Thesis (PhD (Physics))--University of Stelllenbosch, 2010. / ENGLISH ABSTRACT: In this dissertation a fully relativistic model for polarized inclusive quasielastic proton-nucleus scattering is developed. Using a standard relativistic impulse approximation (RIA) treatment of quasielastic scattering and a two-body SPVAT form of the current operator, it is shown how the behaviour of projectile and target can be decoupled. Subsequently, different models for projectile and target can be adopted and combined to examine a variety of relativistic effects. The most simplistic model of the target is provided by a mean-field nuclear matter approximation to the relativistic meson-nucleon model, quantum hadrodynamics (QHD). Here relativistic effects manifest as an effective mass, which is lower than the free mass, of the constituent nucleons. This model is improved upon by including many-body correlations through medium-modification of meson propagators in the relativistic random-phase approximation (RPA). Since it is generally accepted that the strong nuclear force and the extended range of the nuclear potential lead to distortion effects on the projectile and ejectile (seen as a modulation of the wave functions), our formalism is geared towards the use of relativistic distorted waves (RDWIA). The distorted waves are written as partial wave expansions and are solutions to the Dirac equation with potentials. The inclusion of distortions, however, greatly increases the computational burden and we show how a number of analytical and numerical techniques can be used to facilitate the process of calculation. It is also shown how the standard relativistic plane wave treatment (RPWIA) can, instead, be easily employed to obtain a baseline for determining the impact of distortions. A calculation is performed for the reaction 40Ca(!p, !p !) at a beam energy of 500 MeV. Here it is found that the effect of correlations on the RPWIA calculation can be seen as a quenching of the cross section that is expected to become more pronounced at lower energies or for higher density targets. A RDWIA calculation shows additional reduction and if target correlations are included this effect is enhanced. To our knowledge this is the first calculation that attempts to include both these effects (RPA and RDWIA) in the context of quasielastic proton-nucleus scattering. / AFRIKAANSE OPSOMMING: In hierdie proefskrif word ’n ten volle relatiwistiese model vir die berekening van inklusiewe kwasielastiese proton-kern verstrooiing daargestel. Deur gebruik te maak van ’n standaard relatiwistiese impulsbenadering (RIA) vir kwasi-elastiese verstrooiing asook ’n twee-deeltjie-SPVAT-vorm vir die stroom-operator, word daar gewys hoedat die gedrag van die projektiel en teiken ontkoppel kan word. Verskillende modelle kan dus vir die projektiel en teiken gebruik word om ’n verskeidenheid relatiwistiese effekte te bestudeer. Die mees simplistiese model vir die teiken word verskaf deur ’n gemiddelde-veld kernmateriaalbenadering tot die relatiwistiese meson-nukleon-model, kwantum-hadrodinamika (QHD). In hierdie model manifesteer relatiwistiese effekte as ’n effektiewe massa, wat kleiner is as die vrye massa, van nukleone in die kern. Hierdie model word verbeter deur die inagneming van veeldeeltjie korrelasies deur medium-gewysigde meson-propagators in die relatiwistiese ewekansige-fase-benadering (RPA). Aangesien dit algemeen aanvaar word dat die sterk-wisselwerking en die reikwydte van die kernpotensiaal aanleiding gee tot vervormingseffekte op die projektiel en ejektiel (gesien as die modulasie van golffunksies), is ons model optimaal geformuleer om gebruik te maak van relatiwistiese vervormde golwe (RDWIA). Die vervormde golwe word geskryf as parsi¨elegolf uitbreidings en dien as oplossings vir die Dirac-vergelyking met potensiale. Insluiting van vervormings vermeerder egter die berekeningslas geweldig en ons toon hoedat ’n aantal analitiese en numeriese tegnieke gebruik kan word om die proses te vergemaklik. Daar word ook aangetoon hoe die standaard- relatiwistiese-vlakgolf-benadering (RPWIA), in plaas van vevormde golwe, maklik gebruik kan word om ’n verwysingspunt vir die meting van die effek van vervormings te bepaal. ’n Berekening vir die reaksie 40Ca(!p, !p !) teen ’n projektiel-energie van 500 MeV word getoon. Hier word dit gevind dat die effek van korrelasies op die RPWIA-berekening gesien kan word as ’n verlaging van die kansvlak. Daar word verwag dat hierdie effek duideliker sal word by laer energie¨e en ho¨er kerndigthede. ’n RDWIA-berekening word getoon wat daarop dui dat addisionele verlaging in die kansvlak voorkom en indien korrelasies hier ingesluit word, word hierdie effek vergroot. Sover ons kennis strek, is hierdie die eerste berekening wat poog om beide hierdie effekte (RPA en RDWIA) in die konteks van kwasi-elastiese proton-kern verstrooiing in te sluit.

The aim of nuclear structure studies is to observe and describe the structures and associated symmetries in nuclei, which in turn help us in understanding the nature of nucleon-nucleon interactions in a nucleus as a many-body quantum system. The protons and neutrons as constituents of a nucleus and their interactions are responsible for nuclear properties. The evolution of nuclear structure as a function of valence nucleon number, i.e., the number of nucleons beyond a magic number, can be inferred from the experimental level scheme and transition rates. In particular, the studies of low-lying, low-spin excited states in stable nuclei provide valuable information on the interplay of valence neutrons and protons in nuclear structure. The decay scheme and knowledge of transition strengths in the low-lying states become a benchmark for testing theoretical model predictions and understanding the underlying microscopic foundations of nuclear structure. Along with the experimental techniques, theoretical models have been developed to explain and describe the observed nuclear properties, e.g., shell model, Fermi-gas model, optical and liquid-drop models, and several “collective” models. 94/40Zr50 nucleus with 2 protons and 4 neutrons above the shell closures of the 88/38Sr50 core nucleus is considered as a nearly spherical nucleus. Such nuclei present a vibrational structure; surface vibration of the nucleus about a spherical shape. In addition to the symmetric excitations, in which proton and neutron oscillations are in phase, there are another class of excitations in which the wave function is not fully symmetric with respect to the exchange of protons and neutrons. These states are so called mixed-symmetry (MS) states. Such excitations have been observed in the N= 52 neighboring isotones. In this study, the low-lying structure of 94/40Zr has been studied with the (n, n'ƴ) reaction at the University of Kentucky and Triangle Universities Nuclear Laboratories (TUNL) facilities, to identify symmetric and MS excitations in this nucleus. A decay scheme has been established based on excitation function and coincidence measurements. Branching ratios, multipole mixing ratios, and spin assignments have been determined from angular distribution measurements at En= 2.3, 2.8, and 3.5 MeV. Lifetimes of levels up to 3.4 MeV were measured by the Doppler-shift attenuation method (DSAM), and for many transitions reduced transition probabilities were determined. The experimental results were used for the identification of collective symmetric and mixed-symmetric (MS) multiphonon excitations. The 2+/2 state at 1671.4 keV has been identified as the lowest MS state in 94Zr; B(M1; 2+/ms → 2+/1 ) = 0.31(3) μ2/N. This state has an anomalous decay behavior, i.e., B(E2; 2+/ ms → 0+/1 ) = 7.8(7) W.u., which is unusually large compared to the B(E2; 2+/1 → 0+/1 ) = 4.9(3) W.u. More anomalies were identified in the states above the 2+/ms state. For example, the 4+/2 state at 2330 keV decays strongly to the 2+/1 state, B(E2; 4+/2 → 2+/1 ) = 20+3/−2 W.u., compared to the 4+/1 state at 1469 keV, B(E2; 4+/1 → 2+/1 ) = 0.878(23) W.u. The experimental results revealed additional interesting and unusual properties of the low-lying states in 94Zr. Shell model calculations were performed with the Oxbash code, using the Vlow k interaction. Also, the IBM-2 predictions in the vibrational limit were compared with the experimental results. The results from neither of these nuclear models were in good agreement with the observed transition strengths, e.g., the B(E2; 2+/ms → 0+/1 ) value. These observations may indicate that the contributions of valence nucleons in the low-lying excited states of 94Zr differ from what has been perscribed by the shell model and the IBM-2 model. The effects of the Z = 40 and N = 56 subshell closures should be also considered. In a simple interpretation, the excited states are classified in two distinct categories, i.e., those populating the 2+/2 state and those decaying to the 2+/1 state. This approach suggests that in 94Zr the low-lying states may be related to two-configurations coexistence.

Magnetic recording media refers to the disc shaped thin film magnetic medium present inside the hard disk drive of a computer. Magnetic recording is an important function of the hard disk drive by which information such as text, pictures, audio and videos are stored. Information is broken down to a simple binary format and is stored as magnetised bits along the tracks of the disk forming the hard drive. Over the years advancements in research on the type of magnetic materials used has allowed increased data storage capacities by reducing magnetic bit sizes. It is with this advancement in magnetic data storage, that we have today's hard disk drive technology, which uses a perpendicular magnetic medium to store data. A perpendicular magnetic medium is a multi-layered magnetic thin film structure with the topmost layer comprising nanoscale magnetic grains of high perpendicular anisotropy. The topmost recording layer (RL) is mapped into individual bits of 80-100 nm² area that consist of 5-10 nm diameter CoCrPt grains, embedded in an oxide matrix. A bit area is defined to ensure a significant number of stable grains allowing data to be stored in each bit as a ‘0' or a ‘1' depending on its switched magnetic state. The magnetic grains if sputtered below a threshold grain size tend to suffer from thermal fluctuation and instability due to super-paramagnetic effects, hence bringing limitations to grain size. As a result of this, research in recent years has been directed at introducing a softer magnetic exchange coupled composite (ECC) layer above the recording layer. This layer facilitates the delicate balance of switching smaller grains with strong magneto-crystalline anisotropy at lower magnetic fields, by exchange coupling with the CoCrPt grains in the recording layer. However this technique of increasing the efficiency in the perpendicular magnetic medium by introducing ‘facilitating' layers is an area that is still being widely researched and understood. Although numerous surface and bulk analysis techniques exist to study magnetic and surface properties of these materials, there is limited information on the structural and magnetic properties of these materials at the nanoscale level. The reported work investigates the structural and magnetic properties of the magnetic grains and multi-layers in the perpendicular magnetic medium using polarised neutron scattering and reflectivity techniques. The work investigates the structural and magnetic properties of the CoCrPt grains, apart from understanding the CoCrPt magnetic grain switching. The work also investigates the magnetisation in the layers of the thin film perpendicular media structure using polarised neutron reflectivity (PNR). Using polarised small angle neutron scattering (PolSANS), it has been shown that ferromagnetic ordered core region of the CoCrPt grain in the recording layer is smaller than the physical CoCrPt granular structure. The magnetic switching behaviour of the CoCrPt grain at different magnetic fields is also analysed and the experimental PolSANS data is fitted with non-interacting size-dependent analytical grain switching models. This result provides significant evidence that the magnetic anisotropy increases with grain size, with larger magnetic grains having larger magnetic anisotropy. Polarised neutron scattering experiments are carried out with the magnetically softer exchange coupled composite (ECC) layer included in the thin film magnetic structure. The first experiments investigate if the ECC layer contributes to the nuclear and magnetic interference scattering term in the experimenting scattering data. The experiments clearly show that there is no contribution from the ECC layer in the nuclear and magnetic scattering interference term. The role of the ECC layer in the magnetic switching process is then investigated at different magnetic fields. The ECC layer was found to influence the size-dependent magnetic grain switching of the CoCrPt grains in the recording layer and a detailed investigation is presented in the reported work. Polarised neutron reflectivity (PNR) experiments have also been carried out with the ECC layer on the perpendicular magnetic media samples. These experiments investigate the composition and thickness of the thin film structure, while also providing information on the magnetic state of the thin films under the influence of an in-plane magnetic field. The in-plane magnetisation in the recording and ECC layer is determined at different in-plane magnetic fields. The magnetisation values determined for the ECC layer and the recording layer (RL) at different in-plane magnetic fields help better understand the differences in their magnetic properties.

This thesis presents details of x-ray and neutron scattering experiments used to probe quantum magnets with strong spin-orbit interaction. The first of these systems are the three-dimensional iridate compounds, in which the three-fold co-ordination of IrO₆ octahedra has been theoretically hypothesized to stabilize anisotropic exchange between Ir⁴⁺ ions. This novel interaction between these spin-orbital entangled, J_eff=1/2 moments is described by a Hamiltonian first proposed by Kitaev, and would be the first physical realization of this Hamiltonian in a condensed matter system. This thesis details the determination of the structure of a new polytype within these compounds, the 'stripyhoneycomb' &gamma;-Li₂IrO₃. Furthermore, through resonant magnetic x-ray diffraction experiments on single crystals of &beta;-Li₂IrO₃ and &gamma;-Li₂IrO₃, an incommensurate, non-coplanar structure with counter-rotating moments is found. The counter-rotating moment structure is a rather counter-intuitive result, as it is not stabilizied by Heisenberg exchange between magnetic sites, however, the Kitaev exchange naturally accounts for this feature. As such, these experiments reveal, for the first time, systems which exhibit dominant Kitaev interactions. The ordering wavevector of both &beta;- and &gamma;-Li₂IrO₃ polytypes are found to be identical, suggesting that the same magnetic interactions are responsible for stabilizing magnetic order in both materials, despite their different lattice topologies. Following this, the spinel FeSc₂S₄ is considered. Here, despite the presence of strong exchange between Fe<sup>2+,/sup>, and the fact that these ions sit in a Jahn-Teller active environment, the system does not order in the spin or orbital degrees of freedom. A 'spin-orbital singlet' has been theoretically proposed to describe the groundstate of this system, and here inelastic neutron scattering (INS) is used to probe the resulting triplon excitations. This allows determination of microscopic parameters in the single ion and exchange Hamiltonians, and moreover experiments in external magnetic field reveal the true spin-and-orbital nature of these triplon excitations. Finally, Ba₃CoSb₂O₉, a physical realization of the canonical triangular antiferromagnet model is explored with INS and the high energy excitations from the 120 degree magnetic structure are found to display significant differences from those calculated by linear spin wave theory, suggesting the presence of quantum dynamics not captured in the 1/S linear spin wave expansion.

Ce travail de thèse présente les résultats obtenus lors de l'étude des mécanismes élémentaires à l'origine de la forte conduction protonique mesurée dans le cas de clathrates hydrates d'acides forts. Une méthodologie combinant diffusion neutronique, résonance magnétique nucléaire et simulation de dynamique moléculaire "ab-initio" a permis de modéliser les différents processus dynamiques impliqués, se produisant sur des temps allant de la nanoseconde à la femtoseconde. Le modèle proposé explique la forte conduction de ces systèmes aqueux par la délocalisation à longue distance de leurs protons résultant d'un mécanisme de type Grotthuss gouverné par la relaxation des molécules aqueuses environnant les protons en excès. / This work shows the results obtain about the study of elementary mechanisms behind the high protonic conduction of strong acids clathrate hydrate. A method using quasiélastic neutron scattering and pulse field gradient NMR experiments both with DFT molecular dynamic simulations allowed to establish a model which describe the several dynamical processes involve occuring on timescales from nanosecond to femtosecond. The model deduced explain the high conduction property of ionic clathrate hydrate by a delocalization of their protons following a grotthuss type mecanism managed by the relaxation of water molecules around the excess protons.

Le but de ce travail était de réaliser une étude systématique de la structure électronique et magnétique de la famille des manganites semi-dopés du Ca: Ln0.50Ca0.50MnO3 (Ln=REE). Nous avons focalisé notre attention sur l'ordre de charge (CO) et l'ordre orbital (OO) présents dans les manganites. Nous avons dérivé un modèle microscopique de structure nucléaire et magnétique à partir de la diffraction neutronique sur les poudres (NPD) et de calculs ab-initio afin de comparer les résultats expérimentaux et les modèles numériques et comprendre ainsi le rôle de l'inhomogénéité chimique et magnétique dans ces systèmes. La modification de l'état de spin électronique et du métal de transition par le dopage correspond à une modification structurale de la géométrie du polyèdre de coordination des atomes autour du métal de transition, induisant des changements structurels de coopération. En contraste avec l'ordre par le dopage chimique, un désordre chimique intrinsèque est associé à l'élément de dopage sur le site A du perovskite (formule générale ABO3) où sont placés les ions trivalents (RE3+) et bivalents (Ca2+). Ceci est dû à la différence de rayon ionique et d'affinité chimique entre ces ions. Afin d'étudier systématiquement l'effet de la substitution au niveau du site A et la relation entre les propriétés structurales et magnétiques, plusieurs échantillons ont été caractérisés. Les résultats de NPD sont une étape fondamentale vers la compréhension de la relation entre les propriétés structurales et magnétique et sont une source de motivation pour l'étude de la structure magnétique et des phénomènes de CO/OO par des simulations ab-initio. L'effet Jahn-Teller, les interactions de double- et super-échange, et le modèle de Zener seront introduits. Les propriétés magnétiques macroscopiques ont été mesurées en fonction de la température á l'aide d'un SQUID. La technique microscopique principale utilisée pour cette étude a été la NPD. Les instruments utilisés à l'institut Laue Langevin à Grenoble, D20 et D1A, et la méthode de Rietveld utilisée pour affiner les données expérimentales et en extraire les informations structurales seront décrits. Les résultats expérimentaux correspondant à l'étude systématique sur les échantillons de manganites de Ln0.50Ca0.50MnO3 (Ln = Pr, Nd, Tb, Dy, Ho, Tm, Yb and Lu) et une description de leur préparation seront présentés. La susceptibilité magnétique mesurée jusqu'à 530 K présente un pic large à températures élevées correspondant à la température de CO (TCO). Nous définissons la nature des corrélations magnétiques au-dessus et en-dessous de TCO dans le cadre du modèle des polarons de Zener. Nous présentons la structure nucléaire et magnétique pour tous les échantillons en fonction de la température et les déformations dues au dopage et à l'effet du rayon ionique. Tous nos systèmes ont une configuration magnétique de type pseudo-CE à la plus basse température correspondant à un état de type CE avec un effet de canting. Nous décrirons les calculs ab-initio pour modéliser notre série : le programme VASP, utilisé pour les calculs, la théorie DFT, les approximations faite, comme le fonctionnelle d'échange-corrélation (GGA-PBE), la correction d'Hubbard (GGA+U) seront présentée. Les calculs ont été effectués pour confirmer les résultats expérimentaux et pour accéder à d'autres quantités significatives comme la densité d'états électroniques. Les simulations ont été effectuées avec la DFT spin-polarisée, le GGA-PBE, et la GGA+U, pour considérer la corrélation électronique forte. Nous avons choisi deux systèmes purs: CaMnO3 et NdMnO3. Deux systèmes semi-dopés (Ln=Nd et Lu), ont été considérés, parce que les composés avec le La et le Pr ont été déjà étudié (Picozzi, Anisimov), et nous suivons la série avec Ln=Nd, et l’outre parce que le Lu, à l'instar de La, est saturé au niveau de ses orbitales 4f et qu'il présente de surcroit le plus petit rayon ionique dans la série de lanthanides. / The aim of this work was to realize a systematic study of the electronic and magnetic structure of Ca half-doped manganite family: Ln0.50Ca0.50MnO3 (Ln=REE). In particular, we focused our attention on charge ordering (CO) and orbital ordering (OO) phenomena present in manganites. We derived a microscopic model of nuclear and magnetic structure using both neutron powder diffraction (NPD) techniques and ab-initio calculations in order to compare experimental results and numerical models and to understand the role of chemical and magnetic in-homogeneity in our systems. The change of the electronic and spin state of the transition metal by doping, corresponds to a structural modification of the coordination polyhedron geometry of the atoms around the transition metal, inducing cooperative structural changes. In contrast with this order induced by doping, an intrinsic chemical disorder is associated with the doping element on the A site of the perovskite (general formula ABO3) on which the trivalent (RE3+) and divalent ions (Ca2+) reside. This disorder is due to the difference of the ionic radius and chemical affinity between the ions. In order to study systematically the effect of the A site substitution and the relation between the structural properties and the macroscopic magnetic properties, several samples have been synthesized and characterized by macroscopic magnetic measurements. Neutron diffraction is a fundamental step towards understanding the relation between the structural and macroscopic properties. The resulting structures represent a good starting point for ab-initio calculations in the study of magnetic structure and CO/OO phenomena. Important concepts and models are described: Jahn-Teller effect, double and super-exchange interaction and the Zener polarons model. The macroscopic magnetic properties have been measured versus temperature by using a SQUID magnetometer. The principal microscopic technique used for this thesis was NPD. The technique and the layout of the instruments - D20 and D1A at the Institute Laue Langevin, Grenoble - are described together with details of the Rietveld method used to refine the diffraction data. Experimental results from the systematic study of the Ln0.50Ca0.50MnO3 (Ln = Pr, Nd, Tb, Dy, Ho, Tm, Yb and Lu) manganites, are presented, with a description of sample preparation. The magnetic susceptibility, measured up to 530 K for our samples, presents a broad peak at high temperatures corresponding to the onset of the CO (TCO). From these results we define the nature of the magnetic correlations above and below TCO in the framework of the Zener polarons model. We also present the details of the nuclear and magnetic structure for all samples versus temperature, analyzing the distortions due to the doping and the effect of the ionic radius of the cations. All our samples have a pseudo-CE magnetic configuration at the lowest temperatures, corresponding to a CE-type ground state with canting. We describe the ab-initio method using the density functional theory (DFT), that have been used to model the Ln0.50Ca0.50MnO3 series. We present DFT and we discuss the most important features (spin polarization), approximations (pseudo-potentials and exchange-correlation functional) and (Hubbard) corrections used in this work, including a presentation of the VASP code used for the DFT calculations, with the corresponding input files. These calculations have been performed to confirm our experimental results and to access other significant quantities such as the electronic density of states. The computational approach has been tested on two pure systems: CaMnO3 and NdMnO3. Two half-doped systems have been chosen with Ln=Nd and Lu. The first because the La and Pr compounds were already studied (Picozzi, Anisimov) so we continued the series with the Nd system, and the Lu has the smallest ionic radius in the lanthanides series, its 4f shell is full and Lu is therefore comparable with La.

Une sous-classe intéressante de matériaux multiferroïques est celle des composés multiferroïques magnétoélectriques, dans lesquels il existe un couplage entre les paramètres d’ordres ferroïques (magnétique et électrique). De ce point de vue, la classe des matériaux Ga₂₋ₓFeₓO₃ a attiré l’attention des chercheurs. Ces composés sont actuellement connus pour leur température de transition élevée ainsi que pour l’interaction possible entre leurs propriétés ferrimagnétiques et piézoélectriques. Leur structure cristallographique et magnétique est assez complexe, du fait du désordre de substitution interne Fe/Ga. Les oxydes M₂Ga₂Fe₂O₉ (M=In, Sc) appartiennent à cette même famille de matériaux et ont été synthétisés pour la première fois afin d’obtenir une structure cristallographique ordonnée de GaFeO₃. Afin d’étudier les propriétés physiques de ces différents composés, nous avons synthétisé par la méthode de la zone flottante (au four à image), en utilisant différentes conditions de croissance, des monocristaux de composition Ga₂₋ₓFeₓO₃ (x=0.90, 1.00 et 1.10). Nous avons également élaboré des échantillons polycristallins de composés GaFeO₃ faiblement dopés en indium ainsi que le composé M₂Ga₂Fe₂O₉ (M=In, Sc). Nous avons enfin préparé de monocristaux de composition In₂Ga₂Fe₂O₉ par la méthode de croissance en flux. L’affinement Rietveld des diffractogrammes des rayons X et des neutrons nous a permis de montrer que les céramiques de GaFeO₃ faiblement dopées en indium et les monocristaux de Ga₂₋ₓFeₓO₃ cristallisent dans le groupe d’espace Pc2₁n. Les paramètres cristallins et la température de Néel caractéristiques pour les monocristaux de Ga₂₋ₓFeₓO₃ varient de manière linéaire avec la teneur en fer. Les affinements nous ont permis de conclure que la structure de ces composés est caractérisée par un désordre élevée (25% de la quantité du fer se trouve sur les sites natifs du gallium). L’incorporation graduelle de l’indium s’accompagne d’une augmentation du volume de la maille ainsi qu’à une diminution de la température de transition magnétique. Le spectre d’excitations magnétiques mesuré pour les cristaux de Ga₂₋ₓFeₓO₃ nous a permis de mettre en évidence une coexistence de l’ordre ferrimagnétique à longue portée et d’un signal de diffusion diffuse en-dessous de la température de Néel. Ce signal diffus suggère l’existence d’une composante de type verre de spin du fait du désordre interne des sites. L'étude de la variation thermique de la constante diélectrique sur un cristal de GaFeO₃ révèle l’absence d’un couplage magnétoélectrique au sein de ces matériaux. L’affinement Rietveld des diagrammes de diffraction des rayons X et des neutrons mesurés sur les poudres de M₂Ga₂Fe₂O₉ (M=In, Sc) révèle une structure orthorhombique de type Pba2 fortement désordonnée, avec quatre sites cationiques d’occupation mixte. Les données de susceptibilité DC et AC couplées avec les mesures de chaleur spécifique et les spectres Mössbauer indiquent, en-dessous d’une température de Tg ≈ 19 K, l’existence d’un état fondamental de type verre de spin dans ce système. Les mesures du spectre d’excitations magnétiques ont mis en évidence l’absence d’ordre magnétique à longue portée et confirment l’existence d’une transition d’un état paramagnétique vers un état verre de spins. L’existence d’un comportement de type verre de spin dans les systèmes Ga₂₋ₓFeₓO₃ et M₂Ga₂Fe₂O₉ (M=In, Sc) souligne l’importance du désordre interne pour la caractérisation de l'état fondamental magnétique. / An interesting sub-class of the multiferroic materials are the multiferroic magnetoelectrics, in which exists a coupling between the two ferroic order parameters (magnetic and electric). From this viewpoint, the case of the (Ga₂₋ₓFeₓO₃)-class of materials has retained special attention. These compounds are now well-known for their high transition temperature as well as for the potential interaction between their ferrimagnetic and piezoelectric properties. Their crystallographic and magnetic structure are quite complicated, due to the existence of an internal site disorder. M₂Ga₂Fe₂O₉ (M=In, Sc) belongs to the (Ga₂₋ₓFeₓO₃)-class of materials and it was first synthesized in an attempt to obtain an ordered GaFeO₃ crystallographic structure. In order to study the physical properties of these compounds, Ga₂₋ₓFeₓO₃ (x=0.90, 1.00 and 1.10) single crystals have been synthesized by the floating zone method in an infrared image furnace, using different growth conditions. Indium doped GaFeO₃ (up to 10% indium content amount) and M₂Ga₂Fe₂O₉ (M=In, Sc) polycrystalline materials have been prepared by solid state reaction. Also, In₂Ga₂Fe₂O₉ single crystals were prepared by the flux method. The indium doped GaFeO₃ and Ga₂₋ₓFeₓO₃ samples crystallize in the Pc2₁n space group as determined from Rietveld refinement of the X-ray and neutron single crystals and powder patterns. The cell parameters and the Néel temperature (TN) of the Ga₂₋ₓFeₓO₃ single crystals varies linearly with the iron content amount. The occupation factors were calculated by refinement and the results showed a disordered structure (25% of the iron amount is found on the native gallium sites). The gradual incorporation of indium is accompanied by an increase of the cell volume and a decrease of the magnetic transition temperature. The magnetic excitations spectra measured for the Ga₂₋ₓFeₓO₃ single crystals revealed a coexistence of a ferrimagnetic ordering and a diffuse scattering signal below the Néel temperature. The diffuse signal suggests the existence of a spin glass like component due to the internal site disorder. Dielectric investigations showed no temperature dependent anomaly of the dielectric constant for the GaFeO₃ single crystal, suggesting a lack of a magnetoelectric coupling signal in this system. The Rietveld refinement of the X-ray and neutron powder patterns for the M₂Ga₂Fe₂O₉ (M=In, Sc) revealed a highly disordered orthorhombic Pba2 structure, offering four mixed cationic crystallographic sites. DC and AC susceptibility data in conjunction with the heat capacity data and Mössbauer measurements indicated a spin-glass-like behavior in this system, with a freezing temperature near Tf ≈ 19 K. The absence of an long range magnetic ordering and the existence of a transition from a paramagnetic state to a «frozen» state were showcased by the spin dynamics spectra measurements. The evidence for glassy behavior in the Ga₂₋ₓFeₓO₃ and M₂Ga₂Fe₂O₉ (M=In, Sc) systems highlights the importance of site disorder in determining the ground state magnetic properties.

Cette thèse expérimentale a pour motivation l'étude des propriétés dynamiques des composés multiferroïques : les langasites de fer Ba3NbFe3Si2O14 et Ba3TaFe3Si2O14 et le manganite hexagonal ErMnO3. Ces investigations ont été réalisées grâce à l'utilisation de deux techniques expérimentales complémentaires : les spectroscopies FIR et THz et la diffusion de neutrons (polarisés et non polarisés). Dans les langasites de fer, des excitations magnéto-électriques ont été observées. Celles-ci ont été interprétées comme des modes de rotation atomique excités par la composante magnétique de l'onde électromagnétique. D'autre part, des modulations fines de la structure magnétique ont également été mises en évidence dans le composé Ba3NbFe3Si2O14 par l'observation de faits expérimentaux incompatibles avec la structure magnétique publiée avant cette étude. Il s'agissait de satellites magnétiques interdits et d'ordre supérieurs ainsi qu'une extinction dans les ondes de spin. La structure magnétique déduite de cette étude correspond à une modulation en accordéon des hélices de spin et à une perte structurale de l'axe de rotation d'ordre 3. Ces modulations sont compatibles avec les excitations magnéto-électriques et la multiferroïcité récemment mise en évidence dans ce composé. En parallèle, les propriétés magnéto-électriques dynamiques du manganite hexagonal ErMnO3 ont été étudiées. Un électromagnon a été observé correspondant à un magnon du Mn excité par la composante électrique de l'onde électromagnétique. Par comparaison avec le composé YMnO3, cet électromagnon a été interprété comme résultant d'une hybridation entre une excitation de champ cristallin de l'Er active électriquement et un magnon standard du Mn. / This experimental thesis is motivated by the study of the dynamical properties of multiferroic compounds : the iron langasites Ba3NbFe3Si2O14 and Ba3TaFe3Si2O14 and the hexagonal manganite ErMnO3. These investigations were performed using two complementary experimental techniques : FIR and THz spectroscopy and neutron scattering (with polarized and unpolarized neutrons). In the iron langasites, magnetoelectric excitations were observed. These excitations have been interpreted as atomic rotation modes excited by the magnetic component of the electromagnetic wave. On the other hand, weak modulations of the magnetic structure were also evidence in the Ba3NbFe3Si2O14 compound by observing experimental evidence inconsistent with the published magnetic structure. These evidence were forbidden and higher order magnetic satellites as well as an extinction in the spin-waves spectrum. The magnetic order deduced from this study presents a bunched modulation of the helix and the structural loss of the 3-fold axis. These modulations are compatible with the magnetoelectric excitations and the multiferroicity recently evidenced in this compound. In parallel, the magnetoelectric dynamical properties of the hexagonal manganite ErMnO3 have been investigated. An electromagnon has been observed corresponding to a Mn magnon excited by the electric component of the electromagnetic wave. From comparison with the YMnO3 compound, this electromagnon was interpreted as a hybrid mode between an electricallyactive Er crystal field excitation and a Mn magnon.

Wax anti-settling additives (WASA) are used to mitigate against the problems caused by the settling of n-alkane wax crystals, which crystallise from petroleum diesel. This can result in the blocking of fuel filters and hence vehicle failure. However, the mode of action for such additives is not currently known and two mechanisms have been proposed: they reduce the wax crystal size to such an extent that they settle very slowly; or they induce gelation in the wax suspension. This project aims to elucidate the mechanism of WASA within the diesel system. A room temperature crystallising model diesel (10 wt% n-alkanes in dodecane) has been developed. This model system has given a good response to the additives, with the wax crystals reduced in size, and is hence suitable for mechanistic studies. Differential scanning calorimetry and infra-red spectroscopy both suggest that the WASA is incorporated in or onto the wax crystal. DSC shows that small amounts of WASA suppress the wax crystallisation temperature and change the shape of the heat flow curve. FT-IR shows the WASA amide stretch present within filtered and dried wax crystals. Intriguingly, electrophoresis experiments show that the WASA imparts a positive charge to the wax crystals, suggesting an electrostatic role in the WASA action. Rheological experiments show the presence of a weak gel in the WASA doped model diesel. However, the gel strength is not altered by the presence of an organic salt and thus cannot be purely electrostatic in origin. Small angle neutron scattering has been conducted to help locate the WASA in the system. It has shown that in solution WASA shows a collapsed polymer coil structure with a single molecule occupying a 28 Å diameter sphere and multiple WASA molecules forming a 2400 Å diameter sphere. In the presence of the wax the WASA scatter does not significantly change suggesting that the WASA is on the surface of the wax crystal. By combining these results, a mechanism of WASA action is proposed as WASA cations interactions bridging between the wax crystals causing a weak bridging flocculation gel with electrostatic and steric effects contributing to stabilisation. The WASA charges are partially dissociated thus giving the electrophoretic effect and the long chains on the cations can contribute to stability via steric stabilisation.

Le confinement de la matière condensée dans un milieu nanoporeux peut induire à l'échelle nanométrique des changements structurels ou dynamiques drastiques qui conduisent finalement aux propriétés originales. Le confinement des polyélectrolytes, qui sont des polymères porteurs d'une charge électrique, présente un intérêt particulier. Dans ce projet, des membranes d'alumine nanoporeuse auto-ordonnée (nPAAMs), dont les paramètres structuraux sont réglés par la synthèse, ont été choisies comme milieu de confinement et des approches expérimentales ont été proposées pour étudier le confinement d'un polyélectrolyte fort (PE), polystyrène-sulfonate de sodium. Une partie importante de ce travail a été consacrée à la caractérisation des charges structurales et superficielles des nPAAMs. La structure et la composition du nPAAM sont caractérisées par la combinaison de la microscopie électronique à balayage et de la diffusion neutronique à petit angle (SANS). Une stratégie détaillée est proposée pour mesurer les nPAAM dans des conditions optimales en raison de leur forme anisotrope et de leur pouvoir de diffusion élevé ainsi que des informations sur leur composition chimique. La charge superficielle de la membrane a été déterminée par des mesures de potentiel d’écoulement. La charge de la paroi du pore peut être ajustée à une charge positive ou négative et l'étendue des interactions électrostatiques peut être ajustée, ce qui permet d'adapter le milieu aux études de confinement électrostatique. Le comportement de perméation et l'adsorption du polyélectrolyte à l'intérieur des pores sont étudiés par SANS en combinaison avec des mesures de perméabilité. La cinétique de l'adsorption est obtenue par le potentiel d’écoulement et la possibilité d'utiliser la réflectivité neutronique pour ces études est proposée. Ce travail fournit des approches expérimentales sur la caractérisation de l'PE en milieu confiné. / The confinement of condensed matter in nanoporous medium can induce at the nanoscale drastic structural or dynamical changes that ultimately lead to original properties. Of a specific interest is the confinement of polyelectrolytes that are polymers carrying an electrical charge. In this project, self-ordered nanoporous alumina membranes (nPAAMs), whose structural parameters are tuned through the synthesis, have been chosen as a confining medium and experimental approaches have been proposed to study the confinement of a strong polyelectrolyte (PE), sodium polystyrene-sulfonate . An important part of this work has been devoted to the structural and surface charge characterization of nPAAMs. The nPAAM’s structure and composition are characterized by combining scanning electron microscopy and small angle neutron scattering (SANS). A detail strategy is proposed for measuring the nPAAMs under optimal conditions due to their anisotropic shape and high scattering power and information on their chemical composition. The membrane’s surface charge has been determined by streaming potential measurements. The pore’s wall charge can be adjusted to positive or negative charge and the extent of the electrostatic interactions can be tuned, tailoring the medium for electrostatic confinement studies. The permeation behavior and the adsorption of the polyelectrolyte inside the pores is studied by SANS combined with flow measurements. The kinetics of the adsorption is accessed by streaming potential and the possibility to use of neutron reflectivity for such studies is proposed. This work provides experimental approaches insight into the characterization of PE under confinement.