Carlos A. Avila-Orta

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.

DETERMINATION OF CRYSTALLINE LAMELLAR THICKNESS IN POLY(ETHYLENE TEREPHTHALATE) USING SMALL-ANGLE X-RAY SCATTERING AND TRANSMISSION ELECTRON MICROSCOPY*

The crystalline lamellar thickness of semicrystalline poly(ethylene terephthalate) (PET) was evaluated using small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM) techniques. Both SAXS onedimensional (1D) correlation function and interface distribution function analyses were utilized to determine the crystalline lamellar thickness. The two-dimensional fast Fourier transformation (2D-FFT) of the TEM image and the Gaussian-like lamellar thickness distribution determined from the TEM image were also performed. Results indicate that the larger value of the two correlation lengths calculated from the SAXS analysis should be assigned to the crystalline lamellar thickness in PET. Discussions and comparison among different methods for characterizing the lamellar thickness of semicrystalline polymers are made. *Dedicated to Prof. Francisco J. Baltá Calleja on the occasion of his 65th birthday.

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.

Synthesis of copper nanoparticles coated with nitrogen ligands

The synthesis of copper nanoparticles was studied by wet chemical methods using copper sulfate pentahydrate (CuSO4ċ5H2O) and nitrogen ligands allylamine (AAm) and polyallylamine (PAAm) as stabilizers. The results suggest that the use of these ligands leads to the exclusive formation of metallic copper nanoparticles (Cu-NPs). The use of partially crosslinked polyallylamine (PAAmc) leads to nanoparticles (NPs) with low yields and high coating content, while linear PAAm leads to NPs with high yields and low coating content. The chemical composition of the particles was determined by XRD and average particle diameters were determined by the Debye-Scherrer equation. TGA analysis provided evidence of the content and thermal stability of the coating on the nanoparticles and PAAm. The morphology, particle size distribution, and presence of PAAm coating were observed through TEM. The use of AAm in the synthesis of NPs could be a good alternative to reduce costs. By using TGA, TEM, and DSC techniques, it was determined that synthesized NPs with AAm presented a coating with similar characteristics to NPs with PAAm, suggesting that AAm underwent polymerization during the synthesis.

Synthesis of copper nanoparticles using mixture of allylamine and polyallylamine

Copper nanoparticles (Cu-NPs) with sizes lower than 31 nm were prepared by wet chemical reduction using copper sulfate solution, hydrazine, and mixture of allylamine (AAm) and polyallylamine (PAAm) as stabilizing agents. The use of AAm/PAAm mixture leads to the formation of Cu and CuO nanoparticles. The resulting nanostructures were characterized by XRD, TGA, and TEM. The average particle diameters were determined by the Debye-Scherrer equation. Analysis by TGA, TEM, GS-MS, and HNMR reveals that synthesized NPs with AAm presented a coating with similar characteristics to NPs with PAAm, suggesting that AAm underwent polymerization during the synthesis. The synthesis of NPs using AAm could be a good alternative to reduce production costs.

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.

Ultrasound-Assist Extrusion Methods for the Fabrication of Polymer Nanocomposites Based on Polypropylene/Multi-Wall Carbon Nanotubes

Isotactic polypropylenes (iPP) with different melt flow indexes (MFI) were used to fabricate nanocomposites (NCs) with 10 wt % loadings of multi-wall carbon nanotubes (MWCNTs) using ultrasound-assisted extrusion methods to determine their effect on the morphology, melt flow, and electrical properties of the NCs. Three different types of iPPs were used with MFIs of 2.5, 34 and 1200 g/10 min. Four different NC fabrication methods based on melt extrusion were used. In the first method melt extrusion fabrication without ultrasound assistance was used. In the second and third methods, an ultrasound probe attached to a hot chamber located at the exit of the die was used to subject the sample to fixed frequency and variable frequency, respectively. The fourth method is similar to the first method, with the difference being that the carbon nanotubes were treated in a fluidized air-bed with an ultrasound probe before being used in the fabrication of the NCs with no ultrasound assistance during extrusion. The samples were characterized by MFI, Optical microscopy (OM), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), electrical surface resistivity, and electric charge. MFI decreases in all cases with addition of MWCNTs with the largest decrease observed for samples with the highest MFI. The surface resistivity, which ranged from 1013 to 105 Ω/sq, and electric charge, were observed to depend on the ultrasound-assisted fabrication method as well as on the melt flow index of the iPP. A relationship between agglomerate size and area ratio with electric charge was found. Several trends in the overall data were identified and are discussed in terms of MFI and the different fabrication methods.

Toward Greener Chemistry Methods for Preparation of Hybrid Polymer Materials Based on Carbon Nanotubes

Recent technological advances and the need for materials with new functionalities and bet‐ ter performance have generated an enormous demand for novel materials. Nanostructures such as carbon nanotubes (CNTs) possess outstanding mechanical, electrical, thermal and chemical properties which make them ideal for a wide variety of current or future applica‐ tions [1], especially for the preparation of multifunctional hybrid polymer materials.

Metamaterial Behavior of Polymer Nanocomposites Based on Polypropylene/Multi-Walled Carbon Nanotubes Fabricated by Means of Ultrasound-Assisted Extrusion

Metamaterial behavior of polymer nanocomposites (NCs) based on isotactic polypropylene (iPP) and multi-walled carbon nanotubes (MWCNTs) was investigated based on the observation of a negative dielectric constant (ε′). It is demonstrated that as the dielectric constant switches from negative to positive, the plasma frequency (ωp) depends strongly on the ultrasound-assisted fabrication method, as well as on the melt flow index of the iPP. NCs were fabricated using ultrasound-assisted extrusion methods with 10 wt % loadings of MWCNTs in iPPs with different melt flow indices (MFI). AC electrical conductivity (σ(AC)) as a function of frequency was determined to complement the electrical classification of the NCs, which were previously designated as insulating (I), static-dissipative (SD), and conductive (C) materials. It was found that the SD and C materials can also be classified as metamaterials (M). This type of behavior emerges from the negative dielectric constant observed at low frequencies although, at certain frequencies, the dielectric constant becomes positive. Our method of fabrication allows for the preparation of metamaterials with tunable ωp. iPP pure samples show only positive dielectric constants. Electrical conductivity increases in all cases with the addition of MWCNTs with the largest increases observed for samples with the highest MFI. A relationship between MFI and the fabrication method, with respect to electrical properties, is reported.

Surface Modification of nTiO2/Ag Hybrid Nanoparticles Using Microwave-Assisted Polymerization in the Presence of Bis(2-hydroxyethyl) Terephthalate

Titanium dioxide doped silver (nTiO2/Ag) nanoparticles were surface-modified by microwave-assisted polymerization of 2-bis-(hydroxyethyl) terephthalate (BHET). The modified and unmodified nanoparticles were analyzed by FTIR, XRD, TGA, and TEM. A thin layer of grafted PET on the surface of the nanoparticles was observed and quantified by TGA giving a value of 40źwt-%. XRD and electron diffraction analyses showed traces of AgO2 after the modification. The bactericide activity of modified and unmodified nanoparticles was evaluated; the presence of the thin layer of grafted-PET on the nTiO2/Ag did not change significantly the bactericide activity, showing an excellent performance similar to unmodified nanoparticles.