Effect of Processing and Orientation on Structural and Mechanical Properties of Polypropylene Products

Polypropylene (PP) represents one of the most worldwide used plastics with a large variety of products and applications. As usual for semicrystalline polymers, the properties of PP products strictly depend on the processing (fiber spinning, film extrusion, injection, etc.), where orientation and crystallization phenomena are involved. The object of this communication is the mechanical and structural characterization of oriented products from iPP homopolymers, i.e., injection molded dumbbell specimens (IM), lab-scale single fibers and commercial bulk continuous filament (BCF), woven non-woven fabrics (WNW) by using differential scanning calorimetry (DSC), dynamical mechanical thermal analysis (DMTA), tensile measurements, and X-ray diffraction (XRD) analysis. In particular, a recent methodology to analyze diffraction images of oriented polymers to obtain crystal structure, texture, and microstructural information is presented. The higher the orientation, the higher the mechanical properties and the sharper the texture, as revealed by a quantitative texture analysis that has been also developed and successfully applied to oriented PP nanocomposites

Surface functionalization with phosphazene substrates, Part IV: Silica and Si(100) surface functionalization using cyclophosphazenes partially substituted with trialkoxysilane derivatives and PEG-750 monomethylether, 2,2,3,3-tetrafluoropropanol and 4-hydroxyazobenzene

This paper deals with the possibility of functionalizing the surface of silicon-based materials by exploiting cyclophosphazenes containing suitable substituent groups. Thus, phosphazene trimers were prepared, containing about 50% of the reactive sites substituted by γ-aminopropyltriethoxy silane (APTES), while the residual positions in the cycle contain poly(ethylene glycol) monomethylether (MW approx. 750; PEG-750-ME), tetrafluoropropanol (TFP) and 4-hydroxyazobenzene (AzB). Using these novel materials we succeeded in surface functionalizing SiO2 beads in the coating of silicon wafers or sodalime slides and in the preparation of cyclophosphazene-based monoliths in the presence of hydrolyzed TEOS by sol–gel technique. The whole series of products has been characterized by standard spectroscopic (IR, UV-Vis, 1H-, 13C-, 29Si- and 31P-NMR, both in solution and in solid state) and thermal (DSC and DMTA) techniques. This approach to the surface functionalization of silicon-based materials containing carefully ..

Synergistic effects of metal hydroxides and fumed nanosilica as fire retardants for polyethylene

International audienceThis work aims to study the synergistic effect of aluminum/magnesium hydroxide microfillers and organomodified fumed silica nanoparticles as flame retar-dants (FRs) for linear low-density polyethylene (LLDPE), and to select the best composition to produce a fire-resistant polyethylene-based single-polymer composite. The fillers were added to LLDPE at different concentrations , and the prepared composites were characterized to investigate the individual and combined effects of the fillers on the thermo-oxidation resistance and the fire performance , as well as the microstructural, physical, thermal and mechanical properties. Both filler types were homogeneously distributed in the matrix, with the formation of a network of silica nanoparticles at elevated load-ings. Melt flow index (MFI) tests revealed that the fluid-ity of the material was not considerably impaired upon metal hydroxide introduction, while a heavy reduction of the MFI was detected for silica contents higher than 5 wt%. FRs introduction promoted a noticeable enhancement of the thermo-oxidative stability of the materials, as shown by thermogravimetric analysis (TGA) and onset oxidation temperature (OOT) tests, and superior thermal properties were measured on the samples combining micro-and nanofillers, thus evidencing synergistic effects. Tensile tests showed that the stiffening effect due to a high content of metal hydroxide microparticles was accompanied by a decrease in the strain at break, but nanosilica at low concentration contributed to preserve the ultimate mechanical properties of the neat polymer. The fire performance of the samples with optimized compositions, evaluated through limiting oxygen index (LOI) and cone calorimetry tests, was strongly enhanced with respect to that of the neat LLDPE, and also these tests highlighted the synergistic effect between micro-and nanofillers, as well as an interesting correlation between fire parameters and viscosity

Monitoring of Morphology and Properties During Preparation of PCL/PLA Microfibrillar Composites With Organophilic Montmorillonite

Biodegradable microfibrillar composites PCL/PLA/C15, where PCL is poly(ε-caprolactone), PLA is poly(lactic acid), and C15 is organophilic montmorillonite, have been prepared. Microindentation hardness testing was employed in monitoring the gradual improvement of PCL stiffness due to PLA addition, C15 addition, flow-induced orientation, and changing crystallinity throughout the whole preparation process. Neat PCL after extrusion and injection molding was quite soft, but the stiffness of the material increased after melt-blending with 20 wt.% of PLA, after the addition of 2 wt.% of C15, and after the preparation of the final microfibrillar composite. The indentation modulus and indentation hardness of all intermediate products and the final PCL/PLA/C15 microfibrillar composite were associated not only with the composition and morphology but also with the crystallinity of both components. The modulus of the final PCL/PLA/C15 composite was almost two times higher in comparison with the original PCL matrix

Phase Structure, Compatibility, and Toughness of PLA/PCL Blends: A Review

Results of the studies dealing with the toughness of polylactic acid/polycaprolactone (PLA/PCL) blends are analyzed with respect to the PCL particle size, PLA matrix crystallinity, and presence of a compatibilizer. It is shown that a high toughness or even »super-toughness« of PLA/PCL blends without a compatibilizer can be achieved for blends with the proper size of PCL particles. Nevertheless, the window for obtaining the super-tough PLA/PCL blends is quite narrow, as the final impact strength is very sensitive to multiple parameters: namely the blend composition, PLA matrix crystallinity, and PCL particle size. Available literature data suggest that the optimal composition for PLA/PCL blends is around 80/20 (w/w). The PLA/PCL(80/20) blends keep high stiffness of PLA matrix and the concentration of PCL particles is sufficient to achieve high toughness. The PLA/PCL(80/20) blends with low-crystallinity PLA matrix (below ca 10 %) exhibit the highest toughness for bigger PCL particles (weight average diameter above 1 μm), while the blends with high-crystallinity PLA matrix (above ca 30 %) exhibit the highest toughness for smaller PCL particles (weight average diameter below 0.5 μm). The addition of a compatibilizer may improve the toughness only on condition that it helps to achieve a suitable particle size. The toughness of both non-compatibilized and compatibilized PLA/PCL blends with optimized morphology can be more than 15 times higher in comparison with neat PLA

Thermal Analysis and Kinetic Modeling of Pyrolysis and Oxidation of Hydrochars

This study examines the kinetics of pyrolysis and oxidation of hydrochars through thermal analysis. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) techniques were used to investigate the decomposition profiles and develop two distributed activation energy models (DAEM) of hydrochars derived from the hydrothermal carbonization of grape seeds produced at different temperatures (180, 220, and 250 °C). Data were collected at 1, 3, and 10 °C/min between 30 and 700 °C. TGA data highlighted a decomposition profile similar to that of the raw biomass for hydrochars obtained at 180 and 220 °C (with a clear distinction between oil, cellulosic, hemicellulosic, and lignin-like compounds), while presenting a more stable profile for the 250 °C hydrochar. DSC showed a certain exothermic behavior during pyrolysis of hydrochars, an aspect also investigated through thermodynamic simulations in Aspen Plus. Regarding the DAEM, according to a Gaussian model, the severity of the treatment slightly affects kinetic parameters, with average activation energies between 193 and 220 kJ/mol. Meanwhile, the Miura–Maki model highlights the distributions of the activation energy and the pre-exponential factor during the decomposition

Effects of the Nanofillers on Physical Properties of Acrylonitrile-Butadiene-Styrene Nanocomposites: Comparison of Graphene Nanoplatelets and Multiwall Carbon Nanotubes

The effects of carbonaceous nanoparticles, such as graphene (GNP) and multiwall carbon nanotube (CNT) on the mechanical and electrical properties of acrylonitrile–butadiene–styrene (ABS) nanocomposites have been investigated. Samples with various filler loadings were produced by solvent free process. Composites ABS/GNP showed higher stiffness, better creep stability and processability, but slightly lower tensile strength and electrical properties (low conductivity) when compared with ABS/CNT nanocomposites. Tensile modulus, tensile strength and creep stability of the nanocomposite, with 6 wt % of GNP, were increased by 47%, 1% and 42%, respectively, while analogous ABS/CNT nanocomposite showed respective values of 23%, 12% and 20%. The electrical percolation threshold was achieved at 7.3 wt % for GNP and 0.9 wt % for CNT. The peculiar behaviour of conductive CNT nanocomposites was also evidenced by the observation of the Joule’s effect after application of voltages of 12 and 24 V. Moreover, comparative parameters encompassing stiffness, melt flow and resistivity were proposed for a comprehensive evaluation of the effects of the fillers

Filaments Production and Fused Deposition Modelling of ABS/Carbon Nanotubes Composites

Composite acrylonitrile–butadiene–styrene (ABS)/carbon nanotubes (CNT) filaments at 1, 2, 4, 6 and 8 wt %, suitable for fused deposition modelling (FDM) were obtained by using a completely solvent-free process based on direct melt compounding and extrusion. The optimal CNT content in the filaments for FDM was found to be 6 wt %; for this composite, a detailed investigation of the thermal, mechanical and electrical properties was performed. Presence of CNT in ABS filaments and 3D-printed parts resulted in a significant enhancement of the tensile modulus and strength, accompanied by a reduction of the elongation at break. As documented by dynamic mechanical thermal analysis, the stiffening effect of CNTs in ABS is particularly pronounced at high temperatures. Besides, the presence of CNT in 3D-printed parts accounts for better creep and thermal dimensional stabilities of 3D-printed parts, accompanied by a reduction of the coefficient of thermal expansion). 3D-printed nanocomposite samples with 6 wt % of CNT exhibited a good electrical conductivity, even if lower than pristine composite filaments

Role of Surface-Treated Silica Nanoparticles on the Thermo-Mechanical Behavior of Poly(Lactide)

Surface-treated fumed silica nanoparticles were added at various concentrations (from 1 to 24 vol%) to a commercial poly(lactide) or poly(lactic acid) (PLA) matrix specifically designed for packaging applications. Thermo-mechanical behavior of the resulting nanocomposites was investigated. Field Emission Scanning Electron Microscopy (FESEM) micrographs revealed how a homogeneous nanofiller dispersion was obtained even at elevated filler amounts, with a positive influence of the thermal degradation stability of the materials. Modelization of Differential Scanning Calorimetry (DSC) curves through the Avrami–Ozawa model demonstrated that fumed silica nanoparticles did not substantially affect the crystallization behavior of the material. On the other hand, nanosilica addition was responsible for significant improvements of the storage modulus (E′) above the glass transition temperature and of the Vicat grade. Multifrequency DMTA tests showed that the stabilizing effect due to nanosilica introduction could be effective over the whole range of testing frequencies. Sumita model was used to evaluate the level of filler dispersion. The obtained results demonstrated the potential of functionalized silica nanoparticles in improving the thermo-mechanical stability of biodegradable matrices for packaging applications, especially at elevated service temperatures