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We explore the influence of the interdiffusion of two thermoplastic tougheners and RTM6 epoxy resin precursors on the resulting morphologies after curing and the consequences on delamination toughness of the corresponding carbon fiber reinforced composites. Two thermoplastics with contrasting Tg and compatibility, i.e. poly(ether sulfone) (PES) and phenoxy are compared. The dramatic improvement of the interlaminar fracture toughness (GIC) found for the phenoxy-RTM6 system as compared to the pure thermoset reference can be ascribed to the broad morphology gradient only observed for that system. By contrast, the PES-RTM6 system is characterized by a steep morphology gradient and a corresponding decrease of as compared to the reference.

Toughening of epoxy thermosets with thermoplastics is an important avenue towards improved properties of high-performance systems. The main focus of the work reported was to study the complex issue of interdiffusion between thermoplastics and epoxy resin precursors, using a combination of experimental and numerical simulation methods, in order to understand the key parameters driving the process. Diameter changes of thermoplastic filaments in contact with epoxide and diamine precursors have been followed and an original approach using carbon nanotubes as tracers of the filament swelling front has been developed. This method shows that the improved mobility of low-molecular-weight resin monomers as well as the greater mobility of phenoxy of lower glass transition temperature as compared to poly(ether sulfone) control dissolution by favouring the penetration of precursors into the thermoplastic and lead to both swelling of the outer part of the filaments and reduction of the inner unaffected core. Simulation by molecular dynamics supports the idea that diffusion of polymer macromolecules remains limited compared to the dominant effect of precursor diffusion. Indeed, low diffusion coefficients have been predicted for thermoplastic oligomers compared to resin monomers. For the latter, the calculated values correlate well with the experimental data measured during interdiffusion

19NMR spectroscopy has been performed on PEEK samples in sulphuric acid, revealing that most chain ends are fluorine. Different chemical shifts have been observed on sulphonated samples due to already demonstrated long range shielding effects. The method appears suitable for Mn determination. Substitution of F chain ends, followed by 19NMR, appeared feasible leading to alkaline sulphonate end groups. Ionic chain ends associations act as seeds for nucleation. Fast crystallizing PEEK and PEK are thus obtained. This is a new demonstration of the concept of Chemical Nucleation.

We have developed a sensitive method to detect very low levels of long chain branching in sparsely branched polymers and applied it to high-density polyethylene samples with broad molar mass distribution obtained by Ziegler-Natta, Phillips, and metallocene catalysis. We compare experimental dynamic moduli with predicted values. The predicted moduli, which are only valid for truly linear chains, are computed from a known molar mass distribution by the application of a modified time-dependent diffusion reptation model described in [van Ruymbeke et al., Macromolecules 35, 2689 (2002)]. Discrepancies between experimental and predicted moduli are observed at branching levels below the usual detection limit Of C-13 nuclear magnetic resonance (about I branch per 10000 carbon atoms). Our method is easier to implement and the results more clearcut than those obtained by the zero-shear viscosity method. The sensitivity is comparable with the activation energy spectrum method described in [Wood-Adams et al., Macromolecules 33, 7489 (2000)]. The use of our method is however not restricted to thermorheologically complex polymers. The interest of polymer fractionation is also demonstrated for the detection of extremely low levels of long chain branching. (c) 2005 The Society of Rheology.

The previously developed model [Polym Bull 2000, 44, 525] used to characterize the porous gel inside a gel permeation chromatography (GPC) column, has been extended to also include the interstitial space between the macroscopic gel particles. The hydrodynamic dimensions for 12 polystyrene (PS) standards, measured by GPC with differential refractive index (DRI), differential viscometry (VISCO), and multiangle laser light scattering (MALLS) detectors, have been used to determine the fractal parameters of the polystyrene-divinylbenzene gel corresponding to four commercial columns. The new developed model enables to predict the calibration curve for the sets of coupled columns based on the parameters of each column. (C) 2004 Wiley Periodicals, Inc.

Owing to their low polydispersity and their well controlled molecular architecture, 3-arms stars polystyrenes made by anionic synthesis are suitable models to study the solution proper-ties of long chain branched polymers. A fine characterization of such polymers by size exclusion chromatography-viscometry has shown that they often contain unwanted linear chains, leading to chromatograms presenting overlapping peaks. A mathematical procedure has been developed in order to deconvolute these chromatograms and has been validated, thanks to blends of polystyrene standards. It allows one to calculate the purity of the sample as well as the intrinsic viscosity and molar mass distribution of each component. For stars with three arms of the same length, branching parameters have also been calculated and a viscosity law has been established. (C) 2002 Elsevier Science Ltd. All rights reserved.

The sulfonation kinetics of the fluoroarylketone chain-end repeat unit of PEEK was studied. To achieve this objective, the sulfonation reactions of a trimer, a tetramer and a polymer, each fluoroarylketone ended, were followed by F-19 NMR. A general kinetic model was developed to determine the kinetic constants from F-19 NMR data. The reliability of the kinetic model and of its mathematical expression was ensured. The kinetic constants are then calculated and discussed. In particular, they were compared with the dimer rate constants previously determined. Lastly and as a conclusion of this work, a general kinetic model describing the sulfonation of main chain repeat units of PEEK is proposed. (C) 2001 Society of Chemical Industry.

The sulfonation kinetics of fluorine ended poly(ether ether ketone) (PEEK) in solution in 95.9% and 96.8% concentrated sulfuric acid was studied with the help of a model compound representative of the PEEK chain repeat unit. The reaction rate of the model compound sulfonation was found to be first order with respect to the aromatic ring to be sulfonated. Consequently, PEEK kinetic data were treated following a first order with respect to the unsulfonated repeat unit concentration. Two rate-slowing effects were detected. They were attributed to 'long range' electronic effects resulting from the inductive nature of the fluorine atom, and from the electron-withdrawing character of the grafted sulfonic acid group. (C) 2001 Society of Chemical Industry.

The mechanism and kinetics of sulfonation of two PEEK model compounds in concentrated sulfuric acid were studied. The first model compound (monomer) is representative of a PEEK repeat unit. The second one is a PEEK dimer. Because both model compounds are fluoroarylketone-ended, the sulfonation reactions were followed by F-19 NMR. The sulfonation reactions were treated following a first-order kinetics with respect to the unsulfonated PEEK repeat unit. The comparison between the monomer and dimer results showed two different types of sulfonation behaviour. If only one apparent kinetic constant is considered for monomer sulfonation, two kinetic constants were taken into account to describe the dimer sulfonation process. This is due to a rate slowing effect of a sulfonic acid group on the sulfonation of the adjacent PEEK repeat unit. Furthermore, the results also confirm the rate slowing effect of the fluorine atom on the sulfonation of the neighbouring PEEK repeat unit. (C) 2001 Society of Chemical Industry.

The fractionation of a statistical copolyester made of poly(ethylene terephthalate- isophthalate) has been performed using Temperature Rising Elution Fractionation (TREF). TREF fractions were analyzed by size exclusion chromatography, thermal analysis, H-1-nuclear magnetic resonance and small angle X-Ray diffractometry. Results show that the fractions exhibit both interchain and intrachain defect distribution. As the intrachain defect distribution can not be determined by experimental techniques, a computer simulation based on the determination of terephthalic sequences length in a virtual polymeric distribution was performed. The simulated chains were constructed using a stochastic process. The analysis of the results obtained on the distribution of the simulated sequences in the polymer correlates quantitatively well between the new fractionation mechanism proposed for copolyesters and the experimental results.

HTX, a poly(aryletherketone-co-sulfone), is characterized by size exclusion chromatography (SEC) at room temperature. As HTX is not soluble in any solvent compatible with the SEC instrumentation, a derivatization procedure is applied in order to prepare a modified copolymer with improved solubility properties. This derivatization consists in a sulfonation by concentrated sulfuric acid. The derivative polymer is soluble in N-methyl-2-pyrrolidone (NMP), a classical SEC solvent. Sulfonated HTX (HTXS) is a polyelectrolyte. Consequently, a salt is added to NMP to perform reliable viscometric and SEC analyses. The SEC method is standardized with the establishment of the universal calibration with poly(methyl methacrylate) standards and the determination of the Mark-Houwink-Sakurada relationship of HTXS in NMP-salt at 25-degrees-C. Finally, the reliability of the derivatization procedure and of the SEC method is confirmed by comparison with molecular masses from NMR.

Fast-crystallizing poly(ether ether ketone) (PEEK) and poly(ether ketone) (PEK) samples have been prepared by substitution of the F chain ends, leading to alkaline sulphonate groups. Ionic chain-end associations act as seeds for nucleation. The concept of chemical nucleation already demonstrated with poly(ethylene terephthalate) is shown to apply to PEEK and PEK.

19F n.m.r. spectroscopy of poly(ether ether ketone) (PEEK) and related model compounds has been performed in various solvents including sulphuric acid. Different chemical shifts have been observed on sulphonated samples and long range shielding effects are discussed. An alternative method for the M n evaluation of PEEK is proposed.

Attempts have been made to determine the weight average molecular weight ( M W ), the radius of gyration ( R G ) and the second virial coefficient (A2) of five samples of poly(ether-ether-ketone) (PEEK) by light scattering (LS) in concentrated sulphuric acid. Account has been taken of the sulphonation of the polymer. Correlations between LS-molecular weights, melt viscosities and intrinsic viscosities in sulphuric acid or in a 50 50 phenol-trichlorobenzene mixture have been established. Gel permeation chromatography (g.p.c.) analyses at 115°C have been performed in this latter solvent and two calibration methods were compared.

Two polypropylenes, PP1 and PP2, produced with different heterogeneous Ziegler-Natta catalytic systems were studied in this work. Preliminary characterization of the non-fractionated materials showed that a low difference in their average tacticity (PP2 > PP1) leads to an important modification of their rigidity properties. In order to establish correlation between the molecular structure parameters and the rigidity properties of these polymers, fractionation of the materials according to crystallizability was performed by means of temperature rising elution fractionation (TREF). Analysis of the fractions of both PP1 and PP2 was carried out by means of C-13 NMR, size exclusion chromatography (SEC), differential scanning calorimetry (DSC) and atomic force microscopy (AFM). The results first showed that TREF does not strictly fractionate PP according to tacticity, but according to the longest crystallizable sequence in a chain. C-13 NMR, SEC and DSC analysis of the fractions demonstrated that the inter-chain tacticity distributions of the polypropylenes is affected by the change of the polymerization conditions, which, in turn, modifies the rigidity properties of the materials. Some results also seem to indicate that the intrachain tacticity distributions are different for the two PP. An AFM study of the elastic modulus was carried out for the first time on the TREE fractions. It showed that the rigidity or the fractions strongly increases as the TREF elution temperature increases in accordance with a concomitant increase of isotacticity and the crytallinity of the fractions. PP2 TREE fractions were, moreover, found to exhibit a higher elastic modulus than PP1 TREF fractions at all elution temperatures. This study allowed us to further identify the TREF fractions that were responsible for differences in rigidity. To summarize, it is shown how the experimentally observed increase of the average rigidity of one of these two polypropylenes can be rationalized via information collected from a TREF fractionation. (C) 2000 Published by Elsevier Science Ltd.