Determination of the degree of cure under dynamic and isothermal curing conditions with electrical impedance spectroscopy

This article presents a new methodology for the quantitative determination of the progress of the curing reaction of a thermosetting resin, using the results of electrical impedance spectroscopy. The method is an extension of the use of the imaginary impedance maximum as a reaction progress indicator and is based on the demonstration of a close correlation between the reaction rate, as measured by conventional differential scanning calorimetry, and the rate of change of the value of the imaginary impedance spectrum maximum. Tests on a commercial aerospace epoxy resin under both isothermal and dynamic heating conditions with calorimetry and impedance spectroscopy have demonstrated the validity of the method and set the accuracy limits involved. This technique can be used as a real-time online control tool for thermoset composite manufacturing. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 146–154, 2004     

Solvent‐ and interface‐induced surface segregation in blends of isotactic polypropylene with poly(ethylene‐co‐propylene) rubber

The surface compositions and morphologies of melt‐quenched blends of isotactic polypropylene (iPP) with aspecific poly(ethylene‐co‐propylene) rubber (aEPR) were characterized by atomic force microscopy, optical microscopy, and X‐ray photoelectron spectroscopy. The surface morphologies and compositions formed in the melt are frozen‐in by crystallization of the iPP component and, depending on the processing conditions, are enriched in iPP or aEPR or contain a phase‐separated mix of iPP and aEPR. Enrichment of iPP is observed for blends melted in open air, in agreement with earlier work showing the high surface activity of atactic polypropylene at open interfaces. Surface segregation of iPP is suppressed at confined interfaces. Blends melt‐pressed between hydrophilic and hydrophobic substrates have phase‐separated iPP and aEPR domains present at the surface, which grow in size as the melt time increases. Surface enrichment of aEPR is observed after exposing melt‐pressed blends to n‐hexane vapor, which preferentially solvates aEPR and draws it to the surface. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 421–432, 2004     

Statistical thermodynamics evaluation of polymer–polymer miscibility

The Simha and Somcynsky (S–S) statistical thermodynamics theory was used to compute the solubility parameters as a function of temperature and pressure [δ = δ(T, P)], for a series of polymer melts. The characteristic scaling parameters required for this task, P*, T*, and V*, were extracted from the pressure–temperature–volume (PVT) data. To determine the potential polymer–polymer miscibility, the dependence of δ versus T (at ambient pressure) was computed for 17 polymers. Close proximity of the δ versus T curves for four miscible polymer pairs: PPE/PS, PS/PVME, and PC/PMMA signaled the usefulness of this approach. It is noteworthy, that the tabulated solubility parameters (derived from the solution data under ambient conditions) propounded the immiscibility of the PVC/PVAc pair. The computed values of δ also suggested miscibility for polymer pairs of unknown miscibility, namely PPE/PVC, PPE/PVAc, and PET/PSF. In recognizing the limitations of the solubility parameter approach (the omission of several thermodynamic contributions), these preliminary results are auspicious because they indicate a new route for estimating the miscibility of any polymeric material at a given temperature and pressure. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2909–2915, 2004     

Extractive spectrophotometric determination of Cobalt(II) in synthetic and pharmaceutical samples using Cyanex 923.

Cyanex 923 has been proposed as a sensitive analytical reagent for the direct extractive spectrophotometric determination of cobalt(II). Cobalt(II) forms a blue-colored complex with Cyanex 923 in the organic phase. The maximum absorbance of the complex is measured at 635 nm. Beer's law was obeyed in the range 58.9 - 589.0 microg of cobalt. The molar absorptivitiy and Sandell's sensitivity of the complex was calculated to be 6.79 x 10920 l mol(-1) cm(-1) and 0.088 microg cm(-2), respectively. The nature of the extracted species was found to be Co(SCN)2 x 2S. An excellent linearity with a correlation coefficient value of 0.999 was obtained for the Co(II)-Cyanex 923 complex. Stability and regeneration of the reagent (Cyanex 923) for reuse is the main advantage of the present method. The method was successfully applied to the determination of cobalt in synthetic mixtures and pharmaceutical samples was found to give values close to the actual ones. Standard alloy samples, such as high-speed tool BCS 484 and 485, have been tested for the determination of cobalt for the purpose of validating the present method. The results of the proposed method are comparable with atomic absorption spectrometry and were found to be in good agreement.     

Crystal structure of the 4-chromanone derivative.

The title compound was extracted from a natural product and its structure was characterized by an X-ray diffraction method. It crystallizes in the tetragonal space group P41 with cell parameters a = 15.832(10)A, c = 11.622(10)A, Z = 4; the final residual factor is R1 = 0.0769. The structure has both intra and intermolecular hydrogen bonds.     

A sequential injection system for the spectrophotometric determination of calcium, magnesium and alkalinity in water samples.

A sequential injection methodology for the spectrophotometric determination of calcium, magnesium and alkalinity in water samples is proposed. A single manifold is used for the determination of the three analytes, and the same protocol sequence allows the sequential determination of calcium and magnesium (the sum corresponds to the water hardness). The determination of both metals is based on their reaction with cresolphtalein complexone; mutual interference is minimized by using 8-hydroxyquinoline for the determination of calcium and ethylene glycol-bis(beta-aminoethyl ether)-N,N,N',N'-tetraacetic acid (EGTA) for the determination of magnesium. Alkalinity determination is based on a reaction with acetic acid, and corresponding color change of Bromcresol Green. Working ranges of 0.5 - 5 mg dm(-3) for Ca, 0.5 - 10 mg dm(-3) for Mg, and 10 - 100 mg HCO3- dm(-3), for alkalinity have been achieved. The results for water samples were comparable to those of the reference methods and to a certified reference water sample. RSDs lower than 5% were obtained, a low reagent consumption and a reduced volume of effluent have been accomplished. The determination rate for calcium and magnesium is 80 h(-1), corresponding to 40 h(-1) per element, while 65 determinations of alkalinity per hour could be carried out.     

Addition–fragmentation chain transfer: Molecular weight distributions and retardation in the system methyl methacrylate/methyl α‐(bromomethyl)acrylate

A detailed investigation of addition–fragmentation chain transfer (AFCT) in the free‐radical polymerization of methyl methacrylate (MMA) in the presence of methyl α‐(bromomethyl)acrylate (MBMA) was carried out to elucidate mechanistic details with efficient macromonomer synthesis as an underlying goal. Advanced modeling techniques were used in connection with the experimental work. Curve fitting of simulated and experimental molecular weight distributions with respect to the rate coefficient for addition of propagating radicals to MBMA (k_add) over 60–120 °C resulted in E_add = 21.7 kJ mol^?1 and A_add = 2.18 × 10⁶ M^?1 s^?1 and a very weak temperature dependence of the chain‐transfer constant (E_add ≈ E_p). The rate coefficient for fragmentation of adduct radicals at 60 °C was estimated as k_f ≈ 39 s^?1 on the basis of experimental data of the MMA conversion and the concentration of 2‐carbomethoxy‐2‐propenyl end groups. The approach developed is generic and can be applied to any AFCT system in which copolymerization does not occur and in which the resulting unsaturated end groups do not undergo further reactions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2640–2650, 2004     

Fold‐2‐covering triangular embeddings

For a graph G and a positive integer m, G_(m) is the graph obtained from G by replacing every vertex by an independent set of size m and every edge by m² edges joining all possible new pairs of ends. If G triangulates a surface, then it is easy to see from Euler's formula that G_(m) can, in principle, triangulate a surface. For m prime and at least 7, it has previously been shown that in fact G_(m) does triangulate a surface, and in fact does so as a “covering with folds” of the original triangulation. For m = 5, this would be a consequence of Tutte's 5‐Flow Conjecture. In this work, we investigate the case m = 2 and describe simple classes of triangulations G for which G₍₂₎ does have a triangulation that covers G “with folds,” as well as providing a simple infinite class of triangulations G of the sphere for which G₍₂₎ does not triangulate any surface. © 2003 Wiley Periodicals, Inc. J Graph Theory 43: 79–92, 2003     

Three-dimensional structure of Saccharomyces cerevisiae inorganic pyrophosphatase complexed with cobalt and phosphate ions

Crystals of Saccharomyces cerevisiae inorganic pyrophosphatase suitable for X-ray diffraction study were grown by cocrystallization of the enzyme with cobalt chloride and imidodiphosphate. Saccharomyces cerevisiae is a metal-dependent enzyme which catalyzes hydrolysis of inorganic pyrophosphate to orthophosphate. The three-dimensional structure of this enzyme was solved by the molecular-replacement method and refined at 1.8 Å resolution to an R factor of 19.5%. Cobalt and phosphate ions were revealed in the active centers of both identical subunits (A and B) of the pyrophosphatase molecule. In subunit B, a water molecule was found between two cobalt ions. It is believed that this water molecule acts as an attacking nucleophile in the enzymatic cleavage of the pyrophosphate bond. It was demonstrated that cobalt ions and a phosphate group occupy only part of the potential binding sites (two chemically identical and crystallographically independent subunits have different binding sites). The arrangement of ligands and the structure of the nucleophile-binding site are discussed in relation to the mechanism of action of the enzyme and the nature of the metal activator.