mol% LiTaO(3). Phase segregation, and finite size affects associated with the core-shell structure, account for the occurrence of two dielectric peaks in 5 mol% LiTaO(3), and diffuse dielectric behavior. The value of d(33) piezoelectric charge coefficient increased from ~160 pC/N for 0 mol% LiTaO(3) to 205 to 214 pC/N for 1 to 2 mol% LiTaO3 solid solutions, before falling sharply at 3 mol% LiTaO(3). TEM-EDX analysis revealed core-shell grain structures with segregation of Bi, Sc, and Ta in the outer ~100-nm shell of the 5 mol% LT sample.

Ferroelectric BiFeO3-PbTiO3 thin films on Pt/Si substrates.

In this work we report on the preparation and properties of bismuth ferrite lead titanate films [(1- x)BiFeO(3-x)PbTiO3] with tetragonal compositions (x = 0.8 and 0.7) and compare them with compositions close to the morphotropic phase boundary (MPB; x = 0.4 and 0.3). The films were prepared by pulsed laser deposition on Pt/Si substrates, and exhibited a dense columnar grain growth. X-ray diffraction analysis revealed that the films have a perovskite structure with a preferred (111) texture. The dielectric properties, polarization-field hysteresis, and leakage current behavior of the films is also reported. For MPB compositions, the films exhibited remanent polarizations with 2Pr up to 100 microC cm(-2) and E(c) approximately 185 kV cm(-1) under a maximum applied field of 500 kV cm(-1), while the tetragonal compositions exhibited 2Pr values in the range of 45-52 microC cm(-2) with a coercive field E(c) approximately 118 kV (-1).