Morphology, barrier, and mechanical properties of biaxially deformed poly(ethylene terephthalate)-mica nanocomposites

Nanocomposites of poly(ethylene terephthalate) PET with a partially synthetic fluoromica were prepared by melt mixing and extruded into sheet and subjected to large-scale biaxial stretching. Transmission electron microscopy (TEM) analysis of the mica tactoids showed that biaxial stretching had caused the tactoids to be more orientated and with improved exfoliation. The moduli of the nanocomposites were enhanced with increasing mica loading and the reinforcement effect was higher when the stretch ratio was 2 or 2.5, accommodated by having more aligned tactoids and reduced agglomeration. Enhancement in modulus was less pronounced for a stretch ratio of 3. Storage modulus was enhanced more significantly above the glass transition temperature. The barrier properties were enhanced by addition of mica before and after stretching. The Halpin-Tsai theory underpredicted the relative modulus of the PET nanocomposites, whereas the Nielsen model over-predicted the relative permeability. POLYM. ENG. SCI., 2012. (c) 2011 Society of Plastics Engineers

Carbon nanotubes induced crystallization of poly(ethylene terephthalate)

We have investigated the crystallization characteristics of melt compounded nanocomposites of poly(ethylene terephthalate) (PET) and single walled carbon nanotubes (SWNTs). Differential scanning calorimetry studies showed that SWNTs at weight fractions as low as 0.03 wt% enhance the rate of crystallization in PET, as the cooling nanocomposite melt crystallizes at a temperature 10 °C higher as compared to neat PET. Isothermal crystallization studies also revealed that SWNTs significantly accelerate the crystallization process. WAXD showed oriented crystallization of PET induced by oriented SWNTs in a randomized PET melt, indicating the role of SWNTs as nucleating sites.

Application of Nonisothermal Cure Kinetics to the Interaction of Poly(ethylene terephthalate) with Alkyd Resin Varnish

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Non-isothermal decomposition kinetics of the interaction of poly(ethylene terephthalate) with alkyd varnish

The recycling of soft drink bottles poly(ethylene terephthalate) (PET) has been used as an additive in varnish containing alkyd resin. The PET, called to recycled PET (PET-R), was added to the varnish in increasing amounts. Samples of varnish containing PET-R (VPET-R) were used as a film onto slides and its thermal properties were evaluated using thermogravimetry (TG). Throughout the visual analysis and thermal behavior of VPET-R it is possible to identify that the maximum amount of PET-R added to the varnish without changing in the film properties was 2%.The kinetic parameters, such as activation energy (E) and the pre-exponential factor (A) were calculated by the isoconversional Flynn-Wall-Ozawa method for the samples containing 0.5 to 2.0% PET-R. A decrease in the values of E was verified for lower amounts of PET-R for the thermal decomposition reaction. A kinetic compensation effect (KCE) represented by the lnA=-13.42+0.23E equation was observed for all samples. The most suitable kinetic model to describe this decomposition process is the autocatalytic Sestak-Berggren, being the model applied to heterogeneous systems.

Effect of the catalyst MCM-41 on the kinetic of the thermal decomposition of poly(ethylene terephthalate)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Increasing the dielectric breakdown strength of poly(ethylene terephthalate) films using a coated polyaniline layer

The dielectric strength of films made from poly(ethylene terephthalate) (PET) coated with a thin layer of polyaniline (PANI) was studied. The PANI layer was deposited on the PET films by the 'in situ' chemical polymerization method. The PANI layer of the PANI/PET films was undoped in NH4OH 0.1 M solution and re-doped with aqueous HCl solution under different pH values varying from 1 to 10. Electric breakdown measurements were performed by applying a voltage ramp and the results showed a dependence of the dielectric strength on the pH of the doping solution due to the changes in the electrical conductivity of the PANI layer. The dielectric strength of PET/PANI films treated under higher pH conditions showed an electric strength about 30% larger than the PET films, since it leads to a non-conductive PANI layer.

Application of non-isothermal cure kinetics on the interaction of poly(ethylene terephthalate) - Alkyd resin paints

Samples of paint (P), reused PET (PET-R) and paint/PET-R mixtures (PPET-R) were evaluated using DSC to verify their physical-chemical properties and thermal behavior. Films from paints and PPET-R are visually similar. It was possible to establish that the maximum amount of PET-R that can be added to paint without significantly altering its filming properties is 2%. The cure process (80-203°C) was identified through DSC curves. The kinetic parameters, activation energy (E a) and Arrhenius parameters (A) for the samples containing 0.5 to 1% of PET-R, were calculated using the Flynn-Wall-Ozawa isoconversional method. It was observed that for greater amounts of PET-R added, there is a decrease in the E a values for the cure process. A Kinetic compensation effect (KCE), represented by the equation InA=-2.70+0.31E a was observed for all the samples. The most suitable kinetic model to describe this cure process is the autocatalytic Šesták-Berggreen, model applied to heterogeneous systems. © 2007 Springer Science+Business Media, LLC.

Chain extension of poly (ethylene terephthalate) by reactive extrusion with secondary stabilizer

Poly(ethylene tereftalate) (PET) is a polymer highly susceptible to the hydrolytic reactions that occur during applications and mainly in thermomechanical processing. These reactions lead to the decrease of molecular weight of the polymer, limiting the recycling number of the material. The reactive extrusion of the PET in presence of chain extenders is an alternative to recover mechanical and rheological properties that were depreciated by the polymer degradation. In this study, PET wastes from nonwoven fabrics production were extruded in presence of the secondary stabilizer Irgafos 126 (IRG) on variable concentrations. The results showed that Irgafos 126 increased molecular weight, decreased crystallinity and changed processing behavior of the PET, similarly to the effects produced by the well-known chain extender pyromellitic dianhydride (PMDA), showing that the secondary stabilizer Irgafos 126 can also act as a chain extender for the PET.

Confined crystallization of nanolayered poly(ethylene terephthalate) using X-ray diffraction methods

The development of crystalline lamellae in ultra-thin layers of poly(ethylene terephthalate) PET confined between polycarbonate (PC) layers in an alternating assembly is investigated as a function of layer thickness by means of X-ray diffraction methods. Isothermal crystallization from the glassy state is in-situ followed by means of small-angle X-ray diffraction. It is found that the reduced size of the PET layers influences the lamellar nanostructure and induces a preferential lamellar orientation. Two lamellar populations, flat-on and edge-on, are found to coexist in a wide range of crystallization temperatures (Tc = 117–150 °C) and within layer thicknesses down to 35 nm. Flat-on lamellae appear at a reduced crystallization rate with respect to bulk PET giving rise to crystals of similar dimensions separated by larger amorphous regions. In addition, a narrower distribution of lamellar orientations develops when the layer thickness is reduced or the crystallization temperature is raised. In case of edge-on lamellae, crystallization conditions also influence the development of lamellar orientation; however, the latter is little affected by the reduced size of the layers. Results suggest that flat-on lamellae arise as a consequence of spatial confinement and edge-on lamellae could be generated due to the interactions with the PC interface. En este trabajo se investiga mediante difracción de rayos X a ángulos bajos (SAXS) y a ángulos altos (WAXS), la cristalización de láminas delgadas de Polietilén tereftalato (PET) confinadas entre láminas de Policarbonato (PC), tomando como referencia PET sin confinar. El espesor de las capas de PET varía entre 35nm y 115 nm. Se realizaron medidas de difracción a tres temperaturas de cristalización (117ºC, 132ºC y 150ºC) encontrándose que el reducido espesor de las capas de PET influye en la estructura lamelar que se desarrolla, induciendo una orientación preferente de las láminas. Se integró la intensidad difractada alrededor del máximo en SAXS para obtener una representación de la intensidad en función del ángulo acimutal. Mediante análisis de mínimos cuadrados se separó la curva experimental obtenida en tres contribuciones diferentes: una función Gausiana que describe la distribución de las orientaciones de las lamelas, una función lorenziana asociada a los máximos meridionales (asociados a las interfases PET-PC) y un background constante. Por otra parte la cantidad de material cristalizado se estimó asumiendo que la intensidad del background en el barrido acimutal, una vez restado el background del primer difractograma (sin máximos en SAXS) se asocia con la contribución del material isotrópico que resta en la muestra cristalizada. Se observa la coexistencia de dos poblaciones de lamelas: flat-on y edge-on. A medida que el espesor de las láminas de PET disminuye la población de las lamelas flat-on experimenta los siguientes cambios: 1) la distribución de orientación se estrecha, 2) la fracción de material cristalizado orientado aumenta, 3) la cinética de cristalización se ralentiza y 4) el largo espaciado aumenta es decir las regiones amorfas entre lamelas aumentan su tamaño. Parece demostrarse que es en las primeras etapas del crecimiento lamelar cuando la restricción espacial fuerza a las lamelas a esta orientación tipo flat-on frente a la orientación edge-on.

Effect of poly ethylene glycol on the mechanical and thermal properties of bioactive Poly (ε–caprolactone) melt extrudates for pharmaceutical applications

This paper investigates the effects of polyethylene glycol (PEG), on the mechanical and thermal properties of nalidixic acid/ploy ε-caprolactone (NA)/PCL blends prepared by hot melt extrusion. The blends were characterized by tensile and flexural analysis, dynamic mechanical analysis, differential scanning calorimetry, thermogravimetric analysis and X-ray diffraction. Experimental data indicated that the addition of NA caused loss of the tensile strength and toughness of PCL. Thermal analysis of the PCL showed that on addition of the thermally unstable NA, thermal degradation occurred early and was autocatalytic. However, the NA did benefit from the heat shielding provided by the PCL matrix resulting in more thermally stable NA particles. Results show that loading PEG in the PCL had a detrimental effect on the tensile strength and toughness of the blends, reducing them by 20-40%. The partial miscibility of the PCL-PEG system, causes an increase in Tg. While increases in the crystallinity is attributed to the plasticisation effect of PEG and the nucleation effect of NA. The average crystal size increased by 8% upon PEG addition.

Effect of physical aging on phenolphthalein polyethersulfone/poly(phenylene sulfide) blend .1. Mechanical properties

The effect of physical aging at 210 degrees C on the mechanical properties of phenolphthalein polyether sulfone (PES-C) and a PES-C/poly(phenylene sulfide) (PPS) blend, with 5% content of PPS, were studied using DMA, tensile experiments, an instrumented impact tester, and SEM observations. The blend shows good mechanical properties in comparison with the corresponding PES-C. The mechanical properties of both materials exhibit characteristics of physical aging, with only the aging rate of the blend relatively slower, which should be attributed to the constraint effect of PPS particles and the good interfacial adhesion. The morphology of the PPS phase in the blend did not change with aging time. The principal role of PPS particles is to induce crazes, which dissipate energy, under applied loading; thus, the blend shows good toughness. On the other hand, the multiple crazing mechanism depends on the molecular mobility or structural state of the matrix. (C) 1996 John Wiley & Sons, Inc.

Latex Stage Blending of Natural Rubber and Poly(Vinyl Chloride ) for Improved Mechanical Properties

A novel method of blending natural rubber with polyvinylchloride in the latex stage was developed, Dioctyl phthalate (DOP) and Amine terminated natural rubber (ATNR) were used as plasticisers, for improving the mechanical properties of these blends. Properties of the latex stage blends were compared with those of dry blends. Latex stage blends showed superior mechanical properties compared to the blends prepared in the dry state. The ageing resistance, oil resistance and processability were found to be improved by latex stage blending.

Thermo-Mechanical Properties of Poly ε-Caprolactone/Poly L-Lactic Acid Blends: Addition of Nalidixic Acid and Polyethylene Glycol Additives Journal of the Mechanical Behavior of Biomedical Materials

The search for ideal biomaterials is still on-going for tissue regeneration. In this study, blends of Poly ε-caprolactone (PCL) with Poly l-lactic acid (PLLA), Nalidixic Acid (NA) and Polyethylene glycol (PEG) were prepared. Mechanical and thermal properties of the blends were investigated by tensile and flexural analysis, DSC, TGA, WXRD, MFI, BET, SEM and hot stage optical microscopy. Results showed that the loading of PLLA caused a significant decrease in tensile strength and almost total eradication of the elongation at break of PCL matrix, especially after PEG and NA addition. Increased stiffness was also noted with additional NA, PEG and PLLA, resulting in an increase in the flexural modulus of the blends.
Isothermal degradation indicated that bulk PCL, PLLA and the blends were thermally stable at 200°C for the duration of 2h making extrusion of the blends at this temperature viable. Morphological study showed that increasing the PLLA content and addition of the very low viscosity PEG and powder NA decreased the Melt Flow Indexer and increased the viscosity.
At the higher temperature the PLLA begins to soften and eventually melts allowing for increased flow and, coupling this with, the natural increase in MFI caused by temperature is enhanced further. The PEG and NA addition increased dramatically the pore volume which is important for cell growth and flow transport of nutrients and metabolic waste.