Mechanisms of Solution Reactions of Cyclo-Penta[cd]Pyrene Oxide and Acenaphthylene Oxide

Rates and products of the acid-catalyzed and spontaneous reactions of cyclopenta[cd]pyrene oxide (2) and acenaphthalene oxide (3) in 1:3 dioxane-water and water, respectively, have been determined. Both 2 and 3 undergo acid-catalyzed hydrolyses to yield cis diol as the major product, and undergo spontaneous reactions to yield predominantly ketone products. The mechanisms of these reactions are discussed.     

Airborne Deployment of an Instrument for the Real-Time Analysis of Single Aerosol Particles

An instrument is described that provides real-time chemical analysis of the composition of individual aerosol particles. A differentially pumped aerosol inlet transfers particles from the ambient atmosphere into the source region of a time-of-flight mass spectrometer where they impact on a heated surface and the resulting vapors are ionized by electron ionization prior to mass analysis. Labora tory calibration studies demonstrated that the instrument was capable of detecting particles with diameters greater than approximately 0.4mu m. The instrument was operated on the NASA DC-8 research aircraft as part of the 1996 SUbsonic aircraft: Contrail and Cloud Effects Special Study (SUCCESS) mission with the intent of studying the chemical composition of upper tropospheric particles. More than 25,000 aerosol particle mass spectra were recorded during 19 mission flights. Although approximately 120 of those spectra showed clear evidence of sulfate, nitrate, and other inorganic materials, the remaining spectra contained only mass peaks consistent with water. Moreover, particles were detected only while traversing clouds. These results are not consistent with expectations of the size, quantity, or composition of upper tropospheric particles. It is likely, however, that a subisokinetic aircraft sampling inlet resulted in the collection of only very large ice particles. This situation would account for both the observed preponder ance of water-only spectra and the apparent lack of particles outside of clouds. Despite the sampling problem, the instrument was able to chemically speciate aerosols directly sampled from a medium altitude aircraft. These represent the first examples of aerosol particles chemically speciated in real time from an airborne platform.     

Synthesis of random or tapered solution styrene–butadiene copolymers in the presence of sodium dodecylbenzene sulfonate as a polar modifier

Random or tapered solution styrene–butadiene copolymer (SSBR) is very difficult to prepare in an isothermal batch process without the use of polar modifiers because of the diverse reactivity ratios of the styrene and the butadiene in hydrocarbon solvents. In the presence of polar modifiers, the random SSBR can be synthesized by anionic living polymerization with the variety of microstructures, which results in the change of glass transition temperature (T_g). This article will discuss the use of sodium dodecylbenzene sulfonate as a polar modifier in isothermal batch process that controls the microstructure of the SSBR resulting in a random as well as tapered SSBR with low T_g (?67°C to ?80°C). The T_g of SSBR was controlled by the styrene content rather than the microstructure of polybutadiene. Physical properties of SSBR compounding were discussed for tire tread applications. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and characterization of a positive‐working,aqueous‐base‐developable photosensitive polyimide precursor

A positive‐working, aqueous‐base‐developable photosensitive polyimide precursor based on poly(amic ester)‐bearing phenolic hydroxyl groups and a diazonaphthoquinone photosensitive compound was developed. The poly(amic ester) was prepared from a direct polymerization of 2,2′‐bis‐(3‐amino‐4‐hydroxyphenyl)hexafluoropropane and bis(n‐butyl)ester of pyromellitic acid in the presence of phenylphosphonic dichloride as an activator. Subsequently, the thermal imidization of the poly(amic ester) precursor at 300°C produced the corresponding polyimide. The inherent viscosity of the precursor polymer was 0.23 dL/g. The cyclized polyimide showed a glass‐transition temperature at 356°C and a 5% weight loss at 474°C in nitrogen. The structures of the precursor polymer and the fully cyclized polymer were characterized by Fourier transform infrared spectroscopy and ¹H‐NMR. The photosensitive polyimide precursor containing 25 wt % diazonaphthoquinone photoactive compound showed a sensitivity of 150 mJ/cm² and a contrast of 1.65 in a 3 μm film with 1.25 wt % tetramethylammonium hydroxide developer. A pattern with a resolution of 10 μm was obtained from this composition. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 352–358, 2002     

Particle motion in the fountain flow region during filling of a tube with a viscoelastic fluid

We present the results of an investigation of particle motion behind the advancing free surface during the filling of an initially empty tube with a viscoelastic fluid. Particle motion in the vicinity of an advancing free surface (the fountain flow region) is of significance in a number of processes used to form composite materials, notably injection and compression molding. This motion determines, to a large extent, the distribution of the reinforcing phase in the molded part. We show experimentally that an isolated spherical particle moves behind the interface in characteristic orbits, remaining in close proximity to the advancing free surface. This is in stark contrast to what happens in a Newtonian fluid. In that case, the particle is deposited on the tube walls by the fountain flow and never again reaches the faster moving free surface. The particle motion behind the interface is modeled with a combination of equations that describe the advection of the particle due to convective/fountain flow and its lateral migration due to viscoelasticity. This model neglects the finite size of the particle and is thus unable to capture the full details of the observed motion. However, the qualitative agreement between the experimental results and the modeling predictions suggests that the observed particle motion is the result of the combined effect of viscoelasticity and fountain flow.     

Novel positive‐working aqueous‐base developable photosensitive polyimide precursors based on diazonaphthoquinone‐capped polyamic esters

Novel positive‐working aqueous‐base developable photosensitive polyimide (PSPI) precursors based on partially diazonaphthoquinone (DNQ)‐capped polyamic esters bearing phenolic hydroxyl groups and a DNQ photosensitive compound (PIC‐3) were developed. The partially DNQ capped polyamic esters were prepared from an esterification reaction of 1,2‐naphthoquinone diazide‐5‐sulfonyl chloride with the polyamic esters. The partially DNQ capped polyamic esters decreased the dark film loss effectively in the aqueous‐base developer and were able to make thicker film resists compared to the uncapped polyamic esters. The 25 mol % DNQ‐capped BisAPAF–PMDA polyamic ester and BisAPAF–ODPA polyamic ester containing 25 wt % PIC‐3 photosensitive compound showed a sensitivity of 176 and 185 mJ/cm², and a contrast of 1.68 and 1.02, respectively, in a 3‐μm film with 1.25 wt % tetramethylammonium hydroxide developer. A pattern with a resolution of 5 μm was obtained from both PSPI precursor compositions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2293–2300, 2003     

Dielectric relaxation of high-k oxides

Frequency dispersion of high-k dielectrics was observed and classified into two parts: extrinsic cause and intrinsic cause. Frequency dependence of dielectric constant (dielectric relaxation), that is the intrinsic frequency dispersion, could not be characterized before considering the effects of extrinsic frequency dispersion. Several mathematical models were discussed to describe the dielectric relaxation of high-k dielectrics. For the physical mechanism, dielectric relaxation was found to be related to the degree of polarization, which depended on the structure of the high-k material. It was attributed to the enhancement of the correlations among polar nanodomain. The effect of grain size for the high-k materials'' structure mainly originated from higher surface stress in smaller grain due to its higher concentration of grain boundary.     

Grain size dependence of dielectric relaxation in cerium oxide as high-k layer

Cerium oxide (CeO₂) thin films used liquid injection atomic layer deposition (ALD) for deposition and ALD procedures were run at substrate temperatures of 150°C, 200°C, 250°C, 300°C, and 350°C, respectively. CeO₂ were grown on n-Si(100) wafers. Variations in the grain sizes of the samples are governed by the deposition temperature and have been estimated using Scherrer analysis of the X-ray diffraction patterns. The changing grain size correlates with the changes seen in the Raman spectrum. Strong frequency dispersion is found in the capacitance-voltage measurement. Normalized dielectric constant measurement is quantitatively utilized to characterize the dielectric constant variation. The relationship extracted between grain size and dielectric relaxation for CeO₂ suggests that tuning properties for improved frequency dispersion can be achieved by controlling the grain size, hence the strain at the nanoscale dimensions.     

Cryptosporidium Log-inactivation with Ozone Using Effluent CT10, Geometric Mean CT10, Extended Integrated CT10 and Extended CSTR Calculations

The draft Long-Term 2 Enhanced Surface Water Treatment Rule (LT2ESWTR) contains Cryptosporidium log-inactivation CT tables (ozone-in-water concentration [residual], “C” times contact time, T). Depending on water temperature, Cryptosporidium CT values that are listed are 15 to 25 times greater than CT values for equivalent Giardia log-inactivation credit. The elevated operating dose required for Cryptosporidium log-inactivation credit has the potential to increase disinfection by-product (DBP) formation (e.g., bromate). Calculating CT value accurately will minimize ozone dose, which will decrease operating cost and lower DBP formation, and at the same time maintain disinfection protection through implementation of scientifically based safety factors. Various methods are available for calculating CT value. The method chosen depends largely on the available information concerning ozone residual characteristics and hydrodynamic features of the ozone contactor, plus local regulatory requirements. Four methods are discussed in this paper. Each method can be used to calculate Giardia, virus, and Cryptosporidium log-inactivation credit.