Investigation of the Reaction between a Homemade PEEK Oligomer and an Epoxy Prepolymer: Optimisation of Critical Parameters Using Physico-Chemical Methods.

Several researchers have examined the interest in using a thermoplastic to increase thermoset polymers' shock resistance. However, fewer studies have examined the nature of the mechanisms involved between both kinds of polymers. This was the objective of our work, which was carried out using a gradual approach. First, we describe the synthesis of a poly(ether ether ketone) oligomer (oPEEK) with hydroxyl terminations from the reaction of hydroquinone and 4,4'-difluorobenzophenone in N-methyl-2-pyrrolidone. Then, the main physicochemical properties of this oligomer were determined using different thermal analyses (i.e., differential scanning calorimetry (DSC), thermogravimetric (ATG), and thermomechanical analyses) to isolate its response alone. The chemical characterisation of this compound using conventional analytical chemistry techniques was more complex due to its insolubility. To this end, it was sulfonated, according to a well-known process, to make it soluble and enable nuclear magnetic resonance (NMR) and size exclusion chromatography (SEC) experiments. Additional information about the structural and chemical characteristics of the oligomer and its average molecular weight could thus be obtained. The synthesis of an oligoPEEK with α,ω-hydroxyl end-groups and a molecular weight of around 5070 g/mol was thus confirmed by NMR. This value was in accordance with that determined by SEC analysis. Next, the reaction of oPEEK with an epoxy prepolymer was demonstrated using DSC and dynamic rheometry. To this end, uncured mixtures of epoxy prepolymer (DGEBA) with different proportions of oPEEK (3, 5, 10 and 25%) were prepared and characterised by both techniques. Ultimately, the epoxy-oPEEK mixture was cured with isophorone diamine. Finally, topological analyses were performed by atomic force microscopy (AFM) in tapping mode to investigate the interface quality between the epoxy matrix and the oPEEK particles indirectly. No defects, such as decohesion areas, microvoids, or cracks, were observed between both systems.

Tack Properties of Nanostructured Epoxy-Amine Resins on Plasma-Treated Glass Substrates.

A probe tack test, coupled with in situ imaging, was used to evaluate the influence of an air plasma treatment on glass substrates on the fracture energy of nanostructured epoxy-amine resins. Nanostructuration was achieved by the addition of thermoplastic triblock copolymers. The influence of the surface treatment was assessed by splitting the fracture energy (tack energy) into three main contributions (cavitation, viscous flow, and stretch). We showed that before gelation, the interfacial strength depended on the nature of the copolymers and on their interaction with grafted functions (R-COOH and R-C=O) by air plasma treatment. The latter also influenced the cohesion of the resins, impacting the copolymers' phase separation and, as a consequence, conversion rate. The tack test, coupled with rheology and thermal (differential scanning calorimetry) measurements, was relevant to explain how the balance of interactions contributed to the fracture energy up to the gel point.

Tailoring the Hydroxyl Density of Glass Surface for Anionic Ring-Opening Polymerization of Polyamide 6 to Manufacture Thermoplastic Composites.

Reactive thermoplastics matrices offer ease of processing using well-known molding techniques (such as Resin Transfer Molding) due to their initially low viscosity. For Polyamide 6 (PA6)/glass composites, the hydroxyl groups on the glass surface slow down the anionic ring-opening polymerization (AROP) reaction, and can ultimately inhibit it. This work aims to thoroughly control the hydroxyl groups and the surface chemistry of glass particulates to facilitate in situ AROP-an aspect that has been barely explored until now. A model system composed of a PA6 matrix synthesized by AROP is reinforced with calcinated and silanized glass microparticles. We systematically quantify, by TGA and FTIR, the complete particle surface modification sequence, from the dehydration, dehydroxylation and rehydroxylation processes, to the silanization step. Finally, the impact of the particle surface chemistry on the polymerization and crystallization of the PA6/glass composites was quantified by DSC. The results confirm that a careful balance is required between the dehydroxylation process, the simultaneous rehydroxylation and silane grafting, and the residual hydroxyl groups, in order to maintain fast polymerization and crystallization kinetics and to prevent reaction inhibition. Specifically, a hydroxyl concentration above 0.2 mmol OH·g-1 leads to a slowdown of the PA6 polymerization reaction. This reaction can be completely inhibited when the hydroxyl concentration reaches 0.77 mmol OH·g-1 as in the case of fully rehydroxylated particles or pristine raw particles. Furthermore, both the rehydroxylation and silanization processes can be realized simultaneously without any negative impact on the polymerization. This can be achieved with a silanization time of 2 h under the treatment conditions of the study. In this case, the silane agent gradually replaces the regenerated hydroxyls. This work provides a roadmap for the preparation of reinforced reactive thermoplastic materials.

Parameters Influencing Moisture Diffusion in Epoxy-Based Materials during Hygrothermal Ageing-A Review by Statistical Analysis.

The hygrothermal ageing of epoxy resins and epoxy matrix composite materials has been studied many times in the literature. Models have been developed to represent the diffusion behaviour of the materials. For reversible diffusions, Fick, Dual-Fick and Carter and Kibler models are widely used. Many parameters, correlated or not, have been identified. The objectives of this review by statistical analysis are to confirm or infirm these correlations, to highlight other correlations if they exist, and to establish which are the most important to study. This study focuses on the parameters of the Fick, Dual-Fick and Carter and Kibler models. For this purpose, statistical analyses are performed on data extracted and calculated from individuals described in the literature. Box plot and PCA analyses were chosen. Differences are then noticeable according to the different qualitative parameters chosen in the study. Moreover, correlations, already observed in the literature for quantitative variables, are confirmed. On the other hand, differences appear which may suggest that the models used are inappropriate for certain materials.

Poly(etheretherketone)/Poly(ethersulfone) Blends with Phenolphthalein: Miscibility, Thermomechanical Properties, Crystallization and Morphology.

Polyetheretherketone (PEEK)/polyethersulfone (PES) blends are initially not miscible, except when the blends are prepared by solvent mixing. We propose a route to elaborate PEEK/PES blends with partial miscibility by melt mixing at 375 °C with phenolphthalein. The miscibility of blends has been examined using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMTA). When adding phenolphthalein to PEEK/PES blends, the glass transitions are shifted inward as an indication of miscibility. We suggest that phenolphthalein acts as a compatibilizer by creating cardo side groups on PEEK and PES chains by nucleophilic substitution in the melted state, although this condensation reaction was reported only in the solvent until now. In addition, phenolphthalein acts as a plasticizer for PES by decreasing its glass transition. As a consequence, the PEEK phase is softened which favors the crystallization as the increase of crystalline rate. Due to aromatic moieties in phenolphthalein, the storage modulus of blends in the glassy region is kept identical to pure PEEK. The morphological analysis by SEM pictures displays nano- to microsized PES spherical domains in the PEEK matrix with improved PEEK/PES interfacial adhesion.

Probing Wettability Alteration of the Boron Nitride Surface through Rheometry.

While the surface of many ceramic particles is covered by positive and negative species, boron nitride displays no charge on the surface. Nevertheless, the interest in boron nitride is rising: Little materials combine electrical insulation and high thermal conductivity; both properties are required for many applications, for instance, in electronic devices and sensors. Hydroxyl (-OH) groups are usually created on the surface to increase the hydrophilicity of particles. In this work, we compare four treatments to select the one that increases most significantly the hydrophilicity of hexagonal boron nitride platelets, that is to say, for which the most -OH groups are grafted onto the surface. The treated particles have been studied by SEM, FTIR, and XPS. Our results show that these techniques are not appropriate to probe slight chemical changes. Indeed, hydroxyl groups are more likely introduced on the edges of the platelets. The highest hydroxyl concentration corresponds to 2.4% of boron atoms functionalized. The settling of low concentrated suspensions has been followed by optical visualization. Multiple light scattering was used for high concentrated suspensions. The rheological behavior of stable suspensions in water and isopropanol has been determined by transient flow and dynamic tests. Measuring the viscosity of suspensions appears as a way to evaluate the surface alterations of boron nitride. The method involving thermal treatment is the most efficient to increase the concentration of hydroxyl groups when the particles are suspended in water. The treatment with nitric acid seems to be the most efficient when the particles are suspended in isopropanol. Moreover, the thermal treatment is more environmentally friendly than using strong acids or bases. Hydroxylated particles can be used either as a starting material for further modification such as covalent functionalization or directly to prepare suspensions or polymeric based composites.

High Temperature Epoxy Foam: Optimization of Process Parameters.

For many years, reduction of fuel consumption has been a major aim in terms of both costs and environmental concerns. One option is to reduce the weight of fuel consumers. For this purpose, the use of a lightweight material based on rigid foams is a relevant choice. This paper deals with a new high temperature epoxy expanded material as substitution of phenolic resin, classified as potentially mutagenic by European directive Reach. The optimization of thermoset foam depends on two major parameters, the reticulation process and the expansion of the foaming agent. Controlling these two phenomena can lead to a fully expanded and cured material. The rheological behavior of epoxy resin is studied and gel time is determined at various temperatures. The expansion of foaming agent is investigated by thermomechanical analysis. Results are correlated and compared with samples foamed in the same temperature conditions. The ideal foaming/gelation temperature is then determined. The second part of this research concerns the optimization of curing cycle of a high temperature trifunctional epoxy resin. A two-step curing cycle was defined by considering the influence of different curing schedules on the glass transition temperature of the material. The final foamed material has a glass transition temperature of 270 °C.