Fracture toughening of epoxy matrices with blends of resins of different molecular weights and other modifiers

The microstructure and fracture behavior of epoxy mixtures containing two monomers of different molecular weights were studied. The variation of the fracture toughness by the addition of other modifiers was also investigated. Several amounts of high‐molecular‐weight diglycidyl ether of bisphenol A (DGEBA) oligomer were added to a nearly pure DGEBA monomer. The mixtures were cured with an aromatic amine, showing phase separation after curing. The curing behavior of the epoxy mixtures was investigated with thermal measurements. A significant enhancement of the fracture toughness was accompanied by slight increases in both the rigidity and strength of the mixtures that corresponded to the content of the high‐molecular‐weight epoxy resin. Dynamic mechanical and atomic force microscopy measurements indicated that the generated two‐phase morphology was a function of the content of the epoxy resin added. The influence of the addition of an oligomer or a thermoplastic on the morphologies and mechanical properties of both epoxy‐containing mixtures was also investigated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3920–3933, 2004     

Resonances and Gamow States in Non-Local Potentials

For a large class of non-local, non separable potentials with non-compact support, the solution of the radial integrodifferential equation may be reduced to the solution of a homogeneous linear integral equation of Fredholm type with a quadratically integrable kernel. In this way we derive expansions of the wave functions and the Green's function of the Schrödinger equation with a non-local potential in terms of bound states, resonant states and a continuum of scattering functions with complex wave number. The rules of normalization, orthogonality and completeness satisfied by the eigenstates of the Schrödinger equation belonging to complex eigenvalues with Im E_n < 0, (Gamow or resonant states) are also derived. Finally, by means of a realistic example, it is shown how to use these expansions to exhibit the resonant behaviour of the differential cross section. Explicit expressions for the transition amplitudes and the partial widths in terms of expectation values of operators computed with Gamow functions are given.     

Theoretical study of the interaction of molecular oxygen with copper clusters

A new method based on frontier orbital theory has been used to investigate the binding site of molecular oxygen to neutral and anion copper clusters. It has been shown that one can make useful predictions of the binding sites based on the knowledge of the donor local reactivity of the cluster using the condensed Fukui function, f(-)(Ff). In this way, it was found that Cu(3), Cu(5), and Cu(5)(-) have the highest reactivity toward molecular oxygen.     

Cellulose microfibrils from banana farming residues: isolation and characterization

Cellulose microfibrils have been prepared from banana rachis using a combination of chemical and mechanical treatments. The morphology and structure of the samples were characterized using transmission electron microscopy, atomic force microscopy, and X-ray diffraction. Fourier-transformed infrared spectroscopy (FTIR) was used to characterize the chemical modifications of the samples after each treatment. Suspensions of bundled or individualized 5-nm-wide microfibrils were obtained after homogenization (PH) whereas an organosolv (PO) treatment resulted in shorter aggregates of parallel cellulose microcrystallites. The sharper rings in the X-ray diffraction pattern of the PO-treated sample suggest a higher crystallinity due to a more efficient removal of hemicelluloses and dissolution of amorphous zones by the acid treatment. Both microfibrils and microcrystals prepared by both methods can be used as reinforcing filler in nanocomposite materials.     

Cure kinetics of a cobalt catalysed dicyanate ester monomer in air and argon atmospheres from DSC data

A kinetic analysis of the cyclotrimerisation reaction of a dicyanate ester monomer catalysed by cobalt(II) acetylacetonate and nonylphenol in air and argon atmospheres has been carried out by differential scanning calorimetry (DSC). Dynamic and isothermal DSC scans as well as the glass transition temperature are the experimental data obtained. From isothermal scans a higher cyanate conversion in air than in argon was obtained. The cyanate conversions are satisfactorily described with a second-order kinetic equation in the kinetically controlled region, and by m-order (m<1) equation after vitrification is reached. Activation energies determined by different procedures agree among them, showing slightly higher values in argon than in air.     

Activation energies and structural changes in carbon nanotubes during different acid treatments

In this work, we studied the effect of acid type in the final properties of CNTs as the resistance to air oxidation; for this, different techniques of characterization were used such as Raman spectroscopy, thermogravimetric analysis, and chemical analysis by ICP-AES. Through Raman spectroscopy, it is possible to monitor the structural changes induced by acids and this is reflected in changing of the activation energies for the different processes determined by thermogravimetric analysis; also by ICP-AES analysis, it was shown that the inorganic material was eliminated efficiently with the acid treatments used in this study.     

Green chemistry for the synthesis of methacrylate-based hydrogels crosslinked through Diels–Alder reaction

This study describes an environmentally friendly and green synthetic approach for the preparation of poly(aminoethylmethacrylate)-based hydrogels crosslinked through Diels–Alder (DA) reaction in water. This “click” reaction offers the possibility of preparing chemically crosslinked hydrogels in the absence of any catalyst, initiator or coupling agent, thus preserving the biocompatibility of the material. The suitable furan diene was obtained by modifying a methacrylate polymer by its reaction with furfural, a first generation compound derived from renewable resources. Methacrylate-based complementary polymeric dienophiles were also prepared by introducing maleimide groups into the structure. The products obtained at different steps were characterized by FTIR, NMR and TGA techniques. The study of the rheological properties of the hydrogels proved the success of this green “click” synthetic strategy confirming the formation of chemically crosslinked networks by the use of the Diels–Alder reaction. Furthermore, SEM studies revealed promising morphological properties of the ensuing hydrogels in terms of biomedical applications.     

Surface free energy of films of alkali-treated cellulose microfibrils from banana rachis

Cellulose microfibrils extracted by various alkaline treatments of vascular bundles from banana rachis were used to elaborate films. The films were comparatively studied to determine changes in polarity induced by various treatments. Atomic force microscopy was used to characterize the surface morphology of the films and transmission electron microscopy was employed to characterize the microfibrils used to elaborate the films. Contact angles were measured to determine surface free energy (SFE) and thermogravimetric analyses were carried out to determine changes in composition of the films. The results showed that the films of cellulose microfibrils prepared by the peroxide alkaline (PA) and peroxide alkaline-hydrochloric acid (PA-HCl) treatments had lower content of non-cellulosic constituents like xylose and had lower SFE than films of microfibrils treated with KOH-5. Furthermore, specimens treated with the most concentrated KOH solution (18 wt%) and sodium chloride presented the highest SFE and polar component.     

Correlation between nanohole volume and mechanical properties of amine‐cured epoxy resin blended with poly(ethylene oxide)

A set of diglycidylether of bisphenol‐A (DGEBA)/4,4′‐diaminodiphenylmethane (DDM) epoxy matrix modified with poly(ethylene oxide) (PEO), pre‐cured at two different temperatures, was examined by positron annihilation lifetime spectroscopy (PALS). The aim was to investigate the correlation between local free volume and mechanical properties. A negative deviation from the linear additivity rule of the local free volume is observed at both cure schedules. Using together the local free volume and mechanical results allows to conclude that the cure temperature makes small contribution to the flexural strength and modulus of blends but is responsible for the composition‐dependent rise of the fracture toughness. It is proposed that this behavior is a consequence of the nearest‐neighbor intrachain contacts or self‐association of the epoxy‐OH groups during cure leading to a non‐uniform space distribution of the DGEBA–PEO contacts, which causes the deflection of the crack path. Copyright © 2008 John Wiley & Sons, Ltd.     

Thermal treatment of the carbon nanotubes and their functionalization with styrene

In this work we studied the functionalization of commercially available multiwalled carbon nanotubes (MWCNT) (Nanocyl 3100) with polystyrene by the method so called “grafting from”. The nanotubes were used as received and oxidized in air at 400 °C. The functionalization was started using thionyl chloride under reflux, followed by a reaction with ethylene glycol which allowed the inclusion of hydroxyl groups. The reaction of those with 2-chloropropionyl chloride led to the generation of the polymerization initiator. Last, the radical polymerization of the functionalized nanotubes, using styrene as the monomer, led to new materials which were studied with thermogravimetric analysis (TGA), Fourier transform infrared (FTIR) spectroscopy, transmission electron microscopy (TEM) and ultraviolet–visible (UV–vis) spectroscopy.