Insights on the Molecular Behavior of Polypropylene in the Process of Ultrasonic Injection Molding.

Product miniaturization is a constant trend in industries that demand ever-smaller products that can be mass produced while maintaining high precision dimensions in the final pieces. Ultrasonic micro injection molding (UMIM) technology has emerged as a polymer processing technique capable of achieving the mass production of polymeric parts with micro-features, while still assuring replicability, repeatability, and high precision, contrary to the capabilities of conventional processing technologies of polymers. In this study, it is shown that the variation of parameters during the UMIM process, such as the amplitude of the ultrasound waves and the processing time, lead to significant modification on the molecular structure of the polymer. The variation of both the amplitude and processing time contribute to chain scission; however, the processing time is a more relevant factor for this effect as it is capable of achieving a greater chain scission in different areas of the same specimen. Further, the presence of polymorphism within the samples produced by UMIM is demonstrated. Similarly to conventional processes, the UMIM technique leads to some degree of chain orientation, despite the fact that it is carried out in a relatively small time and space. The results presented here aim to contribute to the optimization of the use of the UMIM process for the manufacture of polymeric micro parts.

Antimicrobial Property of Polypropylene Composites and Functionalized Copper Nanoparticles.

Copper nanoparticles (CuNPs) functionalized with polyethyleneimine (PEI) and 4-aminobutyric acid (GABA) were used to obtain composites with isotactic polypropylene (iPP). The iPP/CuNPs composites were prepared at copper concentrations of 0.25-5.0 wt % by melt mixing, no evidence of oxidation of the CuNP was observed. Furthermore, the release of copper ions from iPP/CuNPs composites in an aqueous medium was studied. The release of cupric ions was higher in the composites with 2.5 and 5.0 wt %. These composites showed excellent antibacterial activity (AA) toward Pseudomona aeruginosa (P. aeruginosa) and Staphylococcus aureus (S. aureus). The incorporation of CuNP into the iPP polymeric matrix slightly decreased the thermal stability of the composite material but improved the crystallinity and the storage modulus. This evidence suggests that CuNPs could work as nucleating agents in the iPP crystallization process. The iPP/CuNPs composites presented better AA properties compared to similar composites reported previously. This behavior indicates that the new materials have great potential to be used in various applications that can be explored in the future.

Ultrasound-Assisted Surface Modification of MWCNT Using Organic Acids.

In the present work, multiple-wall carbon nanotubes (MWCNTs) were surface modified in an environmentally friendly way, using low-frequency ultrasonic energy. This type of modification was carried-out using two different types of organic acids, citric acid (CA) and oxalic acid (OA). The modification of the MWCNTs was confirmed by Fourier-transform infrared spectroscopy (FTIR), where functional groups such as OH, C=O, O-C=O and COOH were detected. By means of Raman spectroscopy, an increase in carbon surface defects was found. On the other hand, using X-ray photoelectron spectroscopy (XPS), oxidation was evidenced on the surface of the modified MWCNT. In both Raman spectroscopy and XPS, the results indicate a greater modification when CA is used, possibly due to the fact that CA has a larger number of functional groups. MWCNT-CA showed good dispersion in methanol, while MWCNT-OA showed good stability in methanol and ethanol. Finally, a 20% removal of creatinine efficiency improvement was found with respect to the unmodified MWCNTs, while no improvement was found in the case of urea and uric acid.

Synthesis of Nylon 6/Modified Carbon Black Nanocomposites for Application in Uric Acid Adsorption.

High uric acid levels cause different clinic conditions. One of them is hyperuricemia, which leads to kidney damage. A solution for eliminating uric acid in the blood is by hemodialysis, which is performed using nanocomposite membranes. In this work, Nylon 6 nanocomposites were synthesized with modified carbon black (MCB), which were considered candidate materials for hemodialysis membranes. The modification of carbon black was made with citric acid using the variable-frequency ultrasound method. The new MCB was characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X-ray diffraction (XRD), transmission electron microscopy (TEM), and dispersion tests. Nylon 6/MCB nanocomposites were processed using the ultrasound-assisted melt-extrusion method to improve the dispersion procedure of the nanoparticles. The Nylon 6/MCB nanocomposites were characterized by FTIR, TGA, and differential scanning calorimetry (DSC). These were assessed for the absorption of toxins and hemocompatibility. MBC and nanocomposites showed excellent uric acid removal (78-82%) and hemocompatibility (1.6-1.8%). These results suggest that Nylon 6/MCB nanocomposites with low loading percentages can be used on a large scale without compatibility problems with blood.

Pigmentation and Degradative Activity of TiO2 on Polyethylene Films Using Masterbatches Fabricated Using Variable-Frequency Ultrasound-Assisted Melt-Extrusion.

Ultrasound-assisted melt-extrusion method (USME) is a high-quality process used to produce polymeric compounds with an adequate homogeneous dispersion. This study evaluates white-color films of linear low-density polyethylene (LLDPE) prepared using TiO2 masterbatch obtained by ultrasound-assisted melt-extrusion at variable frequencies (USME-VF). LLDPE with three different melt-flow indices (2, 20 and 50 g/10 min) were used as the polymer matrix. The films were obtained from the dilution of masterbatches of LLDPE (melt-flow index = 2) at a concentration of 7 wt% TiO2. The morphology, pigmentation, TiO2 reactivity, and the mechanical stability of the films were assessed. The masterbatch compounds were evaluated by melt-flow index (MFI) and scanning electron microscopy (SEM). The contrast ratio, yellowness index and mechanical properties of films were also measured. The properties of whiteness and elongation at break improved in the films prepared using masterbatches with higher dispersion. Though the reactivity of the TiO2 particles increased during accelerated aging, it did not affect the elongation to rupture. The yellowness index was moderately affected in films that included TiO2 particles processed using USME-VF.

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.

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.

Reversible de-intercalation and intercalation induced by polymer crystallization and melting in a poly(ethylene oxide)/organoclay nanocomposite.

Semicrystalline polymer/layered silicate nanocomposites were prepared by solution blending of a low molecular weight poly(ethylene oxide) (PEO) with an organically modified montmorillonite, Cloisite 10A (C10A). The intercalation morphology was studied by temperature-dependent synchrotron wide-angle X-ray diffraction (WAXD). Unlike PEO homopolymers, significant secondary crystallization was observed in the PEO/C10A nanocomposites. Reversible de-intercalation and intercalation processes were detected during secondary crystallization and subsequent melting of secondary crystals. On the basis of two-dimensional WAXD results on oriented samples, an interphase layer between the silicate primary particles and PEO lamellar crystals was proposed. Secondary PEO crystallization in the interphase regions was inferred to be the primary driving force for polymer chains to diffuse out of the silicate gallery. This study provided a useful method to investigate polymer diffusion in nanoconfined spaces, which can be controlled by PEO secondary crystallization and melting outside the silicate gallery.

Unexpected shish-kebab structure in a sheared polyethylene melt.

Scanning electron micrographs of a solvent-extracted sheared polyethylene (PE) blend revealed, for the first time, an unexpected shish-kebab structure with multiple shish. The blend contained 2 wt % of crystallizing ultrahigh molecular weight polyethylene (UHMWPE) and 98 wt % of noncrystallizing PE matrix. The formation of multiple shish was attributed to the coil-stretch transition occurring in sections of UHMWPE chains. Synchrotron x-ray data provided clear evidence of the hypothesis that multiple shish originate from stretched chain sections and kebabs originate from coiled chain sections, following a diffusion-controlled crystallization process.