Cylinder pressure modeling and heat release analysis are today important and standard tools for engineers and researchers, when developing and tuning new engines. Being able to accurately model and extract information from the cylinder pressure is important for the interpretation and validity of the result. The first part of the thesis treats single-zone cylinder pressure modeling, where the specific heat ratio model constitutes a key part. This model component is therefore investigated more thoroughly. For the purpose of reference, the specific heat ratio is calculated for burned and unburned gases, assuming that the unburned mixture is frozen and that the burned mixture is at chemical equilibrium. Use of the reference model in heat release analysis is too time consuming and therefore a set of simpler models, both existing and newly developed, are compared to the reference model. A two-zone mean temperature model and the Vibe function are used to parameterize the mass fraction burned. The mass fraction burned is used to interpolate the specific heats for the unburned and burned mixture, and to form the specific heat ratio, which renders a cylinder pressure modeling error in the same order as the measurement noise, and fifteen times smaller than the model originally suggested in Gatowski et al. (1984). The computational time is increased with 40 % compared to the original setting, but reduced by a factor 70 compared to precomputed tables from the full equilibrium program. The specific heats for the unburned mixture are captured within 0.2 % by linear functions, and the specific heats for the burned mixture are captured within 1 % by higher-order polynomials for the major operating range of a spark ignited (SI) engine. In the second part, four methods for compression ratio estimation based on cylinder pressure traces are developed and evaluated for both simulated and experimental cycles. Three methods rely upon a model of polytropic compression for the cylinder pressure. It is shown that they give a good estimate of the compression ratio at low compression ratios, although the estimates are biased. A method based on a variable projection algorithm with a logarithmic norm of the cylinder pressure yields the smallest confidence intervals and shortest computational time for these three methods. This method is recommended when computational time is an important issue. The polytropic pressure model lacks information about heat transfer and therefore the estimation bias increases with the compression ratio. The fourth method includes heat transfer, crevice effects, and a commonly used heat release model for firing cycles. This method estimates the compression ratio more accurately in terms of bias and variance. The method is more computationally demanding and thus recommended when estimation accuracy is the most important property. In order to estimate the compression ratio as accurately as possible, motored cycles with as high initial pressure as possible should be used. The objective in part 3 is to develop an estimation tool for heat release analysis that is accurate, systematic and efficient. Two methods that incorporate prior knowledge of the parameter nominal value and uncertainty in a systematic manner are presented and evaluated. Method 1 is based on using a singular value decomposition of the estimated hessian, to reduce the number of estimated parameters one-by-one. Then the suggested number of parameters to use is found as the one minimizing the Akaike final prediction error. Method 2 uses a regularization technique to include the prior knowledge in the criterion function. Method 2 gives more accurate estimates than method 1. For method 2, prior knowledge with individually set parameter uncertainties yields more accurate and robust estimates. Once a choice of parameter uncertainty has been done, no user interaction is needed. Method 2 is then formulated for three different versions, which differ in how they determine how strong the regularization should be. The quickest version is based on ad-hoc tuning and should be used when computational time is important. Another version is more accurate and flexible to changing operating conditions, but is more computationally demanding.

The objective of this study is to synthesize nanomaterials by mixing molten salt (alkali nitrate salt eutectics) with inorganic nanoparticles. The thermo-physical properties of the synthesized nanomaterials were characterized experimentally. Experimental results allude to the existence of a distinct compressed phase even for the solid phase (i.e., in the nanocomposite samples). For example, the specific heat capacity of the nanocomposites was observed to be enhanced after melting and re-solidification - immediately after their synthesis; than those of the nanocomposites that were not subjected to melting and re-solidification. This shows that melting and re-solidification induced molecular reordering (i.e., formation of a compressed phase on the nanoparticle surface) even in the solid phase - leading to enhancement in the specific heat capacity. Numerical models (using analytical and computational approaches) were developed to simulate the fundamental transport mechanisms and the energy storage mechanisms responsible for the observed enhancements in the thermo-physical properties. In this study, a simple analytical model was proposed for predicting the specific heat capacity of nanoparticle suspensions in a solvent. The model explores the effect of the compressed phase – that is induced from the solvent molecules - at the interface with individual nanoparticles in the mixture. The results from the numerical simulations indicate that depending on the properties and morphology of the compressed phase – it can cause significant enhancement in the specific heat capacity of nanofluids and nanocomposites. The interfacial thermal resistance (also known as Kapitza resistance, or “Rk”) between a nanoparticle and the surrounding solvent molecules (for these molten salt based nanomaterials) is estimated using Molecular Dynamics (MD) simulations. This exercise is relevant for the design optimization of nanomaterials (nanoparticle size, shape, material, concentration, etc.). The design trade-off is between maximizing the thermal conductivity of the nanomaterial (which typically occurs for nanoparticle size varying between ~ 20-30nm) and maximizing the specific heat capacity (which typically occurs for nanoparticle size less than 5nm), while simultaneously minimizing the viscosity of the nanofluid. The specific heat capacity of nitrate salt-based nanomaterials was measured both for the nanocomposites (solid phase) and nanofluids (liquid phase). The neat salt sample was composed of a mixture of KNO3: NaNO3 (60:40 molar ratio). The enhancement of specific heat capacity of the nanomaterials obtained from the salt samples was found to be very sensitive to minor variations in the synthesis protocol. The measurements for the variation of the specific heat capacity with the mass concentration of nanoparticles were compared to the predictions from the analytical model. Materials characterization was performed using electron microscopy techniques (SEM and TEM). The rheological behavior of nanofluids can be non-Newtonian (e.g., shear thinning) even at very low mass concentrations of nanoparticles, while (in contrast) the pure undoped (neat) molten salt may be a Newtonian fluid. Such viscosity enhancements and change in rheological properties of nanofluids can be detrimental to the operational efficiencies for thermal management as well as energy storage applications (which can effectively lead to higher costs for energy conversion). Hence, the rheological behavior of the nanofluid samples was measured experimentally and compared to that of the neat solvent (pure molten salt eutectic). The viscosity measurements were performed for the nitrate based molten salt samples as a function of temperature, shear rate and the mass concentration of the nanoparticles. The experimental measurements for the rheological behavior were compared with analytical models proposed in the literature. The results from the analytical and computational investigations as well as the experimental measurements performed in this proposed study – were used to formulate the design rules for maximizing the enhancement in the thermo-physical properties (particularly the specific heat capacity) of various molten salt based inorganic nanomaterials. The results from these studies are summarized and the future directions are identified as a conclusion from this study.

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.

The system LiHo_<em>x</em>Y_1-<em>x</em>F₄ is a nearly perfect example of a dilute, dipolar-coupled Ising magnet and, as such, it is an ideal testing ground for many theories in statistical mechanics. At low holmium concentration (<em>x</em> = 0. 045) an unusual spin liquid or "anti-glass" state was discovered in previous work [1]. This state does not exhibit a spin glass freezing transition as is expected for a long-range interaction. Instead, it shows dynamics which are consistent with a collection of low-frequency oscillators [2]. It was also seen to have sharp features in its specific heat [3]. <br /><br /> We present heat capacity measurements on three samples at and around the concentration of the spin liquid state in zero magnetic field and in a temperature range from around 50 mK to 1 K. In contrast to previous measurements, we find no sharp features in the specific heat. The specific heat is a broad feature which is qualitatively consistent with that of a spin glass. The residual entropy as a function of <em>x</em>, obtained through a numerical integral of the data, however, is consistent with numerical simulations which predict a disappearance of spin glass ordering below a critical concentration of dipoles [4]. <br /><br /> Also presented here, is ac susceptibility data on an <em>x</em> = 0. 45 sample which exhibits a paramagnetic to ferromagnetic transition and is found to be consistent with previous work.

The system LiHo_<em>x</em>Y_1-<em>x</em>F₄ is a nearly perfect example of a dilute, dipolar-coupled Ising magnet and, as such, it is an ideal testing ground for many theories in statistical mechanics. At low holmium concentration (<em>x</em> = 0. 045) an unusual spin liquid or "anti-glass" state was discovered in previous work [1]. This state does not exhibit a spin glass freezing transition as is expected for a long-range interaction. Instead, it shows dynamics which are consistent with a collection of low-frequency oscillators [2]. It was also seen to have sharp features in its specific heat [3]. <br /><br /> We present heat capacity measurements on three samples at and around the concentration of the spin liquid state in zero magnetic field and in a temperature range from around 50 mK to 1 K. In contrast to previous measurements, we find no sharp features in the specific heat. The specific heat is a broad feature which is qualitatively consistent with that of a spin glass. The residual entropy as a function of <em>x</em>, obtained through a numerical integral of the data, however, is consistent with numerical simulations which predict a disappearance of spin glass ordering below a critical concentration of dipoles [4]. <br /><br /> Also presented here, is ac susceptibility data on an <em>x</em> = 0. 45 sample which exhibits a paramagnetic to ferromagnetic transition and is found to be consistent with previous work.

This thesis will present research that studies the role of disorder, geometric frustration and the long range dipolar interaction on the collective behaviour of several insulating, rare earth magnets. Experiments were performed at low temperatures to measure the specific heat and magnetic susceptibility of several materials. Susceptibility was measured with a SQUID magnetometer that has been designed and constructed primarily for the study of slow dynamics in glassy systems. Specifically, this thesis will discuss three distinct topics. The first is the series of materials LiHo(x)Y(1-x)F(4), which are manifestations of the dilute, dipolar coupled Ising model. The low-x portion of the phase diagram has become a rather contentious issue in recent years with both theoretical and experimental groups disagreeing on the existence of a spin glass freezing transition and one experimental group arguing for the existence of an exotic "antiglass'' or spin liquid state resulting from quantum entanglement at x=0.045. We present specific heat and dynamical susceptibility measurements on four stoichiometries in this series: x = 0.018, 0.045, 0.080 and 0.012. No evidence of an unusual antiglass state is observed. Instead, our results show evidence, at all dilution levels studied, of a spin glass freezing transition. Interpretation of experimental data is found to be complicated by the anomalously slow dynamics in these materials. The relaxation time scales are found to increase as the concentration of Ho(3+) ions is reduced, an effect which can be attributed to single-ion physics and the importance of the nuclear hyperfine coupling in this system. A second set of materials studied here is a series of several Gd garnet materials, the most famous of which is Gd(3)Ga(5)O(12) (GGG), a material previously argued to be a disorder-free spin glass. Our specific heat experiments reproduce previous experiments on GGG and show that the homologous Gd garnets Gd(3)Te(2)Li(3)O(12) and Ga(3)Al(5)O(12) do not share the same glassy physics but exhibit sharp ordering features. By experimenting with the introduction of random site dilution, it is concluded that a 1-2% off-stoichiometry inherent in GGG is likely a special kind of disorder that is particularly effective in inducing random frustration and the formation of a spin glass. Finally, specific heat measurements on the pyrochlore antiferromagnet Gd(2)Sn(2)O(7) (GSO) are presented. While GSO has generally been found to be a well behaved and well understood model magnet, with long range order developing at around 1 K, like many other geometrically frustrated magnets, it has been discovered to possess persistent spin dynamics down to very low temperatures as measured by μSR and Mössbauer spectroscopy. Measurement of the low temperature limit of the specific heat when compared with linear spin-wave theory, however, presents a consistent picture of gapped magnon excitations that freeze out at low temperatures and make the existence of the proposed dynamic ground state unlikely.

The Department of Energy funded a project to determine if the specific heat of thermal energy storage materials could be improved by adding nanoparticles. The standard thermal energy storage materials are molten salts. The chosen molten salt was a sodium nitrate and potassium nitrate eutectic, commercially called Hitec Solar Salt. Two nanoparticle types were chosen, alumina and silica. The nanoparticle composite materials were fabricated by mixing the components in an aqueous solution, mixing that solution for a set amount of time using a sonic mixer, then removing the water from the aqueous solution, leaving the composite molten salt behind as a fine white powder. The thermal properties of the composite and plain material were measured using two techniques: American Society for Testing and Materials (ASTM) 1269E and Modulating Differential Scanning Calorimetry (MDSC). These two techniques measured the specific heat and the heat of fusion of the plain and composite materials. The results of all the ASTM and MDSC measurements suggest that the addition of the nanoparticles using the given manufacturing technique increased the specific heat of the molten salt by approximately 20 percent, with both measurement techniques showing approximately the same level of increase. The silica and the alumina improved the specific heat by nearly the same amount over the base material. The heat of fusion did not seem to be significantly altered compared to the observed heat of fusion value of the unmodified material. It was also observed that the nitrate and silica composite material's specific heat decreased if the material was raised to a temperature above 400C. The specific heat was observed to decrease over time, even when the temperature was well below 400C. It is unknown why this occurred. The nitrate plus alumina composite and the plain nitrate were stable to a temperature of 450C for the test duration.

The molecular magnet [FeII(£G)FeII(£N)(ox)2(Phen)2]n, whose chemical formula is C28H16Fe2N4O8 for unity, has been studied by magnetization measurements, neutron diffraction, and field-dependent specific heat. From the magnetization measurements, the quasi-ferrimagnetic behavior at T>Tm region can be well described with alternating Land&#x00E9; factors within 1D Ising chain model. However, in T<Tm region, the construction of long-range magnetic ordering due to the increase of interchain interaction was investigated, which is consistent with the anomaly shown in the low temperature specific heat measurement. Furthermore, an intrinsic antiferromagnetic configuration is deduced from analyzing Bragg pattern of neutron scattering. In specific heat measurement, a £f-type anomaly indicating the long-range magnetic ordering was observed. In addition, the magnetic entropy due to this anomaly is much smaller than expected value indicating the spin fluctuated as short-range ordering at T>Tm.

The heat capacity of 3He adsorbed on Grafoil (exfoilated graphite) preplated with four layers of 4He was measured between 1 and 50mK. The heat capacity was found to be linear up to 4OmK. At 3He surface densities below 4nm-2 two dimensional Fermi liquid behaviour was found and values of the hydrodynamic effective mass and Landau parameter Ff inferred. Subsequent steps in the heat capacity as a function of coverage were taken as evidence of independent 2D Fermi fluids. A low field DC SQUID pulsed NMR spectrometer was developed for future studies of magnetic order in 2D solid 3He films at ultralow temperatures

Dissociation and specific heats of synthetic methane and ethane hydrates were measured under high-pressure condition by using a heat-flow type calorimeter to understand thermodynamic properties of gas hydrates under submarine/sublacustrine environments. Ice powder was put into the sample cell and pressurized by methane and ethane up to 5MPa and 2MPa, respectively. After the completion of gas hydrate formation, samples were heated from 263K to 288K at the rate of 0.01 K min-1. Large negative peaks of heat flow corresponded to the dissociation of gas hydrates were detected in a temperature range 279-282K at a pressure of 5MPa for methane hydrate and 283-286K at 2MPa for ethane hydrate, respectively. We also obtained the specific heats of gas hydrates in the range 264-276K for methane and 264-282K for ethane under pressure.