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 diploma thesis deals with the study of the process of grinding aggregates of particles of a mixture of powdered lanthanide oxides in the dowanol solvent. The formed dispersions were characterised and used for the preparation of printing inks and subsequently for the printing of labels with chemical codes readable by XRF spectrometry. The aim was to study the milling process, to verify the reliability of reading and recognition of marks with the appropriate codes and to monitor the influence of the additive of the up-conversion powder on the resulting relative intensities of the elements in the chemical code. The statistical significance of the differences in the averages of relative intensities was assessed based on the Student's t test.

Nesta tese são descritas as preparações e caraterizações dos compostos de trifluorometanossulfonatos de Ln(III) com o ligante ε-caprolactama. Os compostos apresentaram a seguinte estequiometria: a) Ln(C6H11NO)8 (CF3SO3)3: Ln= La, Ce ,Pr, Nd, Sm, Eu. b) Ln(C6H11NO)7 (CF3SO3)3: Ln= Gd, Tb, Dy, Yb, Lu. Medidas de condutividade em acetonitrila indicaram a existência de eletrólitos 1:1, atribuídos a formação de pares iônicos. A coordenação do ligante ε-caprolactama com o metal central ocorre através do oxigênio do grupo carbonila, fato que foi interpretado pelo deslocamento da νCO para regiões de menor energia, comparada com a banda do ligante livre. Os modos vibracionais do ânion CF3SO3-, os estiramentos νasSO3, νsSO3 e a deformação δsSO3 não se desdobram, exceto δasSO3, sugerindo-nos que estes não estão coordenados aos Ln(III). Este aspecto foi confirmado no caso da estrutura do monocristal do Pr(III), obtida por raios-X pelo método do monocristal. Verificou-se também a existência de seis tipos de estruturas cristalinas através de difratogramas de raios-X pelo método do pó. Os espectros de absorção na região do visível do composto de Nd(III) no estado sólido, nos sugerem um envolvimento não cúbico em torno do íon metálico e que a ligação é de caráter iônico. O espectro de emissão do Eu(III) nos sugere que a microsimetria ao redor do Eu(III) corresponde a D2d distorcida para C2v e a intensidade do parâmetro de intensidade Ω(λ=2), obtida experimentalmente para o complexo de Eu(III) e os compostos de lantanídeos(III):La, Ce, Gd, Y e Lu, dopados com Eu(III), nos sugerem a influência do acoplamento dinâmico na transição eletrônica 5D0 → 7F2 do Eu(III), que obedece à regra de seleção ΔJ=2. Também observa-se a inexistência do efeito antena no espectro de excitação do Eu(III). O estudo térmico, por curvas TG e DTG para os compostos de adição, nos mostram a formação dos resíduos LnF3 e LnOF à temperatura aproximada de 900°C. Determinaram-se os parâmetros cinéticos, tanto teoricamente como experimentalmente, da perda de moléculas de água correspondente à primeira etapa da desidratação dos sais de trifluorometanossulfonatos de lantanideos(III) eneaidratados, sob condições isotérmicas. Estes resultados foram obtidos a partir de modelos matemáticos existentes na literatura e com uma expressão matemática que foi derivada neste trabalho. / The preparation and characterization of compounds of trifluoromethanessulfonates with ε-caprolactam are described in this thesis. The compounds presented the following stoichiometries : a) Ln(C6H11NO)8 (CF3SO3)3: Ln= La, Ce ,Pr, Nd, Sm, Eu. b) Ln(C6H11NO)7 (CF3SO3)3: Ln= Gd, Tb, Oy, Yb, Lu. The coordination of the ε-caprolactam with the central metal ions occurs through the carbonyl oxygen. This fact was interpreted by the shift of νCO to lower frequencies in relation to the free ligand. The vibrational modes νasSO3, νsSO3 and deformation δsO3, except for δasSO3, are not splitted, suggesting that the CF3SO3- anions are not coordinated. This aspect was further confirmed in the structure of the Pr(III) compound obtained by x-ray crystallography. The existence of six types of crystalline structures was verified by x-ray powder patterns. The absorption visible spectrum of the Nd(III) compound in the solid state, suggest both the existence of a non-cubic site around the central ion and the ionic character of the bonds. The emission spectrum of Eu(III), suggest that the symmetry is D2d distorted towards C2v The experimental intensity parameter Ω2 obtained for the Eu(III) complex and the compounds of lanthanides(III): La, Ce, Gd, Y and Lu dopped with Eu(III) suggests the influence of the mechanic dynamic coupling in the electronic transition 5Do → 7F2 that obey the selection rule ΔJ=2. The excitation spectrum of Eu(III) compound indicate the inexistence of the antenna effect. The TG and DTG curves of the addition compounds show their thermic behaviour the formation of LnF3 and LnOF as residues at temperatures of 900°C could be identified. The kinetic parameters of the water loss corresponding to the first stage of the dehydration of the lanthanide(III) trifluomethanesulfonate eneahydrated under isotermic conditions were determined both theoretically and experimentally. These results were obtained from mathematical model offered in the literature and a mathematical expression is derived in this work.

Nesta tese são descritas as preparações e caraterizações dos compostos de trifluorometanossulfonatos de Ln(III) com o ligante ε-caprolactama. Os compostos apresentaram a seguinte estequiometria: a) Ln(C6H11NO)8 (CF3SO3)3: Ln= La, Ce ,Pr, Nd, Sm, Eu. b) Ln(C6H11NO)7 (CF3SO3)3: Ln= Gd, Tb, Dy, Yb, Lu. Medidas de condutividade em acetonitrila indicaram a existência de eletrólitos 1:1, atribuídos a formação de pares iônicos. A coordenação do ligante ε-caprolactama com o metal central ocorre através do oxigênio do grupo carbonila, fato que foi interpretado pelo deslocamento da νCO para regiões de menor energia, comparada com a banda do ligante livre. Os modos vibracionais do ânion CF3SO3-, os estiramentos νasSO3, νsSO3 e a deformação δsSO3 não se desdobram, exceto δasSO3, sugerindo-nos que estes não estão coordenados aos Ln(III). Este aspecto foi confirmado no caso da estrutura do monocristal do Pr(III), obtida por raios-X pelo método do monocristal. Verificou-se também a existência de seis tipos de estruturas cristalinas através de difratogramas de raios-X pelo método do pó. Os espectros de absorção na região do visível do composto de Nd(III) no estado sólido, nos sugerem um envolvimento não cúbico em torno do íon metálico e que a ligação é de caráter iônico. O espectro de emissão do Eu(III) nos sugere que a microsimetria ao redor do Eu(III) corresponde a D2d distorcida para C2v e a intensidade do parâmetro de intensidade Ω(λ=2), obtida experimentalmente para o complexo de Eu(III) e os compostos de lantanídeos(III):La, Ce, Gd, Y e Lu, dopados com Eu(III), nos sugerem a influência do acoplamento dinâmico na transição eletrônica 5D0 → 7F2 do Eu(III), que obedece à regra de seleção ΔJ=2. Também observa-se a inexistência do efeito antena no espectro de excitação do Eu(III). O estudo térmico, por curvas TG e DTG para os compostos de adição, nos mostram a formação dos resíduos LnF3 e LnOF à temperatura aproximada de 900°C. Determinaram-se os parâmetros cinéticos, tanto teoricamente como experimentalmente, da perda de moléculas de água correspondente à primeira etapa da desidratação dos sais de trifluorometanossulfonatos de lantanideos(III) eneaidratados, sob condições isotérmicas. Estes resultados foram obtidos a partir de modelos matemáticos existentes na literatura e com uma expressão matemática que foi derivada neste trabalho. / The preparation and characterization of compounds of trifluoromethanessulfonates with ε-caprolactam are described in this thesis. The compounds presented the following stoichiometries : a) Ln(C6H11NO)8 (CF3SO3)3: Ln= La, Ce ,Pr, Nd, Sm, Eu. b) Ln(C6H11NO)7 (CF3SO3)3: Ln= Gd, Tb, Oy, Yb, Lu. The coordination of the ε-caprolactam with the central metal ions occurs through the carbonyl oxygen. This fact was interpreted by the shift of νCO to lower frequencies in relation to the free ligand. The vibrational modes νasSO3, νsSO3 and deformation δsO3, except for δasSO3, are not splitted, suggesting that the CF3SO3- anions are not coordinated. This aspect was further confirmed in the structure of the Pr(III) compound obtained by x-ray crystallography. The existence of six types of crystalline structures was verified by x-ray powder patterns. The absorption visible spectrum of the Nd(III) compound in the solid state, suggest both the existence of a non-cubic site around the central ion and the ionic character of the bonds. The emission spectrum of Eu(III), suggest that the symmetry is D2d distorted towards C2v The experimental intensity parameter Ω2 obtained for the Eu(III) complex and the compounds of lanthanides(III): La, Ce, Gd, Y and Lu dopped with Eu(III) suggests the influence of the mechanic dynamic coupling in the electronic transition 5Do → 7F2 that obey the selection rule ΔJ=2. The excitation spectrum of Eu(III) compound indicate the inexistence of the antenna effect. The TG and DTG curves of the addition compounds show their thermic behaviour the formation of LnF3 and LnOF as residues at temperatures of 900°C could be identified. The kinetic parameters of the water loss corresponding to the first stage of the dehydration of the lanthanide(III) trifluomethanesulfonate eneahydrated under isotermic conditions were determined both theoretically and experimentally. These results were obtained from mathematical model offered in the literature and a mathematical expression is derived in this work.

Pour faire face à l’augmentation des émissions de CO2 dans l’atmosphère à cause de la production électrique dans des centrales à charbon, le captage en post-combustion au moyen d’un procédé VSA est une solution envisageable. Les adsorbants utilisés dans notre étude sont la TEPA imprégnée sur SiO2, les oxydes de terre rare et le MOF (Metal Organic Frameworks) SIM-1. Pour chaque adsorbant, une étude du perçage puis de la régénération a été effectuée à partir d’une alimentation composée de 15%vol de CO2 et de N2. De ces essais, les conditions opératoires des cycles VSA ont été établies (durées des phases courtes, pas de circulation de purge). En cycle, les performances sont comparées à celle du procédé d’absorption avec la monoéthénolamine. La pureté du désorbat varie de 89,2%vol à 97,2%vol selon les adsorbants et les conditions opératoires. Elle est inférieure à celle du procédé d’absorption (99%vol) mais est correcte pour le transport et le stockage. Le taux de captage évolue de 87,2% à 94,9% (absorption : 98%). La consommation énergétique est inférieure à celle du procédé avec la MEA (de 1,53 à 3,45 MJ.kgCO2 1 pour notre procédé et 3,7 MJ.kgCO2¬1 pour l’absorption) Enfin la productivité est du même ordre de grandeur que celle d’autres procédés VSA de la littérature. Avec le modèle numérique, une étude locale de l’adsorbeur a été menée. Puis grâce à une étude paramétrique, des conditions optimales en cycle ont été déterminées. Les résultats obtenus ont permis de mettre en évidence des performances comparables avec les autres procédés VSA de la littérature. De plus, notre procédé est beaucoup moins énergivore que le procédé d’absorption mais la pureté du désorbat et le taux de captage en CO2 restent inférieurs. / To deal with the CO2 emissions increase in the atmosphere due to electricity production, CO2 post-combustion capture by VSA process is a promising solution. The adsorbents used in this study are impregnated TEPA on SiO2, lanthanide oxides and the MOF (Metal Organic Frameworks) SIM-1. For each adsorbent, a study of breakthrough and regeneration was carried out from a feed composed of 15%vol CO2 and N2. From these experiments, the cyclic operating conditions of VSA have been established (short duration phases, no purge). Cyclic performances are compared to that of the absorption process with monoethenolamine. The desorbate purity varies from 89.2% to 97.2%vol according to adsorbent and operating conditions. It is less than that obtained with absorption process (99%vol) but it is correct for transport and storage. The recovery varies from 87.2% to 94.2% (absorption: 98%). The energy consumption is less than that the process with the MEA (from 1.53 to 3.45 MJ.kgCO2 1 for our process and 3.7 MJ.kgCO2 1 for absorption). . Finally, the productivity is of the same order of magnitude as that of other VSA processes from literature. With the numerical model, a local study of the adsorber was carried out. Afterwards, through a parametric study, cycle optimal conditions were determined. The cycle results highlighted comparable performances with the other VSA processes from literature. Moreover, our process needs less energy than absorption process but the desorbate purity and CO2 recovery remain lower.