This research investigates a novel class of active materials for energy and sensing applications. Magnetocaloric alloys, Gd5Si2Ge2, were developed into a composite with poly(vinylidine flouride) (PVDF), piezoelectric polymer. The giant megnetocaloric property combined with the piezoelectricity creates extraordinary properties for composite materials. The research approach was primarily experimental. Activities include synthesis, characterization, and device design and evaluation. Using the arc melting method, the magenetocaloric samples were created. Multi-length scales characterized using atomic force microscopy (AFM), optical microscopy, scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS), X-Ray diffraction (XRD), and X-Ray Photoelectron spectroscopy (XPS). The prototype devices were evaluated for their power generation and efficiency. Through those techniques, the fundamental understanding in the new materials was obtained. The relationships between process-microstructures, microstructure-properties, and structure-power generation were established. Results showed that the phase transformation of the magnetocaloric material at its Curie temperature induced a significant increase in power generation in the peizeoelectric polymer. Such transition was also beneficial for a laminated device for energy harvesting. In addition, it was found that the oxidation that occurred during high temperature melting stabilized the orthorhombic phase at room temperature. The multifunctional composites as well as the laminated structure use the thermal expansion of the magnetocaloric material for energy harvesting, cyclic monitoring, and/or thermal switching. This thesis consists of six chapters. Chapter I provides a history and explanation of the materials used. Chapter II provides an explanation of the motivation for this work. Chapter III addresses the experimental procedures. The results of which are presented in Chapter IV and discussed in Chapter V. The research is summarized and future recommendations are given in Chapter VI.

Complex lanthanide oxide systems are known to host novel phases of matter, while also providing functionality for practical applications. In this dissertation, the structural, magnetic and magnetocaloric properties of three families of lanthanide oxides have been studied with the dual aims of investigating the magnetic behaviour and identifying promising magnetic refrigerants for cooling to temperatures currently accessible using non-renewable liquid He. The thesis presents a two-part study of the magnetic and magnetocaloric properties of the geometrically frustrated lanthanide garnets, where the magnetic $Ln^{3+}$ form corner-sharing triangles. First, the family of garnets $Ln_3A_2X_3$O$_{12}$, $Ln$ = Gd, Tb, Dy, Ho, $A$ = Ga, Sc, In, Te, $X$ = Ga, Al, Li are investigated. Changes to the single-ion anisotropy of the magnetic ion as well as variations in the chemical pressure radically alters the nature of magnetic ordering, the degree of frustration and the magnetocaloric performance. In the second part, the garnets $Ln_3A$Ga$_4$O$_{12}$, $Ln$ = Gd, Tb, Dy, Ho, $A$ = Cr, Mn, are studied. Introducing additional spins significantly reduces the frustration in the garnet lattice. Low temperature powder neutron diffraction of Ho$_3$MnGa$_4$O$_{12}$ reveals concomitant ordering of Ho$^{3+}$ and Mn$^{3+}$ moments below the ordering temperature, $T_N$ = 5.8 K. The magnetocaloric performance of $Ln$_3CrGa$_4$O$_{12}$, $Ln$ = Gd, Dy, Ho, greatly surpasses that of the parent $Ln_3$Ga$_5$O$_{12}$ at $T$ = 2 K. The final results chapters in the thesis describe the magnetism and magnetocaloric effect in the lanthanide orthoborates, $Ln$BO$_3$ , $Ln$ = Eu, Gd, Tb, Dy, Ho, Er, Yb and the lanthanide metaborates, $Ln$(BO$_2$)$_3$, $Ln$ = Pr, Nd, Gd, Tb. The magnetic $Ln^{3+}$ form slightly distorted edge-sharing triangular layers in $Ln$BO$_3$. Unique magnetic features are observed, including short-range ordering and spin reorientation transitions depending on the single-ion anisotropy of the $Ln^{3+}$. The $Ln$BO$_3$ are also efficient magnetocalorics in the liquid helium temperature range. The lanthanide metaborates contain one-dimensional chains of magnetic lanthanide ions. Bulk magnetic measurements show features consistent with low-dimensional magnetism, such as magnetisation plateaux at one-third of the saturation magnetisation for Nd(BO$_2$)$_3$ and Tb(BO$_2$)$_3$ in a field of 14 T. This thesis provides insight into the fundamental magnetic properties of complex lanthanide oxide systems and also demonstrates strategies for identifying new magnetocaloric materials: both through chemical control of the structure of well-known magnetocalorics and by studying materials that have not been explored previously. The results pave the way for further in-depth investigations and finding new magnetic coolants based on complex lanthanide oxide systems.

The magnetocaloric and thermomagnetic properties of the MnNiGe1-xAlx, Ni50Mn35(In1−xCrx)15 and (Mn1−xCrx)NiGe1.05 systems have been studied by x-ray diffraction, differential scanning calorimetry (DSC), and magnetization measurements. Partial substitution of Al for Ge in MnNiGe1−xAlx results in a first-order magnetostructural transition (MST) from a hexagonal ferromagnetic to an orthorhombic antiferromagnetic phase at 186 K (for x = 0.09). A large magnetic entropy change of ∆SM = -17.6 J/kg K for ∆H = 5 T was observed in the vicinity of TM = 186 K for x = 0.09. This value is comparable to those of well-known giant magnetocaloric materials, such as Gd5Si2Ge2, MnFeP0.45As0.55, and Ni50Mn37Sn13 [1]. The values of the latent heat (L = 6.6 J/g) and corresponding total entropy changes (∆ST = 35 J/kg K) have been evaluated for the MST using DSC measurements. Large negative values of ∆SM of -5.8 and -4.8 J/kg K for ∆H = 5 T in the vicinity of TC were observed for x = 0.09 and 0.085, respectively. Partial substitution of Cr for Mn in(Mn1−xCrx)NiGe1.05 results in a MST from a hexagonal paramagnetic to an orthorhombic paramagnetic phase near TM ~ 380 K (for x = 0.07). Partial substitution of Cr for In in Ni50Mn35(In1−xCrx)15 shifts the magnetostructural transition to a higher temperature (TM ~ 450 K) for x = 0.1. Large magnetic entropy changes of ∆SM = -12 (J/kgK) and ∆S = -11 (J/kgK), both for a magnetic field change of 5 T, were observed in the vicinity of TM for (Mn1−xCrx)NiGe1.05 and Ni50Mn35(In1−xCrx)15, respectively. The concentration-dependent (T-x) phase diagram of transition temperatures (magnetic, structural, and magnetostructural) has been generated using magnetic, XRD, and DSC data. The role of magnetic and structural changes on transition temperatures are discussed.

O estudo teórico do efeito magnetocalórico no composto La(FexSi1-x )13 tornouse muito importante, tendo em vista que experimentos recentes revelaram que este composto apresenta grandes valores para a variação isotérmica da entropia (ΔS) e para a variação adiabática da temperatura (ΔTad), que são as grandezas utilizadas para caracterizarem o poder de refrigeração magnética de um composto magnético. Estudamos o efeito magnetocalórico do composto La(FexSi1-x)13, propondo um modelo teórico simples, a uma única banda e a uma única subrede. Tratamos a desordem do sistema com uma aproximação do potencial coerente (CPA)de interesse para obter a função de Greene, com isso, determinar as grandezas termodinâmicas relevantes. Conseguimos uma boa concordância entre os resultados teóricos e os dados experimentais. Nesta dissertação, também estudamos o efeito da adição de hidrogênio nas propriedades magnetocalóricas do composto La(FexSi1-x)13. Os resultados teóricos obtidos para o composto La(FexSi1-x)13Hy , também estão em acordo com os dados experimentais. / The study of the magnetocaloric effect of the compound La(FexSi1-x)13 became very important, once recent experiments revealed that this compound exhibits great values of the isothermal entropy change (Δ S) and the adiabatic temperature change(ΔTad), which are the quantities used to characterize the power of refrigeration of any compound. We studied the magnetocaloric effect of the compound La(FexSi1-x)13 , using a simple theoretical model, in which only one band and only one sublattice are considered. We treated the disorder of the system with then on diagonal Coherent Potential Approximation (CPA). We got a good agreement between our theoretical calculations and experimental data. We also studied the effect of the addition of hydrogen on the magnetocaloric properties of the compound La(FexSi1-x)13. We also found very satisfactory theoretical results for the composition La(FexSi1-x)13Hy , compared with the experimental data.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Nesta dissertação, calculamos as propriedades magnéticas e termodinâmicas e o efeito magnetocalórico em compostos do tipo Gd(A1-xBBx), onde A e B são elementos não magnéticos. Para tal finalidade, usamos um modelo hamiltoniano de spins localizados, incluindo o acoplamento com um campo magnético externo. A interação spin-spin é tratada na aproximação de campo molecular. O parâmetro de interação de troca indireta entre os spins localizados é calculado como uma função da concentração de impurezas. Para esse fim, usamos um modelo no qual a desordem química é tratada na aproximação do potencial coerente. Aplicamos o modelo para estudar o efeito magnetocalórico nos compostos Gd(Zn1-x Cdx) e Gd (Pd1-xRHx). As variações adiabáticas da temperatura e as variações isotérmicas da entropia calculadas para variações de campo magnético estão em bom acordo com os dados experimentais. / In this work we calculated the magnetic and thermodynamic properties as well as the magnetocaloric effect in the compounds Gd(A1−xBBx), where A and B are non-magnetic impurities. For this purpose, we use a model Hamiltonian of interacting spin including the coupling with an external magnetic field. The spin-spin interaction is treated in the molecular field approximation. The indirect exchange interaction parameter between localized spins is calculated as a function of the impurity concentration. To this end we use a model in which the disorder is treated in the coherent potential approximation. We apply the model to study the magnetocaloric effect in the compounds Gd(Zn1−xCdx) and Gd(Pd1−xRhx). The calculated adiabatic temperature changes and isothermal entropy changes upon magnetic field variations are in good agreement with the available experimental data.

O estudo teórico do efeito magnetocalórico no composto La(FexSi1-x )13 tornouse muito importante, tendo em vista que experimentos recentes revelaram que este composto apresenta grandes valores para a variação isotérmica da entropia (ΔS) e para a variação adiabática da temperatura (ΔTad), que são as grandezas utilizadas para caracterizarem o poder de refrigeração magnética de um composto magnético. Estudamos o efeito magnetocalórico do composto La(FexSi1-x)13, propondo um modelo teórico simples, a uma única banda e a uma única subrede. Tratamos a desordem do sistema com uma aproximação do potencial coerente (CPA)de interesse para obter a função de Greene, com isso, determinar as grandezas termodinâmicas relevantes. Conseguimos uma boa concordância entre os resultados teóricos e os dados experimentais. Nesta dissertação, também estudamos o efeito da adição de hidrogênio nas propriedades magnetocalóricas do composto La(FexSi1-x)13. Os resultados teóricos obtidos para o composto La(FexSi1-x)13Hy , também estão em acordo com os dados experimentais. / The study of the magnetocaloric effect of the compound La(FexSi1-x)13 became very important, once recent experiments revealed that this compound exhibits great values of the isothermal entropy change (Δ S) and the adiabatic temperature change(ΔTad), which are the quantities used to characterize the power of refrigeration of any compound. We studied the magnetocaloric effect of the compound La(FexSi1-x)13 , using a simple theoretical model, in which only one band and only one sublattice are considered. We treated the disorder of the system with then on diagonal Coherent Potential Approximation (CPA). We got a good agreement between our theoretical calculations and experimental data. We also studied the effect of the addition of hydrogen on the magnetocaloric properties of the compound La(FexSi1-x)13. We also found very satisfactory theoretical results for the composition La(FexSi1-x)13Hy , compared with the experimental data.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Nesta dissertação, calculamos as propriedades magnéticas e termodinâmicas e o efeito magnetocalórico em compostos do tipo Gd(A1-xBBx), onde A e B são elementos não magnéticos. Para tal finalidade, usamos um modelo hamiltoniano de spins localizados, incluindo o acoplamento com um campo magnético externo. A interação spin-spin é tratada na aproximação de campo molecular. O parâmetro de interação de troca indireta entre os spins localizados é calculado como uma função da concentração de impurezas. Para esse fim, usamos um modelo no qual a desordem química é tratada na aproximação do potencial coerente. Aplicamos o modelo para estudar o efeito magnetocalórico nos compostos Gd(Zn1-x Cdx) e Gd (Pd1-xRHx). As variações adiabáticas da temperatura e as variações isotérmicas da entropia calculadas para variações de campo magnético estão em bom acordo com os dados experimentais. / In this work we calculated the magnetic and thermodynamic properties as well as the magnetocaloric effect in the compounds Gd(A1−xBBx), where A and B are non-magnetic impurities. For this purpose, we use a model Hamiltonian of interacting spin including the coupling with an external magnetic field. The spin-spin interaction is treated in the molecular field approximation. The indirect exchange interaction parameter between localized spins is calculated as a function of the impurity concentration. To this end we use a model in which the disorder is treated in the coherent potential approximation. We apply the model to study the magnetocaloric effect in the compounds Gd(Zn1−xCdx) and Gd(Pd1−xRhx). The calculated adiabatic temperature changes and isothermal entropy changes upon magnetic field variations are in good agreement with the available experimental data.

Anisotropic magnetic materials have been proposed over the past twenty years or so as candidates for high density storage, so-called Single-Molecule Magnets (SMMs). These may in future be used to store data at the level of an individual molecule. Separately, isotropic materials may be harnessed for their large magnetocaloric effect which enables them to be used as refrigerants. This can potentially replace the increasingly rare and therefore expensive 3He and 4He currently employed either separately or in 3He-4He dilution refrigerators. This thesis examines the use of lanthanide(III) ions for these applications, by detailing the synthesis, characterisation and performance of three new classes of zero-dimensional compounds, {LnIII2}, {LnIII2ZnII4} and {LnIII7}. These are assessed by several techniques including SQUID magnetometry, heat capacity measurements luminescence spectroscopy, Electron Paramagnetic Resonance and ab initio calculations. In doing so we extended the use of a tripodal ligand widely employed in 3d chemistry to 4f ions, and found only the second 3d-4f phosphonate SMM. Investigating several members of a known three-dimensional lanthanide(III) polymer, {LnIII}n, showed the isotropic gadolinium(III) analogue is one of the very best of all known magnetic refrigerants in the low-temperature regime.

No description available.

In search of novel magnetocaloric materials, a number of rare earth-based phases were designed, synthesized and investigated. These compounds were prepared by arc-melting or sintering, followed by annealing at high temperature to obtain phase-pure materials. Single crystal and powder X-ray diffraction were employed for phase identification, purity assessment, structure solution and refinement. Energy dispersive X-ray spectroscopy (EDS) was used to determine sample compositions. A Quantum Design SQUID magnetometer equipped with an alternating current (ac) transport controller (model 7100) was employed to measure magnetic data and evaluate magnetocaloric properties. The crystal structure and physical properties were analyzed via electronic structure calculations. In this thesis work, the RE5Ga3 and RECo2 (RE = rare earth) materials were chosen as a starting point for structural modifications. Specifically, substitution of Co for Ga (and vice versa) or rare earth replacement was used to design new materials. In total, four families were investigated: Ho5Ga3-xCox (x = 0, 0.1, 0.2, 0.3, 0.4, 0.5, 1), Er5Ga3-x(Fe/Co)x (x = 0, 0.4), RE(Co0.667Ga0.333)2 (RE = Gd, Tb, Dy, Ho, and Er), and Gd(Co1-xGax)2 (x = 0, 1/6, 1/3, 1/2, 2/3, 5/6, and 1). The samples were prepared by arc-melting, wrapped in Ta foil, sealed in evacuated silica tubes and annealed at specific temperatures. The Ho5Ga3-xCox and Er5Ga3-x(Fe/Co)x systems features a Mn5Si3-type-to-Cr5B3-type structural transformation, driven by geometric factors. On the other hand, the structural transformation in the RE(Co0.667Ga0.333)2 and Gd(Co1-xGax)2 systems appears to be controlled by the valence electron count (VEC). The RE(Co0.667Ga0.333)2 (RE = Gd, Tb, Dy, Ho, and Er) phases adopt a hexagonal MgZn2-type structure (P63/mmc). Structural and magnetic properties of the MgZn2-type RE(Co0.667Ga0.333)2 materials were investigated via single crystal and powder X-ray diffraction, powder neutron diffraction (PND), and magnetic measurements. In addition to the hexagonal MgZn2-type structure, four other structures were discovered in the Gd(Co1-xGax)2 system: cubic MgCu2- (Fd3 ̅m), orthorhombic MgSrSi- (Pnma), orthorhombic CeCu2- (Imma), and hexagonal AlB2-type structure (P6/mmm). When Ga content increases, the structure moves from a “condensed cluster-based arrangement” to a “3D Network” to a “2D Network”. Meanwhile, coordination number (CN) of Co or Ga atoms changes from 6 to 4, and then to 3. Magnetic properties of many of the RE-based phases were evaluated via temperature- and field-dependent magnetization measurement. Materials exhibited a sharp ferromagnetic transition and their MCE in terms of the isothermal magnetic entropy change, was explored. / Thesis / Doctor of Philosophy (PhD)