Sessile Drop in Microgravity: Creation, Contact Angle and Interface

We present in this paper the results obtained from a parabolic flight campaign regarding the contact angle and the drop interface behavior of sessile drops created under terrestrial gravity (1g) or in microgravity (mu g). This is a preliminary study before further investigations on sessile drops evaporation under microgravity. In this study, drops are created by the mean of a syringe pump by injection through the substrate. The created drops are recorded using a video camera to extract the drops contact angles. Three fluids have been used in this study : de-ionized water, HFE-7100 and FC-72 and two heating surfaces: aluminum and PTFE. The results obtained evidence the feasibility of sessile drop creation in microgravity even for low surface tension liquids (below 15 mN m (-aEuro parts per thousand 1)) such as FC-72 and HFE-7100. We also evidence the contact angle behavior depending of the drop diameter and the gravity level. A second objective of this study is to analyze the drop interface shape in microgravity. The goal of the these experiments is to obtain reference data on the sessile drop behavior in microgravity for future experiments to be performed in an French-Chinese scientific instrument (IMPACHT).

CMB as a probe of new physics and old times

Cosmic birefringence (CB)---a rotation of photon-polarization plane in vacuum---is a generic signature of new scalar fields that could provide dark energy. Previously, WMAP observations excluded a uniform CB-rotation angle larger than a degree.

In this thesis, we develop a minimum-variance--estimator formalism for reconstructing direction-dependent rotation from full-sky CMB maps, and forecast more than an order-of-magnitude improvement in sensitivity with incoming Planck data and future satellite missions. Next, we perform the first analysis of WMAP-7 data to look for rotation-angle anisotropies and report null detection of the rotation-angle power-spectrum multipoles below L=512, constraining quadrupole amplitude of a scale-invariant power to less than one degree. We further explore the use of a cross-correlation between CMB temperature and the rotation for detecting the CB signal, for different quintessence models. We find that it may improve sensitivity in case of marginal detection, and provide an empirical handle for distinguishing details of new physics indicated by CB.

We then consider other parity-violating physics beyond standard models---in particular, a chiral inflationary-gravitational-wave background. We show that WMAP has no constraining power, while a cosmic-variance--limited experiment would be capable of detecting only a large parity violation. In case of a strong detection of EB/TB correlations, CB can be readily distinguished from chiral gravity waves.

We next adopt our CB analysis to investigate patchy screening of the CMB, driven by inhomogeneities during the Epoch of Reionization (EoR). We constrain a toy model of reionization with WMAP-7 data, and show that data from Planck should start approaching interesting portions of the EoR parameter space and can be used to exclude reionization tomographies with large ionized bubbles.

In light of the upcoming data from low-frequency radio observations of the redshifted 21-cm line from the EoR, we examine probability-distribution functions (PDFs) and difference PDFs of the simulated 21-cm brightness temperature, and discuss the information that can be recovered using these statistics. We find that PDFs are insensitive to details of small-scale physics, but highly sensitive to the properties of the ionizing sources and the size of ionized bubbles.

Finally, we discuss prospects for related future investigations.

Optical properties of excited silicon and germanium at low temperatures

Part I of this thesis deals with 3 topics concerning the luminescence from bound multi-exciton complexes in Si. Part II presents a model for the decay of electron-hole droplets in pure and doped Ge.

Part I.

We present high resolution photoluminescence data for Si doped With Al, Ga, and In. We observe emission lines due to recombination of electron-hole pairs in bound excitons and satellite lines which have been interpreted in terms of complexes of several excitons bound to an impurity. The bound exciton luminescence in Si:Ga and Si:Al consists of three emission lines due to transitions from the ground state and two low lying excited states. In Si:Ga, we observe a second triplet of emission lines which precisely mirror the triplet due to the bound exciton. This second triplet is interpreted as due to decay of a two exciton complex into the bound exciton. The observation of the second complete triplet in Si:Ga conclusively demonstrates that more than one exciton will bind to an impurity. Similar results are found for Si:Al. The energy of the lines show that the second exciton is less tightly bound than the first in Si:Ga. Other lines are observed at lower energies. The assumption of ground state to ground-state transitions for the lower energy lines is shown to produce a complicated dependence of binding energy of the last exciton on the number of excitons in a complex. No line attributable to the decay of a two exciton complex is observed in Si:In.

We present measurements of the bound exciton lifetimes for the four common acceptors in Si and for the first two bound multi-exciton complexes in Si:Ga and Si:Al. These results are shown to be in agreement with a calculation by Osbourn and Smith of Auger transition rates for acceptor bound excitons in Si. Kinetics determine the relative populations of complexes of various sizes and work functions, at temperatures which do not allow them to thermalize with respect to one another. It is shown that kinetic limitations may make it impossible to form two-exciton complexes in Si:In from a gas of free excitons.

We present direct thermodynamic measurements of the work functions of bound multi-exciton complexes in Al, B, P and Li doped Si. We find that in general the work functions are smaller than previously believed. These data remove one obstacle to the bound multi-exciton complex picture which has been the need to explain the very large apparent work functions for the larger complexes obtained by assuming that some of the observed lines are ground-state to ground-state transitions. None of the measured work functions exceed that of the electron-hole liquid.

Part II.

A new model for the decay of electron-hole-droplets in Ge is presented. The model is based on the existence of a cloud of droplets within the crystal and incorporates exciton flow among the drops in the cloud and the diffusion of excitons away from the cloud. It is able to fit the experimental luminescence decays for pure Ge at different temperatures and pump powers while retaining physically reasonable parameters for the drops. It predicts the shrinkage of the cloud at higher temperatures which has been verified by spatially and temporally resolved infrared absorption experiments. The model also accounts for the nearly exponential decay of electron-hole-droplets in lightly doped Ge at higher temperatures.

The influence of freestream turbulence, freestream nuclei populations and a drag-reducing polymer on cavitation inception on two axisymmetric bodies

The influence upon the basic viscous flow about two axisymmetric bodies of (i) freestream turbulence level and (ii) the injection of small amounts of a drag-reducing polymer (Polyox WSR 301) into the test model boundary layer was investigated by the schlieren flow visualization technique. The changes in the type and occurrence of cavitation inception caused by the subsequent modifications in the viscous flow were studied. A nuclei counter using the holographic technique was built to monitor freestream nuclei populations and a few preliminary tests investigating the consequences of different populations on cavitation inception were carried out.

Both test models were observed to have a laminar separation over their respective test Reynolds number ranges. The separation on one test model was found to be insensitive to freestream turbulence levels of up to 3.75 percent. The second model was found to be very susceptible having its critical velocity reduced from 30 feet per second at a 0.04 percent turbulence level to 10 feet per second at a 3.75 percent turbulence level. Cavitation tests on both models at the lowest turbulence level showed the value of the incipient cavitation number and the type of cavitation were controlled by the presence of the laminar separation. Cavitation tests on the second model at 0.65 percent turbulence level showed no change in the inception index, but the appearance of the developed cavitation was altered.

The presence of Polyox in the boundary layer resulted in a cavitation suppression comparable to that found by other investigators. The elimination of the normally occurring laminar separation on these bodies by a polymer-induced instability in the laminar boundary layer was found to be responsible for the suppression of inception.

Freestream nuclei populations at test conditions were measured and it was found that if there were many freestream gas bubbles the normally present laminar separation was elminated and travelling bubble type cavitation occurred - the value of the inception index then depended upon the nuclei population. In cases where the laminar separation was present it was found that the value of the inception index was insensitive to the free stream nuclei populations.

Oxidation of Volatile Organic Compounds in Aqueous Solution and at the Air-water Interface of Aqueous Microdroplets

Isoprene (ISO),the most abundant non-methane VOC, is the major contributor to secondary organic aerosols (SOA) formation. The mechanisms involved in such transformation, however, are not fully understood. Current mechanisms, which are based on the oxidation of ISO in the gas-phase, underestimate SOA yields. The heightened awareness that ISO is only partially processed in the gas-phase has turned attention to heterogeneous processes as alternative pathways toward SOA.

During my research project, I investigated the photochemical oxidation of isoprene in bulk water. Below, I will report on the λ > 305 nm photolysis of H₂O₂ in dilute ISO solutions. This process yields C₁₀H₁₅OH species as primary products, whose formation both requires and is inhibited by O₂. Several isomers of C₁₀H₁₅OH were resolved by reverse-phase high-performance liquid chromatography and detected as MH⁺ (m/z = 153) and MH⁺-18 (m/z = 135) signals by electrospray ionization mass spectrometry. This finding is consistent with the addition of ·OH to ISO, followed by HO-ISO· reactions with ISO (in competition with O₂) leading to second generation HO(ISO)₂· radicals that terminate as C₁₀H₁₅OH via β-H abstraction by O₂.

It is not generally realized that chemistry on the surface of water cannot be deduced, extrapolated or translated to those in bulk gas and liquid phases. The water density drops a thousand-fold within a few Angstroms through the gas-liquid interfacial region and therefore hydrophobic VOCs such as ISO will likely remain in these relatively 'dry' interfacial water layers rather than proceed into bulk water. In previous experiments from our laboratory, it was found that gas-phase olefins can be protonated on the surface of pH < 4 water. This phenomenon increases the residence time of gases at the interface, an event that makes them increasingly susceptible to interaction with gaseous atmospheric oxidants such as ozone and hydroxyl radicals.

In order to test this hypothesis, I carried out experiments in which ISO(g) collides with the surface of aqueous microdroplets of various compositions. Herein I report that ISO(g) is oxidized into soluble species via Fenton chemistry on the surface of aqueous Fe(II)Cl₂ solutions simultaneously exposed to H₂O₂(g). Monomer and oligomeric species (ISO)1-8H⁺ were detected via online electrospray ionization mass spectrometry (ESI-MS) on the surface of pH ~ 2 water, and were then oxidized into a suite of products whose combined yields exceed ~ 5% of (ISO)1-8H⁺. MS/MS analysis revealed that products mainly consisted of alcohols, ketones, epoxides and acids. Our experiments demonstrated that olefins in ambient air may be oxidized upon impact on the surface of Fe-containing aqueous acidic media, such as those of typical to tropospheric aerosols.

Related experiments involving the reaction of ISO(g) with ·OH radicals from the photolysis of dissolved H₂O₂ were also carried out to test the surface oxidation of ISO(g) by photolyzing H₂O₂(aq) at 266 nm at various pH. The products were analyzed via online electrospray ionization mass spectrometry. Similar to our Fenton experiments, we detected (ISO)1-7H⁺ at pH < 4, and new m/z⁺ = 271 and m/z^- = 76 products at pH > 5.

Stability against crystallization and spectroscopic properties of Tm3+ doped fluorophosphate glasses

Fluorophosphate glasses with various content of Al(PO3)(3) were prepared. With the increment of Al(PO3)(3) content, density decreases while refractive index increases, and transition temperature, crystallization peak temperature and melt temperature increase which were suggested by differential scanning calorimetry. These glasses exhibit the best stability against crystallization with 7-9 mol'Yo Al(PO3)(3) content. Normalized Raman spectra were used to analyze structure and phonon state. The increment of Al(PO3)(3) content does not affect phonon energy but results in the augment of phonon density. Absorption spectra were measured. H-3(6) -> F-3(4) transition exhibits absorption at L band of the third communication window. Compared with the energy of Tm3+ excited states in other glass system, F-3(4) energy of Tm3+ in these glasses is considerable higher and H-3(4) energy is considerable lower, and it can be predicted that emission band of H-3(4) -> F-3(4) transition is close to the amplified band of gain-shift Tm3+ doped fiber amplifier. Analyses of Judd-Ofelt theory suggest when Al(PO3)(3) content is no more than 7 mol%, Judd-Ofelt parameters Omega(t) and the lifetime of H-3(4) energy level of TM3+ vary little with the increment of Al(PO3)(3) content, and when Al(PO3)(3) content is more than 7 mol%, Omega(2) and Omega(6) increase and radiative lifetime of H-3(4) energy level of Tm3+ drops sharply with the increment of Al(PO3)(3) content. (c) 2006 Elsevier B.V. All rights reserved.

Influence of vapor transport equilibration on the crystal quality and thermal-expansion coefficients of gamma-LiAlO2

gamma-LiAlO2 (LAO) single crystal has been grown by the Czochralski method. However, its quality was deteriorated due to lithium volatilization during the crystal growth. The full width at half maximum value drops from 116.9 to 44.2 arc sec after the LAO slice was treated by vapor transport equilibration at 1000, 1100, and 1200 degrees C/48 h in sequence. The treated slice shows higher optical transmission than the as-grown one in the measured wavelength range of 190-1900 nm, meanwhile, its absorption edge exhibits a blueshift. According to Raman spectra, the treated slice has homogeneous quality at different depths from surface to 0.01 mm. The expansion coefficient of the treated slice for a axis drops from 17.2398x10(-6)/degrees C to 16.5240x10(-6)/degrees C, and that for c axis drops from 10.7664x10(-6)/degrees C to 10.0786x10(-6)/degrees C.

Age and growth of the bastard grunt (Pomadasys incisus: Haemulidae) inhabiting the Canarian archipelago, Northwest Africa

The bastard grunt (Pomadasys incisus) is one of the most abundant coastal demersal fishes inhabiting the Canary Islands. Age and growth were studied from samples collected between October 2000 and September 2001. Growth analysis revealed that this species is a fast growing and moderately short-lived species (ages up to seven years recorded). Length-at-age was described by the von Bertalanffy growth model (L∞=309.58 mm; k=0.220/year; t0=–1.865 year), the Schnute growth model (y1=126.66 mm; y2=293.50 mm; a=–0.426; b= 5.963), and the seasonalized von Bertalanffy growth model (L∞=309.93 mm; k=0.218/ year; t0= –1.896 year; C=0.555; ts=0.652). Individuals grow quickly in their first year, attaining approximately 60% of their maximum length; after the first year, their growth rate drops rapidly as energy is probably diverted to reproduction. The parameters of the von Bertalanffy weight growth curve were W∞=788.22 mm; k=0.1567/year; t0= –1.984 year. Fish total length and otolith radius were closely correlated, r2=0.912. A power relationship was estimated between the total length and the otolith radius (a=49.93; ν=0.851). A year’s growth was represented by an opaque and hyaline (translucent) zone—an annulus. Backcalculated lengths were similar to those predicted by the growth models. Growth parameters estimated from the backcalculated sizes at age were L∞=315.23 mm; k=0.217/year; and t0= –1.73 year.

Imbibition dynamics of nano-particulate ink-jet drops on micro-porous media

Ink-jet printing of nano-metallic colloidal fluids on to porous media such as coated papers has become a viable method to produce conductive tracks for low-cost, disposable printed electronic devices. However, the formation of well-defined and functional tracks on an absorbing surface is controlled by the drop imbibition dynamics in addition to the well-studied post-impact drop spreading behavior. This study represents the first investigation of the real-time imbibition of ink-jet deposited nano-Cu colloid drops on to coated paper substrates. In addition, the same ink was deposited on to a non-porous polymer surface as a control substrate. By using high-speed video imaging to capture the deposition of ink-jet drops, the time-scales of drop spreading and imbibition were quantified and compared with model predictions. The influences of the coating pore size on the bulk absorption rate and nano-Cu particle distribution have also been studied.