Lead-free piezoelectric system (Na0.5Bi0.5)TiO3-BaTiO3: Equilibrium structures and irreversible structural transformations driven by electric field and mechanical impact

The structure-property correlation in the lead-free piezoelectric (1 - x)(Na0.5Bi0.5)TiO3-(x)BaTiO3 has been systematically investigated in detail as a function of composition (0 < x <= 0.11), temperature, electric field, and mechanical impact by Raman scattering, ferroelectric, piezoelectric measurement, x-ray, and neutron powder diffraction methods. Although x-ray diffraction study revealed three distinct composition ranges characterizing different structural features in the equilibrium state at room temperature: (i) monoclinic (Cc) + rhombohedral (R3c) for the precritical compositions, 0 <= x <= 0.05, (ii) cubiclike for 0.06 <= x <= 0.0675, and (iii) morphotropic phase boundary (MPB) like for 0.07 <= x < 0.10, Raman and neutron powder diffraction studies revealed identical symmetry for the cubiclike and the MPB compositions. The cubiclike structure undergoes irreversible phase separation by electric poling as well as by pure mechanical impact. This cubiclike phase exhibits relaxor ferroelectricity in its equilibrium state. The short coherence length (similar to 50A degrees) of the out-of-phase octahedral tilts does not allow the normal ferroelectric state to develop below the dipolar freezing temperature, forcing the system to remain in a dipolar glass state at room temperature. Electric poling helps the dipolar glass state to transform to a normal ferroelectric state with a concomitant enhancement in the correlation length of the out-of-phase octahedral tilt.

Analogous stress and electric field driven structural transformation and decrease in polarization coherence on poling around the morphotropic phase boundary in BiScO3-PbTiO3

The nature of the stress and electric field driven structural and microstructural transformations in the morphotropic phase boundary (MPB) compositions of the high Curie point piezoelectric system BiScO3-PbTiO3 has been examined by ex situ based techniques. Using a powder poling technique, which is based on the concept of exploiting the irreversible structural change that occurs after the application of a strong electric field and stress independently, it was possible to ascertain that both moderate stress and electric field induce identical structural transformation-a fraction of the monoclinic phase transforms irreversibly to the tetragonal phase. Moreover, analysis of the dielectric response before and after poling revealed a counterintuitive phenomenon of poling induced decrease in the spatial coherence of polarization for compositions around the MPB and not so for compositions far away from the MPB range. Exploiting the greater sensitivity of this technique, we demonstrate that the criticality associated with the interferroelectric transition spans a wider composition range than what is conventionally reported in the literature based on bulk x-ray/neutron powder diffraction techniques.

Unraveling the nature of electric field- and stress- induced structural transformations in soft PZT by a new powder poling technique

A `powder-poling' technique was developed to study electric field induced structural transformations in ferroelectrics exhibiting a morphotropic phase boundary (MPB). The technique was employed on soft PZT exhibiting a large longitudinal piezoelectric response (d(33) similar to 650 pCN(-1)). It was found that electric poling brings about a considerable degree of irreversible tetragonal to monoclinic transformation. The same transformation was achieved after subjecting the specimen to mechanical stress, which suggests an equivalence of stress and electric field with regard to the structural mechanism in MPB compositions. The electric field induced structural transformation was also found to be accompanied by a decrease in the spatial coherence of polarization.

On Ultrafast Time-Domain TeraHertz Spectroscopy in the Condensed Phase: Linear Spectroscopic Measurements of Hydrogen-Bond Dynamics of Astrochemical Ice Analogs and Nonlinear TeraHertz Kerr Effect Measurements of Vibrational Quantum Beats

Much of the chemistry that affects life on planet Earth occurs in the condensed phase. The TeraHertz (THz) or far-infrared (far-IR) region of the electromagnetic spectrum (from 0.1 THz to 10 THz, 3 cm^-1 to 300 cm^-1, or 3000 μm to 30 μm) has been shown to provide unique possibilities in the study of condensed-phase processes. The goal of this work is to expand the possibilities available in the THz region and undertake new investigations of fundamental interest to chemistry. Since we are fundamentally interested in condensed-phase processes, this thesis focuses on two areas where THz spectroscopy can provide new understanding: astrochemistry and solvation science. To advance these fields, we had to develop new instrumentation that would enable the experiments necessary to answer new questions in either astrochemistry or solvation science. We first developed a new experimental setup capable of studying astrochemical ice analogs in both the TeraHertz (THz), or far-Infrared (far-IR), region (0.3 - 7.5 THz; 10 - 250 cm^-1) and the mid-IR (400 - 4000 cm^-1). The importance of astrochemical ices lies in their key role in the formation of complex organic molecules, such as amino acids and sugars in space. Thus, the instruments are capable of performing variety of spectroscopic studies that can provide especially relevant laboratory data to support astronomical observations from telescopes such as the Herschel Space Telescope, the Stratospheric Observatory for Infrared Astronomy (SOFIA), and the Atacama Large Millimeter Array (ALMA). The experimental apparatus uses a THz time-domain spectrometer, with a 1750/875 nm plasma source and a GaP detector crystal, to cover the bandwidth mentioned above with ~10 GHz (~0.3 cm^-1) resolution.

Using the above instrumentation, experimental spectra of astrochemical ice analogs of water and carbon dioxide in pure, mixed, and layered ices were collected at different temperatures under high vacuum conditions with the goal of investigating the structure of the ice. We tentatively observe a new feature in both amorphous solid water and crystalline water at 33 cm^-1 (1 THz). In addition, our studies of mixed and layered ices show how it is possible to identify the location of carbon dioxide as it segregates within the ice by observing its effect on the THz spectrum of water ice. The THz spectra of mixed and layered ices are further analyzed by fitting their spectra features to those of pure amorphous solid water and crystalline water ice to quantify the effects of temperature changes on structure. From the results of this work, it appears that THz spectroscopy is potentially well suited to study thermal transformations within the ice.

To advance the study of liquids with THz spectroscopy, we developed a new ultrafast nonlinear THz spectroscopic technique: heterodyne-detected, ultrafast THz Kerr effect (TKE) spectroscopy. We implemented a heterodyne-detection scheme into a TKE spectrometer that uses a stilbazoiumbased THz emitter, 4-N,N-dimethylamino-4-N-methyl-stilbazolium 2,4,6-trimethylbenzenesulfonate (DSTMS), and high numerical aperture optics which generates THz electric field in excess of 300 kV/cm, in the sample. This allows us to report the first measurement of quantum beats at terahertz (THz) frequencies that result from vibrational coherences initiated by the nonlinear, dipolar interaction of a broadband, high-energy, (sub)picosecond THz pulse with the sample. Our instrument improves on both the frequency coverage, and sensitivity previously reported; it also ensures a backgroundless measurement of the THz Kerr effect in pure liquids. For liquid diiodomethane, we observe a quantum beat at 3.66 THz (122 cm^-1), in exact agreement with the fundamental transition frequency of the υ4 vibration of the molecule. This result provides new insight into dipolar vs. Raman selection rules at terahertz frequencies.

To conclude we discuss future directions for the nonlinear THz spectroscopy in the Blake lab. We report the first results from an experiment using a plasma-based THz source for nonlinear spectroscopy that has the potential to enable nonlinear THz spectra with a sub-100 fs temporal resolution, and how the optics involved in the plasma mechanism can enable THz pulse shaping. Finally, we discuss how a single-shot THz detection scheme could improve the acquisition of THz data and how such a scheme could be implemented in the Blake lab. The instruments developed herein will hopefully remain a part of the groups core competencies and serve as building blocks for the next generation of THz instrumentation that pushes the frontiers of both chemistry and the scientific enterprise as a whole.

Local equilibrium of the Gibbs interface in two-phase systems

We analyze the local equilibrium assumption for interfaces from the perspective of gauge transformations, which are the small displacements of Gibbs' dividing surface. The gauge invariance of thermodynamic properties turns out to be equivalent to conditions for jumps of bulk densities across the interface. This insight strengthens the foundations of the local equilibrium assumption for interfaces and can be used to characterize nonequilibrium interfaces in a compact and consistent way, with a clear focus on gauge-invariant properties. Using the principle of gauge invariance, we show that the validity of Clapeyron equations can be extended to nonequilibrium interfaces, and an additional jump condition for the momentum density is recognized to be of the Clapeyron type. © 2012 Europhysics Letters Association.

An investigation on the pressure-induced phase transition of nanocrystalline ZnS

An in situ energy dispersive x-ray diffraction study on nanocrystalline ZnS was carried out under high pressure up to 30.8 GPa by using a diamond anvil cell. The phase transition from the wurtzite to the zinc-blende structure occurred at 11.5 GPa, and another obvious transition to a new phase with rock-salt structure also appeared at 16.0 GPa-which was higher than the value for the bulk material. The bulk modulus and the pressure derivative of nanocrystalline ZnS were derived by fitting the Birch-Murnaghan equation. The resulting modulus was higher than that of the corresponding bulk material, indicating that the nanomaterial has higher hardness than the bulk material.

Developments and applications of supported liquid phase catalysts

Supported liquid phase catalyst (SLPC) is one of effectively heterogenized homogeneous catalysts using organometallic complexes as active components, which are dissolved in a small quantity of liquid phase dispersed in the form of isle or film on the surface of supports. The SLPC has successfully been applied for several chemical transformations and this article will review recent results with respect to the preparation and catalytic performance, the applicability to continuous flow operations, and the capability of multifunctional catalysis.

Mechanical and thermal induced chain conformational transformations in syndiotactic polypropylene (sPP)

Stretching a stacked sPP lamellar morphology at room temperature leads to a mechanical induced transformation from the (t(2)g(2))(2) (helical) into the (tttt) (zigzag) chain conformation of the polymer. The so prepared samples exhibit after annealing above 80 degreesC a thermal induced retransformation into the cell I and cell III crystal structure of the helical chain conformation. The mechanical induced chain conformational transformation as well as the thermal induced retransformation was studied by means of transmission electron microscopy and electron diffraction. (C) 2001 Kluwer Academic Publishers.

Investigation of catalyst effects in enantioselective copper- and rhodium-mediated transformations of α-diazocarbonyl compounds

This thesis describes the synthesis and reactivity of a series of α-diazocarbonyl compounds with particular emphasis on the use of copper-bis(oxazoline)-mediated enantioselective C–H insertion reactions leading to enantioenriched cyclopentanone derivatives. Through the use of additives, the enantioselectivity achieved with the copper catalysts for the first time reaches synthetically useful levels (up to 91% ee). Chapter one provides a comprehensive overview of enantioselective C–H insertions with α-diazocarbonyl compounds from the literature. The majority of reports in this section involve rhodium-catalysed systems with limited reports to date of asymmetric C–H insertion reactions in the presence of copper catalysts. Chapter two focuses on the synthesis and C–H insertion reactions of α-diazo-β-keto sulfones leading to α-sulfonyl cyclopentanones as the major product. Detailed investigation of the impact of substrate structure (both the sulfonyl substitutent and the substituent at the site of insertion), the copper source, ligand, counterion, additive and solvent was undertaken to provide an insight into the mechanistic basis for enantiocontrol in the synthetically powerful C–H insertion process and to enable optimisation of enantiocontrol and ligand design. Perhaps the most significant outcome of this work is the enhanced enantioselection achieved through use of additives, substantially improving the synthetic utility of the asymmetric C–H insertion process. In addition to the C–H insertion reaction, mechanistically interesting competing reaction pathways involving hydride transfer are observed. Chapter three reports the extension of the catalyst-additive systems, developed for C–H insertions with α-diazo-β-keto sulfones in chapter two, to C–H insertion in analogous α-diazo-β-keto phosphonate and α-diazo-β-keto ester systems. While similar patterns were seen in terms of ligand effects, the enantiopurities achieved for these reactions were lower than those in the cyclisations with analogous α-diazo-β-keto sulfones. Extension of this methodology to cyclopropanation and oxium ylide formation/[2,3]-sigmatropic rearrangement was also explored. Chapter four contains the full experimental details and spectral characterisation of all novel compounds synthesised in this project, while details of chiral stationary phase HPLC analysis and X-ray crystallography are included in the appendix.

A Phase-field Model for Computer Simulation of Lamellar Structure Formation in y-TiAI

In the present paper, a phase-field model is developed to simulate the formation and evolution of lamellar microstructure in γ-TiAl alloys. The mechanism of formation of TiAl lamellae proposed by Denquin and Naka is incorporated into the model. The model describes the formation and evolution of the face-centered cubic (fcc) stacking lamellar zone followed by the subsequent appearance and growth of the γ-phase, involving both the chemical composition change by atom transfer and the ordering of the fcc lattice. The thermodynamics of the model system and the interaction between the displacive and diffusional transformations are described by a non-equilibrium free energy formulated as a function of concentration and structural order parameter fields. The long-range elastic interactions, arising from the lattice misfit between the α, fcc (A1) and the various orientation variants of the γ-phase are taken into account by incorporating of the elastic strain energy into the total free energy. Simulation studies based on the model successfully predicted some essential features of the lamellar structure. It is found that the formation and evolution of the lamellar structure are predominantly controlled by the minimization of the elastic energy of the interfaces between the different fcc stacking groups, low-symmetry product phase γ and the high-symmetry α-phase, as well as between the various orientation variants of the product phase.

Cloning transformations in spin networks without external control

In this paper we present an approach to quantum cloning with unmodulated spin networks. The cloner is realized by a proper design of the network and a choice of the coupling between the qubits. We show that in the case of phase covariant cloner the XY coupling gives the best results. In the 1 -> 2 cloning we find that the value for the fidelity of the optimal cloner is achieved, and values comparable to the optimal ones in the general N -> M case can be attained. If a suitable set of network symmetries are satisfied, the output fidelity of the clones does not depend on the specific choice of the graph. We show that spin network cloning is robust against the presence of static imperfections. Moreover, in the presence of noise, it outperforms the conventional approach. In this case the fidelity exceeds the corresponding value obtained by quantum gates even for a very small amount of noise. Furthermore, we show how to use this method to clone qutrits and qudits. By means of the Heisenberg coupling it is also possible to implement the universal cloner although in this case the fidelity is 10% off that of the optimal cloner.

Adaptation de la phase de planification et d’initiation du mouvement d’atteinte visuellement guidé à différentes dissociations visuomotrices.

L’hypothèse générale de ce projet soutient que le système moteur doit performer des transformations sensorimotrices afin de convertir les entrées sensorielles, concernant la position de la cible à atteindre, en commande motrice, afin de produire un mouvement du bras et de la main vers la cible à atteindre. Ce type de conversion doit être fait autant au niveau de la planification du mouvement que pour une éventuelle correction d’erreur de planification ou d’un changement inopiné de la position de la cible. La question de recherche du présent mémoire porte sur le ou les mécanismes, circuits neuronaux, impliqués dans ce type de transformation. Y a-t-il un seul circuit neuronal qui produit l’ensemble des transformations visuomotrices entre les entrées sensorielles et les sorties motrices, avant l’initiation du mouvement et la correction en temps réel du mouvement, lorsqu’une erreur ou un changement inattendu survient suite à l’initiation, ou sont-ils minimalement partiellement indépendants sur le plan fonctionnel? L’hypothèse de travail suppose qu’il n’y ait qu’un seul circuit responsable des transformations sensorimotrices, alors l’analyse des résultats obtenus par les participants devrait démontrer des changements identiques dans la performance pendant la phase de planification du mouvement d’atteinte et la phase de correction en temps réel après l’adaptation à des dissociations sensorimotrices arbitraires. L’approche expérimentale : Dans la perspective d’examiner cette question et vérifier notre hypothèse, nous avons jumelé deux paradigmes expérimentaux. En effet, les mouvements d’atteinte étaient soumis à une dissociation visuomotrice ainsi qu’à de rares essais composés de saut de cible. L’utilisation de dissociation visuomotrice permettait d’évaluer le degré d’adaptation des mécanismes impliqués dans le mouvement atteint. Les sauts de cible avaient l’avantage de permettre d’examiner la capacité d’adaptation à une dissociation visuomotrice des mécanismes impliqués dans la correction du mouvement (miroir : sur l’axe y, ou complète : inversion sur les axes x et y). Les résultats obtenus lors des analyses effectuées dans ce mémoire portent exclusivement sur l’habileté des participants à s’adapter aux deux dissociations visuomotrices à la première phase de planification du mouvement. Les résultats suggèrent que les mécanismes de planification du mouvement possèdent une grande capacité d’adaptation aux deux différentes dissociations visuomotrices. Les conclusions liées aux analyses présentées dans ce mémoire suggèrent que les mécanismes impliqués dans la phase de planification et d’initiation du mouvement parviennent relativement bien à s’adapter aux dissociations visuomotrices, miroir et inverse. Bien que les résultats démontrent une certaine distinction, entre les deux groupes à l’étude, quant aux délais nécessaires à cette adaptation, ils illustrent aussi un taux d’adaptation finale relativement similaire. L’analyse des réponses aux sauts de cible pourra être comparée aux résultats présentés dans ce mémoire afin de répondre à l’hypothèse de travail proposée par l’objectif initial de l’étude.

On the stability of the bcc phase in Cu-Al-Mn shape memory alloys

Measurements of the entropy change at the martensitic transition of two composition-related sets of Cu-Al-Mn shape-memory alloys are reported. It is found that most of the entropy change has a vibrational origin, and depends only on the particular close-packed structure of the low-temperature phase. Using data from the literature for other Cu-based alloys, this result is shown to be general. In addition, it is shown that the martensitic structure changes from 18R to 2H when the ratio of conduction electrons per atom reaches the same value as the eutectoid point in the equilibrium phase diagram. This finding indicates that the structure of the metastable low-temperature phase is reminiscent of the equilibrium structure.

Premartensitic and martensitic phase transitions in ferromagnetic Ni2MnGa

We present an experimental study of the premartensitic and martensitic phase transitions in a Ni2MnGa single crystal by using ultrasonic techniques. The effect of applied magnetic field and uniaxial compressive stress has been investigated. It has been found that they substantially modify the elastic and magnetic behavior of the alloy. These experimental findings are a consequence of magnetoelastic effects. The measured magnetic and vibrational behavior agrees with the predictions of a recently proposed Landau-type model [A. Planes et al., Phys. Rev. Lett. 79, 3926 (1997)] that incorporates a magnetoelastic coupling as a key ingredient.

Hysteresis in a system driven by either generalized force or displacement variables: martensitic phase transition in single-crystalline Cu-Zn-Al

We report on experiments aimed at comparing the hysteretic response of a Cu-Zn-Al single crystal undergoing a martensitic transition under strain-driven and stress-driven conditions. Strain-driven experiments were performed using a conventional tensile machine while a special device was designed to perform stress-driven experiments. Significant differences in the hysteresis loops were found. The strain-driven curves show reentrant behavior yield point which is not observed in the stress-driven case. The dissipated energy in the stress-driven curves is larger than in the strain-driven ones. Results from recently proposed models qualitatively agree with experiments.