Pressure cell experiments

Gridneva et al. [5], and later CJerk and Tabor [85], noted the similarity of Si hardness as measured at low temperatures and the pressure of Si-I Si-Il transformation known from the high-pressure cell experiments [50, 51]. They sug-... 

We should emphasize that the formation of amorphous silicon in the preceding references was confirmed using electron diffraction and diffraction contrast methods. As pointed out by Suzuki and Ohmura [77], the material appeared amorphous only on a diffiaction scale it might as well be polycrystalline of very fine grain or nanocrystalline. Another inconsistency was the persistent absence of any traces of a-Si after decompression from Si-II in the related high-pressure cell experiments [52,53,61,62]. 

In particular, phase transformations under contact loading need a more detailed investigation. Both static and dynamic interactions between hard surfaces may result in phase transformations. Hydrostatic and deviatoric stresses must be taken into account and phase transformations in contact loading can be described as deformation-induced transformations. At the same time, the transformation pressures for silicon obtained in indentation tests are in good agreement with the results from high-pressure cell experiments, which utilize hydrostatic loading. 

The pressure cell experiment was used to compare the performance of powder san les of MIC materials. Samples were placed in the same volume for each experiment. It must be noted tl t the bulk density can vary between experiments but efforts were made to ensure consistancy. The bulk density is determined for each test by measuring the sanq)le mass while keeping the sample volume fixed. Ignition time is defined as the time required for the reaction to produce 5% of the maximum pressure. This turn is measured fi om the initial laser pulse. This parameter is indicative of the reactivity of the material. 

Neumann has adapted the pendant drop experiment (see Section II-7) to measure the surface pressure of insoluble monolayers [70]. By varying the droplet volume with a motor-driven syringe, they measure the surface pressure as a function of area in both expansion and compression. In tests with octadecanol monolayers, they found excellent agreement between axisymmetric drop shape analysis and a conventional film balance. Unlike the Wilhelmy plate and film balance, the pendant drop experiment can be readily adapted to studies in a pressure cell [70]. In studies of the rate dependence of the molecular area at collapse, Neumann and co-workers found more consistent and reproducible results with the actual area at collapse rather than that determined by conventional extrapolation to zero surface pressure [71]. The collapse pressure and shape of the pressure-area isotherm change with the compression rate [72]. 

Quednau J and Schneider G M 1989 A new high-pressure cell for differential pressure-jump experiments using optical detection Rev. Sc/. Instnim. 60 3685-7... 

At high pressure experiments the reactor should be installed in a pressure cell. All check valves before it, and the filter with the flow controller after it, can be kept in the vented operating room. As a minimum, the bypass valve and the flow controller must be accessible to the operator. This can be done by extended valve stems that reach through the protecting wall. Both the operating room and the pressure cell should be well ventilated and equipped by CO alarm instruments. 

Please notice that in a well-ventilated laboratory and a pressure cell, these experiments can be executed safely. In seven years of graduate research activity at the Chemical Engineering Department of the University of Akron, only one catalyst ignition and one real CO alarm occurred. Several false CO alarms were sounded until someone noticed that they always happened about 2 30 PM. As it turned out, one maintenance employee parked his old car right in front of the air intake to the lab ventilation. He warmed up his car for a while before he started to go home after his shift, and the motor exhaust gas set off the false alarms. 

This section reviews the criteria for hazards testing of reactions on a small scale, particularly whether the experiments should be run in an open laboratory or in a high-pressure cell. 

High-pressure experiments promise to provide insight into chemical reactivity under extreme conditions. For instance, chemical equilibrium analysis of shocked hydrocarbons predicts the formation of condensed carbon and molecular hydrogen.17 Similar mechanisms are at play when detonating energetic materials form condensed carbon.10 Diamond anvil cell experiments have been used to determine the equation of state of methanol under high pressures.18 We can then use a thermodynamic model to estimate the amount of methanol formed under detonation conditions.19... 

The relatively long timescales of the ionization, isolation, thermalization, reaction, and detection sequences associated with low-pressure FTICR experiments are generally thought to preclude the use of this technique as a means of examining the unimolecular dissociation of conventional metastable ions occurring on the microsecond to millisecond timescale. Nonetheless, as just demonstrated (Section IIIC), intermediates with this order of magnitude of lifetime are routinely formed in the bimolecular reactions of gaseous ions with neutral molecules at low pressures in the FTICR cell, as in Equation (13). 

The high-pressure phase behavior of polymer-solvent-supercritical carbon dioxide systems was investigated experimentally The polymers used were poly(methyl methacrylate), polystyrene, polybutadiene, and poly(vinyl ethyl ether) at concentrations ranging from 5 to 10% in mixtures with toluene or tetrahydrofuran. The experiments were conducted for temperatures from 25 to 70°C and pressures up to 2200 psi in a high-pressure cell (Kiamos and Donohue, 1994). 

A variety of experimental techniques have been used for the determination of uptake coefficients and especially Knudsen cells and flow tubes have found most application [42]. Knudsen cells are low-pressure reactors in which the rate of interaction with the surface (solid or liquid) is measured relative to the escape through an aperture, which can readily be calibrated, thus putting the gas-surface rate measurement on an absolute basis. Usually, a mass spectrometer detection system monitors the disappearance of reactant species, as well as the appearance of gas-phase products. The timescale of Knudsen cell experiments ranges from a few seconds to h lindens of seconds. A description of Knudsen cell applied to low temperature studies is given [66,67]. 

The high-pressure cells and temperature control units are similar to the ones described by Betts and Bright (29). Samples for analysis were prepared by directly pipetting the appropriate amount of stock solution into the cell. To remove residual alcohol solvent, the optical cell was placed in a heated oven (60 °C) for several hrs. The cell was then removed from the oven, connected to the high-pressure pumping system (29), and a vacuum (50 pm Hg) maintained on the entire system for 10-15 minutes. The system was then charged with CF3H and pressurized to the desired value with the pump (Isco, model SFC-500). Typically, we performed experiments at 10 /xM PRODAN and there was no evidence for primary or secondary interfilter effects. HPLC analysis of PRODAN subjected to supercritical solvents showed no evidence of decomposition or additional components. 

Figure 6.12 Rejection of 1 % dextran solutions as a function of pressure using Dextran 20 (MW 20000), Dextran 40 (MW 40000), and Dextran 80 (MW 80000). Batch cell experiments performed at a constant stirring speed [17]...

Abstract This paper is concerned with the experimental identification of some chemo-poroelastic parameters of a reactive shale from data obtained in pore pressure transmission - chemical potential tests. The parameter identification is done by matching the observed pressure response with a theoretical solution of the experiment. This solution is obtained within the framework of Biot theory of poroelasticity, extended to include physico-chemical interactions. Results of an experiment on a Pierre II shale performed in a pressure cell are reported and analyzed. 

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