F. P. La Mantia

A non-linear viscoelastic model with structure-dependent relaxation times: I. Basic formulation

Abstract A non-linear constitutive equation for polymer melts and concentrated solutions is presented. Based on known results of network theories, the model contains a distinctive feature: that of letting the relaxation times depend upon the existing structure. The model extends the constitutive equation of linear viscoelasticity to the non-linear region in a well-defined way, with the uncertainty of just a single adjustable parameter. Predictions of the model for common cases of non-linear response are derived and discussed.

Recycling of high density polyethylene containers

The recycling of homogeneous high density polyethylene from containers for liquids gives rise to materials having mechanical properties that are strongly dependent on the reprocessing apparatus and the processing conditions. The thermomechanical degradation during processing gives rise to different modifications of the structure depending on the temperature, residence time and applied stress. In general, it is possible to say that if the reprocessing operations are carried out in apparatus with low residence time, the mechanical and rheological properties of the raw materials are only slightly influenced by the recycling operations. Significant degradation phenomena and reduction of some mechanical properties are observed on increasing the number of recycling steps in apparatus with large residence times. By adding antioxidant agents the polymer maintains the initial properties even after several recycling cycles. The competition between formation of chain branching and chain scission can be considered to be responsible for this behaviour.

Competition between degradation and chain extension during processing of reclaimed poly(ethylene terephthalate)

During processing of poly(ethylene terephthalate) (PET) hydrolytic chain scission, induced by the presence of small amounts of water, is the main cause of degradation. During repeated reprocessing chain scission can also occur because of the presence of other polymeric contaminants like PVC. In order to avoid or to limit hydrolytic chain cleavage adequate drying of PET before melt processing is necessary. Of course this practice is even more recommended when repeated processing steps are used, as for PET recycling. The behavior of recycling PET obtained from post-consumer water bottles when treated in a melt mixer under different conditions has been investigated in order to better understand the processing conditions that can reduce or avoid the hydrolytic chain scission. During processing both degradation (chain scission) and chain extension occur. When the processing is carried out under a nitrogen atmosphere the latter mechanism prevails leading to a polymer having larger molecular weight.

A non-linear viscoelastic model with structure-dependent relaxation times: II. Comparison with l.d. polyethylene transient stress results

Abstract A model of non-linear viscoelasticity with relaxation times which depend on the structure is compared with experimental results reported in the literature for a L.D. polyethylene. The single parameter of the model is determined by comparison with steadystate shear results. The model is then used to interpret various transient data. These are: tangential and normal stress growth in shear, stress growth in elongation, normal stresses in shear creep. The comparison shows a good general agreement, thus supporting the suggestion of relating the change in time of the relaxation spectrum to structural variables.

Recycling of plastics from packaging

Plastic waste coming from the separate collection of packaging film was recycled and characterized. The material is a blend of low density and linear low density polyethylene and after recycling shows mechanical and rheological properties depending on the processing conditions and apparatus. High processing temperature and high residence times strongly enhance the degradation processes and reduce the mechanical properties, in particular the elongation at break. A possible use of this recycled plastic is for the production of low pressure pipes but the properties are lower than those of virgin pipe grade polyethylene. By introducing additives, like antioxidants, inert fillers and impact modifiers, the mechanical properties improve and approach those of virgin pipe grade polyethylene.

On the compatibilization of PET/HDPE blends through a new class of copolyesters

Polyethyleneterephthalate (PET) and polyethylene are incompatible polymers and their blends show, in general, poor properties. Compatibilization is then a necessary step to obtain blends with good mechanical and barrier properties. In this work different compatibilizing agents were used, i.e. a maleic anhydride elastomer and some new products containing graft-copolymers having polyester segments grafted onto polyethylene backbone chains. Both the functionalized elastomer and the new products drastically improve the morphology and the ductility of the blend. In the case of the modified elastomer the compatibilizing action has been attributed to the formation of H-bonds whereas the copolymers contained in the new products act as compatibilizing agents as they contain polyester segments and polyethylene segments with thermodynamic affinity with PET and polyethylene, respectively.

Recycling of the “light fraction” from municipal post‐consumer plastics: effect of adding wood fibers

At present the recycling of plastic materials is mostly done using homogeneous polymers. Therefore a separation from a municipal collection of plastic objects is necessary before recycling operations. The easiest way of separation is by flotation in water, i.e. the separation of the different plastics based on the different densities with respect to water. This means that all the plastic materials are separated in a “light fraction” mostly of polypropylene and polyethylene and in a “heavy fraction” mainly of poly(vinyl chloride) (PVC) and poly(ethylene terephthalate). The recycling of the light fraction should, in principle, be easy because of the relative similarity of the chemical structure of the components. The presence of small amounts of polystyrene foam (lighter than water) or of some polymer, such as PVC, or non-polymeric impurities can, however, make the properties of the secondary material quite poor. In this work, the recycling of a light fraction sample has been studied, considering also the effect of the addition of wood fibers, an “environment friendly” filler. Although the similar chemical nature of the two main components, the mechanical properties of the recycled mixture are quite scarce, mainly because of the incompatibility and the possible presence of some heterogeneous particles. The addition of wood fibers (20–40 wt%) leads to a remarkable increase of the elastic modulus while elongation at break and impact strength decrease and the tensile strength remains almost unchanged. Thermomechanical properties are also improved. In order to improve these properties, two functionalized polypropylene samples were used as adhesion promoters. Both polypropylene-grafted maleic anhydride and polypropylene-grafted acrylic acid improve the mechanical properties in particular at very low concentrations. Copyright

Characterization and reprocessing of greenhouse films

Films for greenhouses are an attractive source of post-consumer plastic materials because they are mainly made of polyethylene and can be easily collected in large amounts in small zones. The types of polymers for this application are, however, increasing and the films contain not only additives and stabilisers, but also fertiliser and pesticide residues. Finally, the extent of photooxidative degradation undergone during the use can strongly influence the recycling operations and the final properties of the secondary material. In this work, a complete characterisation of post-consumer films for greenhouses has been carried out and the properties of the recycled material have been correlated with the number of reprocessing steps and compared with those obtained by reprocessing virgin scraps of the same composition. The presence of small amounts of low molecular weight compounds (photooxidized species and pesticide residues) does not compromise the use of the recycled plastic in many applications. The mechanical properties decrease with the number of reprocessing steps and with increasing level of photooxidative degradation but are good enough for many applications.

Study on compatibilization of polypropylene-liquid crystalline polymer blends

The mechanical properties, melt rheology, and morphology of binary blends comprised of two polypropylene (PP) grades and two liquid crystalline polymers (LCP) have been studied. Compatibilization with polypropylene grafted with maleic anhydride (PP-g-MAH) has been attempted. A moderate increase in the tensile moduli and no enhancements in tensile strength have been revealed. Those findings have been attributed to the morphology of the blends, which is predominantly of the disperse mode. LCP fibers responsible for mechanical reinforcement were only exceptionally evidenced. Discussion of PP-LCP interfacial characteristics with respect to mechanical properties-morphology interrelations allowed evaluation of the compatibilizing efficiency of PP-g-MAH. Factors important for successful reinforcement of PP with LCP have been specified.

Processing and mechanical properties of recycled PVC and of homopolymer blends with virgin PVC

Mechanical and processing properties of recycled polyvinylchloride (PVC, from bottles and pipes) were compared with those of virgin pipe grade PVC. Blends of recycled and pipe grade PVC were also prepared and characterized. It was found that the particle size and the restabilization of the recycled PVC are the two main points to be considered for obtaining virgin/recycled PVC blends with uniform and good mechanical properties. In general, recycled PVC not only does not significantly reduce the modulus and tensile strength, but also improves the impact strength and processing behavior of pipe grade virgin PVC. Only the thermomechanical resistance is slightly lowered. The latter points hold, of course, only when the recycled PVC contains both reinforcing and modifier agents.