Recycling ground tire rubber (GTR) scraps as high‐impact filler of in situ produced polyketone matrix

A sustainable procedure for recycling powdered rubber coming from scrap tires (ground tire rubber [GTR]) is proposed as based on the dispersion in polyketone (PK) matrix, obtained in situ by CO/ethylene copolymerization. Three types of catalysts are used operative in solvents of different polarities. The catalyst productivity and the hybrids morphology are evaluated and optimized to final composites features. The obtained products are characterized by scanning electron microscopy, atomic force microscopy, and solvent extractions in order to investigate the occurrence and the extent of interactions between PK macromolecular chains and the GTR components; and their effects on the final properties were tested by differential scanning calorimetry, thermogravimetric analysis, and rheological measurements. For comparison purpose, a composite with GTR included into the matrix through blending is prepared. The results evidenced the key role exerted by the catalyst that, when operative in apolar solvent (able to swell the rubber phase), provides composites with good interfacial adhesion and breaking up of the particles with beneficial effects on final properties particularly thermal features and processability. Copyright © 2014 John Wiley & Sons, Ltd.     

Understanding the Effects of Crosslinking and Reinforcement Agents on the Performance and Durability of Biopolymer Films for Cultural Heritage Protection

In the last two decades, the naturally occurring polysaccharides, such as chitosan and pectin, have gained great attention having potential applications in different sectors, from biomedical to new generation packaging. Currently, the chitosan and pectic have been proposed as suitable materials also for the formulation of films and coatings for cultural heritage protection, as well as packaging films. Therefore, the formulation of biopolymer films, considering only naturally occurring polymers and additives, is a current challenging trend. This work reports on the formulation of chitosan (CS), pectin (PC), and chitosan:pectin (CS:PC) films, also containing natural crosslinking and reinforcement agents, such as citric acid (CA) and halloysite nanotubes (HNT), through the solvent casting technique. The produced films are characterized through water contact angle measurements, infrared and UV–visible spectroscopy and tensile test, while the durability of the CS:PC films is evaluated subjecting the film to accelerated UVB exposure and monitoring the photo-oxidation degradation in time though infrared spectroscopy. All obtained results suggest that both crosslinking and reinforcement agents have beneficial effects on the wettability, rigidity, and photo-oxidation resistance of biopolymer films. Therefore, these biopolymer films, also containing naturally occurring additives, have good properties and performance and they are suitable as coverage films for cultural heritage protection.     

High‐performance laminates through chemical welding of thin liquid crystalline polymer films

A systematic study of the welding (healing) process of polymers with different chemical compositions, structures and properties was carried out. It was shown that welding can be due to a number of physical and/or chemical factors. Diffusion alone led to a relatively weak welding under the selected conditions. A jump was observed in the temperature dependence of the shear stress of polyimides. The abrupt increase in the activation energy of welding can be explained by assuming a change in the nature of the created bonds from physical to chemical ones. For the first time the chemical reactions taking place at the contacting surfaces were directly experimentally proved by electron spin resonance. In some cases, for the first time, the healing process was carried out at temperatures below the glass transition temperature. In this way, the contribution of the diffusion process to the healing may be distinguished from that of the chemical reactions. On the basis of a poly(ethylene terephthalate) copolyester containing 60 mol% p‐hydroxybenzoic acid thin liquid crystalline films (160 µm thick) are obtained by melting the polymer at 300°C and chilling at 0°C. The undrawn films have a high degree of orientation as shown by X‐ray measurements. These films have excellent mechanical properties because of the molecular orientation. In order to avoid losses in the mechanical strength due to increase in their thickness, laminates were prepared using thin liquid crystalline films. Lamination was carried out by annealing under pressure at 170°C for 6 hr, resulting in samples with excellent mechanical properties regardless of their thickness. A method is proposed that makes it possible to combine the unique mechanical properties of thin films of liquid crystalline polymers with a lamination process in order to obtain thick and very strong materials. Copyright © 1999 John Wiley & Sons, Ltd.     

On the interlayer spacing collapse of Cloisite 30B organoclay

When used as a nanofiller for the preparation of polymer/clay nanocomposites (PCNs), Cloisite^® 30B (30B) often undergoes a d-spacing collapse, as demonstrated by a shift to wider angles of the XRD basal reflection. Such collapse has been variously attributed to organoclay contamination or, more often, to thermal degradation of the organic modifier with expulsion of the volatile products from the galleries. In this work, several PCNs loaded with 30B have been prepared by melt compounding, using different polymer matrices, and have subsequently been subjected to dissolution in appropriate solvents followed by precipitation in excess non-solvent and room temperature drying. An XRD analysis of the products has shown that this treatment makes the 30B basal plane reflection go back to the original angular position. These experiments indicate that, contrary to the situation prevailing when 30B is subjected to thermal treatments at temperatures well above the onset of degradation (∼180 °C), the d-spacing collapse observed after melt compounding 30B with polymer matrices at moderate temperatures is in fact a reversible phenomenon probably due to rearrangement of the alkyl chains of the clay modifier in a disposition intermediate between bilayer and monolayer.     

Photochemical stabilization of linear low-density polyethylene/clay nanocomposites: Towards durable nanocomposites

This article reports a study of the chemical modifications of LLDPE/nanoblend nanocomposites exposed to UV light in conditions of artificially accelerated ageing and natural weathering. Analysis by infrared spectroscopy of the chemical modifications produced by photoageing shows that the presence of an organo-clay leads to the decrease of the oxidation induction time of the polymer (LLDPE), which results in lower durability of the nanocomposites. Protection against photooxidation was tested with different kinds of UV stabilizers and with a metal deactivator. It is shown that the metal deactivator is very efficient in stabilizing the nanocomposite since it totally cancels the prodegradant effect of the organo-clay. This confirms the role played by iron impurities in natural clays. The use of a metal deactivator offers a new insight into the stabilization strategy for nanocomposites.     

Kinetic method for the study of xylan hydrolysis by xylan hydrolases

Summary The Somogyi-Nelson colorimetric method was used in a new manner more suitable for evaluating the kinetics of the enzyme hydrolysis of xylan catalyzed by xylan hydrolases. The values of the Michaelis parameters (Km=5.56 g l^–1 andV=2.94 · 10^–5 M s^–1) were determined.

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Eine kinetische Methode zur Untersuchung der Hydrolyse von Xylan durch Xylan-Hydrolase

Zusammenfassung Die kolorimetrische Methode nach Somogyi-Nelson wurde nach einem neuen Verfahren zur Verfolgung der Kinetik der hydrolytischen Spaltung von Xylan, katalysiert durch Xylan-Hydrolasen vonAspergillus oryzae, angewandt. Es wurden die Michaelis-Parameter (Km=5.56 g l^–1 undV=2.94 · 10^–5 M s^–1) bestimmt.

     

Re‐Gradation of Photo‐Oxidized Post‐Consumer Greenhouse Films

Summary: The degradation undergone by the polymers during their use and because of the thermo‐mechanical degradation undergone during the reprocessing operations provokes, among other effects, the decrease of the molecular weight. The change of the molecular architecture is responsible for the deterioration of all the properties. In order to restore the properties of post‐consumer recycled plastics, some rebuilding of the molecular structure is necessary. In this work, photo‐oxidized films for greenhouses were reprocessed in presence of additives able to react with the polyethylene in order to form branching and cross‐linking, improving the properties of these post‐consumer plastic.

Pressure as a function of time in the mini twin‐screw extruder, processing speed 70 rpm.     

Effect of different matrices and nanofillers on the rheological behavior of polymer‐clay nanocomposites

In this work, a comprehensive study of the rheological behavior under shear and isothermal and nonisothermal elongational flow of low density polyethylene (LDPE) and ethylene‐vinyl acetate copolymer (EVA) based nanocomposites was reported to evaluate their “filmability”, that is, the ability of these material to be processed for film forming applications. The influence of two different kinds of organoclay – namely Cloisite 15A and Cloisite 30B – and their concentration was evaluated. The presence of filler clearly affects the rheological behavior in oscillatory state of polyolefin‐based nanocomposites but the increase of complex viscosity and the shear thinning are not dramatic. A larger strain‐hardening effect in isothermal elongational flow is shown by the nanocomposites compared to that of the pure matrix, particularly for EVA based nanocomposites. The melt strength measured under nonisothermal elongational flow increases in the presence of the nanofiller, while the drawability is only slightly lower than that measured for the neat matrix. Moreover, the rheological behavior under nonisothermal elongational flow of EVA‐based nanocomposites is similar for both nanoclays used. Differently, LDPE‐based nanocomposites show a strong dependence on the type of organoclay. Finally, the mechanical properties of the materials were measured by tensile tests. They revealed that the presence of the filler provokes, in all the cases, an increase of the rigidity. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 344–355, 2010     

Photooxidative behaviour of polyethylene/polyamide-6 blends

The photochemical behaviour of several polyethylene/polyamide-6 blends was studied under conditions of artificial accelerated weathering. Particular attention was paid to five different compositions ranging from pure polyethylene to pure polyamide with blends of PE/PA-6 of various compositions: 75/25, 50/50 and 25/75 wt/wt%. Analysis by infrared spectroscopy of the chemical modifications caused by photooxidation showed that exposing the polyethylene/polyamide-6 blends to UV-light irradiation led to the formation of oxidation photoproducts in both polymer phases. In agreement with both the mechanical and spectroscopic analyses, the photooxidation rate of the blends was observed to be much higher than that of the homopolymers. The results given in this paper suggest that photooxidation of the PE/PA blends starts in the polyamide phase and that the subsequent photooxidation of the polyethylene phase may be initiated by the radicals coming from the oxidation of PA.