Fabrication and Phase Transformation in Crystalline Nanoparticles of PbZrO3 Derived By Sol-Gel

In this research fabrication of crystalline PbZrO3 (PZ) nanoparticles and their phase transformation behavior is investigated. A novel sol-gel method was used for the synthesis of air-stable and precipitate-free diol-based sol of PZ, which was dried at 150 degrees C and then calcined at 300-700 degrees C for 1 h. The morphology, crystallinity and phase formation of as synthesized nanoparticles were studied by the selected-area electron diffraction (SAED), X-ray diffraction (XRD), thermal gravimetric analysis/differential scanning calorimetry (TGA-DSC), and high resolution transmission electron microscope (HRTEM). The XRD, SAED, and TGA-DSC analyses confirmed the tetragonal lead rich zirconia phase (t-Z phase) and monoclinic zirconia phase (m-Z phase) as the intermediate phases during the calcinations process followed by crystallization of single orthorhombic PZ phase at about 700 degrees C. The average PZ particle size was observed about 20 nm as confirmed by TEM study. Energy-dispersive X-ray spectroscopy (EDX) analysis demonstrated that stoichiometric PbZrO3 was formed.

Direct physical evidence for the back-transformation of stress-induced martensite in the vicinity of cracks in pseudoelastic NiTi shape memory alloys

Crack loading and crack extension in pseudoelastic binary NiTi shape memory alloy (SMA) miniature compact tension (CT) specimens with 50.7 at.% Ni (austenitic, pseudoelastic) was investigated using infrared (IR) thermography during in situ loading and unloading. IR thermographic measurements allow for the observation of heat effects associated with the stress-induced transformation of martensite from B2 to BIT during loading and the reverse transformation during unloading. The results are compared with optical images and discussed in terms of the crack growth mechanisms in pseudoelastic NiTi SMAs. Direct experimental evidence is presented which shows that crack growth occurs into a stress-induced martensitic microstructure, which immediately retransforms to austenite in the wake of the crack.

Co(II) and Cr(III) complexes of formate-formamide mixed ligands: synthesis, structures, single crystal-to-single crystal transformation and magnetic behaviour

Solvothermal treatment of an equimolar mixture of Co(NO3)(2)center dot 6H(2)O, HCONH2 and NaN3 in MeOH at 100 degrees C yielded a three-dimensional NaCl type network Co(HCOO)(2)(HCONH2)(2) center dot HCONH2 (1a) containing formamides in the pores of the structure. Solvated pink 1a undergoes single crystal-to-single crystal (SCSC) transformation at 215 degrees C to form the desolvated dark brown product Co(HCOO)(2)-( HCONH2)(2) (1b) with the retention of the original framework. Reversible single crystal-to-single crystal transformation of 1b (brown) to 1a (pink) in the presence of excess formamide was also established at room temperature. The coordination environment around Co(II) in both 1a and 1b is octahedral with a CoN2O4 coordination composition. A similar reaction replacing Co(II) by Cr(III) produced a heterometallic 3D extended network Na[Cr(HCOO)(4)(HCONH2)(2)]center dot 2H(2)O (2a) at 100 degrees C. An increase in reaction temperature to 150 degrees C produced a simple mononuclear complex Cr(HCOO)(3)(HCONH2)(3) center dot 3H(2)O (2b). Variable temperature magnetic studies revealed the presence of a canting phenomena in both 1a and 1b, and hysteresis loop in the field dependent magnetisation plot at 2 K whereas complex 2a is simply paramagnetic in nature.

Synthesis, Structure, and Transformation Studies in a Family of Inorganic-Organic Hybrid Framework Structures Based on Indium

Eight new open-framework inorganic-organic hybrid compounds based on indium have been synthesized employing hydrothermal methods. All of the compounds have InO6, C2O4, and HPO3/HPO4/SO4 units connected to form structures of different dimensionality Thus, the compounds have zero- (I), two- (II, III, IV, V, VII, and VIII), and three-dimensionally (VI) extended networks. The formation of the first zero-dimensional hybrid compound is noteworthy In addition, concomitant polymorphic structures have been observed in the present study. The molecular compound, I, was found to be reactive, and the transformation studies in the presence of a base (pyridine) give rise to the polymorphic structures of II and III, while the addition of an acid (H3PO3) gives rise to a new indium phosphite with a pillared layer structure (T1). Preliminary density functional theory calculations suggest that the stabilities of the polymorphs are different, with one of the forms (II) being preferred over the other, which is consistent with the observed experimental behavior. The oxalate units perform more than one role in the present structures. Thus, the oxalate units connect two In centers to satisfy the coordination requirements as well as to achieve charge balance in compounds II, IV, and VI. The terminal oxalate units observed in compounds I, IV, and V suggest the possibility of intermediate structures. Both in-plane and out-of-plane connectivity of the oxalate units were observed in compound VI. The 31 compounds have been characterized by powder X-ray diffraction, IR spectroscopy, thermogravimetric analysis, and P-31 NMR studies.

Selective detection of single-enantiomer spectrum of chiral molecules aligned in the polypeptide liquid crystalline solvent: Transition selective one-dimensional H-1-H-1 COSY

One-dimensional (1D) proton NMR spectra of enantiomers are generally undecipherable in chiral orienting poly-gamma-benzyl-L-glutamate (PBLG)/CDCl3 solvent. This arises due to large number of couplings, in addition to superposition of spectra from both the enantiomers, severely hindering the H-1 detection. On the other hand in the present study the benefit is derived front the presence of several couplings among the entire network of interacting protons. Transition selective 1D H-1-H-1 correlation experiment (1D-COSY) which utilizes the Coupling assisted transfer of magnetization not only for unraveling the overlap but also for the selective detection of enantiopure spectrum is reported. The experiment is simple, easy to implement and provides accurate eanantiomeric excess in addition to the determination of the proton-proton couplings of an enantiomer within a short experimental time (few minutes). (C) 2009 Elsevier Inc. All rights reserved.

Application of z-COSY experiment and its variant for accurate chiral discrimination by H-1 NMR

We report the application of z-COSY experiment and a band selected version of it by employing a selective 90 degrees pulse entitled BASE-z-COSY for precise chiral discrimination, quantification of enantiomeric excess and the analyses of the H-1 NMR spectra of chiral molecules aligned in the chiral liquid crystalline solvent poly-gamma-benzyl-L-glutamate (PBLG). We have demonstrated their applicability for obtaining very high resolution in the H-1 NMR spectra of small organic molecules. It is well known that the commonly employed z-COSY experiment disentangles the spectral complexity, provides pure phase spectra with high resolution, aids in the complete spectral analyses, in addition to yielding information on relative signs of the Couplings. The BASE-z-COSY experiment possesses all these properties, permits the measure of enantiomeric excess, in addition to large saving of instrument time.

Amino Acid Based MOFs: Synthesis, Structure, Single Crystal to Single Crystal Transformation, Magnetic and Related Studies in a Family of Cobalt and Nickel Aminoisophthales

Four new 5-aminoisophthalates of cobalt and nickel have been prepared employing hydro/solvothermal methods: [Co2(C8H5NO4)2(C4H4N2)(H2O)2]·3H2O (I), [Ni2(C8H5NO4)2(C4H4N2)(H2O)2]·3H2O (II), [Co2(H2O)(μ3-OH)2(C8H5NO4)] (III), and [Ni2(H2O)(μ3-OH)2(C8H5NO4)] (IV). Compounds I and II are isostructural, having anion-deficient CdCl2 related layers bridged by a pyrazine ligand, giving rise to a bilayer arrangement. Compounds III and IV have one-dimensional M−O(H)−M chains connected by the 5-aminoisophthalate units forming a three-dimensional structure. The coordinated as well as the lattice water molecules of I and II could be removed and inserted by simple heating−cooling cycles under the atmospheric conditions. The removal of the coordinated water molecule is accompanied by changes in the coordination environment around the M2+ (M = Co, Ni) and color of the samples (purple to blue, Co; green to dark yellow, Ni). This change has been examined by a variety of techniques that include in situ single crystal to single crystal transformation studies and in situ IR and UV−vis spectroscopic studies. Magnetic studies indicate antiferromagnetic behavior in I and II, a field-induced magnetism in III, and a canted antiferromagnetic behavior in IV.

Bond graph model of doubly fed three phase induction motor using the Axis Rotator element for frame transformation

Induction motor is a typical member of a multi-domain, non-linear, high order dynamic system. For speed control a three phase induction motor is modelled as a d–q model where linearity is assumed and non-idealities are ignored. Approximation of the physical characteristic gives a simulated behaviour away from the natural behaviour. This paper proposes a bond graph model of an induction motor that can incorporate the non-linearities and non-idealities thereby resembling the physical system more closely. The model is validated by applying the linearity and idealities constraints which shows that the conventional ‘abc’ model is a special case of the proposed generalised model.

Single and multi-step phase transformation in CuZr nanowire under compressive/tensile loading

A novel stress induced martenistic phase transformation is reported in an initial B2-CuZr nanowire of cross-sectional dimensions in the range of 19.44 x 19.44-38.88 x 38.88 angstrom(2) and temperature in the range of 10-400 K under both tensile and compressive loading. Extensive Molecular Dynamic simulations are performed using an inter-atomic potential of type Finnis and Sinclair. The nanowire shows a phase transformation from an initial B2 phase to BCT (body-centered-tetragonal) phase with failure strain of similar to 40% in tension, whereas in compression, comparatively a small B2 -> BCT phase transformation is observed with failure strain of similar to 25%. Size and temperature dependent deformation mechanisms which control ultimately the B2 -> BCT phase transformation are found to be completely different for tensile and compressive loadings. Under tensile loading, small cross-sectional nanowire shows a single step phase transformation, i.e. B2 -> BCT via twinning along {100} plane, whereas nanowires with larger cross-sectional area show a two step phase transformation, i.e. B2 -> R phase -> BCT along with intermediate hardening. In the first step, nanowire shows phase transformation from B2 -> R phase via twinning along {100} plane, afterwards the nanowire deforms via twinning along {110} plane which cause further transformation from R phase -> BCT phase. Under compressive loading, the nanowire shows crushing along {100} plane after a single step phase transformation from B2 -> BCT. Proper tailoring of such size and temperature dependent phase transformation can be useful in designing nanowire for high strength applications with corrosion and fatigue resistance. (C) 2009 Elsevier Ltd. All rights reserved.

Observation of a chiral smectic phase in azobenzene-linked bolaamphiphiles containing free sugars

Amphiphilic sugars exhibit both lyotropic and thermotropic liquid-crystalline behavior. Interestingly, in spite of the abundance of chiral centers in amphiphilic sugars, their liquid-crystalline phases do not exhibit macroscopic chirality. Herein, we report on the first observation of macroscopic chirality in sugar-based bolaamphiphiles containing free hydroxyl groups. The manifestation of the chiral smectic C* phase in these bolaamphiphiles has been observed to be critically dependent on the presence of the azobenzene moiety and the suitable length of the methylene spacer. These results imply that by suitable selection of linker groups, mesogenic bolaamphiphiles possessing macroscopic chirality can be designed using a variety of naturally available sugar derivatives.

Selective Homonuclear Decoupling in H-1 NMR: Application to Visualization of Enantiomers in Chiral Aligning Medium and Simplified Analyses of Spectra in Isotropic Solutions

The proton NMR spectral complexity arising due to severe overlap of peaks hampers their analyses in diverse situations, even by the application of two-dimensional experiments. The selective or complete removal of the couplings and retention of only the chemical shift interactions in indirect dimension aids in the simplification of the spectrum to a large extent with little investment of the instrument time. The present study provides precise enantiodiscrimination employing more anisotropic NMR parameters in the chiral liquid crystalline medium and differentiates the overlapped peaks of many organic molecules and peptides dissolved in isotropic solvents.

Transformation reactions of α-pinene—I : Reactions of ethyl (−)-2,2-dimethyl-3-ketocyclobutyl acetate

Some transformation reactions of α-pinene to give 4- and 3-membered ring compounds, not hitherto obtained from this source, are described. The study furnished a convenient method of preparation of the optically active cyclobutanone IVa, the title compound which served as the key substrate for all the transformations reported.

A novel sheet 4f-3d mixed-metal pyridine dicarboxylate: synthesis, structure, photophysical properties and its transformation to a perovskite oxide

The synthesis, characterization and photophysical properties of a 4f-3d mixed metal compound, Gd(H2O)(3)Co[C5N1H3-(COO)(2)](3), are described; the structure is unique, consisting of sheets with large pores ( ca. 7 angstrom diameter) in the sheets and transforms to a perovskite oxide at moderate temperatures.

Phase transformation, oxidation and hydration of raseodymium sesquioxide

The C→A transformation of Pr2O3 has been examined. The transformation is sluggish and takes place at and above 750°C. C-Pr2O3 is oxidized at a lower temperature than the A-form and oxidation proceeds in two stages in both cases. A hydrate Pr 2O3 . H2O, formed by the interaction of C-Pr2O3 and water at relatively high temperature, is described and its behaviour compared with that of Pr(OH)3. The C-form undergoes hydration at 40°C while the A-form does not. All the observations have been explained in terms of the defect structure of C-Pr2O 3.