MAX-phase materials are a new type of material class. These materials are potentiallyt echnologically important as they show unique physical properties due to the combination of metals and ceramics. In this project, spectroscopic ellipsometry in the spectral range of 0.06 eV –6.0 eV was used to probe the linear optical response of MAX-phases in terms of the complexd dielectric function ε(ω) = ε1(ω) + iε2(ω). Measured data were fit to theoretical models using the Lorentz and generalized oscillator models. Data from seven different samples of MAX-phase materials were obtained using two ellipsometers. Each sample dielectric function was determined, including their infrared spectrum.

The Large Hadron Collider (LHC) at CERN have a capacity to produce protonproton collisions with an energy of 14 TeV. Four particle detectors are included in the LHC with the purpose to detect all the particles that are created in the collisions. In one of these detectors are scintillating lead tungstate crystals used, to detect the energy of photons and electrons created in the collisions. The energy is detected by measuring of the emitted light from the scintillating crystals. As much knowledge as possible about the optical properties of the crystals are desired to be able to analyze the acquired data from the crystals. This thesis work presents some techniques used for the characterization of the optical properties for the crystals. It also presents measurements done on the decay time of lead tungstate crystals and on the temperature influence to the light yield from the crystals. These measurement results are in addition used in an attempt to estimate how big influence the Cherenkov radiation has to the total amount of emitted light from the scintillating crystals. The influence from the temperature to the light yield is around −2.02 %/◦C for BTCP and around −1.75 %/◦C for SIC1. No conclusions could been drawn concerning the influence from the Cherenkov radiation to the total amount of emitted light from the temperature measurements.The decay time measurements showed an influence from the Cherenkov radiation to the total amount of emitted light of; 8 % for crystal 1003, 47 % for crystal 1002 and 19 % for crystal 1001. 1BTCP (Bogoroditsk Technical Chemical Plant) and SIC (Shanghai Institute of Ceramics) are the two different crystal production facilities used for the production of the crystals.

Graduation date: 1994

For high-resolution X-ray imaging scintillator applications, we have prepared and optically characterized divalent samarium doped fluorochlorozirconate (FCZ:Sm2+) glasses and glass-ceramics. Sm2+ doped FCZ glasses were obtained by adding a reducing agent, NaBH4 into the initial melt to convert some of the Sm3+ to Sm2+. However, the Sm2+ concentration at most was estimated to be only approximately 0.003 %. The as-prepared glass samples were further heat treated to obtain glass-ceramics; the nucleation and growth of BaCl2 nanocrystals were confirmed by powdered X-ray diffraction (XRD) experiments. Depending on the heat treatment conditions (temperature and time), the average nanocrystal size varies from 8 to 170 nm, and the sample contains BaCl2 nanocrystals with the orthorhombic and/or hexagonal structure. The optical absorption spectra for our glass-ceramic samples suggested the substitution of Sm2+ ions into the BaCl2 lattice site. The FCZ:Sm2+ glass-ceramics samples showed strong fluorescence in the red region of spectrum (approximately 8 times that of an as-prepared glass), and the transparency can be very high (transmittance > 80 % for samples with thickness about 0.5 mm) and can be equivalent to that of an as-prepared glass . These two results promise potential as a high-resolution X-ray scintillator due to the emission wavelength range and high transparency. Extensive studies of photoluminescence (PL) spectra at low temperatures (12 -- 200 K) for FCZ:Sm2+ glass-ceramics suggested useful indicators of the crystal structure and average size of embedded BaCl2 nanocrystals. A detailed analysis of the optical spectra has lead to the identification of the origin of the emission peaks and the location of Sm ions at specific crystallographic sites. X-ray induced luminescence (XL) studies have suggested a strong dependence of the fluorescence intensity on the concentration of Sm2+ ions. In addition, for more efficient fluorescence, a sample should be heat treated in a hydrogen containing atmosphere (e.g. H2 + Ar gas), and the heat treatment conditions should be such that the nanocrystals grow in the hexagonal structure.

Mercury cadmium telluride is important in the detection of electromagnetic radiation in the eight to twelve micron atmospheric window for infrared imaging systems. High resolution infrared imaging systems use either large (256x256 element to 1024x1024 element) staring arrays or much smaller (1-6 element) scanned arrays in which the image is optically scanned across the detectors. In scanned arrays, high resolution and sensitivity may result in the scan direction not being parallel to the detector bias current. The response of an infrared detector to uniform illumination is investigated. It is found that variations in the detector thickness result in significant changes in output voltage. Scanned detectors are modeled in five different orientations; scan parallel to bias, scan opposite to bias, scan perpendicular to bias, and two orientations of the scan diagonal to the bias. The response is analyzed for two cases: 1) the size of the scanned radiation equal to the size of the detector and 2) when the pixel width is half of the width of the detector, but of equal length. Results of the simulation show that the fastest response occurs when the scan and bias are parallel. The largest response occurs when the scan direction is diagonal to the bias, but the response time is much slower than when the bias is parallel to the scan. Therefore, a tradeoff must be made between maximum signal and speed of response. Test detectors are being fabricated and will be tested at FLIR Systems Inc., Portland, Oregon, to confirm the model predictions. / Graduation date: 1992

For high-resolution X-ray imaging scintillator applications, we have prepared and optically characterized divalent samarium doped fluorochlorozirconate (FCZ:Sm2+) glasses and glass-ceramics. Sm2+ doped FCZ glasses were obtained by adding a reducing agent, NaBH4 into the initial melt to convert some of the Sm3+ to Sm2+. However, the Sm2+ concentration at most was estimated to be only approximately 0.003 %. The as-prepared glass samples were further heat treated to obtain glass-ceramics; the nucleation and growth of BaCl2 nanocrystals were confirmed by powdered X-ray diffraction (XRD) experiments. Depending on the heat treatment conditions (temperature and time), the average nanocrystal size varies from 8 to 170 nm, and the sample contains BaCl2 nanocrystals with the orthorhombic and/or hexagonal structure. The optical absorption spectra for our glass-ceramic samples suggested the substitution of Sm2+ ions into the BaCl2 lattice site. The FCZ:Sm2+ glass-ceramics samples showed strong fluorescence in the red region of spectrum (approximately 8 times that of an as-prepared glass), and the transparency can be very high (transmittance > 80 % for samples with thickness about 0.5 mm) and can be equivalent to that of an as-prepared glass . These two results promise potential as a high-resolution X-ray scintillator due to the emission wavelength range and high transparency. Extensive studies of photoluminescence (PL) spectra at low temperatures (12 -- 200 K) for FCZ:Sm2+ glass-ceramics suggested useful indicators of the crystal structure and average size of embedded BaCl2 nanocrystals. A detailed analysis of the optical spectra has lead to the identification of the origin of the emission peaks and the location of Sm ions at specific crystallographic sites. X-ray induced luminescence (XL) studies have suggested a strong dependence of the fluorescence intensity on the concentration of Sm2+ ions. In addition, for more efficient fluorescence, a sample should be heat treated in a hydrogen containing atmosphere (e.g. H2 + Ar gas), and the heat treatment conditions should be such that the nanocrystals grow in the hexagonal structure.

<p>Variations in hemoglobin concentration can be indicative of a number of serious complications, including blood loss and anemia. Rapid, noninvasive measurements of hemoglobin are important in applications where blood status is reflective of patient well-being, such as in the emergency room, operating room, or the battlefield. Probe-based diffuse reflectance spectroscopy is capable of noninvasively quantifying tissue optical properties, including hemoglobin concentration. The quantification of hemoglobin concentration using optical methods is complicated by tissue scattering and the robustness of the algorithm and instrumentation used to interrogate the tissue. The sensing depth of diffuse reflectance spectroscopy can be tailored by the wavelengths of light and probe design used.</p><p>In this thesis, the accuracy and clinical viability of different diffuse reflectance spectroscopy implementations are presented. The robustness of an inverse Monte Carlo model, in which tissue optical properties are determined from measured reflectance using ultraviolet-visible (UV-VIS) wavelengths and a steady-state instrument, was tested using laboratory measurements. From the laboratory measurements, a set of references was identified which provided accurate absorption and scattering measurements, independent of the optical properties of the target. In addition, the ability to quantify hemoglobin concentration and saturation over large ranges and concentrations of multiple absorbers was established. </p><p>Following the laboratory measurements, a clinical study in which UV-VIS spectra were measured from the sublingual mucosa of patients undergoing surgeries was carried out. From this study, the correlations of extracted hemoglobin to expected blood hemoglobin were found to be improved when a simple ratiometric method based on isosbestic wavelengths of hemoglobin was used. During this study, the probe positioning in the mouth was found to be unwieldy, and so the transition to a more secure probe that could be taped to the hand was made. </p><p>In order to penetrate the overlying skin, near-infrared (NIR) wavelengths with a different probe geometry was explored. Further investigation of the inverse Monte Carlo model with NIR wavelengths was executed, and while in theory this combination should yield accurate optical property estimation, laboratory measurements indicated large errors, presumably due to the instrument or low magnitude and reduced spectral features of hemoglobin absorption in the NIR. Instead, the use of a well-established frequency-domain instrument coupled with diffusion approximation was implemented to measure spectra from the thenar eminence of volunteers undergoing induced hypovolemia and subsequent retransfusion. There were some moderate correlations with blood hemoglobin, but because both this method and the Monte Carlo method with mucosal probe placement showed higher variability with probe pressure than the isosbestic ratiometric method, further development of the ratiometric method was made. </p><p>The ratiometric method was developed using simulations and validated with phantoms and clinical data. Monte Carlo modeled reflectance was generated for a large range of biologically-relevant absorption and scattering values. The modeled reflectance was scaled by a calibration spectra obtained from a single laboratory phantom measurement so that linear regression equations relating hemoglobin concentration to ratios could be applied directly to clinical or laboratory measurements. Ratios which could best estimate hemoglobin concentration independent of saturation and scattering were determined through the simulation and laboratory measurements. Three isosbestic ratios - 545/390, 452/390, and 529/390 nm - were determined to best estimate hemoglobin concentration, and ratiometric-extracted hemoglobin was shown to correlate well to Monte Carlo-extracted hemoglobin in clinical measurements. Because only a single calibration measurement (which can be measured on a different day) is required per instrument and probe combination, this method can be implemented in near real-time and is thus appropriate for applications where hemoglobin concentration must be measured rapidly.</p> / Dissertation

No description available.

The single scattering properties of atmospheric particles are fundamental to radiative simulations and remote sensing applications. In this study, an efficient technique, namely, the pseudo-spectral time-domain (PSTD) method which was first developed to study acoustic wave propagation, is applied to the scattering of light by nonspherical particles with small and moderate size. Five different methods are used to discretize Maxwell’s equations in the time domain. The perfectly matched layer (PML) absorbing boundary condition is employed in the present simulation for eliminating spurious wave propagations caused by the spectral method. A 3-D PSTD code has been developed on the basis of the five aforementioned discretization methods. These methods provide essentially the same solutions in both absorptive and nonabsorptive cases. In this study, the applicability of the PSTD method is investigated in comparison with the Mie theory and the T-matrix method. The effects of size parameter and refractive index on simulation accuracy are discussed. It is shown that the PSTD method is quite accurate when it is applied to the scattering of light by spherical and nonspherical particles, if the spatial resolution is properly selected. Accurate solutions can also be obtained from the PSTD method for size parameter of 80 or refractive index of 2.0+j0. Six ice crystal habits are defined for the PSTD computational code. The PSTD results are compared with the results acquired from the finite difference time domain (FDTD) method at size parameter 20. The PSTD method is about 8-10 times more efficient than the conventional FDTD method with similar accuracy. In this study, the PSTD is also applied to the computation of the phase functions of ice crystals with a size parameter of 50. Furthermore, the PSTD, the FDTD, and T-matrix methods are applied to the study of the optical properties of horizontally oriented ice crystals. Three numerical schemes for averaging horizontal orientations are developed in this study. The feasibility of using equivalent circular cylinders as surrogates of hexagonal prisms is discussed. The horizontally oriented hexagonal plates and the equivalent circular cylinders have similar optical properties when the size parameter is in the region about from 10 to 40. Otherwise, the results of the two geometries are substantially different.

Nanoparticles have garnered much attention in pharmaceutical and biomedical fields because their small size and high surface area facilitate drug absorption, improve access to cells and organs, and enhance optical imaging. However, delivery of nanoparticles to the body is not always feasible or effective. Here, nanoparticle assemblies (flocs or clusters) for pulmonary drug delivery and biomedical imaging in cells are shown to facilitate delivery, interactions with cells, and manipulation of optical properties of inorganic/organic nanocomposites. The formation of aggregates by physical techniques and their mechanisms are described in detail. For pulmonary delivery, particles with aerodynamic diameters between 1-5 [mu]m deposit efficiently in the deep lungs. However, crystalline, non-porous, poorly water soluble drugs of this size require long dissolution times, limiting absorption by the body. Therefore, drug dissolution must be “decoupled” from deposition to improve absorption. To address this challenge, drug nanoparticles were dispersed within 4-[mu]m water droplets when administered via nebulization or as micron-sized flocs using a pressurized metered dose inhaler (pMDI). Upon deposition in aqueous media, the aerosolized nanoparticle assemblies dissociated into constituent nanoparticles, raising the available surface area for dissolution and increasing dissolution rates, relative to solid particles. Poorly water soluble drug nanoparticles were prepared using a controlled precipitation (CP) or thin film freezing (TFF) process, in which stable nanoparticles (30-300 nm in diameter) with high potencies (>90 wt% drug) were produced by rapidly nucleating drug solutions in the presence of strongly adsorbing polymers or by freezing, respectively. Amorphous, nanoparticles prepared by CP produced stable aqueous dispersions with high fine particle fractions (FPF) of 77% and total emitted doses (TED) of 1.5 mg/min upon nebulization. CP and TFF also produced anisotropic particles (aspect ratios >5), which formed stable suspensions in a hydrofluoroalkane propellant. Inefficient packing of anisotropic particles formed loose, open flocs that stacked upon each other to prevent settling. Upon pMDI actuation, atomized propellant droplets shear apart and template portions of the floc to yield porous particles with high FPFs (49-64%) and TEDs (2.4 mg/actuation). The controlled assembly of gold nanoparticles into clusters is also of great interest for biomedical imaging and therapy because clusters exhibit improved near infrared absorbance (where blood and tissue are most transparent), relative to single spherical particles, and can biodegrade into clearable particles. Gold nanoparticles (5 nm) were assembled into clusters between 30 to 100 nm in diameter with high gold loadings, resulting in strong NIR absorbance. The assembly was kinetically controlled with weakly adsorbing polymers by manipulating electrostatic, van der Waals, steric, and depletion forces. Furthermore, clusters assembled with a biodegradable polymer deaggregated back into primary particles in physiological media and within cells. This kinetic assembly platform is applicable to a wide variety of fields that require high metal loadings and small particle sizes. / text