Francisco J. Medellín-Rodríguez

The triple melting behavior of poly(ethylene terephthalate): Molecular weight effects

The melting behavior of isothermally crystallized PET has been studied using linear heating in a differential scanning calorimeter (DSC). Variables such as crystallization temperature, crystallization time, heating rate, and average molecular weight are the main focus of the study. On the basis of several experimental techniques, a correlation of the melting behavior of PET with the amount of secondary crystallization was found to exist. It was observed that the triple melting of PET is a function of programmable DSC variables such as crystallization temperature, crystallization time, and heating rate. However, in testing the hypothesis that there was a correlation between melting endotherms and secondary crystallization inside spherulites, it was found necessary to use a DSC-independent variable in order to enhance the observed effects. Therefore, on the basis of a crystallization model that involves secondary branching along the edges of parent lamellar structures, it was speculated that an increase in the average molecular weight could affect the triple melting of PET due to an increase of rejected portions of the macromolecules. It was found that the second melting endotherm increased, apparently, at the expense of the third one as the average molecular weight was increased. The second melting endotherm was also found to correlate proportionally with the amount of secondary crystallization inside spherulites. The results support a model of crystallization which basically consists of parent crystals and at least one population of secondary, probably metastable, crystals. This latter structural component must involve excluded portions of the macromolecules that did not crystallize during the isothermal crystallization period of the parent crystals. An increase of molecular weight gives rise to a higher entanglement density which in turn increases the fraction of initially rejected chain sections and therefore the amount of secondary crystallization.

On the nature of multiple melting in poly(ethylene terephthalate) (PET) and its copolymers with cyclohexylene dimethylene terephthalate (PET/CT)

The multiple melting behavior of poly(ethylene terephthalate) (PET) homopolymers of different molecular weights and its cyclohexylene dimethylene (PET/CT) copolymers was studied by time-resolved simultaneous small-angle X-ray scattering/wide-angle X-ray scattering diffraction and differential scanning calorimetry techniques using a heating rate of 2 °C/min after isothermal crystallization at 200 °C for 30 min. The copolymer containing random incorporation of 1,4-cyclohexylene dimethylene terephthalate monomer cannot be cocrystallized with the ethylene terephthalate moiety. Isothermally crystallized samples were found to possess primary and secondary crystals. The statistical distribution of the primary crystals was found to be broad compared to that of the secondary crystals. During heating, the following mechanisms were assumed to explain the multiple melting behavior. The first endotherm is related to the non-reversing melting of very thin and defective secondary crystals formed during the late stages of crystallization. The second endotherm is associated with the melting of secondary crystals and partial melting of less stable primary crystals. The third endotherm is associated with the melting of the remaining stable primary crystals and the recrystallized crystals. Due to their large statistical distribution, the primary crystals melt in a broad temperature range, which includes both second and third melting endotherms. The amounts of secondary, primary and recrystallized crystals, being molten in each endotherm, are different in various PET samples, depending on variables such as isothermal crystallization temperature, time, molecular weight and co-monomer content.

Solid-state polymerization and bulk crystallization behavior of poly(ethylene terephthalate) (PET)

The main variables involved in solid-state polymerization of PET homopolymers, originally with molecular weight within the commercial range, were sequentially studied to determine their influence in polymerized products. These variables were precursor crystallinity, catalyst, and time and reaction temperature. An increasing molecular weight sequence was then used to study the bulk crystallization behavior with Avrami analyses. It was determined that thermal conditions at dissolution affect the prereaction morphology. This was important in the polymerization process because it was found that high crystallinity levels in precursors result in higher molecular weights. In agreement with other reports, typical catalysts used in melt polymerizations enhance postpolycondensation processes in the solid state. High reaction times and temperatures were also required to obtain high molecular weights. As the molecular weight increased, there was a decrease in nucleation density and Avrami analyses, applied to the isothermal bulk crystallization, indicating that the nucleation process changed from instantaneous to spontaneous with the increase in molecular weight. The consequences and relative importance of the observed results is discussed.

Morphology, Thermal Stability, and Electrical Conductivity of Polymer Nanocomposites of Isotactic Polypropylene/Multi-Walled Carbon Nanotubes

Molecular weight of isotactic polypropylene (iPP) and concentration of multi-walled carbon nanotubes (MWCNT) effects on the morphology, thermal stability, and electrical conductivity for iPP/MWCNT nanocomposites were evaluated. Nanocomposites were prepared by solution mixing followed by non-isothermal crystallization from the melt. The samples were characterized by different physical-chemical techniques. Electrical conductivity was obtained from electrical resistance measured using a source meter. It was determined that the morphology of the nanocomposites shows a change from spherulitic to fibrillar to undefined depending on the molecular weight of iPP and concentration of MWCNT. Morphology was correlated with thermal stability and electrical conductivity.

Effects on the Thermo-Mechanical and Crystallinity Properties of Nylon 6,6 Electrospun Fibres Reinforced with One Dimensional (1D) and Two Dimensional (2D) Carbon

Electrospun one dimensional (1D) and two dimensional (2D) carbon based polymer nanocomposites are studied in order to determine the effect provided by the two differently structured nanofillers on crystallinity and thermo-mechanical properties of the nanofibres. The nanomaterials studied are pristine carbon nanotubes, oxidised carbon nanotubes, reduced graphene oxide and graphene oxide. Functional groups associated with the order structure of the polymers are analysed by infrared and Raman spectroscopies; the morphology is studied by scanning electron microscopy and the crystallinity properties are investigated by differential scanning calorimetry and X-ray diffraction. Differences in crystallisation behaviour between 1D and 2D carbon based nanofibres are shown by their crystallinity degree and their crystal sizes. The nanocomposite crystal sizes perpendicular to the plane (100) decrease with nanofiller content in all cases. The crystallinity trend and crystal sizes are in accordance with storage modulus response. The results also suggest that functionalisation favours interfacial bonding and dispersion of the nanomaterials within the polymer matrix. As a consequence the number of nucleating sites increases which in turn decreases the crystal size in the nanocomposites. These features explain the improved thermo-mechanical properties in the nanocomposites.

Uniaxial Deformation of Nylon 6–Clay Nanocomposites by In-Situ Synchrotron X-Ray Measurements

An in-situ uniaxial deformation study of nylon 6–clay hybrid (NCH) nanocomposites was carried out using simultaneous wide-angle x-ray diffraction (WAXD) and small-angle x-ray scattering (SAXS) techniques with synchrotron radiation. This nanocomposite system exhibited the partial exfoliated clay morphology. The WAXD patterns along the through-and edge-views from the as-pressed film samples indicated that both clay platelets and nylon 6 crystallites were parallel to the film plane but oriented randomly in the plane. During uniaxial deformation, the orientation of the molecular axis in the crystals increased with strain but decreased with the clay content. This behavior could be attributed to the rotation of clay platelets during deformation, which hindered the orientation of nylon 6 crystals. The corresponding tensile mechanical properties indicated that the elongation at break decreased and the tensile modulus and strength increased with the clay concentration, which has been observed before.

A turn-on fluorescent solid-sensor for Hg(II) detection

A rhodamine organosilane derivative (Rh-UTES) has been obtained by one-pot synthesis. The chemical structure of Rh-UTES was confirmed by nuclear magnetic resonance (NMR) and infrared (FTIR) techniques. To obtain an inorganic-organic hybrid sensor, Rh-UTES was covalently immobilized on a porous silicon microcavity (PSiMc) via triethoxysilane groups. The attachment of the organic derivative into PSiMc was confirmed by FTIR, specular reflectance, and scanning electron microscopy (SEM). The optical performance of Rh-UTES receptor for Hg2+ detection was investigated by fluorescent spectroscopy and microscopy. Upon the addition of increasing amounts of Hg2+ ions, a remarkable enhancement in emission intensity was produced in both systems. In the solid phase, an increase of integrated fluorescent emission of 0.12- and 0.15-fold after Hg2+ receptor coordination was observed. The light harvesting capability of PSiMc devices allowed obtaining an enhanced fluorescent emission after Rh-UTES immobilization (277-fold). The fluorescence microscopy of hybrid PSiMc sensor provided an optical qualitative test for Hg2+ detection.

Nucleation mechanisms of aromatic polyesters, PET, PBT, and PEN, on single-wall carbon nanotubes: early nucleation stages

Nucleation mechanisms of poly (ethylene terephthalate) (PET), poly (butylene terephthalate) (PBT), and poly (ethylene naphthalate) (PEN) on single-wall carbon nanotubes (SWNTs) are proposed, based on experimental evidence, theoretical epitaxy analysis, and semiempirical quantum chemical calculations. In order to elucidate early nucleation stages polyester-coated nanotubes were obtained from highly diluted solutions. High-resolution transmission electron microscopy (HRTEM) revealed helical morphologies for PET/SWNTs and PEN/SWNTs and the formation of lobules with different orientations for PBT/SWNTs. To explain the morphological behavior one model was proposed based on crystallographic interactions, that is, epitaxy. Theoretical epitaxy calculations indicated that epitaxy is not possible from the strict epitaxy point of view. Instead, aromatic self-assembly mechanism was proposed based on p-p interactions and the chirality of the nanotube. It was proposed that themechanism implies two steps to produce helical or lobular morphologies with different orientations. In the first step polymer chains were approached, aligned parallel to the nanotube axis and adsorbed due to electrostatic interactions and the flexibility of the molecule. However, due to p-p interactions between the aromatic rings of the polymer and the nanotube, in the second step chains reoriented on the nanotube surface depending on the chirality of the nanotube. The mechanism was supported by semi-empirical calculations.

Nylon 6,6 electrospun fibres reinforced by amino functionalised 1D and 2D carbon

Nylon 6,6 electrospun nanocomposites were prepared and reinforced with 0.1, 0.5 and 1wt.% of 1D and 2D carbon. Both carbon nanotubes and graphene were functionalised with amino groups (f-CNT and f-Ge respectively). The morphology and graphitization changes of carbon nanomaterials were evaluated by transmission electron microscopy (TEM) and Raman spectroscopy; functional groups of modified nanomaterials was analysed by infrared spectroscopy. The mechanical response and the crystallinity of the fibres were measured by dynamical mechanical analysis, differential scanning calorimetry and wide angle x-ray diffraction. The morphology and dispersion of the nanomaterials in the nanofibres was studied by scanning electron microscopy and TEM. The storage modulus was improved by 118% for f- CNT and 116% for f-Ge. The mechanical response of the nanocomposites exhibited different behaviour upon loading of 1D and 2D carbon. This trend is consistent with the crystallinity of the nanofibres. This study showed f-CNT resulted in better mechanical properties at the lowest loading. On the other hand f-Ge showed improved reinforcing effect by increasing the filler loading. The two-dimensional structure of graphene was an important factor for the higher crystallinity in the electrospun nanofibres.

Influence of 1D and 2D carbon fillers and their functionalisation on crystallisation and thermomechanical properties of injection moulded nylon 6,6 nanocomposites

Carbon nanotubes (CNTs) and graphene were used as reinforcing fillers in nylon 6,6 in order to obtain nanocomposites by using an injection moulding process. The two differently structured nanofillers were used in their pristine or reduced form, after oxidation treatment and after amino functionalisation. Three low nanofiller contents were employed. Crystallisation behaviour and perfection of nylon 6,6 crystals were determined by differential scanning calorimetry and wide angle X-ray diffraction, respectively. Crystallinity was slightly enhanced in most samples as the content of the nanofillers was increased. The dimensionality of the materials was found to provide different interfaces and therefore different features in the nylon 6,6 crystal growth resulting in improved crystal perfection. Dynamical, mechanical analysis showed the maximum increases provided by the two nanostructures correspond to the addition of 0.1 wt.% amino functionalised CNTs, enhancing in 30% the storage modulus and the incorporation of 0.5 wt.% of graphene oxide caused an increase of 44% in this property. The latter also provided better thermal stability when compared to pure nylon 6,6 under inert conditions. The superior properties of graphene nanocomposites were attributed to the larger surface area of the two-dimensional graphene compared to the one-dimensional CNTs.