Comparison of the Recycling Behavior of a Polypropylene Sample Aged in Air and in Marine Water.

During the processing and during their lifetime, polymers are subjected to several environmental stresses-thermomechanical, photo-oxidative, etc.-that can strongly modify their chemical and molecular structure and, consequently, their morphology. Reduction of the molecular weight and formation of double bonds and oxygenated groups are the main changes observed as a consequence of the degradation. As a result of these changes, the macroscopic properties are dramatically modified. These changes can have a relevant effect if the post-consumer plastic manufacts are recycled. In this work, a sample of polypropylene subjected to two different degradation histories-photo-oxidation in air and in marine water-is reprocessed two times in a mini twin-screw extruder in the same processing conditions. The effect of the thermomechanical degradation during the reprocessing is different. Indeed, the less severe degraded sample shows a higher degradation level during reprocessing because the shear stress is larger. This means that the thermomechanical degradation kinetics is larger in the less degraded samples. Nevertheless, the final properties of the recycled polymers are different because the properties of the photo-oxidized samples before reprocessing were very different.

A Green Approach for Recycling Compact Discs.

Compact discs (CDs) and digital versatile discs (DVDs) are mainly made by polycarbonate disc, a thin layer of aluminum or silver, a thin layer of a coating and a thin layer of a label of paper or PET. The recycling of these discs is difficult due to the removal of these non-polymeric layers and to our best knowledge, no industrial plants have been resent for their recycling. In this work, we propose a facile way to remove the non-polymeric layers and investigate the effect of the repetitive extrusion process on the processability and on the mechanical properties of the recycled polycarbonate. A few works have been published dealing with both the removal of the non-polymeric layers and the mechanical recycling of the disk of polycarbonate. In our approach, the removal of the non-polymeric layers is easily obtained through a thermo-mechanical treatment in a basic solution by ammonia. This process can be considered green because is made at a low temperature with a small amount of water and a very small amount of ammonia, saving energy and water. The properties of the polycarbonate remain good if the mechanical recycling is made after drying the post-consumer polycarbonate.

Toward the Decarbonization of Plastic: Monopolymer Blend of Virgin and Recycled Bio-Based, Biodegradable Polymer.

Decarbonization of plastics is based on two main pillars: bio-based polymers and recycling. Mechanical recycling of biodegradable polymers could improve the social, economic and environmental impact of the use of these materials. In this regard, the aim of this study was to investigate whether concentrations of the same recycled biopolymer could significantly affect the rheological and mechanical properties of biodegradable monopolymer blends. Monopolymer blends are blends made of the same polymers, virgin and recycled. A sample of commercially available biodegradable blend was reprocessed in a single-screw extruder until two extrusion cycles were completed. These samples were exposed to grinding and melt reprocessed with 75% and 90% of the same virgin polymer. The blends were characterized by tensile tests and rheological tests. The results obtained showed that while multiple extrusions affected the mechanical and rheological properties of the polymer, the concentration of the reprocessed material present in the blends only very slightly affected the properties of the virgin material. In addition, the experimentally observed trends were accurately predicted by the additive model adopted.

Influence of Calcium Carbonate Nanoparticles on the Soil Burial Degradation of Polybutyleneadipate-Co-Butylenetherephthalate Films.

A polybutyleneadipate-co-butylenetherephthalate (PBAT) sample, commercially known as Ecoflex®, was processed via melt extrusion with CaCO3 nanoparticles coated with a hydrophobic coating. Blown films of PBAT and two composites with nanofiller (2% and 5%wt) were prepared and degradation tests in soil at 30 °C up to 180 days were carried out with weight loss measurements. Furthermore, biodegradation test according to ISO 14851 was carried out at 30 °C. The effect of CaCO3 on soil burial degradation was assessed by surface wettability and SEM. ATR-FTIR and XPS analyses highlighted chemical modifications induced by soil degradation. CaCO3 nanoparticles decreased surface wettability and discouraged the disintegration in soil. Interestingly, SEM images after soil degradation highlighted in the nanocomposite films selective zones of disintegration. XPS showed an increasing peak area C 1s ratio of C-O to C=O with degradation time. Moreover, after the soil burial test, carbonyl index determined by ATR-FTIR increased in both nanocomposites. In fact, the addition of CaCO3 leads to a rise in the carbonyl zone due to the presence of the carbonate group. Remarkably, FTIR data after soil degradation showed an enrichment of the aromatic content, a preferential cleavage and erosion of the aliphatic moiety in PBAT films, amplified by the presence of the CaCO3 nanofiller.

The Use of Waste Hazelnut Shells as a Reinforcement in the Development of Green Biocomposites.

Biodegradable Mater-Bi (MB) composites reinforced with hazelnut shell (HS) powder were prepared in a co-rotating twin-screw extruder followed by compression molding and injection molding. The effects of reinforcement on the morphology, static and dynamic mechanical properties, and thermal and rheological properties of MB/HS biocomposites were studied. Rheological tests showed that the incorporation of HS significantly increased the viscosity of composites with non-Newtonian behavior at low frequencies. On the other hand, a scanning electron microscope (SEM) examination revealed poor interfacial adhesion between the matrix and the filler. The thermal property results indicated that HS could act as a nucleating agent to promote the crystallization properties of biocomposites. Furthermore, the experimental results indicated that the addition of HS led to a significant improvement in the thermomechanical stability of the composites. This paper demonstrates that the incorporation of a low-cost waste product, such as hazelnut shells, is a practical way to produce low-cost biocomposites with good properties. With a content of HS of 10%, a remarkable improvement in the elastic modulus and impact strength was observed in both compression and injection-molded samples. With a higher content of HS, however, the processability in injection molding was strongly worsened.

Influence of Different Environments and Temperatures on the Photo-Oxidation Behaviour of the Polypropylene.

The photo-oxidation of polypropylene at two different temperatures and in three different environments-air, distilled water and sea water-has been followed as a function of the irradiation time. The photo-oxidation kinetic is dramatically dependent on the amount of oxygen available for the oxidation reactions and on the temperature. While the photo-oxidation is very fast in air, the degradation is much slower in the two aqueous media. The degradation in sea water is slightly slower than in distilled water. In all cases, the degradation kinetic increases remarkably with the temperature. This behavior has been attributed to the lower oxygen availability for the oxidation reactions of the polymers. The light difference of the degradation kinetic between the two aqueous media depends on the small difference of the oxygen concentration at the test temperatures of 40 and 70 °C. At the latter temperature, the difference between the degradation kinetic in distilled water and sea water is still less important because increasing the temperature decreases the solubility of the oxygen, and it tends to became very similar in both samples of water.

PBAT Based Composites Reinforced with Microcrystalline Cellulose Obtained from Softwood Almond Shells.

This study explores the processability, mechanical, and thermal properties of biocompostable composites based on poly (butylene adipate-co-terephthalate) (PBAT) as polymer matrix and microcrystalline cellulose (MCC) derived from softwood almond (Prunus dulcis) shells (as-MCC) as filler at two different weight concentration, i.e., 10 wt% and 20 wt%. The materials were processed by melt mixing and a commercial MCC (c-MCC) was used as filler comparison. The fibrillar shape of as-MCC particles was found to change the rheological behavior of PBAT, particularly at the highest concentration. The melt mixing processing allowed obtaining a uniform dispersion of both kinds of fillers, slightly reducing the L/D ratio of as-MCC fibers. The as-MCC particles led to a higher increase of the elastic modulus of PBAT if compared to the c-MCC counterparts. Both the MCC fillers caused a drastic reduction of the elongation at break, although it was higher than 120% also at the highest filler concentrations. DSC analysis revealed that both MCC fillers poorly affected the matrix crystallinity, although as-MCC induced a slight PBAT crystallinity increase from 8.8% up to 10.9% for PBAT/as-MCC 20%. Therefore, this work demonstrates the great potential of MCC particles derived from almond shells as filler for biocompostable composites fabrication.

Investigation on the Properties and on the Photo-Oxidation Behaviour of Polypropylene/Fumed Silica Nanocomposites.

This work investigates the effects of very small amounts of fumed silica on the morphology and on the rheological and mechanical behaviour of polypropylene nanocomposites and on their photo-oxidation behaviour. Polypropylene nanocomposites were prepared using a twin-screw corotating extruder with 0, 1 and 2 wt/wt% of SiO2. Morphological, mechanical, thermomechanical and rheological properties were examined. It was found that the viscosity of the matrix is reduced by the presence of the silica nanoparticles, suggesting a poor adhesion between the two phases and probably some lubricating effect. On the contrary, the mechanical and, in particular, the thermomechanical properties of the matrix are considerably improved by the presence of the silica. In particular, elastic modulus and tensile strength increases remarkably, and this effect becomes more and more remarkable with an increasing temperature. As for the photo-oxidation behaviour, the presence of silica improves the photostability of the polypropylene matrix. This effect has been attributed to both the barrier to the oxygen and to the absorbance of the UV radiation from the silica nanoparticles. Finally, no significant effect of the silica nanoparticles has been put in evidence on the crystallisation behaviour of the polypropylene. As for the effect of the silica content, the difference in the properties of the two nanocomposites is relatively small and all the measured properties depend much less than linearly with its amount. This has been correlated with the reaggregation of the nanoparticles that, having a larger size, decrease the contact area between the matrix and the filler.

Structure-Property Relationships in Bionanocomposites for Pipe Extrusion Applications.

In this work, bionanocomposites based on different biodegradable polymers and two types of nanofillers, namely a nanosized calcium carbonate and an organomodified nanoclay, were produced through melt extrusion, with the aim to evaluate the possible applications of these materials as a potential alternative to traditional fossil fuel-derived polyolefins, for the production of irrigation pipes. The rheological behavior of the formulated systems was thoroughly evaluated by exploiting different flow regimes, and the obtained results indicated a remarkable effect of the introduced nanofillers on the low-frequency rheological response, especially in nanoclay-based bionanocomposites. Conversely, the shear viscosity at a high shear rate was almost unaffected by the presence of both types of nanofillers, as well as the rheological response under nonisothermal elongational flow. In addition, the analysis of the mechanical properties of the formulated materials indicated that the embedded nanofillers increased the elastic modulus when compared to the unfilled counterparts, notwithstanding a slight decrease of the material ductility. Finally, the processing behavior of unfilled biopolymers and bionanocomposites was evaluated, allowing for selecting the most suitable material and thus fulfilling the processability requirements for pipe extrusion applications.

Bionanocomposite Blown Films: Insights on the Rheological and Mechanical Behavior.

In this work, bionanocomposites based on two different types of biopolymers belonging to the MaterBi® family and containing two kinds of modified nanoclays were compounded in a twin-screw extruder and then subjected to a film blowing process, aiming at obtaining sustainable films potentially suitable for packaging applications. The preliminary characterization of the extruded bionanocomposites allowed establishing some correlations between the obtained morphology and the material rheological and mechanical behavior. More specifically, the morphological analysis showed that, regardless of the type of biopolymeric matrix, a homogeneous nanofiller dispersion was achieved; furthermore, the established biopolymer/nanofiller interactions caused a restrain of the dynamics of the biopolymer chains, thus inducing a significant modification of the material rheological response, which involves the appearance of an apparent yield stress and the amplification of the elastic feature of the viscoelastic behavior. Besides, the rheological characterization under non-isothermal elongational flow revealed a marginal effect of the embedded nanofillers on the biopolymers behavior, thus indicating their suitability for film blowing processing. Additionally, the processing behavior of the bionanocomposites was evaluated and compared to that of similar systems based on a low-density polyethylene matrix: this way, it was possible to identify the most suitable materials for film blowing operations. Finally, the assessment of the mechanical properties of the produced blown films documented the potential exploitation of the selected materials for packaging applications, also at an industrial level.

Recycling of a Biodegradable Polymer Blend.

Mechanical recycling is one of the possible ways to enhance the value of postconsumer plastic materials. However, the final performance of the recycled material will strongly depend on the quality of the selection made on the recycled product and on the degradation of the properties. In this context, the present study examines the effect of reprocessing for five successive extrusion cycles on the rheological, mechanical and thermal properties of a poly(butylene adipate-co-terephthalate) (PBAT)-based blend on samples reprocessed in both dry and wet conditions. The results showed that when the sample was processed after drying, degradation of the material was less than when it was processed in wet conditions. However, the experimental results showed that the decrease of rheological and mechanical properties was not so dramatic, and therefore the material could be reused in both cases.

Influence of Short-Term Aging on Mechanical Properties and Morphology of Polymer-Modified Bitumen with Recycled Plastics from Waste Materials.

Polymer-modified bitumen (PMB) is bitumen that has been specifically engineered with polymer for providing enhanced performance in service. The aging of bitumen is a main aspect that is able to affect its final performance: during the production phase in a hot mix plant, all the binders experience short-term aging due to the high processing temperature. The same is true during the production of the modified binder, when the polymer is dispersed at high temperature in the bitumen mass. This paper aims at studying the effect of short-term aging when using different types of modifiers such as recycled polymers obtained from waste materials. A 50/70 penetration-grade bitumen has been modified, and bitumen characterization has been carried out before and after short-term aging; conventional tests, viscosity measurements, and dynamical mechanical analysis have been used to investigate the properties. Different aging indices have been determined for predicting the effect of short-term aging based on the type of modifier. Furthermore, the morphology of the modified bitumen has been investigated via fluorescent microscopy, before and after aging, in order to highlight morphological changes due to aging. The results confirm that aging affects all the modified binders, due to the thermal stress imposed during PMBs production. Nevertheless, polymer modification is proved to reduce the aging effect in terms of an increase in the elastic modulus as experienced by the original binder.

Comparative Investigation on the Soil Burial Degradation Behaviour of Polymer Films for Agriculture before and after Photo-Oxidation.

Polymer films based on biodegradable polymers, polyethylene (PE) and modified PE with oxo-degradable additive were prepared by film blowing. Carbon black (1%) was added to all the films. Commercial biodegradable Ecovio® and Mater-Bi® samples were used. Mechanical properties, soil burial degradation and surface wettability were investigated, before and after UV irradiation. Chemical modifications induced by UV and soil degradation, or a synergic effect, were highlighted by Attenuated Total Reflection-Fourier Transform Infra-Red (ATR-FTIR). Photo-oxidized film samples with an elongation at break equal to 50% and 0.5 the initial value were selected for the soil burial degradation test at 30 °C. Weight loss measurements were used to follow biodegradation in soil. Predictably, the degradation in soil was higher for biodegradable polymer-based films than for the PE-based ones. UV irradiation increased surface wettability and encouraged the disintegration in soil of all the samples. In fact, photo-oxidation produced a molar mass reduction and hydrophilic end groups, thus increasing surface erosion and weight loss. This paper not only supplies new criteria to evaluate the performance of biodegradable films in agriculture, before and after lifetime, but also provides a comparative analysis on the soil burial degradation behaviour with traditional ones.

Effect of environmental conditions on the durability of polycarbonate for the protection of cultural heritage sites.

Polycarbonate is a good material for covering and protecting cultural heritage sites because of its durability, mechanical properties, and transparency. However, polycarbonate degrades under environmental weathering with a significant decrease of physical and mechanical properties and loss of transparency. In this work, the contemporary presence of ultraviolet irradiation and different temperature and moisture conditions have been taken into account to study the environmental degradation of this polymer with regard to its mechanical and optical properties. The photo-oxidation reactions cause a decrease in the molecular weight and the formation of many oxygenated species. The hydrolytic scission, instead, gives rise to a remarkable reduction in the molecular weight. These two different degradation mechanisms do not seem interconnected because at the lowest degradation temperature and high humidity levels, the reduction of the molecular weight is more pronounced than that observed at the highest temperature but at a lower humidity level. Transparency decreases with the degradative processes, but even after severe degradation the loss of transparency is only about 10%. The yellowness index increases during the first stages of degradation, which has been attributed to the fast formation of carbonyl groups due to photo-oxidation.

Photo-Oxidative and Soil Burial Degradation of Irrigation Tubes Based on Biodegradable Polymer Blends.

Irrigation tubes based on biodegradable polymers were prepared via an extrusion-drawing process by Irritec and compared to conventional pipes made of high-density polyethylene (HDPE). A commercial polylactide/poly (butyleneadipate-co-butyleneterephthalate) (PLA/PBAT) blend (Bio-Flex®) and Mater-Bi® were used. The polymers were characterized from rheological and mechanical points of view. Irrigation pipes were subjected to photoaging with continued exposure to UV radiation up to 22 days. The degradability in the soil of irrigation tube samples was studied. The influence of temperature and UV irradiation on soil burial degradation was investigated. A soil burial degradation test was carried out at 30 °C and 50 °C for up to 70 days. The degree of degradation was evaluated from the weight loss percentage. The degradation rate of irrigation tube samples based on Mater-Bi® was higher at 30 °C and was stimulated after 14 days of UV irradiation. Higher temperatures or UV aging encouraged the disintegration in soil of Bio-Flex®-based irrigation tubes. Furthermore, tube samples, before and after UV and soil burial degradation, were analyzed by Attenuated Total Reflection-Fourier Transform Infra-Red (ATR-FTIR) spectroscopy.

Compatibilization of Polypropylene/Polyamide 6 Blend Fibers Using Photo-Oxidized Polypropylene.

The use of polyamide/polyolefin blends has gained importance and concern for years, but they also show some issues to be adequately addressed, such as the incompatibility between the two components. This is usually overcome by using suitable compatibilizers, typically based on functionalized polyolefins. However, there is only little information about the use of a degraded polyolefins to induce compatibilization. This is even truer, as far as polyamide 6/polypropylene (PA6/PP) blends are concerned. In this work, compatibilization of PA6/PP blends by using small amounts of photo-oxidized PP was investigated; furthermore, the effects due to the presence of the photo-oxidized PP were studied also in relationship to the spinning operation, where the existence of the non-isothermal elongational flow can lead to significant, further morphological changes. It was found that isotropic samples showed significant enhancements of the tensile properties upon adding the photo-oxidized PP. Under non-isothermal elongational flow conditions, the presence of the photo-oxidized PP was particularly effective in improving the mechanical properties in comparison to the uncompatibilized blend fibers. Furthermore, an important result was found: The elongational-flow processing allowed obtaining anisotropic samples where the improvements of the properties, in comparison to the isotropic samples, were similar to those achieved by using a compatibilizer.

"Compatibilization" through Elongational Flow Processing of LDPE/PA6 Blends.

Polyamide/polyolefin blends have gained attention from the academia and the industry for several years. However, in order to optimize their properties, some drawbacks such as chemical incompatibility must be adequately overcome. This can be done by adding suitable compatibilizers. On the other hand, it is less known that suitable processing techniques may also lead to significant results. In a previous work on a low-density polyethylene/polyamide 6 (LDPE/PA6) blend, we found that the orientation due to elongational flow processing conditions could lead to an unexpected brittle⁻ductile transition. In this work, this phenomenon was further investigated and the attention was mainly focused on the effects that processing can have on the morphology and, as a consequence, on the final properties of a polymer blends. With regard to LDPE/PA6 blend, an important result was found, i.e., the effects on the ductility induced by the elongational flow orientation are similar to those obtained by using an ethylene-glycidyl methacrylate compatibilizer.

Injection Molding and Mechanical Properties of Bio-Based Polymer Nanocomposites.

The use of biodegradable/bio-based polymers is of great importance in addressing several issues related to environmental protection, public health, and new, stricter legislation. Yet some applications require improved properties (such as barrier or mechanical properties), suggesting the use of nanosized fillers in order to obtain bio-based polymer nanocomposites. In this work, bionanocomposites based on two different biodegradable polymers (coming from the Bioflex and MaterBi families) and two different nanosized fillers (organo-modified clay and hydrophobic-coated precipitated calcium carbonate) were prepared and compared with traditional nanocomposites with high-density polyethylene (HDPE) as matrix. In particular, the injection molding processability, as well as the mechanical and rheological properties of the so-obtained bionanocomposites were investigated. It was found that the processability of the two biodegradable polymers and the related nanocomposites can be compared to that of the HDPE-based systems and that, in general, the bio-based systems can be taken into account as suitable alternatives.

Creep Behavior of Poly(lactic acid) Based Biocomposites.

Polymer composites containing natural fibers are receiving growing attention as possible alternatives for composites containing synthetic fibers. The use of biodegradable matrices obtained from renewable sources in replacement for synthetic ones is also increasing. However, only limited information is available about the creep behavior of the obtained composites. In this work, the tensile creep behavior of PLA based composites, containing flax and jute twill weave woven fabrics, produced through compression molding, was investigated. Tensile creep tests were performed at different temperatures (i.e., 40 and 60 °C). The results showed that the creep behavior of the composites is strongly influenced by the temperature and the woven fabrics used. As preliminary characterization, quasi-static tensile tests and dynamic mechanical tests were carried out on the composites. Furthermore, fabrics (both flax and jute) were tested as received by means of quasi-static tests and creep tests to evaluate the influence of fabrics mechanical behavior on the mechanical response of the resulting composites. The morphological analysis of the fracture surface of the tensile samples showed the better fiber-matrix adhesion between PLA and jute fabric.

Reprocessing of PLA/Graphene Nanoplatelets Nanocomposites.

This work reports a study on the effect of multiple reprocessing on the properties of poly(lactic acid) (PLA) filled with graphene nanoplatelets (GnP) compared to the melt reprocessed neat polymeric matrix. In particular, morphological, X-Ray Diffraction and Micro-Raman analyses, intrinsic viscosity measurements, thermal, rheological and mechanical tests were carried out on materials reprocessed up five times by means of a single screw extruder. The results indicated that the presence of GnP decreased the degradation rate as a function of the reprocessing cycles in comparison with the neat PLA that, on the contrary, showed a more drastic reduction of the molecular weight. Moreover, the reprocessing improved the particle dispersion and reduced the presence of GnP aggregates.