An experimental investigation of the heat transfer from a buoyant gas plume to a horizontal unobstructed ceiling

This thesis presents an experimental investigation of the axisymmetric heat transfer from a small scale fire and resulting buoyant plume to a horizontal, unobstructed ceiling during the initial stages of development. A propane-air burner yielding a heat source strength between 1.0 kW and 1.6 kW was used to simulate the fire, and measurements proved that this heat source did satisfactorily represent a source of buoyancy only. The ceiling consisted of a 1/16" steel plate of 0.91 m. diameter, insulated on the upper side. The ceiling height was adjustable between 0.5 m and 0.91 m. Temperature measurements were carried out in the plume, ceiling jet, and on the ceiling.

Heat transfer data were obtained by using the transient method and applying corrections for the radial conduction along the ceiling and losses through the insulation material. The ceiling heat transfer coefficient was based on the adiabatic ceiling jet temperature (recovery temperature) reached after a long time. A parameter involving the source strength Q and ceiling height H was found to correlate measurements of this temperature and its radial variation. A similar parameter for estimating the ceiling heat transfer coefficient was confirmed by the experimental results.

This investigation therefore provides reasonable estimates for the heat transfer from a buoyant gas plume to a ceiling in the axisymmetric case, for the stagnation region where such heat transfer is a maximum and for the ceiling jet region (r/H ≤ 0.7). A comparison with data from experiments which involved larger heat sources indicates that the predicted scaling of temperatures and heat transfer rates for larger scale fires is adequate.

Theoretical studies of novel organic systems : biradicals, polyradicals, and conducting polymers

Chapter 1

Cyclobutanediyl has been studied in both its singlet and triplet states by ab initio electronic structure theory. The triplet, which is the ground state of the molecule, exists in both C_(2h) and C_(2v) forms, which interconvert via a C_s transition state. For the singlet, only a C_(2h) form is found. It passes, via a C_s transition state, onto the C_(2v) surface on which bicyclobutane is the only minimum. The ring-flipping (inversion) process in bicyclobutane includes the singlet biradical as an intermediate, and involves a novel, nonleast motion pathway. Semiclassical periodic orbit theory indicates that the various minima on both the singlet and triplet surfaces can interconvert via quantum mechanical tunneling.

Chapter 2

The dimethylenepolycyclobutadienes (n) are the non-Kekulé analogues of the classical acenes. Application of a variety of theoretical methods reveals several novel features of such structures. Most interesting is the emergence of a parity rule. When n is even, n is predicted to be a singlet, with n disjoint NBMOs. When n is odd, theory predicts a triplet ground state with (n+1) NBMOs that are not fully disjoint.

Chapter 3

Bi(cyclobutadienyl) (2), the cyclobutadiene analogue of biphenyl, and its homologues tri- (3) and tetra(cyclobutadienyl) (4) have been studied using electronic structure theory. Ab initio calculations on 2 reveal that the central bond is a true double bond, and that the structure is best thought of as two allyl radicals plus an ethylene. The singlet and triplet states are essentially degenerate. Trimer 3 is two allyls plus a dimethylenecyclobutanediyl, while 4 is two coplanar bi(cyclobutadienyl) units connected by a single bond. For both 3 and 4, the quintet, triplet, and singlet states are essentially degenerate, indicating that they are tetraradicals. The infinite polymer, polycyclobutadiene, has been studied by HMO, EHCO, and VEH methods. Several geometries based on the structures of 3 and 4 have been studied, and the band structures are quite intriguing. A novel crossing between the valence and conduction bands produces a small band gap and a high density of states at the Fermi level.

Chapter 4

At the level of Hückel theory, polyfulvene has a HOCO-LUCO degeneracy much like that seen in polyacetylene. Higher levels of theory remove the degeneracy, but the band gap (E_g) is predicted to be significantly smaller than analogous structures such as polythiophene and polypyrrole at the fulvenoid geometry. An alternative geometry, which we have termed quinoid, is also conceivable for polyfulvene, and it is predicted to have a much larger E_g. The effects of benzannelation to produce analogues of polyisothianaphthene have been evaluated. We propose a new model for such structures based on conventional orbital mixing arguments. Several of the proposed structures have quite interesting properties, which suggest that they are excellent candidates for conducting polymers.

Chapter 5

Theoretical studies of polydimethylenecyclobutene and polydiisopropylidene- cyclobutene reveal that, because of steric crowding, they cannot achieve a planar, fully conjugated structure in either their undoped or doped states. Rather, the structure consists of essentially orthogonal hexatriene units. Such a structure is incompatible with conventional conduction mechanisms involving polarons and bipolarons.

Ultrafast dynamics in ZnO thin films irradiated by femtosecond lasers

The damage morphologies, threshold fluences in ZnO films were studied with femtosecond laser pulses. Time-resolved reflectivity and transmissivity have been measured by the pump-probe technique at different pump fluences and wavelengths. The results indicate that two-phase transition is the dominant damage mechanism, which is similar to that in narrow band gap semiconductors. The estimated energy loss rate of conduction electrons is 1.5 eV/ps. (c) 2005 Elsevier Ltd. All rights reserved.

Theoretical and experimental study on femtosecond laser induced damage in CaF2 crystals

We report on the damage threshold in CaF2 crystals induced by femtosecond laser at wavelengths of 800 nm and 400 nm, respectively. The dependences of ablation depths and ablation volumes on laser fluences are also presented. We investigate theoretically the coupling constants between phonon and conduction band electrons (CBE), and calculate the rates of CBE absorbing laser energy. A theoretical model including CBE production, laser energy deposition, and CBE diffusion is applied to study the damage mechanisms. Our results indicate that energy diffusion greatly influences damage threshold and ablation depth.

Measurement of the band bending and surface dipole at chemically functionalized Si(111)/vacuum interfaces

The core-level energy shifts observed using X-ray photoelectron spectroscopy (XPS) have been used to determine the band bending at Si(111) surfaces terminated with Si-Br, Si-H, and Si-CH₃ groups, respectively. The surface termination influenced the band bending, with the Si 2p_3/2 binding energy affected more by the surface chemistry than by the dopant type. The highest binding energies were measured on Si(111)-Br (whose Fermi level was positioned near the conduction band at the surface), followed by Si(111)-H, followed by Si(111)-CH₃ (whose Fermi level was positioned near mid-gap at the surface). Si(111)-CH₃ surfaces exposed to Br₂(g) yielded the lowest binding energies, with the Fermi level positioned between mid-gap and the valence band. The Fermi level position of Br₂(g)-exposed Si(111)-CH₃ was consistent with the presence of negatively charged bromine-containing ions on such surfaces. The binding energies of all of the species detected on the surface (C, O, Br) shifted with the band bending, illustrating the importance of isolating the effects of band bending when measuring chemical shifts on semiconductor surfaces. The influence of band bending was confirmed by surface photovoltage (SPV) measurements, which showed that the core levels shifted toward their flat-band values upon illumination. Where applicable, the contribution from the X-ray source to the SPV was isolated and quantified. Work functions were measured by ultraviolet photoelectron spectroscopy (UPS), allowing for calculation of the sign and magnitude of the surface dipole in such systems. The values of the surface dipoles were in good agreement with previous measurements as well as with electronegativity considerations. The binding energies of the adventitious carbon signals were affected by band bending as well as by the surface dipole. A model of band bending in which charged surface states are located exterior to the surface dipole is consistent with the XPS and UPS behavior of the chemically functionalized Si(111) surfaces investigated herein.

The ultrafast excitation processes in femtosecond laser-induced damage in dielectric omnidirectional reflectors

A pump and probe system is developed, where the probe pulse duration tau is less than 60 fs while the pump pulse is stretched up to 150-670 fs. The time-resolved excitation processes and damage mechanisms in the omnidirectional reflectors SiO2/TiO2 and ZnS/MgF2 are studied. It is found that as the pump pulse energy is higher than the threshold value, the reflectivity of the probe pulse decreases rapidly during the former half, rather than around the peak of the pump pulse. A coupled dynamic model based on the avalanche ionization (AI) theory is used to study the excitation processes in the sample and its inverse influences on the pump pulse. The results indicate that as pulse duration is longer than 150 fs, photoionization (PI) and AI both play important roles in the generation of conduction band electrons (CBEs); the CBE density generated via AI is higher than that via PI by a factor of 10(2)-10(4). The theory explains well the experimental results about the ultrafast excitation processes and the threshold fluences. (c) 2006 American Institute of Physics.

Ultraviolet-infrared femtosecond laser-induced damage in fused silica and CaF2 crystals

The damage in fused silica and CaF2 crystals induced by wavelength tunable femtosecond lasers is studied. The threshold fluence is observed to increase rapidly with laser wavelength lambda in the region of 250-800 nm, while it is nearly a constant for 800 conduction band electrons (CBEs). We study the CBEs absorption via subconduction-band (sub-CB) transition, and develop a coupled avalanche model. Our results indicate that the CBEs absorption via sub-CB transition plays an important role in the damage in dielectrics irradiated by the visible and near ultraviolet femtosecond lasers. Our theory explains well the experiments.

Conical emission of Ti : sapphire femtosecond laser pulses propagating in water

Conical emission is investigated for Ti:sapphire femtosecond laser pulses propagating in water. The colored rings can be observed in the forward direction due to the constructive and destructive interference of transverse wavevector, which are induced by the spatio-temporal gradient of the free-electron density. With increasing input laser energy, due to filamentation and pulse splitting induced by the plasma created by multiphoton excitation of electrons from the valence band to the conduction band, the on-axis spectrum of the conical emission is widely broadened and strongly modulated with respect to input laser spectrum, and finally remains fairly constant at higher laser energy due to intensity clamping in the filaments.

High temperature transport properties of lead chalcogenides and their alloys

This thesis describes a series of experimental studies of lead chalcogenide thermoelectric semiconductors, mainly PbSe. Focusing on a well-studied semiconductor and reporting good but not extraordinary zT, this thesis distinguishes itself by answering the following questions that haven’t been answered: What represents the thermoelectric performance of PbSe? Where does the high zT come from? How (and how much) can we make it better? For the first question, samples were made with highest quality. Each transport property was carefully measured, cross-verified and compared with both historical and contemporary report to overturn commonly believed underestimation of zT. For n- and p-type PbSe zT at 850 K can be 1.1 and 1.0, respectively. For the second question, a systematic approach of quality factor B was used. In n-type PbSe zT is benefited from its high-quality conduction band that combines good degeneracy, low band mass and low deformation potential, whereas zT of p-type is boosted when two mediocre valence bands converge (in band edge energy). In both cases the thermal conductivity from PbSe lattice is inherently low. For the third question, the use of solid solution lead chalcogenide alloys was first evaluated. Simple criteria were proposed to help quickly evaluate the potential of improving zT by introducing atomic disorder. For both PbTe1-xSex and PbSe1-xSx, the impacts in electron and phonon transport compensate each other. Thus, zT in each case was roughly the average of two binary compounds. In p-type Pb1-xSrxSe alloys an improvement of zT from 1.1 to 1.5 at 900 K was achieved, due to the band engineering effect that moves the two valence bands closer in energy. To date, making n-type PbSe better hasn’t been accomplished, but possible strategy is discussed.

Electronic states in disordered topological insulators

We present a theoretical study of electronic states in topological insulators with impurities. Chiral edge states in 2d topological insulators and helical surface states in 3d topological insulators show a robust transport against nonmagnetic impurities. Such a nontrivial character inspired physicists to come up with applications such as spintronic devices [1], thermoelectric materials [2], photovoltaics [3], and quantum computation [4]. Not only has it provided new opportunities from a practical point of view, but its theoretical study has deepened the understanding of the topological nature of condensed matter systems. However, experimental realizations of topological insulators have been challenging. For example, a 2d topological insulator fabricated in a HeTe quantum well structure by Konig et al. [5] shows a longitudinal conductance which is not well quantized and varies with temperature. 3d topological insulators such as Bi₂Se₃ and Bi₂Te₃ exhibit not only a signature of surface states, but they also show a bulk conduction [6]. The series of experiments motivated us to study the effects of impurities and coexisting bulk Fermi surface in topological insulators. We first address a single impurity problem in a topological insulator using a semiclassical approach. Then we study the conductance behavior of a disordered topological-metal strip where bulk modes are associated with the transport of edge modes via impurity scattering. We verify that the conduction through a chiral edge channel retains its topological signature, and we discovered that the transmission can be succinctly expressed in a closed form as a ratio of determinants of the bulk Green's function and impurity potentials. We further study the transport of 1d systems which can be decomposed in terms of chiral modes. Lastly, the surface impurity effect on the local density of surface states over layers into the bulk is studied between weak and strong disorder strength limits.

Investigation of bulk indium antimonide as heterodyne detector for the submillimeter wavelength region

Bulk n-lnSb is investigated at a heterodyne detector for the submillimeter wavelength region. Two modes or operation are investigated: (1) the Rollin or hot electron bolometer mode (zero magnetic field), and (2) the Putley mode (quantizing magnetic field). The highlight of the thesis work is the pioneering demonstration or the Putley mode mixer at several frequencies. For example, a double-sideband system noise temperature of about 510K was obtained using a 812 GHz methanol laser for the local oscillator. This performance is at least a factor or 10 more sensitive than any other performance reported to date at the same frequency. In addition, the Putley mode mixer achieved system noise temperatures of 250K at 492 GHz and 350K at 625 GHz. The 492 GHz performance is about 50% better and the 625 GHz is about 100% better than previous best performances established by the Rollin-mode mixer. To achieve these results, it was necessary to design a totally new ultra-low noise, room-temperature preamp to handle the higher source impedance imposed by the Putley mode operation. This preamp has considerably less input capacitance than comparably noisy, ambient designs.

In addition to advancing receiver technology, this thesis also presents several novel results regarding the physics of n-lnSb at low temperatures. A Fourier transform spectrometer was constructed and used to measure the submillimeter wave absorption coefficient of relatively pure material at liquid helium temperatures and in zero magnetic field. Below 4.2K, the absorption coefficient was found to decrease with frequency much faster than predicted by Drudian theory. Much better agreement with experiment was obtained using a quantum theory based on inverse-Bremmstrahlung in a solid. Also the noise of the Rollin-mode detector at 4.2K was accurately measured and compared with theory. The power spectrum is found to be well fit by a recent theory of non- equilibrium noise due to Mather. Surprisingly, when biased for optimum detector performance, high purity lnSb cooled to liquid helium temperatures generates less noise than that predicted by simple non-equilibrium Johnson noise theory alone. This explains in part the excellent performance of the Rollin-mode detector in the millimeter wavelength region.

Again using the Fourier transform spectrometer, spectra are obtained of the responsivity and direct detection NEP as a function of magnetic field in the range 20-110 cm^-1. The results show a discernable peak in the detector response at the conduction electron cyclotron resonance frequency tor magnetic fields as low as 3 KG at bath temperatures of 2.0K. The spectra also display the well-known peak due to the cyclotron resonance of electrons bound to impurity states. The magnitude of responsivity at both peaks is roughly constant with magnet1c field and is comparable to the low frequency Rollin-mode response. The NEP at the peaks is found to be much better than previous values at the same frequency and comparable to the best long wavelength results previously reported. For example, a value NEP=4.5x10^-13/Hz^1/2 is measured at 4.2K, 6 KG and 40 cm^-1. Study of the responsivity under conditions of impact ionization showed a dramatic disappearance of the impurity electron resonance while the conduction electron resonance remained constant. This observation offers the first concrete evidence that the mobility of an electron in the N=0 and N=1 Landau levels is different. Finally, these direct detection experiments indicate that the excellent heterodyne performance achieved at 812 GHz should be attainable up to frequencies of at least 1200 GHz.

Pulse NMR in solids : chemical shift, lead fluoride and thorium hydride

Part one of this thesis consists of two sections. In the first section the fluorine chemical shift of a single crystal CaF_2 has been measured as a function of external pressure up to 4 kilobar at room temperature using multiple pulse NMR techniques. The pressure dependence of the shift is found to be -1.7 ± 1 ppm/kbar, while a theoretical calculation using an overlap model predicts a shift of -0.46 ppm/kbar. In the second section a separation of the chemical shift tensor into physically meaningful "geometrical" and "chemical" contributions is presented and a comparison of the proposed model calculations with recently reported data on hydroxyl proton chemical shift tensors demonstrates, that for this system, the geometrical portion accounts for the qualitative features of the measured tensors.

Part two of the thesis consists of a study of fluoride ion motion in β-PbF_2 doped with NaF by measurement of the ^(19)F transverse relaxation time (T_2), spin lattice relaxation time (T_1) and the spin lattice relaxation time in the rotating frame (T_(1r)). Measurements over the temperature range of -50°C to 160°C lead to activation energies for T_1, T_(1r) and T_2 of 0.205 ± 0.01, 0.29 + 0.02 and 0.27 ± 0.01 ev/ion, and a T_(1r) minimum at 56°C yields a correlation time of 0.74 μsec. Pressure dependence of T_1 and T_2 yields activation volumes of <0.2 cm^3/g-mole and 1.76 ± 0.05 cm^3/g-mole respectively. These data along with the measured magnetic field independence of T_1 suggest that the measured T_1's are not caused by ^(19)F motion, but by thermally excited carriers.

Part three of the thesis consists of a study of two samples of Th_4H_(15), prepared under different conditions but both having the proper ratio of H/Th (to within 1%). The structure of the Th_4H_(15) as suggested by X-ray measurements is confirmed through a moment analysis of the rigid lattice line shape. T_1 and T_2 measurements above 390 K furnish activation energies of 16.3 ± 1.2 kcal/mole and 18.0 ± 3.0 kcal/mole, respectively. Below 350 K, T_(1r) measurements furnish an activation energy of 10.9 ± 0.7 kcal/mole, indicating most probably more than a single mechanism for proton motion. A time-temperature hysteresis effect of the proton motion was found in one of the two samples and is strongly indicative of a phase change. T_1 at room temperature and below is dominated by relaxation due to conduction electrons with the product T_1T being 180 ± 10 K-sec. Using multiple pulse techniques to greatly reduce homonuclear dipolar broadening, a temperature-dependent line shift was observed, and the chemical shift anisotropy is estimated to be less than 16 ppm.

Investigations of noise and of quantum interference in proximity effect bridges

This work reports investigations upon weakly superconducting proximity effect bridges. These bridges, which exhibit the Josephson effects, are produced by bisecting a superconductor with a short (<1µ) region of material whose superconducting transition temperature is below that of the adjacent superconductors. These bridges are fabricated from layered refractory metal thin films whose transition temperature will depend upon the thickness ratio of the materials involved. The thickness ratio is changed in the area of the bridge to lower its transition temperature. This is done through novel photolithographic techniques described in the text, Chapter 2.

If two such proximity effect bridges are connected in parallel, they form a quantum interferometer. The maximum zero voltage current through this circuit is periodically modulated by the magnetic flux through the circuit. At a constant bias current, the modulation of the critical current produces a modulation in the dc voltage across the bridge. This change in dc voltage has been found to be the result of a change in the internal dissipation in the device. A simple model using lumped circuit theory and treating the bridges as quantum oscillators of frequency ω = 2eV/h, where V is the time average voltage across the device, has been found to adequately describe the observed voltage modulation.

The quantum interferometers have been converted to a galvanometer through the inclusion of an integral thin film current path which couples magnetic flux through the interferometer. Thus a change in signal current produces a change in the voltage across the interferometer at a constant bias current. This work is described in Chapter 3 of the text.

The sensitivity of any device incorporating proximity effect bridges will ultimately be determined by the fluctuations in their electrical parameters. He have measured the spectral power density of the voltage fluctuations in proximity effect bridges using a room temperature electronics and a liquid helium temperature transformer to match the very low (~ 0.1 Ω) impedances characteristic of these devices.

We find the voltage noise to agree quite well with that predicted by phonon noise in the normal conduction through the bridge plus a contribution from the superconducting pair current through the bridge which is proportional to the ratios of this current to the time average voltage across the bridge. The total voltage fluctuations are given by <V^2(f ) > = 4kTR^2_d I/V where R_d is the dynamic resistance, I the total current, and V the voltage across the bridge . An additional noise source appears with a strong 1/f^(n) dependence , 1.5 < n < 2, if the bridges are fabricated upon a glass substrate. This excess noise, attributed to thermodynamic temperature fluctuations in the volume of the bridge, increases dramatically on a glass substrate due to the greatly diminished thermal diffusivity of the glass as compared to sapphire.

Electrical resistance and thermoelectric power of the metastable phases in tellurium-base alloys

By using techniques of rapid quenching from the melt, metastable phases have been obtained in ternary alloys which contain tellurium as a major component and two of the three noble metals (Cu, Ag, Au) as minor components. The metastable phases found in this investigation are either simple cubic or amorphous. The formation of the simple cubic phase is discussed. The electrical resistance and the thermoelectric power of the simple cubic alloy (Au₃₀Te₇₀) have been measured and interpreted in terms of atomic bondings. The semiconducting properties of a metastable amorphous alloy (Au₅Cu₂₅Te₇₀) have been measured. The experimental results are discussed in connection with a theoretical consideration of the validity of band theory in an amorphous solid. The existence of extrinsic conduction in an amorphous semiconductor is suggested by the result of electrical resistance and thermoelectric power measurements.

Theory of s-d exchange scattering in dilute magnetic alloys

The problem of s-d exchange scattering of conduction electrons off localized magnetic moments in dilute magnetic alloys is considered employing formal methods of quantum field theoretical scattering. It is shown that such a treatment not only allows for the first time, the inclusion of multiparticle intermediate states in single particle scattering equations but also results in extremely simple and straight forward mathematical analysis. These equations are proved to be exact in the thermodynamic limit. A self-consistent integral equation for electron self energy is derived and approximately solved. The ground state and physical parameters of dilute magnetic alloys are discussed in terms of the theoretical results. Within the approximation of single particle intermediate states our results reduce to earlier versions. The following additional features are found as a consequence of the inclusion of multiparticle intermediate states;

(i) A non analytic binding energy is pre sent for both, antiferromagnetic (J < o) and ferromagnetic (J > o) couplings of the electron plus impurity system.

(ii) The correct behavior of the energy difference of the conduction electron plus impurity system and the free electron system is found which is free of unphysical singularities present in earlier versions of the theories.

(iii) The ground state of the conduction electron plus impurity system is shown to be a many-body condensate state for J < o and J > o, both. However, a distinction is made between the usual terminology of "Singlet" and "Triplet" ground states and nature of our ground state.

(iv) It is shown that a long range ordering, leading to an ordering of the magnetic moments can result from a contact interaction such as the s-d exchange interaction.

(v) The explicit dependence of the excess specific heat of the Kondo systems is obtained and found to be linear in temperatures as T→ o and T ℓnT for 0.3 T_K ≤ T ≤ 0.6 T_K. A rise in (ΔC/T) for temperatures in the region 0 < T ≤ 0.1 T_K is predicted. These results are found to be in excellent agreement with experiments.

(vi) The existence of a critical temperature for Ferromagnetic coupling (J > o) is shown. On the basis of this the apparent contradiction of the simultaneous existence of giant moments and Kondo effect is resolved.