Temperature measurements in a decaying laser-induced plasma in air at elevated pressures

This article discusses two measurement techniques for temperature determination of laser-induced plasmas in a gas at pressures relevant for combustion engines. Plasmas induced by laser breakdown in air at initial pressures ranging from 0.3 MPa to 2.5 MPa are investigated using optical spectroscopy. Results for 0.8 MPa, 1.2 MPa and 1.6 MPa are reported here. Due to the elevated pressure, a significant contribution from continuum radiation is apparent. The first temperature measurement technique relies on the interpretation of the continuum emission. The second technique is based on the line emissions from different elements and ionization stages in the plasma and is implemented with the multi-element Saha-Boltzmann plot method. The methodology may be applicable for temperature measurements under various conditions, e.g., for plasmas in high pressure gas environments such as in industrial applications of laser-induced breakdown spectroscopy or for plasma sources for illumination purposes. We investigate optimizations of laser-induced spark ignition. The energy released in the laser-induced plasma is determined based on temperature measurements.     

Vapor-liquid equilibrium for phenanthrene-toluene mixtures at elevated temperatures and pressures

Vapor and liquid equilibrium compositions are reported for the phenanthrene-toluene system at 593, 633, and 675 K and at pressures ranging from 7.3 bar to the binary mixture critical pressure at each temperature. Mixture critical pressures were obtained by visual observation of critical opalescence within a view cell. A flow apparatus for measuring VLE and LLE that is capable of operation at pressures up to 350 bar and temperatures to 675 K is also described. The apparatus can be used with materials such as phenanthrene and petroleum pitches which are solids at room temperature.     

Swelling and sorption in polymer–CO2 mixtures at elevated pressures

Experimental data on gas sorption and polymer swelling in glassy polymer—gas systems at elevated pressures are presented for CO₂ with polycarbonate, poly(methyl methacrylate), and polystyrene over a range of temperatures from 33 to 65°C and pressures up to 100 atm. The swelling and sorption behavior were found to depend on the occurrence of a glass transition for the polymer induced by the sorption of CO₂. Two distinct types of swelling and sorption isotherms were measured. One isotherm is characterized by swelling and sorption that reach limiting values at elevated pressures. The other isotherm is characterized by swelling and sorption that continue to increase with pressure and a pressure effect on swelling that is somewhat greater than the effect of pressure on sorption. Glass transition pressures estimated from the experimental results for polystyrene with CO₂ are used to obtain the relationship between CO₂ solubility and the glass transition temperature for the polymer. This relationship is in very good agreement with a theoretical corresponding-states correlation for glass transition temperatures of polystyrene-liquid diluent mixtures.     

Gas-liquid equilibria in nitrogen + n-hexadecane mixtures at elevated temperatures and pressures

Gas-liquid equilibrium in the temperature range 463–703 K in nitrogen + n-hexadecane mixtures was determined by a flow method. At each temperature, measurements were made at pressures from 20 to 255 bar or to near the critical pressure of the mixture.     

PVT measurements on n -octyl-isothiocyanato-biphenyl (8BT) at elevated pressures

For the first time pressure-volume-temperature (PVT) measurements for the crystal-like smectic E phase have been performed. The phase diagram of 4′-n -octyl-4-isothiocyanatobiphenyl 8BT has been recently established using differential thermal analysis up to 250 MPa. 8BT exhibits a splitting of the clearing line above 170 MPa. PVT data have been measured in the same pressure range for temperatures between 313 and 393 K. Volume and enthalpy changes accompanying the clearing line of 8BT are also presented. The configurational part of the entropy change at the CrE-I transition of 8BT amounts to ≈ 60%. Using the PVT data and recently published dielectric relaxation results, the isochoric activation energy was calculated (giving ≈ 50% of the activation enthalpy); this is compared with analogous results for other liquid crystals.     

PVT measurements on n -octyl-isothiocyanato-biphenyl (8BT) at elevated pressures

For the first time pressure-volume-temperature (PVT) measurements for the crystal-like smectic E phase have been performed. The phase diagram of 4'- n -octyl-4-isothiocyanatobiphenyl 8BT has been recently established using differential thermal analysis up to 250 MPa. 8BT exhibits a splitting of the clearing line above 170 MPa. PVT data have been measured in the same pressure range for temperatures between 313 and 393 K. Volume and enthalpy changes accompanying the clearing line of 8BT are also presented. The configurational part of the entropy change at the CrE-I transition of 8BT amounts to ≈60%. Using the PVT data and recently published dielectric relaxation results, the isochoric activation energy was calculated (giving ≈50% of the activation enthalpy); this is compared with analogous results for other liquid crystals.     

A light-scattering photometer for use at elevated pressures

A new light scattering photometer has been designed in order to perform light-scattering measurements at various temperatures and under pressures of 1–1000 atm. Since the scattering angle is constant (90°C), the dimensions of the dissolved molecules are determined by measuring the intensity at different wavelengths. The method of measurement, the calibration of the instrument, and the treatment of data are described. By a series of test measurements on polystyrene in trans-decalin solutions it is shown that one obtains reliable results and finds considerable effects of pressure on the radius of gyration and the fundamental thermodynamic properties of the system.     

Measurement and prediction of solubilities and diffusion coefficients of carbon dioxide in starch–water mixtures at elevated pressures

The solubility and diffusion coefficient of carbon dioxide in intermediate‐moisture starch–water mixtures were determined both experimentally and theoretically at elevated pressures up to 16 MPa at 50 °C. A high‐pressure decay sorption system was assembled to measure the equilibrium CO₂ mass uptake by the starch–water system. The experimentally measured solubilities accounted for the estimated swollen volume by Sanchez–Lacombe equation of state (S‐L EOS) were found to increase almost linearly with pressure, yielding 4.0 g CO₂/g starch–water system at 16 MPa. Moreover, CO₂ solubilities above 5 MPa displayed a solubility increase, which was not contributed by the water fraction in the starch–water mixture. The solubilities, however, showed no dependence on the degree of gelatinization (DG) of starch. The diffusion coefficient of CO₂ was found to increase with concentration of dissolved CO₂, which is pressure‐dependent, and decrease with increasing DG in the range of 50–100%. A free‐volume‐based diffusion model proposed by Areerat was employed to predict the CO₂ diffusivity in terms of pressure, temperature, and the concentration of dissolved CO₂. S‐L EOS was once more used to determine the specific free volume of the mixture system. The predicted diffusion coefficients showed to correlate well with the measured values for all starch–water mixtures. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 607–621, 2006     

Ignition of hydrogen–methane–air mixtures over Pd foil at atmospheric pressure

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Crystallization of polyethylene at elevated pressures

The crystallization from the melt of three sharp polyethylene fractions has been studied at 5 kbar. It has been shown that the thickness of so-called extended-chain lamellae is a function of time, temperature, and molecular weight. There is by no means just the fully extended molecular configuration present. Crystallization is qualitatively similar to that of chain-folded crystals at 1 bar, giving an optimum lamellar thickness which increases with time and decreasing supercooling. Fractional crystallization is widespread and is a major cause of disparate lamellar thickness. Isothermal thickening of lamellae during crystallization has been established directly. Morphological detail suggests further that layers can increase their thickness tenfold over their initial size.     

Palladium-free Suzuki-Miyaura cross-coupling at elevated pressures

Elevated pressure (15 kbar) in the liquid phase improves yields and permits the use of cheaper Fe(III), Co(II), and Ni(II) metal salts as catalysts for the Suzuki-Miyaura cross-coupling of aryl halides and aryl boronic acids.     

Ignition of hydrogen–oxygen and stoichiometric hydrogen–methane–oxygen mixtures on hot wires at low pressures

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Thermodynamic and acoustic properties of (heptane + dodecane) mixtures under elevated pressures

The speed of sound in (heptane + dodecane) mixtures was measured over the whole concentration range at pressures up to 101 MPa and within the temperature range from (293 to 318) K. The density of (heptane + dodecane) was measured in the whole composition range under atmospheric pressure and at temperatures from (293 to 318) K. The densities and heat capacities of these binaries at the same temperatures were calculated for pressures up to 100 MPa from the speeds of sound under elevated pressures together with the densities and heat capacities at atmospheric pressure. The effects of pressure and temperature on the excess molar volume and the excess molar heat capacity are discussed.     

Preparation of stable gas mixtures with microconcentrations of volatile substances in vapor-phase sources at elevated pressures

Tools are proposed for the preparation of stable vapor-gas mixtures with microconcentrations of volatile components (vapor-phase sources of gas mixtures). These work at elevated pressures and ensure the generation of gas flows with component concentrations differing within an order of magnitude from one and the same source.     

Continuous dynamic-gravimetric preparation of calibration gas mixtures for air pollution measurements

 The preparation of calibration gas mixtures for air pollution measurements by the dynamic-gravimetric method was investigated using sulphur dioxide in nitrogen as a model. The target mole fraction was 200×10^–9 mol/mol, with the option of also getting smaller mole fractions. Thermal mass flow meters calibrated with reference mass flows were used to measure the dilution gas flow (nitrogen). The relative standard uncertainty of the dilution gas flows between 10 mg/s (approx. 500 ml/min) and 40 mg/s (approx. 2000 ml/min) was 0.15%. The mass flow of the target component measured as the permeation rate was determined via the quasi-continuous observation of the loss in the permeation tube mass during the measuring time. A magnetic coupling system and an adapted microbalance were used for this purpose. The results presented show permeation rates measured over the lifetime of a tubular permeation source. The measurement cycles took between 3 days and 7 h at least. The relative standard uncertainty of the mixture composition did not exceed 2%. First comparisons with gas mixtures prepared by the static-gravimetric method show compatibility. The applicability of the system is not restricted to the SO₂/N₂ mixture. It can also be used for preparing other gas mixtures in this field of application. Received: 26 April 2000 / Accepted: 12 September 2000     

Study of a thermotropic liquid-crystalline polyester at elevated pressures

A thermotropic liquid-crystalline copolyester of 20% hydroxybenzoic acid, 40% isophthalic acid, and 40% hydroquinone polymer was studied at elevated pressures. The characterization techniques at elevated pressures (0–1000 bar) included high-pressure differential thermal analysis and dilatometry; at atmospheric pressure, differential scanning calorimetry, thermal optical analysis, and x-ray analysis were employed. The mechanical properties of the solid specimens prepared at different pressures were studied by compression and dynamic rotation mechanical testing techniques. High-pressure induced a new crystal habit in the solid state and a new mesophase in the melt. These transitions are summarized in a proposed phase diagram. Mechanical tests on the material produced at elevated pressure indicate the possibility of improved properties, implying that the pressure-dependent morphological changes in thermotropic copolyesters could be of practical significance. The finding of a pressure-induced mesophase also confirmed the possibility of extending the range of polymers which might exhibit liquid crystallinity via the application of pressure.     

Spectroscopic study of water-NaCl-benzene mixtures at high temperatures and pressures

Near-infrared and ultraviolet spectra of water-NaCl-benzene mixtures have been measured in the 473-573 K and 100-400 bar range and 373-498 K and 50-300 bar range, respectively. Concentrations of water in the benzene-rich phase and benzene in the water-rich phase were estimated from integrated intensities of the absorption bands. It is found that addition of NaCl in the aqueous phase suppresses transfer of water into the benzene-rich phase, and the relative decrease in water solubility in benzene exhibits good correlation with an increase in density of the aqueous NaCl solution relative to that of neat water. The salting-out constant for the water-NaCl-benzene system, which is estimated from a relative decrease in benzene solubility in the aqueous phase by addition of sodium chloride, increases significantly with increasing temperature. It is suggested that the effect of sodium chloride on the water-benzene mutual solubilities can be explained by ion-induced electrostriction of the aqueous phase.