Low‐Temperature Magnetic and Dielectric Anomalies in Rare‐Earth‐Substituted BiFeO3 Ceramics

In this work, we report on the magnetic and dielectric anomalies observed in dense Bi_1–xRE_xFeO₃ ceramics (RE = Dy, Tb; 0 ≤ x ≤ 0.3) at cryogenic temperatures. For compositions with a high content of rare‐earth ions, thermomagnetic experiments revealed a distinct anomaly in the magnetization curves at temperatures below 200 K. The temperature of the magnetic anomaly along with a thermal hysteresis was found to be dependent on the rare‐earth concentration and magnetic field strength. Low‐temperature dielectric measurements showed an anomalous relaxor‐like behavior of the relative permittivity and dielectric loss in highly doped ceramic samples. The anomalies in low‐temperature magnetization and dielectric response are suggested to result from the presence of GdFeO₃‐like orthoferrite phase and/or bismuth rare‐earth‐mixed iron garnet impurities.     

High‐Temperature Properties and Ferroelastic Phase Transitions in Rare‐Earth Niobates (LnNbO4)

Phase transition and high‐temperature properties of rare‐earth niobates (LnNbO₄, where Ln = La, Dy and Y) were studied in situ at high temperatures using powder X‐ray diffraction and thermal analysis methods. These materials undergo a reversible, pure ferroelastic phase transition from a monoclinic (S.G. I2/a) phase at low temperatures to a tetragonal (S.G. I4₁/a) phase at high temperatures. While the size of the rare‐earth cation is identified as the key parameter, which determines the transition temperature in these materials, it is the niobium cation which defines the mechanism. Based on detailed crystallographic analysis, it was concluded that only distortion of the NbO₄ tetrahedra is associated with the ferroelastic transition in the rare‐earth niobates, and no change in coordination of Nb⁵⁺ cation. The distorted NbO₄ tetrahedron, it is proposed, is energetically more stable than a regular tetrahedron (in tetragonal symmetry) due to decrease in the average Nb–O bond distance. The distortion is affected by the movement of Nb⁵⁺ cation along the monoclinic b‐axis (tetragonal c‐axis before transition), and is in opposite directions in alternate layers parallel to the (010). The net effect on transition is a shear parallel to the monoclinic [100] and a contraction along the monoclinic b‐axis. In addition, anisotropic thermal expansion properties and specific heat capacity changes accompanying the transition in the studied rare‐earth niobate systems are also discussed.     

Rare‐Earth Dopant Effects on the Structural,Energetic, and Magnetic Properties of Alumina from First Principles

Density functional theory was used to study the effect of rare‐earth dopants on the structure, phase stability, and magnetic properties of α‐ and θ‐Al₂O₃. Lanthanide series rare‐earth dopants (Pr, Nd, Gd, Er, and Yb) were considered at a doping concentration of 0.83 at.%. Incorporation of rare‐earth dopants was found to increase the lattice parameters and exaggerate the local structural distortion around the dopant. The extent of local lattice distortion was correlated with the dopant ionic radii. The phase stability of rare‐earth‐doped Al₂O₃ was assessed by comparing cohesive and defect formation energies for doped and undoped α‐ and θ‐Al₂O₃. Rare‐earth dopants increased the relative stability of the metastable θ‐Al₂O₃, although doped α‐Al₂O₃ remained more stable. The total magnetic moment of the doped Al₂O₃ was shown to correlate with the number of unpaired electrons. The magnetic moment was also found to be strongly localized on the rare‐earth dopant for Er, Gd, Nd, and Pr‐doped Al₂O₃. In contrast, the Yb dopant induced a delocalized magnetic moment on ~80% of the oxygen atoms. These results further the understanding of dopant incorporation mechanisms, as well as the doping effect on phase stability and magnetic properties that may be applied to advanced field‐assisted material synthesis and processing for enhanced properties.     

Formation of Hexagonal Metastable Phases from an Undercooled LuFeO3 Melt in an Atmosphere with Low Oxygen Partial Pressure

Controlling the oxygen partial pressure ( P _O2) in the ambient atmosphere is an important parameter for material processing because the transition metal ion changes its valence depending on P _O2. In the present study, containerless solidification of the LuFeO₃ melt, where the undercooling level can be treated as another experimental parameter, was carried out in order to explore the unidentified metastable phases under the controlled P _O2 using an aerodynamic levitator. Decreasing P _O2 down to 1 × 10³ Pa, the unidentified phase was solidified from the undercooled melt. The X-ray diffractometry results after annealing at 1 × 10³ Pa showed the peak profile of the stable perovskite LuFeO₃ phase, suggesting that this unidentified phase was thermodynamically metastable. Thermogravimetric analysis showed that the mass of the sample solidified at P _O2= 1 × 10³ Pa significantly increased, suggesting that the formation of the metastable phases might be related to the presence of Fe²⁺ ions.     

Effect of Oxygen Partial Pressure on the Formation of Metastable Phases from an Undercooled YbFeO3 Melt Using an Aerodynamic Levitator

The Yb₂O₃–Fe₂O₃ system was studied to investigate the effect of oxygen partial pressure on the formation of metastable phases over a wide range of oxygen partial pressures from 10⁵ to 10⁻¹ Pa. Two kinds of metastable phases, with space groups of P 6₃ cm and P 6₃/ mmc , were found through rapid solidification of an undercooled YbFeO₃ melt in an atmosphere with reduced P o₂. The crystal structure of the as-solidified samples changed from orthorhombic Pbnm to hexagonal P 6₃ cm and P 6₃/ mmc with decreasing P o₂. X-ray diffractometric and scanning electron microscopic results confirmed the existence of various phases in the as-solidified samples. The stabilities of each phase were studied by annealing the bulk sample in the thermogravimetric–differential thermal analysis (TG-DTA) furnace up to 1673 K, and the equilibrium phase diagram was constructed for the Yb–Fe–O system at 1473 K. TG analysis showed an increase of the sample mass during annealing and revealed that the existence of Fe²⁺, which has an ionic radius larger than that of Fe³⁺, decreases the tolerance factor and therefore destabilizes the perovskite structure.     

Microstructure and Magnetic Properties of (Co-Fe)-Al-O Thin Films

(Co-Fe)-Al-O soft magnetic thin films were fabricated by cosputtering Co-Fe alloy and Al₂O₃ ceramic targets using an inductively coupled RF (radio frequency) sputtering system. The microstructure and magnetic properties of various (Co-Fe)/(Al-O) thin-film compositions were systematically characterized. A specimen with the composition (Co₇₂Fe₁₇Al₁₁)-O exhibited excellent high-frequency magnetic properties, with a value >300 for the real part of the permeability and >2 GHz for the self-resonant frequency. High-resolution transmission electron images revealed nanometer-order Al₂O₃ amorphous phases separating the Co-Fe alloy nanograins. The excellent high-frequency magnetic properties were derived from the particular microstructure of these thin films.     

Improvement of Electrical Conductivity of Trivalent Rare‐earth Cation‐doped Neodymium Zirconate by Co‐doping Gadolinium and Ytterbium

Pyrochlore oxides of A₂Zr₂O₇, where A represents trivalent rare‐earth elements, have a high electrical conductivity, which makes them suitable for applications as high‐temperature solid electrolytes. The influence of Gd and Yb cations co‐doping at the Nd site on structure and electrical conductivity of a pyrochlore oxide Nd₂Zr₂O₇ is investigated using X‐ray diffraction and impedance spectra measurements. Different zirconate ceramics of Nd₂Zr₂O₇, Nd_1.8Gd_0.2Zr₂O₇, Nd_1.8Gd_0.1Yb_0.1Zr₂O₇, Nd_1.4Gd_0.6Zr₂O₇ and Nd_1.4Gd_0.3Yb_0.3Zr₂O₇ are prepared by pressureless‐sintering method at 1,973 K for 10 h in air. Nd₂Zr₂O₇ doped with Gd and Yb cations at the Nd site exhibit a single phase of pyrochlore‐type structure. The measured values of the total conductivity obey the Arrhenius relation. Nd₂Zr₂O₇ and its doped zirconate ceramics are oxide‐ion conductors in the oxygen partial pressure range of 1.0 × 10^–4 to 1.0 atm at all test temperature levels. The total conductivity increases with reducing average ionic radii of A‐site rare‐earth cations. The dual Yb+Gd intermix doping causes a distinctly enhanced total conductivity as compared to unmodified Nd₂Zr₂O₇ and singly Gd‐doped zirconate ceramics. The highest total conductivity value obtained in this work is 1.02 × 10^–2 S cm × ¹ at 1,173 K for Nd_1.4Gd_0.3Yb_0.3Zr₂O₇ ceramic.     

Melt electrospinning from poly(L‐lactide) rods coated with poly(ethylene‐co‐vinyl alcohol)

Rodlike poly(L ‐lactide) (PLLA) samples coated with poly(ethylene‐co‐vinyl alcohol) (EVOH) were made. Fibers were produced from these rodlike samples by using a melt electrospinning system equipped with a laser irradiating device, and the effects of EVOH content and the processing parameters of the melt electrospinning on fiber diameters were investigated. We also studied the fiber formation mechanism from the rods during the laser melt electrospinning process. The following conclusions were reached: (i) coating of EVOH on PLLA rods has a remarkable effect on decreasing fiber diameter from 3 μm to around 1 μm; (ii) increases in the electric field strength and temperature of spinning space decrease the average diameter of fibers produced from pure PLLA rods, and longer collector distance leads to lager PLLA fiber diameter; and (iii) the migration of PLLA component from the core to the surface of electrospun fibers takes place during the fiber formation process. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Hollow Poly(3‐hydroxybutyrate) Fibers Produced by Melt Spinning

Native and nucleated PHB has been melt‐spun and the properties of the resulting fibers have been investigated. Biocompatible nucleating agents such as HAP and THY were compared to BN as a reference material. DSC was used to investigate the non‐isothermal crystallization kinetics as a function of processing temperature and cooling rate. It was found that particularly the choice of process temperature can ensure sufficient primary crystallization of native PHB: heating not higher than 10–15 K above the melting temperature induced a favorable crystallization behavior of native PHB. Thus, melt spinning at low process temperatures without additives was demonstrated to be the key to the formation of well‐defined hollow PHB fibers.

     

Melt rheology of poly(ϵ‐caprolactone)/poly(styrene‐co‐acrylonitrile) blends

Dynamic viscoelastic properties for miscible blends of poly(?‐caprolactone) (PCL) and poly(styrene‐co‐acrylonitrile) (SAN) were measured. It was found that the time–temperature superposition principle is applicable over the entire temperature range studied for the blends. The temperature dependency of the shift factors a_T can be expressed by the Williams–Landel–Ferry equation: log a_T = ?8.86(T ? T_s)/(101.6 + T ? T_s). The compositional dependency of T_s represents the Gordon–Taylor equation. The zero‐shear viscosities are found to increase concavely upward with an increase in weight fraction of SAN at constant temperature, but concavely downward at constant free volume fraction. It is concluded that the relaxation behavior of the PCL/SAN blends is similar to that of a blend consisting of homologous polymers. It is emphasized that the viscoelastic functions of the miscible blends should be compared in the iso‐free volume state. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2037–2041, 2001     

Melt electrospinning writing of three‐dimensional star poly(ϵ‐caprolactone) scaffolds

In the last decade, the melt‐electrospinning technique has gained attention for the production of highly porous microfibrous tissue engineering scaffolds. The possibility of processing polymers without the use of organic solvents is one of the main advantages over solution electrospinning. In this study, computer‐controlled melt‐electrospinning of a commercial poly(?‐caprolactone) and of two batches with different molecular weights of a three‐arm star poly(?‐caprolactone) by means of a screw‐extruder‐based additive manufacturing system is reported. Experimental parameters such as processing temperature, extrusion flow rate and applied voltage were studied and optimized in order to obtain non‐woven meshes with uniform fibre morphology. Applying the optimized parameters, three‐dimensional scaffolds were produced using a layer‐by‐layer approach (0 ? 90° lay‐down pattern). © 2013 Society of Chemical Industry     

Magnetic Properties of Mixed Valence La(AgSr)MnO3 Manganites Obtained by Solid‐State Reaction Method

In this work, we present a systematic study on the effect of monovalent and divalent cation inclusion on the magnetic properties of the manganites series La_0.80(Ag_1?xSr_x)_0.20MnO₃ (x = 0.0–1.0) synthesized by the solid‐state reaction method. The decreasing Sr:Ag proportion across the compositional series was verified by X‐ray photoelectron spectroscopy. Concerning magnetic properties, the hysteresis curves manifested an initial paramagnetic response at x = 0.0, followed by a progressive ferromagnetic behavior with an optimum Ag:Sr ratio at x = 0.75, for which an enhanced saturation magnetization of 51 Am²/kg and a Curie temperature of 336 K were recorded. Results are explained on the basis of the effect of the increasing unit cell volume on the double exchange interaction between magnetic Mn³⁺– Mn⁴⁺ atoms.     

Thermal and Combustion Properties of 3,4‐Bis(3‐nitrofurazan‐4‐yl)furoxan (DNTF)

Thermal decomposition of melted 3,4‐bis(3‐nitrofurazan‐4‐yl)furoxan (DNTF) in isothermal conditions was studied. The burning rates of DNTF were measured in the pressure interval of 0.1–15 MPa. The thermal stability of DNTF was found to be close to the stability of HMX, while the burning rate of DNTF was close to the burning rate of CL‐20. The thermocouple measurements in the combustion wave of DNTF showed that combustion of DNTF was controlled by the gas‐phase mechanism. The DNTF vapor pressure was determined from thermocouple measurements and agreed well with data obtained at low temperatures under isothermal conditions.     

Synthesis and Biological Characterization of (3R,4R)‐4‐(2‐(Benzhydryloxy)ethyl)‐1‐((R)‐2‐hydroxy‐2‐phenylethyl)‐piperidin‐3‐ol and Its Stereoisomers for Activity toward Monoamine Transporters

A novel series of optically active molecules based on a 4‐(2‐(benzhydryloxy)ethyl)‐1‐((R)‐2‐hydroxy‐2‐phenylethyl)‐piperidin‐3‐ol template were developed. Depending on stereochemistry, the compounds exhibit various degrees of affinity for three dopamine, serotonin, and norepinephrine transporters. These molecules have the potential for treating several neurological disorders such as drug abuse, depression, and attention deficit hyperactivity disorder.

     

Poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) and Poly(propylene carbonate) Blends: an Efficient Method to Finely Adjust Properties of Functional Materials

Polyhydroxyalkanoate (PHA) and poly(propylene carbonate) (PPC) are blended in order to investigate their mutual contributions in terms of functional properties. A wide range of blend composition is processed through extrusion from dry blends. Droplet‐matrix morphology is observed for all samples. Thermal investigations reveal the PPC effect on the PHA crystallization process with a decrease and broadening of the crystallization temperature window and on the depression of its glass transition temperature. This investigation also confirms the as yet un‐reported non‐miscibility of this kind of blend. However, a slight phase interaction is expected since thermal behavior of PHA is impacted. The fragile behavior of PHA is balanced by the high ductility of PPC. The weak strain at break of PHA can thus be increased by up to 200% although a significant amount of PPC is needed to start modifying this property. Stress at break and modulus are linearly decreased from pure PHA to pure PPC values. PPC also acts as an impact modifier for PHA. In terms of barrier properties, PHA brings a large contribution even at low content to the initially high oxygen and water vapor permeability of PPC.

     

(R/S)‐BINOL‐α‐Phosphoryloxy Enecarbamate‐Mediated and (R/S)‐Titanium(IV) BINOLates‐Catalyzed Enantioselective Intramolecular Heck/Aza‐Diels–Alder Cycloaddition (IHADA): An Expedient Methodology

An (R/S)‐titanium(IV) BINOLate‐catalyzed highly enantioselective intramolecular Heck/aza‐Diels–Alder cycloaddition (IHADA) cascade was developed to prepare tetrahydropyridoindoles (tHPs) and octahydropyrazinopyridoindoles (oHPPs) from in situ generated (R/S)‐BINOL α‐phosphoryloxy carbamate ( αPPC2 ) in one pot. Chiral cooperativity between (R/S)‐αPPC2 and (R/S)‐titanium(IV) BINOLate was observed and successfully utilized for the construction of various tHPs (7 examples) and oHPPs (17 examples).

     

Microstructure and Electrical Properties of Nonstoichiometric 0.94(Na0.5Bi0.5+x)TiO3–0.06BaTiO3 Lead‐Free Ceramics

0.94(Na_0.5Bi_0.5+x)TiO₃–0.06BaTiO₃ (x = ?0.04, 0, 0.02; named NB_0.46T‐6BT, NB_0.50T‐6BT, NB_0.52T‐6BT, respectively) lead‐free piezoelectric ceramics were prepared via the solid‐state reaction method. Effects of Bi³⁺ nonstoichiometry on microstructure, dielectric, ferroelectric, and piezoelectric properties were studied. All ceramics show typical X‐ray diffraction peaks of ABO₃ perovskite structure. The lattice parameters increase with the increase in the Bi³⁺ content. The electron probe microanalysis demonstrates that the excess Bi₂O₃ in the starting composition can compensate the Bi₂O₃ loss induced during sample processing. The size and shape of grains are closely related to the Bi³⁺ content. For the unpoled NB_0.50T‐6BT and NB_0.52T‐6BT, there are two dielectric anomalies in the dielectric constant–temperature curves. The unpoled NB_0.46T‐6BT shows one dielectric anomaly accompanied by high dielectric constant and dielectric loss at low frequencies. After poling, a new dielectric anomaly appears around depolarization temperature (T_d) for all ceramics and the T_d values increase with the Bi³⁺ amount decreasing from excess to deficiency. The diffuse phase transition character was studied via the Curie–Weiss law and modified Curie–Weiss law. The activation energy values obtained via the impedance analysis are 0.69, 1.05, and 1.16 eV for NB_0.46T‐6BT, NB_0.50T‐6BT and NB_0.52T‐6BT, respectively, implying the change in oxygen vacancy concentration in the ceramics. The piezoelectric constant, polarization, and coercive field of the ceramics change with the variation in the Bi³⁺ content. The Rayleigh analysis suggests that the change in electrical properties of the ceramics with the variation in the Bi³⁺ amount is related to the effect of oxygen vacancies.     

Miscibility and Physical Properties of Poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate)/Poly(ethylene oxide) Binary Blends

In order to improve some inferior physical properties of bacterial poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate) [P(3HB‐co‐3HHx)] by blending with PEO, the miscibility, spherulite morphology, crystallization behavior and mechanical properties of P(3HB‐co‐3HHx)/PEO binary biodegradable polymer blends were investigated. A good miscibility between P(3HB‐co‐3HHx) with a 3HHx unit content of 11 mol‐% and PEO in the amorphous state was found when the PEO weight fraction was 10 wt.‐%, while the miscibility decreased dramatically when the PEO weight fraction exceeded 20 wt.‐%. Strongly depending on the blend composition, the mechanical properties of P(3HB‐co‐3HHx) was found to be significantly improved by blending with PEO with a weight fraction of ≈5–17.5 wt.‐%.