In this thesis, specific heat, magnetic susceptibility and resistivity studies on the iron-pnictide superconductors LiFeAs, NaFe1-xCoxAs, AFe2As2 (A = K, Ca, Ba), M1-xNaxFe2As2 (M = Ca, Ba), and Ca(Fe1-xCox)2Fe2As2 are presented, from which different intrinsic physical properties are resolved. The combined first-order spindensity wave/structural transition which occurs in the parent compounds of the 122 pnictide systems is shown to gradually shift to lower temperature for low doping levels. Upon higher doping, this transition is completely suppressed and simultaneously, superconductivity appears at lower temperature. In contrast, the phase diagram in Ca(Fe1-xCox)2Fe2As2 is shown to exhibit a pronounced region of coexistence of magnetism and superconductivity. Further important results reported in this work concern the electronic properties and superconducting-gap characteristics. In LiFeAs, the zero-field temperature dependence of the electronic specific heat can be well described by two s-wave gaps, whose magnitudes are in agreement with ARPES results. Our gap analysis in KFe2As2, Ca0.32Na0.68Fe2As2, and Ba0.65Na0.35Fe2As2 single crystals also implies the presence of two s-wave-like gaps. The magnetic phase diagram of LiFeAs and KFe2As2 for magnetic fields along both principal orientations has been constructed and an anisotropy of Hc2(T) of 3 and 5, respectively, has been obtained.

A small-scale adiabatic calorimeter has been constructed as part of a larger project to study nano-particles and to facilitate specific heat measurements on samples where it is difficult to obtain enough material to run on the current large-scale adiabatic apparatus. This calorimeter is designed to measure sample sizes of less than 0.8 cc over a temperature range from 13 K to 350 K. Specific heat results on copper, sapphire, and benzoic acid show the accuracy of the measurements to be better than ±0.4% for temperatures higher than 50 K. The reproducibility of these measurements is generally better than ±0.25%. Experimental specific heat data was collected on this new apparatus for synthetic akaganeite, β-FeOOH, for samples with varying degrees of hydration. Our results yield values for Δ_0^298.15S°m of 79.94 ±0.20 J•K^-1•mol^-1 and 85.33 ±0.021 J•K^-1•mol^-1 for samples of β-FeOOH0.551H2O and β-FeOOH0.652H2O, respectively. From this data, we were able to determine the standard molar entropy for bare β-FeOOH, as Δ_0^298.15S°m = 53.8 ±3.3 J•K^-1•mol^-1, based on subtractions of the estimated contribution of water from the hydrated species. Additionally, the specific heats of α-uranium, titanium diboride, and lithium flouride have been measured on a low-temperature, semi-adiabatic calorimeter down to 0.5 K. For the α-uranium, the specific heat of a polycrystalline sample was compared to that of a single crystal, and it was found that there was a significant difference in the specific heats, which has been attributed to microstrain in the polycrystal. The third law entropy for the polycrystal at 298.15 K, Δ_0^298.15S°m, calculated from these heat capacities is 50.21 ±0.1 J•K^-1•mol^-1, which is good in agreement with previously published values of polycrystal samples. For the single crystal Δ_0^298.15S°m, calculated using the thermodynamic microstrain model, is 49.02 ±0.2 J•K^-1•mol^-1. The low-temperature specific heats of titanium diboride and lithium fluoride have been measured from 0.5 K to 30 K as part of a larger project in the construction of a neutron spectrometer. For this application, the measured specific heats were used to extrapolate the specific heats down to 0.1 K with lattice, electronic, and Schottky equations for the respective samples. The resultant specific heat values at 0.1 K for TiB2 and 6LiF are 4.08E-4 ±0.27E-4 J•K^-1•mol^-1 and 9.19E-9 ±0.15E-9 J•K^-1•mol^-1, respectively.

Adiabatic calorimetry provides accurate and precise specific heat (Cp) data. From this data, thermodynamic functions may be calculated. Cu2OCl2, melanothallite, became of interest as part of a study of a particular thermochemical cycle. The experimental specific heat data and the calculated thermodynamic functions are reported here. Free energies of formation, calculated from the thermodynamic functions, suggest the particular cycle of interest with this compound as an intermediate is not feasible; uncertainty as to the accuracy of CuO and CuCl2 data used in the calculations indicate further study may be necessary. Upon collection of the specific heat data, an antiferromagnetic transition was observed at 70 K; this led to examination of the magnetic heat capacity and entropy of the transition in melanothallite. The entropy of the transition was estimated to be 18.1 % and 7.5 % of 2Rln2 by two methods. A theoretical calculation using an Ising model produced a result of 39 %. This is consistently low when compared to the entropies of the antiferromagnetic transitions of CuO and CuCl2. This suggests geometric frustration. This thesis reports the thermodynamic functions calculated from the specific heat; the examination of the magnetic entropy; and repairs to an adiabatic apparatus involved in the collection of this data.

[pt] Neste trabalho foi feita um análise teórica, da influência da relação densidade-temperatura, nas proximidades da densidade máxima, sobre a transferência de calor por convecção natural. Para este estudo foi considerado o sistema formado por uma esfera isotérmica imersa em água: Usando as simplificações da camada limite e a transformação de similaridade, as equação de conservação de massa, momentum e energia, foram reduzidas a sistemas de duas equações diferencias ordinárias, não lineares, de condições de contorno. Estas equações diferenciais simultâneas as quais descrevem os campos de velocidade e temperatura da superfície da esfera, como da temperatura da água. A solução destas equações dão dois tipos de regimes de fluxo, o primeiro o usual fluxo unidirecional e o segundo o bidirecional no qual existe fluxo inverso. Em ambos regimens a direção do fluxo depende tanto da temperatura da superfície da esfera, como da temperatura da água. O objetivo principal deste estudo foi obter a variação do coeficiente de transmissão de calor, o qual depende tanto da temperatura de superfície da esfera, como da temperatura da água. Tendo em vista que a densidade máxima da água ocorre na temperatura de 3,98 graus Celsius , e a temperatura da esfera de 0 graus Celsius a 35 graus Celsius. Os resultados numéricos foram obtidos com o emprego dos computadores digitais IBM-1130 e /370 do Rio Datacentro da Puc. / [en] In this work a theoretical analysis was made on the influence of the temperature density relationship on natural convetion heat transfer in the region of maximum desity. An Isothermal sphere immersed in water was considered in this study. Using boundary layer simplifications and similarity transformationhs, thecontinity, momentum, and energy equations which are non linear and depend on the boudary conditions. These symultaneous differential equations, which describe the velocity and temperature of the sphere as well as the water. The sotution of these equations gives twotypes of flow regimes; the first, the common unidirectional one., and the second, a bidirectional one, in which there is flow reversal. In both of theases regimes of the sphere and water. The principle objective oh this study was to abtain the variation in the heat transfer coefficient wich is dependent on the velocity field, wich in turn is dependent upo the temperatures of the sphere and water. Since the maximum desity of water occurs at 3,98 Celsius degrees, the temperature of the water in this study was varied between 0 Celsius degrees and 20 Celsius degrees, while the temperature of the sphere was varied between 0 Celsius degrees and 35 Celsius degrees. Numerical results were obtain with the use of the IBM-1130 and 370 computors at Rio Datacentro of PUC.

This licentiate thesis presents developments of nanocalorimetry systems tailored for use under extreme conditions such as high pressure, intense magnetic fields, and low temperature. Nanocalorimetry is a powerful approach to study strongly correlated systems like superconductors, heavy fermions, and quantum materials with non-trivial magnetic or electronic properties, materials with emergent magnetic orders, as well as quasicrystals. Introducing high pressure or magnetic fields as tuning parameters in specific heat measurements at low temperatures can enhance the understanding of underlying physical properties of such materials. The key component of calorimeters is the thermometer. A thin-film thermometer based on a composite ceramic metal oxide has been developed. It shows high sensitivity and negligible magnetoresistance over a broad temperature range. Two different nanocalorimeters are fabricated starting from an existing nanocalorimeter design, a high-pressure nanocalorimeter and a calorimeter for sample rotations in high magnetic fields. The high-pressure nanocalorimetry setup involves a nanocalorimeter built on a robust substrate combined with a diamond anvil cell, a gasket sandwich with electric leads, and an optical setup for pressure detection through ruby fluorescence spectroscopy. The high-field nanocalorimeters are fabricated on SiNx membranes for specific heat measurements down to 30 mK. Miniaturization is performed to extend their use for angular-dependent measurements in high magnetic fields, so far used up to 41 T. Reducing the calorimeter platform size in both calorimeters is achieved by a method of plasma etching performed after device fabrication. Specific heat measurements of Eu-doped GdCd7.88 quasicrystals and GdCd6 approximant systems are performed in fields up to 12 T. The preliminary results show the presence of spin-glass behavior in the quasicrystals and an antiferromagnetic transition in the approximant crystals at low temperatures.

No description available.

Made available in DSpace on 2015-03-03T15:16:23Z (GMT). No. of bitstreams: 1 LeonardoM.pdf: 1880413 bytes, checksum: c785ee7cbc933eb3ac782dc9ac382e6c (MD5) Previous issue date: 2009-12-18 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / We use a tight-binding formulation to investigate the transmissivity and the currentvoltage (I_V) characteristics of sequences of double-strand DNA molecules. In order to reveal the relevance of the underlying correlations in the nucleotides distribution, we compare theresults for the genomic DNA sequence with those of arti_cial sequences (the long-range correlated Fibonacci and RudinShapiro one) and a random sequence, which is a kind of prototype of a short-range correlated system. The random sequence is presented here with the same _rst neighbors pair correlations of the human DNA sequence. We found that the long-range character of the correlations is important to the transmissivity spectra, although the I_V curves seem to be mostly inuenced by the short-range correlations. We also analyze in this work the electronic and thermal properties along an _-helix sequence obtained from an _3 peptide which has the uni-dimensional sequence (Leu-Glu-Thr- Leu-Ala-Lys-Ala)3. An ab initio quantum chemical calculation procedure is used to obtain the highest occupied molecular orbital (HOMO) as well as their charge transfer integrals, when the _-helix sequence forms two di_erent variants with (the so-called 5Q variant) and without (the 7Q variant) _brous assemblies that can be observed by transmission electron microscopy. The di_erence between the two structures is that the 5Q (7Q) structure have Ala ! Gln substitution at the 5th (7th) position, respectively. We estimate theoretically the density of states as well as the electronic transmission spectra for the peptides using a tight-binding Hamiltonian model together with the Dyson's equation. Besides, we solve the time dependent Schrodinger equation to compute the spread of an initially localized wave-packet. We also compute the localization length in the _nite _-helix segment and the quantum especi_c heat. Keeping in mind that _brous protein can be associated with diseases, the important di_erences observed in the present vi electronic transport studies encourage us to suggest this method as a molecular diagnostic tool / Nesta tese, investigamos a transmissividade e as caracter?sticas de corrente como fun??o da diferen?a de potencial, no contexto da liga??o forte, em seq??ncias de dupla fita do DNA. Com o intuito de investigar a relev?ncia das correla??es subjacentes nas distribui??es dos nucleot?deos, comparamos os resultados de uma seq??ncia gen?mica do DNA com duas seq??ncias artificiais (Fibonacci e Rudin-Shapiro, que apresentam correla??o de longo alcance) e uma seq??ncia aleat?ria, prot?tipo de sistemas de correla??o de curto alcance. A seq??ncia aleat?ria utilizada apresenta a mesma correla??o de pares de primeiros vizinhos que a seq??ncia do DNA humano. Observamos que a caracter?stica de correla??o de longo alcance ? importante para o espectro de transmissividade, apesar das curvas IXV serem mais influenciadas por correla??es de curto alcance. Neste trabalho, analisamos tamb?m as propriedades t?rmicas e eletr?nicas de uma seq?encia α-h?lice, obtida de um pept?deo α3, o qual apresenta a seguinte seq??ncia unidimensional (Leu-Glu-Thr-Leu-Ala-Lys-Ala)3 (estrutura prim?ria). C?lculos ab initio qu?nticos s?o utilizados para obter as energias dos orbitais moleculares mais altos (HOMO, highest occupied molecular orbital), bem como suas integrais de transfer?ncias de cargas quando a seq??ncia α-h?lice forma uma estrutura fibrosa (variante 5Q) e n?o fibrosa (variante 7Q), as quais podem ser observadas atrav?s de microscopia eletr?nica de transmiss?o. A diferen?a entre as duas estruturas ? que a estrutura 5Q (7Q) apresenta a substitui??o Ala → Gln na 5a (7a) posi??o, respectivamente. N?s estimamos, teoricamente, a densidade de estado bem como o espectro de transmiss?o eletr?nico dos pept?deos, utilizando um Hamiltoniano no formalismo da liga??o-forte juntamente com a equa??o de Dyson. Al?m disso, n?s resolvemos a equa??o de Schr?dinger dependente do tempo para obter o espalhamento de um pacote de onda inicialmente localizado. N?s calculamos tamb?m o comprimento de localiza??o e, por fim, o calor espec?fico qu?ntico. Vale lembrar que a forma??o de prote?nas fibrosas podem estar associadas ? doen?as, de forma que as importantes diferen?as observadas no estudo das propriedades eletr?nicas de transporte nos encorajam a sugerir este m?todo como uma ferramenta de diagn?stico molecular

Im Jahr 1964 wurde eine Theorie der Supraleitung vorgestellt, welche Cooper-Paarbindungen mit nichtverschwindendem Gesamtimpuls berücksichtigt. Sie wird nach den maßgeblich beteiligten Physikern P. Fulde, R. A. Ferrell, A. I. Larkin und Y. N. Ovchinnikov als FFLO-Supraleitung bezeichnet [1, 2]. Aufgrund recht anspruchsvoller Voraussetzungen kommen nur wenige Festkörper-Systeme in Frage, die eine FFLO-Phase ausbilden könnten. Im Jahr 2007 konnte R. Lortz durch Messungen der spezifischen Wärme an dem organischen Supraleiter kappa-(ET)2Cu(NCS)2 einen soliden Nachweis für eine weitere thermodynamische Supraleitungs-Phase in hohen Magnetfeldern erbringen [3]. ET steht hierbei für Bis-(ethylen-dithiolo)-tetrathiafulvalen. Die Hochfeld-Phase von kappa-(ET)2Cu(NCS)2 erfüllt alle bekannten Bedingungen für einen FFLO-Zustand. Diese Arbeit befasst sich mit der Erbringung eines gleichwertigen Beweises einer thermodynamischen Hochfeld-Supraleitungs-Phase in dem quasi-zweidimensionalen und vollständig organischen Supraleiter beta\'\'-(ET)2SF5CH2CF2SO3 durch hochauflösende Messungen der spezifischen Wärme. Darüber hinaus sollte durch eine präzise Ausrichtung der Probe zum Magnetfeldvektor die Feldorientierungsabhängigkeit der spezifischen Wärme und damit der supraleitenden Phasen bestimmt werden. [1] - P. Fulde and R.A. Ferrell, Phys. Rev., 135:A550, (1964). [2] - A.I. Larkin and Y.N. Ovchinnikov, Zh. Eksp. Teor. Fiz., 47:1136,(1964). [3] - R. Lortz et al., Phys. Rev. Lett., 99:187002, (2007).

The interaction between magnetism and the nuclear lattice is investigated experimentally, using thermal expansion, magnetostriction, specific heat, magnetisation and neutron scattering measurements. Both localised moment systems, as represented by the rare earth compounds Tb2Agln, Pd2Gdln and Cu2Gdln, as well as transition metal compounds, Ni2MnGa and V20 3 have been characterised at low temperatures. Measurements of the lattice properties are important due to the intrinsic coupling of magnetic degrees of freedom to them. The response of the lattice to magnetic order, and also to applied magnetic fields have been probed by the use of the aforementioned techniques. Such techniques allow the direct determination of the coefficient of linear thermal expansion, over a wide temperature range and the forced magnetostriclion in applied fields of 0 to 7T. Indirect determination of the spontaneous magnetostriction and the total magnetic entropy contribution via measurements of isostructural compounds further enhance the range of experimental data available. The dynamic properties are characterised by spin polarised neutron scattering measurements. The experimental results are presented and discussed. Various methods of coupling lattice and electronic degrees of freedom have been investigated. It is argued that in order to fully understand and appreciate the low temperature properties of the materials investigated such a coupling must be taken into account.

A differential, membrane-based nanocalorimeter has been designed and constructed for thermal studies of mesoscopic samples at low temperatures. The calorimeter is intended for sample masses from mg to sub-μg and a broad temperature range from above room temperature down to the sub-K region. It allows concurrent use of ac steady state and relaxation methods. Effort was spent to achieve good absolute accuracy to enable investigations of the electronic contribution to the heat capacity of superconductors. The calorimeter consists of a pair of cells, each of which is a stack of heaters and thermometer in the center of a silicon nitride membrane, in total giving a background heat capacity less than 100 nJ/K at 300 K, decreasing to 10 pJ/K at 1 K. The device has several distinctive features: i) The resistive thermometer, made of a GeAu alloy, displays a high sensitivity, dlnR/dlnT ≈ −1 over the entire temperature range. ii) The sample is placed in direct contact with the thermometer, which is allowed to self-heat. The thermometer can thus be operated at high dc current to increase the resolution. iii) Data are acquired with a set of eight synchronized lock-in amplifiers measuring dc, 1st and 2nd harmonic signals of heaters and thermometer. iv) Absolute accuracy is achieved via a novel variable-frequency fixed-phase technique in which the measurement frequency is automatically adjusted during ac-calorimetry measurements to account for the temperature variation of the sample specific heat and the device thermal conductance. The properties of the empty cell and the effect of the thermal link between sample and cell were analytically studied. Practical expressions for describing the frequency dependence of heat capacity, thermal conductance, and temperature oscillation amplitude of the system were formulated. Comparisons with measurements and numerical simulations show excellent agreement. Calibration procedures are simple, but care should be taken to minimize thermal radiation effects. The experimental setup is operated with self-regulation of heater powers and thermometer bias, including compensation to zero the differential dc signal. As a result its high resolution and compact format, the calorimeter is well suited for studies of phase transitions and phase diagrams as well as electronic specific heat. The performance of the device is demonstrated by a study of the superconducting state of a small lead crystal. / En differentiell, membran-baserad nanocalorimeter har designats och tillverkats för termiska studier av mesoskopiska prover vid låg temperatur. Kalorimetern är avsedd för provmassor från mg till sub-μg och ett brett temperaturområde från över rumstemperatur till under 1 K. Den tillåter samtidig användning av både ac steady state och relaxations-metod. Fokus har lagts på att uppnå en god absolut noggrannhet för att möjliggöra studier av det elektroniska bidraget till värmekapaciteten hos supraledare. Kalorimetern består av två celler, var och en uppbyggd som en stack med värmeelement och termometer i mitten av ett kiselnitrid-membran, med en total bakgrundsvärmekapacitet på mindre än 100 nJ/K vid 300 K, minskande till 10 pJ/K vid 1 K. Kalorimetern har flera särdrag: i) Den resistiva termometern, gjord av en GeAu legering, visar en hög känslighet, dlnR/dlnT ≈ −1 över hela temperaturområdet. ii) Provet placeras i direkt kontakt med termometern, som tillåts att självvärma. Termometern kan alltså användas vid hög dc ström för att öka upplösningen. iii) Mätningarna genomförs med en uppsättning av åtta synkroniserade lock-in förstärkare, som mäter dc, grundfrekvens och 1:a övertonen hos värme-element och termometer. iv) Absolut noggrannhet uppnås genom en ny variabel-frekvens konstant-fas teknik där mätfrekvensen justeras automatiskt under ac-kalorimetrimätningar för att kompensera temperaturberoendet hos provets specifika värmekapacitet och kalorimetercellens värmeledningsförmåga. Egenskaperna hos den tomma cellen och inverkan av den termiska länken mellan prov och cell studerades analytiskt. Praktiska uttryck för att beskriva frekvens beroendet hos systemets värmekapacitet, värmeledningsförmåga, och temperaturoscillationer har formulerats. Jämförelser mellan mätningar och numeriska simuleringar visar mycket bra överensstämmelse. Kalibreringsförfarandet är enkelt, men försiktighet bör vidtas för att minimera värmestrålningseffekter. Experimentuppställningen drivs med självreglering av värmare och termometer, inklusive kompensation för att nollställa den differentiella dc signalen. Som en följd av dess höga upplösning och kompakta format är kalorimetern väl lämpad för studier av fasövergångar och fasdiagram såväl som det elektroniska specifika värmet. Kalorimeterns prestanda demonstreras genom en studie av det supraledande tillståndet hos en liten blykristall. / At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 5: Accepted.