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Report describes synthesis and properties of trifluorophenylethylidene (3F) condensation polyimides. Properties of these new polymers make suitable thermal-control coatings, interlayer dielectrics in advanced wafer chips, and electronic-multilevel-interconnection layers.
Nine new condensation polyimides containing the trifluorophenylethylidene linkage were synthesized by the amic-acid route. Several other polyimides, including some with the hexafluoroisopropylidene linkage, were also prepared as controls. Amic-acid solutions were characterized by determining their inherent viscosities prior to thermal conversion into polyimide films. Glass transition temperatures (T sug g), thermogravimetric analysis (TGA), and isothermal weight loss data were obtained for the films. The films were pulverized into molding powders which, in turn, were thermally processed under pressure into neat resin discs. The discs were also characterized by T sub gs and 316 C and 371 C isothermal weight losses. The film study identified two new polyimides with T sub gs greater that 371 C and two new polyimides with low rates of weight loss. The resin discs exhibited the same overall trends in T sub g and weight loss as the respective films, however the weight loss per unit surface area was always greater, presumably due to voids or to mechanical degradation induced during preparation of the molding powders.
Nitric acid and hydrochloric acid vapors may condense in the winter polar stratospheres. Nitric acid clouds, unlike water ice clouds, would form at the temperatures at which polar stratospheric clouds (PSCs) are observed and would have optical depths of the magnitude observed suggesting that HNO3 is a dominant component of PSCs. ClO, N2O5 and ClNO3 may react on cloud particle surfaces yielding additional HNO3, HCl, and HOCL. In the vicinity of PSCs these reactions could deplete the stratosphere of photochemically active NO(x) species. The sedimentation of PSCs may remove these materials from the stratosphere. The loss of vapor phase NO(x) might allow halogen-based chemistry to create the ozone hole.
The series of self-consistent, two-dimensional, MHD calculations used to explore the reconnection dynamics implicit in the two-ribbon flare model of Kopp and Pneumann (1976) indicate that there exists, in addition to the standard, slow mode MHD shocks generated by reconnection, a standing, fast mode MHD shock. Due to thermal conduction, the slow shocks generate an evaporative upflow of chromospheric plasma into the reconnection region; an analysis of these effects of radiative and conductive cooling suggests that at least some of this evaporated plasma will undergo thermal condensation in passing through the fast shock.
A well-resolved two-dimensional nonlinear numerical simulation of the radiative/thermal instability in a sheared magnetic field is described which leads to filament formation. The condensation is initiated by a linearly unstable mode and widens until it is slowed by thermal conduction parallel to B. During the nonlinear evolution, the minimum temperature falls from 10 to the 6th K to 10 to the 4th K and eventually reaches a state of local thermal equilibrium in about five e-folding times.
A digital simulation of the behavior of amphoteric sample components in moving steady state boundaries is presented. Complete computer simulation data, including profiles of concentration, conductivity and pH as functions of time, are given for both cationic and anionic electrolyte configurations which incorporate one amphoteric sample constituent. The condensation of ampholytes in steady state moving boundaries is shown to proceed via an isotachophoretic mechanism and not by isoelectric focusing. Mobility (velocity) relationships necessary for sample components to form steady state zones are discussed.
The possibility that collective effects may dramatically influence autoionization-limited lifetimes of condensed excited states is investigated in the context of a two-band model of an insulator in a strong magnetic field. Two different mechanisms for suppressing autoionization are discussed which may prevent the potentially catastrophic destruction of the excited state. Under appropriate circumstances, the residual low-density Auger electrons may be confined in a superconducting state and paired by excitonic fluctuations in the conduction band.
The characteristics and origin of lower-stratosphere haze on Uranus are investigated on the basis of high-phase-angle images obtained at 430-600 nm with the wide-angle and narrow-angle cameras of Voyager 2 during its encounter with Uranus in January 1986. The data-reduction and model-fitting procedures are explained in detail, and the results are presented in extensive tables and graphs. The data are found to be best matched by a haze consisting of particles of modal radius 130 + or - 20 nm and number density 2 + or - 1 per cu cm at the 44-mbar level; such aerosols could be formed by the stratospheric condensation of photochemically produced hydrocarbon gases (locally formed diacetylene and ethane, acetylene, and diacetylene formed at higher altitudes). A total aerosol production rate of (2-15) x 10 to the -17th g/sq cm sec is estimated.
The spectrometers aboard the IUE are used to obtain UV spectroscopy of the jetlike condensations seen extending 18 arcsec from the nucleus of the nearby Seyfert 1 galaxy NGC 4151. New data reduction techniques are used to detect, delineate, and measure weak nebular emission in IUE spectra. Spatially resolved extended emission is seen in both semiforbidden C III 1909 A and C IV 1549 A. The deduced integrated fluxes in the jet are 10 to the 14th and 4 x 10 to the 14th ergs/sq cm/s for C III and C IV, respectively. The observed fluxes are compared with predictions based upon a central source photoionization model. The implied high C IV/C III flux ratio is shown to be inconsistent with this model and suggests an additional source of ionization for the jet.
The effect of oxygen fugacity on the partitioning of REEs between hibonite and silicate melt is investigated in hibonite-growth experiments at 1470 C. The experimental procedures and apparatus are described, and the results are presented in extensive tables and graphs and characterized in detail. The absolute activity coefficients in hibonite are estimated as 330 for La, 1200 for Eu(3+), and 24,000 for Yb. It is inferred that ideal solution behavior cannot be assumed when calculating REE condensation temperatures for (Ca, Al)-rich inclusions in carbonaceous chondrites.
Future large space based facilities, such as Space Station, will require energy management systems capable of transporting tens of kilowatts of heat over a hundred meters or more. This represents better than an order of magnitude improvement over current technology. Two-phase thermal systems are currently being developed to meet this challenge. Condensation heat transfer plays a very important role in this system. The present study attempts an analytic solution to the set of linearized partial differential equations. The axial velocity and temperature functions were found to be Bessel functions which have oscillatory behavior. This result agrees qualitatively with the experimental evidence from tests at both NASA Goddard Space Flight Center and elsewhere.
A boiling and condensing test article consisting of two straight tube boilers, one quartz and one stainless steel, and two 1.5 m long glass-in-glass heat exchangers, on 6 mm ID and one 10 mm ID, was flown on the NASA KC-135 0-G aircraft. Using water as the working fluid, the 5 kw boiler produces two phase mixtures of varying quality for mass flow rates between 0.005 and 0.1 kg/sec. The test section is instrumented at eight locations with absolute and differential pressure transducers and thermocouples. A gamma densitometer is used to measure void fraction, and high speed photography records the flow regimes. A three axis accelerometer provides aircraft acceleration data (+ or - 0.01G). Data are collected via an analog-to-digital conversion and data acquisition system. Bubbly, annular, and slug flow regimes were observed in the test section under microgravity conditions. Flow oscillations were observed for some operating conditions and the effect of the 2-G pullout prior to the 0-G period was observed by continuously recording data throughout the parabolas. A total fo 300 parabolas was flown.
This paper reports preliminary measurements of the oxygen isotopic fractionation that occurs during the condensation of refractory metal oxide smokes. Fractionation occurred at temperatures in excess of 500 K during and/or subsequent to reaction of SiH4, Fe(CO)5, Al(CH3)3, and O2 in a H2 carrier gas. Observed isotopic fractionation was as high as -15 per mil/amu. The magnitude of the isotopic fractionation suggests that the process is kinetically controlled since the effect is greatly in excess of that expected for equilibrium isotopic exchange.
Studies on an intense cold air outbreak that took place after a cold air cyclogenesis on January 27, 1986 are reviewed. Particular attention is given to data obtained during a multiaircraft research mission carried out on January 28, 1986 as part of the Genesis of Atlantic Lows Experiment. It was found that condensation heating of the subcloud layer air was comparable to heating by turbulent flux divergence.
Nine new condensation polyimides containing the phenyltrifluoroethylidene (3F) linkage were synthesized by the amic-acid route. Several other polyimides, including some with hexafluoroisopropylidene (6F) linkage, were also prepared as controls. Amic-acid solutions were characterized by determining their inherent viscosities prior to thermal conversion into polyimide films. Glass transition temperatures (T sub g), thermogravimetric analysis (TGA), and isothermal weight loss data (at 316, 371, and 371 C under 0.5 MPa air pressure) were obtained for the films. The films were pulverized into molding powders which, in turn, were thermally processed under pressure into neat resin disks. The disks were also characterized by T sub g's and 316 and 371 C isothermal weight losses. The film study identified two new polyimides with T sub g's greater than 371 C and two new polyimides with low rates of weight loss. The resin disks exhibited the same overall trends in T sub g and weight loss as the respective films, however the weight loss per unit surface area was always greater, presumably due to molecular degradation induced during preparation of the molding powders. The overall results indicate that polyimides containing the 3F linkage have T sub g's and thermo-oxidative stability comparable to polyimides containing the 6F group. Alternate technology was also shown by the synthesis of two new polyalkyl substituted 3F diamines and five more new 3F polymers. Their potential as photoresists was demonstrated by T sub g advancement after ultraviolet exposure. Last, four U.S. patents on 3F monomers and polymers were issued and up to eight more are pending.
Interpretation of the volatile abundances in Halley's comet in terms of models for chemical and physical processes in the solar nebula are discussed. Key ratios of the oxidized and reduced species of nitrogen and carbon are identified which tell something of the chemical history of the environment in which cometary grains accreted to form the nucleus. Isotopic abundances are also applied to this problem. It will be shown that the abundances of methane and carbon monoxide are consistent both with models of solar nebula chemistry and chemical processing on grains in star-forming regions. Ultimately, limitations of the current data set on molecular abundances in comets and star-forming regions prevent a definitive choice between the two. Processes important to the composition of outer solar system bodies are: (1) gas phase chemistry in the solar nebula; (2) imperfect mixing in the solar nebula; (3) condensation; (4) clathration; (5) adsorption; and (6) processing of interstellar material.
The work described is concerned with laboratory studies of the processes that produce the ejection of molecules from the surfaces of condensed gas solids, the change in the chemistry of the surface materials, and the relationship of these results to processes occurring in the solar system. Included is a discussion of the experimental techniques employed in making these laboratory measurements.
The ER-2 Condensation Nucleus Counter (ER-2 CNC) was operated in the Airborne Arctic Stratospheric Expedition (AASE) in January and February 1989. The ER-2 CNC measures the mixing ratio of particles, CN, with diameters from approximately 0.02 to approximately 1 micron. The spatial distribution of CN in the Arctic polar vortex was found to resemble that measured in the Antarctic in the Spring of 1987. The vertical profile of CN in the vortex was lowered by subsidence. At altitudes above the minimum in the CN mixing ratio profile, CN mixing ratios correlated negatively with that of N2O, demonstrating new particle production. CN serve as nuclei in the formation of Polar Stratospheric Clouds (PSCs) and the concentration of CN can affect PSC properties.