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The effect of doping on the crystal structure, magnetic, magnetocaloric and transport properties of MnM′Ge (M′ = Ni, Co) intermetallic compounds and NiMnX (X = Sn, In) Heusler alloys have been studied by room temperature X-ray diffraction (XRD), differential scanning calorimetry (DSC), and magnetization measurements. The studied magnetic systems include Ni1-xCrxMnGe1.05 (0 ≤ x ≤ 0.120), Mn1-xAlxCoGe (0 ≤ x ≤ 0.05), MnCo1-xZrxGe (0.01 ≤ x ≤ 0.04), Mn1-xAgxCoGe (0.01 ≤ x ≤ 0.10), Ni50-xRxMn35Sn15 (x = 0, 1 and R = La, Pr, Sm), Ni43-xRxMn46Sn11 (x = 0, 1 and R = Pr, Gd, Ho, Er), and Ni50Mn35In15-xBix (0 ≤ x ≤ 1.5).A temperature induced first-order structural transition characterized by a change in crystal structure from high temperature austenite phase (AP) with Ni2In-type Hexagonal structure to low temperature martensite phase (MP) with TiNiSi-type orthorhombic structure was observed at T = TM (martensitic transition temperature) in some of the MnM′Ge-based compounds. The partial substitution of doping elements such as Cr, Al, Zr, and Ag resulted in a decrease in TM and at certain concentration, TM was found to decrease below / coincide with the ferromagnetic transition temperature (TC) of AP. Therefore, such system show a first-order magnetostructural transition (MST).In Ni1-xCrxMnGe1.05, a MST from antiferromagnetic (AFM) orthorhombic to ferromagnetic (FM) hexagonal phase was observed for 0.105 ≤ x ≤ 0.120. Both direct and inverse MCE were observed in this compound. The peak values of the magnetic entropy change (ΔSMpeak ) in the vicinity of TC for ΔH = 5T were found to be 4.5 J/kg K, 5.6 J/Kg K, and 5.1 J/Kg K for x = 0.105, 0.115, and 0.120 respectively. A magnetic field-induced transition from an AFM to a FM state in the martensite structure was observed in annealed Ni0.895Cr0.105MnGe1.05 melt-spun ribbons, which led to a coupled MST from a FM martensite to a PM austenite phase with a large change in magnetization. As a result of the field-induced MST, a large ΔSMpeak value of 16.1 J kg-1 K-1 (which is about a four times larger than the bulk) and Refrigeration capacity (RC-1) =144 J kg-1 at μ0∆H = 5 T was found. It was also found that the ribbon samples showed excellent magnetic reversibility that is important for application. MCE parameters, adiabatic temperature change (∆Tad) and |〖∆S〗_M |, with maximum value of ~ 2.6 K (µoH = 10 T) and 4.4 J kg-1 K-1(µo∆H = 5 T), respectively, were observed in the vicinity of TC. The ∆Tad (T) curves obtained for µoΔH = 10 T and magnetization isotherms were found to be completely reversible, which indicates the reversibility of the MCE in this system. A large temperature span (of about 61 K) and a non-saturating behavior of ∆Tad were observed at magnetic fields up to 10 T. The adiabatic temperature change was found to be a linear function of (µoH)2/3 near TC in accordance with Landau’s theory of phase transitions.In MnCoGe compounds doped with Al, Zr, and Ag, a tunable MST from the paramagnetic hexagonal to ferromagnetic orthorhombic phase was observed. The maximum ΔSM values of about 18, 7.2, and 22 J kg-1 K-1for ∆H = 5T at TM was observed for Al, Zr, and Ag doped compounds, respectively. The corresponding maximum value of RC was found to be (303, 266, and 308) JKg-1.The new compounds containing low concentration of rare earth (R) metals: Ni50-xRxMn35Sn15, Ni43-xRxMn46Sn11, with R = La, Pr, Sm, Gd, Ho, Er and Ni50Mn35In15-xBix were synthesized. The compounds crystallized in the cubic L21 austenite phase (AP) or a mixture of AP and low temperature martensitic phase (MP) at room temperature. For Ni50-xRxMn35Sn15 and Ni43-xRxMn46Sn11 alloys, TM shifted towards higher temperature with rare-earth doping, thus stabilizing the MP at higher temperature. A maximum shift in TM by ~ 60-62 K relative to the parent compound (TM = 190-195 K) was observed for the Ni49LaMn35Sn15 and Ni42PrMn46Sn11. TM shifted towards lower temperature if Bi is placed in In position in Ni50Mn35In15-xBix. A maximum shift of ~ 36 K was detected for x = 1.5. Abnormal shifts in TC and TM to higher temperatures were observed at high field for Bi concentration ≥ 0.5.The ground state magnetization decreased with the rare-earth doping and increasing Bi content. The compounds exhibit both inverse and normal magnetocaloric effects. Large values of ∆SM = 12 (Ni49PrMn35Sn15), 32 Jkg-1K-1(Ni42PrMn46Sn11), 28 Jkg-1K-1 (Ni42GdMn46Sn11), 25 Jkg-1K-1 (Ni42HoMn46Sn11), 40 J/kg K (Ni50Mn35In15) and 34 J/kg K (Ni50Mn35In15-xBix, x = 0.25) were found at TM for ∆H = 5T that can be tuned in a wide temperature range. RC values ranging from 267-336 Jkg-1 at TC, 182 -250 Jkg-1 at TM and 144-165 Jkg-1 at TC were found with ∆H = 5T for Ni50-xRxMn35Sn15, Ni43-xRxMn46Sn11, and Ni50Mn35In15-xBix, respectively. Significant magnetoresistance (MR) values of -30%, -20 % and -30% were observed in Ni49LaMn35Sn15, Ni42GdMn46Sn11, and Ni50Mn35In14.5Bi0.5 compounds, respectively, at TM and ∆H = 5T. A large exchange bias effect with HEB ~ 1.1 kOe at 10 K was observed for the Ni42PrMn46Sn11 compound in its MP. Thus, the pronounced multifunctional properties such as shape memory effects, MCE, EB, and MR make these new systems promising for the ongoing development of magnetocaloric and multifunctional technologies.

This diploma thesis is devoted to systematic study of structural trans- formations of Heusler alloys by means of spectroscopic ellipsometry and magneto-optical spectroscopy. Structural transformations in these alloys are induced by different microscopic mechanisms. Obtained experimental results were confronted with theoretical calculations. This allowed the discussion of obtained results and suggestion of their interpretation. In the case of Co- Fe-Si alloys, changes in optical and magneto-optical properties with change of Co-Fe ratio were observer. This was explained by lowering of the gap for minority spins with increasing Fe concentrations. Temperature dependent optical and magneto-optical properties of Ni-Mn-Ga alloy showed the pres- ence of so-called Martensitic transformation from cubic to tetragonal phase. A study of Mn-Rh-Co-Sn alloys did not show a clear dependence of physical properties upon the concentration of Rh and Mn. This was explained by strong strain inside the samples, which distorted obtained results. 1

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The magnetic properties of NiMnGe1−xAlx, Ni50Mn35(In1−xBx)15, Ni50Mn35In14.5B0.5 (Bulk, As-Solidified and Annealed melt-spun ribbon) and RE-Infuse Carbon Nanotubes, have been studied by x-ray diffraction, differential scanning calorimetry (DSC), and magnetization measurements. Partial substitution of Al for Ge in NiMnGe1−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. 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 and up to 9T in the vicinity of TC were observed for x = 0.09 and 0.085, respectively. The impact of B substitution in Ni50Mn35In15-xBx Heusler alloys on the structural, magnetic, transport, and parameters of the magnetocaloric effect (MCE) has been studied by means of room-temperature X-ray diffraction and thermomagnetic measurements (in magnetic fields (H) up to 5 T, and in the temperature interval 5-400 K ). Direct adiabatic temperature change (ΔTAD) measurements have been carried out for an applied magnetic field change of 1.8 T. The transition temperatures (T-x) phase diagram has been constructed for H = 0.005 T. The MCE parameters were found to be comparable to those observed in other MCE materials such as Ni50Mn34.8In14.2B and Ni50Mn35In14X (X=In, Al, and Ge) Heusler alloys. The maximum absolute value of ΔTAD = 2.5 K was observed at the magnetostructural transition for Ni50Mn35In14.5B0.5. The structural phase transition temperatures, phase structure, and parameters of the magnetocaloric effect (MCE) of Ni50Mn35In14.5B0.5 as Bulk, As-Solidified and Annealed melt-spun ribbon has been studied by means of room-temperature X-ray diffraction and thermomagnetic measurements (in magnetic fields (oH) up to 5 T, and in the temperature interval 5–400 K). Magnetic and structural transitions in Ni50Mn35In14.5B0.5 as ribbons were found to coincide in Ni50Mn35In14.5B0.5 bulk sample, leading to a large magnetocaloric effects associated with the first-order magnetostructural phase transition. In comparison to the bulk Ni50Mn35In14.5B0.5 alloys, both the martensitic transition temperature (TM) and Curie temperature (TC) shifted to lower temperatures. Magnetic measurements revealed that the ribbons undergo a structure transformation similar to the bulk material at the martensitic transformation. The temperature of the transformation depends strongly on lattice parameters of the ribbons. MST shows a weak broad magnetic transition at TCM∼ 160 K, while the Curie temperature of AST TCA is ∼ 297 K. The MCE parameters were found to be comparable to those observed in other MCE materials such as Ni50Mn34.8In14.2B and Ni50Mn35In14X (X = In, Al, and Ge) Heusler alloys. These results suggest the possibility to control the martensitic transition in Ni50Mn35In14.5B0.5 through rapid solidification process. A comparison of magnetic properties and magnetocaloric effects in Ni50Mn35In14.5B0.5 alloys as Bulk, As-Solidified and Annealed ribbons is discussed. Carbon nanotube (CNT)/metal-cluster-based composites are envisioned as new materials that possess unique electronic properties which may be utilized in a variety of future applications. Super paramagnetic behavior was reported for CNTs with Gd ions introduced into the CNT openings by internal loading with an aqueous GdCl3 chemical process. In the current work, the magnetic properties of the CNT/Gd composites were obtained by the joining and annealing of Gd metal and CNTs at 850 °C for 48 h. Energy dispersive X-ray analysis shows the presence of Gd intermingled with the CNT walls with maximum and average Gd concentrations of about 20% and 4% (by weight), respectively. The Gd clusters have a non-uniform distribution and are mostly concentrated at the ends of the CNTs. A ferromagnetic-type transition at TC ∼ 320 K, accompanied by jump like change in magnetization and temperature hysteresis typical for the temperature induced first order phase transitions has been observed by magnetization measurements. It was found that Gd infused into the CNTs by the annealing results in a first order paramagnetic-ferromagnetic transition at TC = 320 K.

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