Polymers

This paper describes the processing conditions needed to produce low density nanocellular polymers based on polymethylmethacrylate (PMMA) with relative densities between 0.45 and 0.25, cell sizes between 200 and 250 nm and cell densities higher than 1014 cells/cm3. To produce these nanocellular polymers, the foaming parameters of the gas dissolution foaming technique using CO2 as blowing agent have been optimized. Taking into account previous works, the amount of CO2 uptake was maintained constant (31% by weight) for all the materials. Foaming parameters were modified between 40 °C and 110 °C for the foaming temperature and from 1 to 5 min for the foaming time. Foaming temperatures in the range of 80 to 100 °C and foaming times of 2 min allow for production of nanocellular polymers with relative densities as low as 0.25. Cellular structure has been studied in-depth to obtain the processing-cellular structure relationship. In addition, it has been proved that the glass transition temperature depends on the cellular structure. This effect is associated with a confinement of the polymer in the cell walls, and is one of the key reasons for the improved properties of nanocellular polymers.

The waste rubber vulcanizate, on account of its stable, cross-linked and three-dimensional structural arrangement, is difficult to biodegrade. Thus, the ever-increasing bulk of worn-out tires is a serious environmental issue and its safe disposal is still a challenging task reported widely by the scientific community. The rubber materials, once they end their useful life, may present difficulties to be reused or recycled. At present, only one tire recycling method is used, which involves grinding and separating steel and fibers from vulcanized rubber, and then using rubber for industrial applications, such as flooring, insulation, footwear. In this paper, a new compound material is presented from a base of reused tire powder (Ground Tire Rubber: GTR) as a mixer and linear low-density polyethylene (LLDPE) as a matrix. The reused tire powder, resulting from grinding industrial processes, is separated by sieving into just one category of particle size (<200 μm) and mixed with the LLDPE in different amounts (0%, 5%, 10%, 20%, 40%, 50% and 70% GTR). Due to the good electrical properties of the LLDPE, this study’s focus is settled on the electrical behavior of the obtained composites. The test of the dielectric behavior is carried out by means of DEA test (Dynamic Electric Analysis), undertaken at a range of temperatures varying from 30 to 120 °C, and with a range of frequencies from 1 to 102, to 3·106 Hz, from which permittivity, conductivity, dielectric constant and electric modulus have been obtained. From these experimental results and their analysis, it can be drawn that the additions of different quantities of GTR to LLDPE could be used as industrial applications, such as universal electrical cable joint, filler for electrical applications or cable tray systems and cable ladder system.

The copper II complex (HLCuCl) carrying 2,4 dinitrophenylhydrazone (L) is synthesized and evaluated as a new photoredox catalyst/photoinitiator in combination with triethylamine (TEA) and iodonium salt (Iod) for the radical polymerization of ethylene glycol diacrylate during exposure to visible light using a photoreactor at 419 nm. The copper complex reactivity with TEA/Iod salt/gold chloride showed a good production and stability of gold nanoparticles. Finally, the high performance of Cu (II) complex for radical photopolymerization incorporating gold nanoparticles is provided. The photochemical mechanisms for the production of initiating radicals are studied using cyclic voltammetry. Polymer nanocomposites containing gold nanoparticles (Au NPs) in situ photogenerated during the irradiation process were prepared. The formation of Au NPs inside the polymer matrix was through UV–Vis and EDS/SEM analyses.

In the current work, a series of black polyimide (PI) films with excellent thermal and dimensional stability at elevated temperatures were successfully developed. For this purpose, two aromatic diamines including 4,4′-iminodianline (NDA) and 2-(4-aminophenyl)-5- aminobenzimidazole (APBI) were copolymerized with pyromellitic dianhydride (PMDA) to afford PIs containing imino groups (–NH–) in the molecular structures. The referenced PI film, PI-ref, was simultaneously prepared from PMDA and 4,4′-oxydianiline (ODA). The introduction of imino groups endowed the PI films with excellent blackness and opaqueness with the optical transmittance lower than 2% at the wavelength of 600 nm at a thickness of 25 μm and lightness (L*) below 10 for the CIE (Commission International Eclairage) Lab optical parameters. Meanwhile, the introduction of rigid benzimidazole units apparently improved the thermal and dimensional stability of the PI films. The PI-d film based on PMDA and mixed diamines (NDA:APBI = 70:30, molar ratio) showed a glass transition temperature (Tg) of 445.5 °C and a coefficient of thermal expansion (CTE) of 8.9 × 10−6/K in the temperature range of 50 to 250 °C, respectively. It is obviously superior to those of the PI-a (PMDA-NDA, Tg = 431.6 °C; CTE = 18.8 × 10−6/K) and PI-ref (PMDA-ODA, Tg = 418.8 °C; CTE: 29.5 × 10−6/K) films.

A series of new organic dyes comprising different amines as electron donors, 2-(6-substituted-anthracen-2-yl)-thiophene as the π-conjugated bridge, and cyanoacrylic acid group as an electron acceptor and anchoring group, have been synthesized. There exists charge transfer transition from arylamine and anthracene to the acceptor in these compounds, as evidenced from the photophysical measurements and the computational results. Under one sun (AM 1.5) illumination, dye-sensitized solar cells (DSSCs) using these dyes as the sensitizers exhibited efficiencies ranging from 1.62% to 2.88%, surpassing that using 9,10-difunctionalized anthracene-based sensitizer.

This work deals with the influence of functionalization degree on the thermogravimetric and rheological behaviour of NCO-functionalized chitosan- and chitin-based oleogels. Chitosan and chitin were functionalized using different proportions of 1,6-hexamethylene diisocyanate (HMDI) and subsequently dispersed in castor oil to promote the chemical reaction between the –NCO group of the modified biopolymer and the –OH group located in the ricinoleic fatty acid chain of castor oil, thus resulting in different oleogels with specific thermogravimetric and rheological characteristics. Biopolymers and oleogels were characterized through Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). Small-amplitude oscillatory shear (SAOS) measurements were performed on the oleogels. Oleogels presented suitable thermal resistance, despite the fact that the inclusion of HMDI moieties in the polymer structure led to a reduction in the onset temperature of thermal degradation. The insertion of low amounts of HMDI in both chitin and chitosan produces a drastic reduction in the values of oleogel viscoelastic functions but, above a critical threshold, they increase with the functionalization degree so that isocyanate functionalization results in a chemical tool to modulate oleogel rheological response. Several NCO-functionalized chitosan- and chitin-based oleogel formulations present suitable thermal resistance and rheological characteristics to be proposed as bio-based alternatives to traditional lubricating greases.