The Head-On Colliding Process Of Binary Liquid Droplets At Low Velocity: High-Speed Photography Experiments And Modeling

The experimental and theoretical studies are reported in this paper for the head-on collisions of a liquid droplet with another of the same fluid resting on a solid substrate. The droplet on the hydrophobic polydimethylsiloxane (PDMS) substrate remains in a shape of an approximately spherical segment and is isometric to an incoming droplet. The colliding process of the binary droplets was recorded with high-speed photography. Head-on collisions saw four different types of response in our experiments: complete rebound, coalescence, partial rebound With conglutination, and coalescence accompanied by conglutination. For a complete rebound, both droplets exhibited remarkable elasticity and the contact time of the two colliding droplets was found to be in the range of 10-20 ms. With both droplets approximately considered as elastic bodies, Hertz contact theory was introduced to estimate the contact time for the complete rebound case. The estimated result Was found to be on the same order of magnitude as the experimental data, which indicates that the present model is reasonable. (C) 2008 Elsevier Inc. All rights reserved.

Thermocapillary Motion Of Droplets At Large Marangoni Numbers

In this paper, the thermocapillary motion problem of drops is investigated using the axisymmetric model. The front-tracking method is employed to capture the drop interface. We find that the migration velocity of the drop is greatly influenced by the temperature field in the drop when Ma is fairly large (>100), which leads to an increase-decrease migration velocity at the beginning of our simulations. (C) 2007 COSPAR. Published by Elsevier Ltd. All rights reserved.

Experimental Observation Of Electrical Instability Of Droplets On Dielectric Layer

Polydimethylsiloxane ( PDMS) has become the most widely used silicon-based organic polymer in bio-MEMS/NEMS devices. However, the inherent hydrophobic nature of PDMS hinders its wide applications in bio-MEMS/NEMS for efficient transport of liquids. Electrowetting is a useful tool to reduce the apparent contact angle of partially wetting conductive liquids and has been utilized widely in bio-MEMS/NEMS. Our experimental results show that the thin PDMS membranes exhibit good properties in electrowetting-on-dielectric. The electrical instability phenomenon of droplets was observed in our experiment. The sessile droplet lying on the PDMS membrane will lose its stability with the touch of the wire electrode to make the apparent contact angle change suddenly larger than 35 degrees. Contact mode can protect the dielectric layer from electrical breakdown effectively. Electrical breakdown process of dielectric layer was recorded by a high speed camera. It is found experimentally that a PDMS membrane of 4.8 mu m thick will not be destroyed due to the electric breakdown even at 800 V in the contact mode.

Bimetallic olefin polymerization catalysis : mechanisms and applications of proximal effects

This dissertation covers progress with bimetallic polymerization catalysts. The complexes we have designed were aimed at expanding the capabilities of homogeneous polymerization catalysts by taking advantage of multimetallic effects. Such effects were examined in group 4 and group 10 bimetallic complexes; proximity and steric repulsion were determined to be major factors in the effects observed.

Chapters 2 and 3 introduce the rigid p-terphenyl dinucleating framework utilized in most of this thesis. The permethylation of the central arene allows for the separation of syn and anti atropisomers of the terphenyl compounds. Kinetic studies were carried out to examine the isomerization of the dinucleating bis(salicylaldimine) ligand precursors. Metallation of the syn and anti bis(salicylaldimine)s using Ni(Me)2(tmeda) and excess pyridine afforded dinickel bisphenoxyiminato complexes with a methyl and a pyridyl ligand on each nickel. The syn and anti atropisomers of the dinickel complexes were structurally characterized and utilized in ethylene and ethylene/α-olefin polymerizations. Monometallic analogues were also synthesized and tested for polymerization activity. Ethylene polymerizations were performed in the presence of primary, secondary, and tertiary amines – additives that generally deactivate nickel polymerization catalysts. Inhibition of this deactivation was observed with the syn atropisomer of the bimetallic species, but not with the anti or monometallic analogues. A mechanism was proposed wherein steric repulsion of the substituents on proximal nickel centers disfavors simultaneous ligation of base to both of the metal centers. The bimetallic effect has been explored with respect to size and binding ability of the added base.

Chapter 4 presents the optimization of the bisphenoxyimine ligand synthesis and synthesis of syn and anti m-terphenyl analogues. Metallation with NiClMe(PMe₃)₂ yielded phosphine-ligated dinickel complexes, which have been structurally characterized. Ethylene/1-hexene copolymerizations in the presence of amines using Ni(COD)₂ as a phosphine scavenger showed significantly improved activity relative to the pyridine-ligated analogues. Incorporation of amino olefins in copolymerizations with ethylene was accomplished, and a mechanism was proposed based on proximal effects. Copolymerization trials with a variety of amino olefins and ethylene/1-hexene/amino olefin terpolymerizations were completed.

Early transition metal complexes based on the rigid p-terphenyl framework were designed with a variety of donor sets (Chapter 5 and Appendix B). Chapter 5 details the use of syn dizirconium di[amine bis(phenolate)] complexes for isoselective 1-hexene and propylene homopolymerizations. Ligand variation and monometallic complexes were studied to determine the origin of tacticity control. A mechanistic proposal was presented based on the symmetry at zirconium and the steric effects of the proximal metal center. Appendix B covers additional studies of bimetallic early transition metal complexes based on the p-terphenyl. Dititanium, dizirconium, and asymmetric complexes with bisphenoxyiminato ligands and derivatives thereof were targeted. Progress toward the synthesis of these complexes is described along with preliminary polymerization data. 1-hexene/diene copolymerizations and attempted polymerizations in the presence of ethers and esters with the syn dizirconium di[amine bis(phenolate)] complexes demonstrate the potential for further applications of this system in catalysis.

Appendix A includes work toward palladium catalysts for insertion polymerization of polar monomers. These complexes were based on dioxime and diimine frameworks with the intent of binding Lewis acidic metals at the oxime oxygens, at pendant phenolic donors, or at pendant aminediol moieties. The synthesis and structural characterization of a number of palladium and Lewis acid complexes is presented. Due to the instability of the desired species, efforts toward isolation of the desired complexes proved unsuccessful, though preliminary ethylene/methyl acrylate copolymerizations using in situ activation of the palladium species were attempted.

Experimental chemical physics of droplets and clusters

Time-of-flight measurements of energetic He atoms, field ionization of cryogenic liquid helium clusters, and time-of-flight and REMPI spectroscopy of radical salt clusters were investigated experimentally. The excited He atoms were generated in a corona discharge. Two strong neutral peaks were observed, accompanied by a prompt photon peak and a charged peak. All peaks were correlated with the pulsing of the discharge. The neutral hyperthermal and metastable atoms were formed by different mechanisms at different stages of the corona discharge. Positively charged helium droplets were produced by ionization of liquid helium in an electrostatic spraying experiment. The fluid emerging from a thin glass capillary was ionized by a high voltage applied to a needle inside the capillary. Fine droplets (less than 10 µm in diameter) were produced in showers with currents as high as 0.4 µA at 2-4 kV. The high currents resulting from field ionization in helium and the low surface tension of He I, led to charge densities that greatly exceeded the Rayleigh limit, thus resulting in coulombic explosion of the liquid. In contrast, liquid nitrogen formed a well-defined Taylor cone with droplets having diameters comparable to the jet (≈100 µm) at lower currents (10 nA) and higher voltages (8 kV). The metal-halide clusters of calcium and chlorine were generated by laser ablation of calcium metal in a Ar/CCl₄ expansion. A visible spectrum of the Ca₂Cl₃ cluster was observed from 651 to 630 nm by 1 +1' REMPI. The spectra were composed of a strong origin band at 15 350.8 cm^-1 and several weak vibronic bands. Density functional calculations predicted three minimum energy isomers. The spectrum was assigned to the ²B₂ ← X ²A₁ transition of a planar C_2V structure having a ring of two Cl and two Ca atoms and a terminal Cl atom. The ring isomer of Ca₂Cl₃ has the unpaired electron localized on one Ca²⁺ ion to form a Ca⁺ chromophore. A second electronic band of Ca₂Cl₃ was observed at 720 nm. The band is sharply different from the 650 nm band and likely due to a different isomer.

Luminescence properties of electron-hole-droplets in pure and doped germanium

This work contains 4 topics dealing with the properties of the luminescence from Ge.

The temperature, pump-power and time dependences of the photoluminescence spectra of Li-, As-, Ga-, and Sb-doped Ge crystals were studied. For impurity concentrations less than about 10¹⁵cm^-3, emissions due to electron-hole droplets can clearly be identified. For impurity concentrations on the order of 10¹⁶cm^-3, the broad lines in the spectra, which have previously been attributed to the emission from the electron-hole-droplet, were found to possess pump-power and time dependent line shape. These properties show that these broad lines cannot be due to emission of electron-hole-droplets alone. We interpret these lines to be due to a combination of emissions from (1) electron-hole- droplets, (2) broadened multiexciton complexes, (3) broadened bound-exciton, and (4) plasma of electrons and holes. The properties of the electron-hole-droplet in As-doped Ge were shown to agree with theoretical predictions.

The time dependences of the luminescence intensities of the electron-hole-droplet in pure and doped Ge were investigated at 2 and 4.2°K. The decay of the electron-hole-droplet in pure Ge at 4.2°K was found to be pump-power dependent and too slow to be explained by the widely accepted model due to Pokrovskii and Hensel et al. Detailed study of the decay of the electron-hole-droplets in doped Ge were carried out for the first time, and we find no evidence of evaporation of excitons by electron-hole-droplets at 4.2°K. This doped Ge result is unexplained by the model of Pokrovskii and Hensel et al. It is shown that a model based on a cloud of electron-hole-droplets generated in the crystal and incorporating (1) exciton flow among electron-hole-droplets in the cloud and (2) exciton diffusion away from the cloud is capable of explaining the observed results.

It is shown that impurities, introduced during device fabrication, can lead to the previously reported differences of the spectra of laser-excited high-purity Ge and electrically excited Ge double injection devices. By properly choosing the device geometry so as to minimize this Li contamination, it is shown that the Li concentration in double injection devices may be reduced to less than about 10¹⁵cm^-3 and electrically excited luminescence spectra similar to the photoluminescence spectra of pure Ge may be produced. This proves conclusively that electron-hole-droplets may be created in double injection devices by electrical excitation.

The ratio of the LA- to TO-phonon-assisted luminescence intensities of the electron-hole-droplet is demonstrated to be equal to the high temperature limit of the same ratio of the exciton for Ge. This result gives one confidence to determine similar ratios for the electron-hole-droplet from the corresponding exciton ratio in semiconductors in which the ratio for the electron-hole-droplet cannot be determined (e.g., Si and GaP). Knowing the value of this ratio for the electron-hole-droplet, one can obtain accurate values of many parameters of the electron-hole-droplet in these semiconductors spectroscopically.

Análise comparativa in vivo da detecção de lesões de cárie oclusal e proximal por meio de exame visual (ICDAS), exame radiográfico e transiluminação por fibra ótica (FOTI)

O objetivo do presente trabalho foi avaliar in vivo a detecção de cárie através do exame visual ICDAS, transiluminação por fibra ótica combinado ao ICDAS e exame radiográfico. Um total de 2.279 superfícies proximais e cicatrículas e fissuras em incisivos superiores, pré-molares e molares permanentes e 272 superfícies em molares decíduos em72 escolares (8 a 18 anos) foram avaliadas por um examinador treinado. Os sete escores para detecção de cárie primária do sistema visual ICDAS foram aplicados. Dois equipamentos de transiluminação por fibra ótica foram avaliados: FOTI Schott (SCH), com ponta de fibra ótica com 0,5mm de diâmetro, e FOTI Microlux (MIC), com diâmetro da ponta 3 mm. Durante o exame combinado FOTI/ICDAS, a fibra ótica era utilizada tanto para iluminar quanto para transiluminar a superfície sob avaliação. O exame radiográfico (RX) consistiu de radiografias interproximais posteriores e periapicais anteriores. Os exames foram realizados em consultório odontológico após escovação supervisionada. No primeiro dia de exame, o exame visual utilizando o ICDAS era realizado e em seguida, o exame combinado ao MIC ou SCH. Logo após era realizado o exame radiográfico. Após uma semana, novamente o ICDAS era realizado, e em seguida o exame combinado com o equipamento de FOTI não utilizado na semana anterior. Os exames foram repetidos em 10 pacientes após intervalo mínimo de uma semana para avaliação da reprodutibilidade intra-examinador, a qual apresentou valores de 0,95 (ICDAS), 0,94 (MIC), 0,95 (SCH) e 0,99 (RX) pelo kappa ponderado. Em cicatrículas e fissuras de permanentes, o RX julgou que um número maior de superfícies apresentava lesão em dentina (53) do que os outros métodos (34 a 36); porém não detectou nenhuma lesão em esmalte, as quais foram identificadas pelo ICDAS (94), SCH (107) e MIC (91). Em proximais permanentes, a transiluminação por fibra ótica identificou maior número de proximais como lesão em esmalte - 150 (SCH) e 139 (MIC) - do que o exame visual (106), enquanto o RX identificou somente 43. Em oclusais de decíduos, os quatro métodos julgaram um número aproximadamente similar de superfícies sem lesão (52 a 59) ou com lesão em dentina (21 a 26), assim como para lesões proximais em dentina (31 a 36). Entretanto um número reduzido de lesões proximais decíduas em esmalte foi julgado pelo exame radiográfico (3) em comparação com os outros métodos (15 a 16). Em decíduos, o ICDAS e o FOTI combinado ao exame visual julgaram maior número de lesões proximais em esmalte que o exame radiográfico, sendo que número similar de lesões em dentina foram classificadas pelos quatro métodos em oclusais e proximais de molares decíduos. Em cicatrículas e fissuras de permanentes, tanto o exame visual ICDAS quanto sua combinação aos dois equipamentos de transiluminação apresentaram maior similaridade de superfícies julgadas como lesão em esmalte ou como lesão em dentina, enquanto o exame radiográfico classificou mais superfícies como lesão em dentina e nenhuma como lesão em esmalte. A adição da transiluminação por fibra ótica ao exame visual aumentou em um terço a detecção das lesões cariosas proximais julgadas em dentina pelo ICDAS isoladamente e aproximadamente quadruplicou o número daquelas assim classificadas pela avaliação radiográfica em permanentes.

Results on proximal and generalized weak proximal contractions including the case of iteration-dependent range sets

This paper presents some further results on proximal and asymptotic proximal contractions and on a class of generalized weak proximal contractions in metric spaces. The generalizations are stated for non-self-mappings of the forms for and , or , subject to and , such that converges uniformly to T, and the distances are iteration-dependent, where , , and are non-empty subsets of X, for , where is a metric space, provided that the set-theoretic limit of the sequences of closed sets and exist as and that the countable infinite unions of the closed sets are closed. The convergence of the sequences in the domain and the image sets of the non-self-mapping, as well as the existence and uniqueness of the best proximity points, are also investigated if the metric space is complete. Two application examples are also given, being concerned, respectively, with the solutions through pseudo-inverses of both compatible and incompatible linear algebraic systems and with the parametrical