Dynamic relaxation characteristics of thermally rearranged aromatic polyimides

The glass–rubber and sub-glass relaxation characteristics of ortho-functionalized aromatic polyimides and thermally rearranged polymers were investigated by dynamic mechanical and dielectric methods. Soluble polyimides (HAB–6FDA; APAF–ODPA) were synthesized by chemical and thermal imidization and subject to thermal rearrangement at elevated temperature. For the thermal exposure histories investigated, mass loss studies indicated partial conversion of the polyimide precursor, suggesting the formation of TR copolymers containing both benzoxazole units and residual imide segments. Measurement of storage modulus and loss tangent was used to follow the thermal rearrangement process in-situ as reflected in the suppression of the polyimide glass transition as a function of precursor structure, the nature of the ortho functional groups and prior thermal exposure. In addition, changes in the position and intensity of local relaxations detected across the sub-glass temperature range were correlated with the degree of thermal rearrangement in these polymers.     

Low‐velocity impact of nanocomposite and polymer plates

Nanocomposites are more widely studied today because of higher stiffness, decreased permeability, thermal stability, and many other properties superior to those of regular polymers. However, manufacturers are concerned about implementing nanocomposites because of their lower impact properties with respect to the base polymer. This study focused on low‐velocity impact tests of a thermoplastic olefin by itself and with 5 wt % nanoclay. The impact tests were conducted at ?40, 23.9, and 65.6°C until the polymer and nanocomposite plates experienced complete striker penetration. The force–time and force–deflection responses obtained from the impact testing provided a means of comparing the impact performances of the two materials. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2309–2315, 2005     

Use of the frequency dependence of the impedance to monitor viscosity during cure

The ability to conveniently and continuously measure the processing properties of polymer resins is important both to the resin supplier and to the fabricator. Frequency dependent electromagnetic sensors (FDEMS) provide an in-situ technique for continuous measurement of the resin's rheological changes both in a laboratory press and in manufacturing tools in an autoclave. In this paper the frequency dependence of ?*(w) is used to quantitatively monitor the viscosity for a tetraglycidyl 4,4′-diaminodiphenyl methane (TGDDM) amine epoxy, to quantitatively monitor the viscosity during processing In a styrene-polyester resin, and to monitor the cure process in an autoclave during cure of a high temperature polyimide-graphite prepreg. In addition, the technique is used to measure the viscosity at various ply positions in a thick TGDDM graphite epoxy laminate during processing in an autoclave.     

Research Note Interferences due to Ozone-Scavenging Reagents in the GC-ECD Determination of Aldehydes and Ketones as the (2, 3, 4, 5, 6, -Pentafluorobenzyl) oximes

In order to study ozonation byproduct (OBP) formation as a function of time, it is necessary to quench ozone and thereby fix the concentrations of the byproducts. Reagents chosen for this purpose must not react with the OBPs or otherwise adversely impact the analysis. Six potential ozone-scavenging reagents were tested for possible interference in the GC-ECD determination of aldehydes and ketones after derivatization with O-(2,3,4,5,6-pentafluorobenzyl)oxylamine (PFBOA). All six—sodium nitrite, sodium cyanide, sodium methanoate (formate), indigo-5,5′-disulfonate disodium (Indigo Carmine), indigo-5,5′,7-trisulfonate tripotassium, and tin(II) chloride—were found to interfere in the analysis.     

Dynamic multiphase modeling and optimization of fluid jet polishing process

Fluid jet polishing is a machining process used increasingly in the ultra-precision manufacture of optical components and replication molds. While the process bears some similarities with abrasive water jet machining, it operates at much lower pressure and grit size. This paper presents a computational fluid dynamics model based on latest multiphase turbulent flow computational methods, simulating dynamically the interface between fluid and air. The model is then used to optimize surface texture performance down to 1 nm Ra on electroless nickel plated optical dies, while removing diamond turning marks. Some conclusions are drawn regarding the nature of the removal mechanism.     

Kinetic modelling of nickel powder precipitation by high-pressure hydrogen reduction

The active mechanisms in the precipitation of nickel powder by hydrogen reduction were investigated by means of mathematical models based on the moment form of the population balance equation (PBE). The objective of the work was to establish the mechanisms involved in powder formation and how these are affected by the presence of impurities. The effects of two major impurities were considered namely; iron, inherently present as ferrous sulphate, and a morphology modifier, a polyacrylic acid derivative used as an additive. Experiments were conducted on a laboratory and pilot-plant scale using a 0.5 and 75 L stainless steel autoclave, respectively. Nickel powder samples were collected from the autoclaves after each successive batch reduction (densification) and the particle size distribution (PSD) analysed using a laser diffraction technique. The PSD data was then transformed into moments and the experimental values were compared with those simulated using different models based on the moment form of the PBE. Five models were tested namely: (a) aggregation-only; (b) aggregation and growth; (c) nucleation and aggregation; (d) nucleation and growth and (e) aggregation and breakage. Under standard operating conditions, the process was best simulated by a size-independent aggregation and growth model in the early stages of the cycle, with breakage and growth becoming significant in later stages of the cycle when large particles have been formed. Crystallisation in the presence of Fe was characterised by a size-independent aggregation and growth model with varying degrees of nucleation depending on the Fe concentration and the available surface area. At modifier dosages of 0.25 and 5 vol% the process was best modelled by a size-independent aggregation and growth model coupled with a constant breakage frequency model. Based on the mathematical modelling results and evidence from scanning electron micrographs, the spherically shaped nickel powder particles were proposed to be formed through the formation of a pre-cursor by secondary aggregation followed by spherulitic growth. The degree of compactness of the spherulites was proposed to be determined by the number of active growth sites on the nickel particle surface. The morphology modifier was found to act as a growth inhibitor, decreasing the number of growth sites leading to more open spherulites. Iron was found to induce surface nucleation, thus, creating more growth sites on the particle surface and leading to more compact spherulites.     

Synthesis and crosslinking of partially disulfonated poly(arylene ether sulfone) random copolymers as candidates for chlorine resistant reverse osmosis membranes

Biphenol-based, partially disulfonated poly(arylene ether sulfone)s synthesized by direct copolymerization show promise as potential reverse osmosis membranes. They have excellent chlorine resistance over a wide range of pHs and good anti-protein and anti-oily water fouling behavior. Crosslinking of these copolymers that have high degrees of disulfonation may improve salt rejection of the membranes for reverse osmosis performance. A series of controlled molecular weight, phenoxide-endcapped, 50% disulfonated poly(arylene ether sulfone)s were synthesized. The copolymers were reacted with a multifunctional epoxy resin and crosslinked thermally. The effects on network properties of various factors such as crosslinking time, copolymer molecular weight and epoxy concentration were investigated. The crosslinked membranes were characterized in terms of gel fraction, water uptake, swelling and self-diffusion coefficients of water. The salt rejection of the cured membranes was significantly higher than that for the uncrosslinked copolymer precursors.     

Simultaneous Chemical Vapor Deposition of Boron Nitride and Aluminum Nitride

Two chemically different phases, hexagonal BN and AIN, were simultaneously produced by chemical vapor deposition (CVD) using an impinging jet reactor and the BCl₃─AlCl₃─NH₃─Ar reagent system. The microstructure of the BN + AIN composite coatings was strongly dependent on temperature, pressure, and BCl₃ and AlCl₃ concentrations. The growth characteristics of BN and AIN in the codeposition system were similar to those expected from the single-phase deposition processes (i.e., BN-CVD and AIN-CVD), except the growth of AIN whiskers was accentuated, and competition between BN and AIN deposition in the composites was suspected to be the cause of less-crystalline deposits. In both BN + AIN-CVD and AIN-CVD, the growth of AIN whiskers became more apparent with increasing pressure or temperature. The codeposition behavior observed experimentally was compared with thermodynamic predictions.     

Linear sweep voltammetry of manganate(VII), manganate(VI), and manganate(V) in alkaline media

Electrochemical reactions were assigned to the voltammetric waves obtained in alkaline KMnO₄ and K₂MnO₄ solutions. Plots of i_p (AC°ν^{$\text{1}\text{2}$})^?1 and i_api_cp^?1 νs log ν indicate that at slow potential scan rates in MnO^?₄ solutions ranging from 0·07 to 0·19 F in NaOH the first step in MnO^?₄ reduction is a l-electron reversible charge transfer with no coupled chemical reaction; at fast scan rates (? V s^?1 the process becomes quasi-reversible. The standard rate constant and the activation energy for the MnO^?₄/MnO^2?₄ charge transfer step were estimated. Plots of i_p (AC°ν^{$\text{1}\text{2}$})^?1 and i_api_cp^?1 νs log ν indicate that in 4·O F KOH and at potential scan rates between 0·005 and 2·V s^?1 the reduction of MNO^2?₄ to MnO^3?₄ is a reversible charge transfer with no coupled chemical reaction. The diffusion coefficients of MnO^?₄ and MnO^2?₄ in alkaline solutions are reported.     

Ecological consequences of hydropower development in Central America: impacts of small dams and water diversion on neotropical stream fish assemblages

Small dams for hydropower have caused widespread alteration of Central American rivers, yet much of recent development has gone undocumented by scientists and conservationists. We examined the ecological effects of a small hydropower plant (Doña Julia Hydroelectric Center) on two low‐order streams (the Puerto Viejo River and Quebradon stream) draining a mountainous area of Costa Rica. Operation of the Doña Julia plant has dewatered these streams, reducing discharge to ～10% of average annual flow. This study compared fish assemblage composition and aquatic habitat upstream and downstream of diversion dams on two streams and along a ～4 km dewatered reach of the Puerto Viejo River in an attempt to evaluate current instream flow recommendations for regulated Costa Rican streams. Our results indicated that fish assemblages directly upstream and downstream of the dam on the third order Puerto Viejo River were dissimilar, suggesting that the small dam (< 15 m high) hindered movement of fishes. Along the ～4 km dewatered reach of the Puerto Viejo River, species count increased with downstream distance from the dam. However, estimated species richness and overall fish abundance were not significantly correlated with downstream distance from the dam. Our results suggested that effects of stream dewatering may be most pronounced for a subset of species with more complex reproductive requirements, classified as equilibrium‐type species based on their life‐history. In the absence of changes to current operations, we expect that fish assemblages in the Puerto Viejo River will be increasingly dominated by opportunistic‐type, colonizing fish species. Operations of many other small hydropower plants in Costa Rica and other parts of Central America mirror those of Doña Julia; the methods and results of this study may be applicable to some of those projects. Copyright © 2006 John Wiley & Sons, Ltd.