Synthesis of copolyimide containing fluorine and naphthalene with synergizing effect on dielectric constants

Summary Novel copolyimides containing fluorine and naphthalene groups were synthesized from 4,4-(Hexafluoroisopropylidene)diphthalic dianhydride (6FDA) and two diamines, 1,4-Bis(4-amino-2-trifluoromethylphenoxy) benzene (BATB) and 2,7-bis(4-aminophenoxy) naphthalene (BAPN) in various ratios via thermal imidization. The introduction of fluorinated groups into dianhydride improved transparency of copolyimides. All films are transparent. The structures and physical properties of copolyimides were characterized by FT-IR, DSC, TGA, XRD, UV-Vis and dielectric analyzer to study the effect of diamines on the physical properties of modified polymers. Copolyimides containing a higher percentage of BAPN have higher glass transition temperature and are less soluble in organic solvents. The copolyimide consisting of 50/50 mole% of BATB/BAPN has the lowest dielectric constant (2.60 at 1 KHz), reflecting the synergizing effect from both diamines.     

A novel synthesis method for the preparation of aromatic poly(imide benzoxazole) from trimellitic anhydride chloride and bis(o‐aminophenol)

A poly(imide benzoxazole) was prepared directly from trimellitic anhydride chloride and 2,2‐bis(3‐amino‐4‐hydroxyphenyl)hexafluoropropane (BisAPAF) monomers in a two‐step method. In the first step, a poly(hydroxyamide amic acid) precursor was synthesized by the low‐temperature solution polymerization in an organic solvent. Subsequently, thermal cyclodehydration of the poly(hydroxyamide amic acid) precursor at 350°C produced the corresponding poly(imide benzoxazole). The inherent viscosity of the precursor polymer was 0.22 dL/g. The cyclized poly(imide benzoxazole) showed a glass transition temperature (T_g) at 329°C and a 5% weight loss temperature at 530°C in nitrogen and at 525°C in air. The poly(imide benzoxazole) is amorphous as evidenced by the wide‐angle X‐ray diffraction measurement. The structures of the precursor polymer and the fully cyclized polymer were characterized by Fourier transform infrared (FTIR) and proton nuclear magnetic resonance spectroscopy (¹H NMR). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2388–2391, 2003     

Restructuring butterfat through blending and chemical interesterification. 3. Rheology

Interesterified and noninteresterified butterfat-canola oil blends, ranging from 100% butterfat to 60∶40 butterfat-canola oil (w/w) in 10% increments, were evaluated for hardness index (HI), dropping point, viscosity, and viscoelastic properties at small deformation. Both blending and chemical interesterification diminished HI in a nonlinear fashion. HI changes in interesterified blends were more pronounced than in noninteresterified blends. Dropping points yielded information on the structure of the blends. Butterfat’s dropping point (DP) was 34.4°C, whereas that of interesterified butterfat was 37.0°C, which is indicative of a more structured network for the latter. DP values of blends with 60–90% butterfat (interesterified vs. noninteresterified) were not significantly different (P<0.05). Interesterified blends had a higher crystallization onset temperature than did noninteresterified blends. All blends in the liquid state displayed Newtonian behavior. Oscillatory frequency sweep measurements at small amplitude showed that interesterified blends generally had lower storage moduli (G′) than their noninteresterified counterparts. BothG′ andG″ were frequency-dependent. Replacement of 30% butterfat by canola oil led to notable changes in small deformation measurements, whereas replacement of 20% butterfat led to big changes in large deformation measurements.     

Oxidation of pyrite in coal to magnetite

When bituminous coal is heated in an inert atmosphere (He) containing small amounts of oxygen at 393–455 °C, pyrite (FeS₂) in coal is partially converted to magnetite (Fe₃0₄). The maximum amount of Fe₃0₄ formed during the time of heating corresponds to 5–20% of the total pyrite present, depending on the coal sample. The magnetite forms as an outer crust on the pyrite grains. The fact that the magnetic properties of the pyrite grains are substantially increased by the magnetite crust suggests that pyrite can be separated from coal by use of a low magnetic field. In a laboratory test, 75% removal is obtained by means of a 500 Oe magnet on three samples, and 60% on a fourth sample.     

The Effects of Experience and Strategy on Visual Attention Allocation in an Automated Multiple-Task Environment

Operators and users interacting with computer environments often have to deal with multiple tasks at once, responding to each in series. Diagnostic automation, that is, automation that alerts users when and where to look, has been suggested to support the unique challenges of multiple task environments: activating tasks, switching between tasks, and tasks interfering with each other. Automation is not always reliable, however. Because of the common interaction with novel systems and the importance of training, the Simultaneous Task Environment Platform program—a multiple-task environment—was developed to understand the effects of experience on interaction with these automation-supported systems, as well as what strategies were developed. It was found that participants became more efficient with experience only when they interacted with higher reliability automation. Furthermore, the strategies participants developed focused on the differences between tasks and patterns across those tasks. Automated systems training should be sure to employ these findings.     

Electron spin resonance studies of interactions of ammonia,copper, and cupriammonia with cellulose

The electron spin resonance spectra (ESR) of complexes of copper with fibrous cotton cellulose under various experimental conditions were determined. Cupric ions dissolved in solutions of strong bases, such as concentrated ammonium hydroxide, sodium hydroxide, and potassium hydroxide, formed complexes with fibrous cotton cellulose. These complexes had paramagnetic resonance properties and generated characteristic ESR spectra. Cupric ions dissolved in solutions of highly ionized neutral salts, such as sodium chloride, formed complexes with cellulose. These complexes also generated the same characteristic ESR spectra as the complexes formed in solutions of strong base. The reaction between cupric ions and cellulose was evidently very rapid and reversible. When the concentration of ammonia was decreased in, or ammonia was removed from, the cupric ion–ammonium hydroxide–cellulose complexes, the paramagnetic resonance properties of the complex were decreased or lost. Similar results were received when potassium hydroxide was removed from the complexes. The compositions of the complexes evidently are variable, that is, under different experimental conditions the relative intensities of the lines of the ESR spectra of the complexes varied, although the hyperfine splittings of the lines were constant. It was concluded that reactions of cupric ions to form complexes with adjacent hydroxyl groups on the cellulose molecule depended on an optimum spatial arrangement of the hydroxyl groups, that is, distance between the groups. Evidently, wetting of cotton cellulosic fibers with solutions of strong bases or neutral salt allowed rotation about the C₂–C₃ bond to yield this optimum arrangement. When the base or salt was removed, rotation occurred to give less favorable positions of the hydroxyl groups for complexing with cupric ions.     

Linear Chain Ferromagnetic Charge Transfer Compounds

Charge transfer complexes possessing a … DADA … structure with both the donor, D, and acceptor, A, being S = 1/2 radicals may exhibit cooperative magnetic phenomena. The complex [Fe(C₅Me₅)₂]⁺·[TCNQ]⁻· exhibits metamagnetic behavior. The similarly structured [TCNE]⁻· and [C₄(CN)₆]⁻· complexes are ferromagnets, whereas the [DDQ]⁻· salt is a paramagnet. The high temperature magnetic susceptibility obeys the Curie-Weiss expression with θ = + 30, + 30, and + 3 for the [TCNE]⁻·, [C₄(CN)₆]⁻·, and [TCNQ]⁻· salts, respectively. The ferromagnetic [TCNE]⁻· salt exhibits zero field Zeeman split ⁵⁷Fe Mossbauer spectra with an internal field of 425.6 kOe at 4.23 K. After reviewing the current papers discussing ferromagnetism in molecular (organic) compounds, a qualitative model consistent with the necessary bulk spin alignment required for a ferromagnet is presented.     

Properties and pervaporation separation of hydroxyl‐terminated polybutadiene‐based polyurethane/poly(methyl metharcylate) interpenetrating networks membranes

Hydroxyl‐terminated polybutadiene (HTPB), 4,4′‐dicyclohexyl methane diiscyanate (H₁₂MDI), and 1,4‐butane diol are used to synthesize polyurethane (PU) solutions by two‐stage process. Interpenetrating networks (IPNs) of HTPB‐based PU and poly(methyl methacrylate) (PMMA) with HTPB/MMA (wt/wt % ratio) = 2.0, 1.5, 1.0, 1.5, 0.8, and 0.6, which are designated as IPN1 to IPN5, respectively, are synthesized by sequential polymerization technique. Thermal properties, tensile strength, and contact angle of membranes increase with the increase of MMA content, while the elongation of membranes show the reverse trend. Characterization of membranes are investigated by C?C/C?O absorption ratio and infrared absorption frequency shiftment. These PU and IPN membranes are used for the separation of ethanol/water and isopropanol/water solution by pervaporation test. IPN3 membrane possesses the largest pervaporation permeability and the separation factor. The pervaporation results of ethanol/water feed has the same trend as that of isopropyl alcohol (IPA)/water solution. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Equilibrium and kinetic studies of the extraction of chelated copper(II) anions with Aliquat 336

The equilibrium and kinetics of solvent extraction of Cu²⁺ from aqueous solutions containing equimolar EDTA with Aliquat 336 in n‐decanol and kerosene at 298 K were investigated. The concentrations of Cu²⁺ (8–50 mol m^?3), Cl^? (5–60 mol m^?3), and Aliquat 336 (20–100 mol m^?3) were varied. A semi‐empirical model with three parameters was proposed to describe the equilibrium behavior, in which the non‐idealities in both aqueous and organic phases were considered. Over the ranges studied, the model agreed reasonably well with the experimental data (standard deviation, 15%). The forward and backward reaction rate constants were determined as (5.31 ± 0.16)×10^?6 m^9/4 mol^?3/4 s^?1 and (2.62 ± 0.09)×10^?7 s^?1, respectively, at 298 K. An interfacial reaction mechanism was proposed, which revealed that the reaction between the chelated anions and trimeric amine molecules at the interface was rate limiting. The derived rate laws were consistent with the experimental results. © 2002 Society of Chemical Industry     

Effects of Copper Coating on the Crystalline Structure of Fine Barium Titanate Particles

We have investigated the effect of a metal coating—copper—on the tetragonal structure of fine barium titanate (BaTiO₃) particles. The BaTiO₃ particles were synthesized by a sol-gel method and heat treated at temperatures >900°C for various amounts of time before coating. The copper coating was achieved by an electroless coating technique. The transmission electron microscopy micrographs revealed that the coated powder contained fine BaTiO₃ particles that were embedded in copper patches. The X-ray diffractometry patterns showed that the copper coating increased the c/a ratio of the fine BaTiO₃ particles. For powders that were heat treated at 900°C for 10 h and were initially cubic, the copper coating changed the c/a ratio, from 1 to 1.0034. For powders that were calcined at 900°C for 20 h and were initially tetragonal, the copper coating further enhanced the c/a ratio, from 1.0028 to 1.0043. When the copper-coated BaTiO₃ particles were oxidized, the c/a ratio was reduced to a value that was approximately equal to or below that of the uncoated powders. A conductive coating can eliminate the depolarization energy of an insulating polar particle. The fact that the copper coating promoted the polar tetragonal phase but the nonconductive copper-oxide coating did not was consistent with the interpretation that the presence of the cubic phase (nonpolar) in small BaTiO₃ particles was caused by the depolarization effect.