Effect of compatibilization on the photo-oxidation behaviour of polyethylene/polyamide 6 blends and their nanocomposites

Abstract Polymer based nanocomposites are increasingly attracting interest from academia and industry, and the use of polymer blends as matrices greatly increase their potential field of application. In order to improve their characteristics, the use of compatibilizers acting on the blend components is mandatory. However, this also leads to rising concerns regarding the behaviour of polymer blend based nanocomposites upon being subjected to photo-oxidative degradation. It is known that morphology can deeply influence the photo-oxidative behaviour, and this can be therefore deeply influenced by the blend components and by the use of compatibilizers. In this work, polymer blend nanocomposites…

Compatibilization of blends of polyethylene with a semirigid liquid crystalline polymer by PE-g-LCP copolymers

The blends of thermoplastics with liquid crystalline polymers show, in general, poor properties because of the lack of adherence between the two phases. The use of ad hoc synthesized copolymers containing the monomer units of the two polymers has been recently considered by some of us for blend compatibilization, and the results appear promising. In this work, new PE-g-LCP copolymers, prepared either by the synthesis of the LCP in the presence of a functionalized PE, or by reactive blending of the latter polymer with preformed LCP, have been employed as compatibilizing additives for blends of PE with a semirigid LCP. The morphology and the rheological and mechanical properties of the ternar…

Time–carbonyl groups equivalence in photo-oxidative aging of virgin/recycled polymer blends

AbstractThe photo-oxidation behaviour of polymers is strongly dependent on the initial amount of carbonyl groups along the chains. The growing use of recycled post-consumer polymers coming from products used outdoors and then photo-oxidised, both pure and blended with the same virgin polymer, gives rise to an unpredictable behaviour of weathering resistance of products made with these materials. The present work shows that the carbonyl group–exposure time curves can be shifted along the time axis to give a single generalised master plot. It is then possible to predict the formation of the new carbonyl groups by knowing only the initial amount of the same carbonyl groups. The same shift fact…

Synthesis of PP-LCP graft copolymers and their compatibilizing activity for PP/LCP blends

The aim of this work was the synthesis of new graft copolymers consisting of polypropylene (PP) backbones and liquid crystalline polymer (LCP) branches, to be used as compatibilizing agents for PP/LCP blends. The PP-g-LCP copolymers have been prepared by polycondensation of the monomers of a semiflexible liquid crystalline polyester (SBH 1 : 1 : 2), that is, sebacic acid (S), 4,4′-dihydroxybiphenyl (B), and 4-hydroxybenzoic acid (H) in the mole ratio of 1 : 1 : 2, carried out in the presence of appropriate amounts of a commercial acrylic-acid-functionalized polypropylene (PPAA). The polycondensation products, referred to as COPP50 and COPP70, having a calculated PPAA concentration of 50 and…

New phosphazene-based chain extenders containing allyl and epoxide groups

In this paper we present the synthesis and the characterization of cyclophosphazenes substituted with allyl groups, their transformation in epoxide-containing cyclophosphazenes and the final utilization of these compounds as chain extenders in combination with polyamides. The reaction at high temperature of Nylon-6 with epoxy-functionalized cyclophosphazenes leads to the opening of the epoxy units by the action of both amino (--NH2) and carboxylic (--COOH) end-groups of the polymer to enhance the final molecular weight of this material. The consequences of this fact on the thermal, mechanical and visco-elastic properties of treated Nylon-6 have been also evaluated and compared to those of t…

Characterization of blends of polypropylene with a semirigid liquid-crystal copolyester

Abstract Blends with a liquid-crystal polymers (LCP) as one component show, in general, very interesting properties. Reduction of shear viscosity and improvement of mechanical properties are very remarkable. High melting temperatures and high costs of the LCP limit the use of these blends. A new class of thermotropic LCPs with flexible spaces, with relatively low melting temperatures, can overcome the first problem. In this work, rheological and mechanical properties of blends of polypropylene with low contents of this LCP are presented. Torque during extrusion and viscosity decrease with LCP content. Elastic modulus is remarkably increased when the LCP phase is oriented.

Influence of the molecular structure on the melt strength and extensibility of polyethylenes

Melt strength (MS) and breaking stretching ratio (BSR) data relative to polyethylenes with different molecular structure (high density (HDPE), low density (LDPE), and linear low density (LLDPE)) are shown. HDPE and LLDPE samples show high breaking stretching ratio and low melt strength values. The LDPE samples exhibit very large melt strength values but low breaking stretching ratio values. For the last mentioned samples, differences are shown in the non-isothermal elongational behavior between samples polymerized with tubular and vessel technology. For all the samples, MS decreases with increasing melt index while BSR increases with melt index.

Compatibilized Polyamide 6/Polyethylene Blends Clay Nanocomposites: Effect of the Degradation and Stabilization of the Clay Modifier

Abstract Blends of polyamide 6 (PA6) and high-density polyethylene (HDPE) were compatibilized using an already investigated method and a sample of Cloisite 15A, a montmorillonite modified with ammonium quaternary salts was added. The blends were prepared in a twin screw extruder and characterized from a morphological, rheological and mechanical point of view. The results indicated that, despite a good morphology achieved in the filled blends and a moderate intercalation of the clay, the mechanical properties are far from being good, especially the ultimate properties. In order to investigate the possible influence of the inhibition of the crystallization and of the degradation of the organi…

Shear characterization of CaCO3-filled linear low density polyethylene

Shear properties of CaCO3-filled linear low density polyethylene have been determined over a wide range of filler loading. The viscosity rises with the filler loading especially at low shear rates and a yield value appears for CaCO3-contents larger than 5%. The decrease of the die-swell ratios of the filled samples indicates a reduction of the melt elasticity.

Closed-loop recycling. A case study of films for greenhouses

Abstract The degradation undergone by plastic films used for greenhouse coverage is the main cause of the worsening of the processability, of the mechanical properties and of the durability of secondary materials obtained by their recycling. This means that this secondary material cannot be processed to produce films for the same applications (closed-loop recycling). In this work different strategies are proposed to improve the processability, some mechanical properties and the resistance to photo-oxidation of these secondary materials. In particular, homopolymer blends or multilayer films where the secondary material is used in combination with virgin polymer give the best results.

Transient response in nonlinear region of molten polymers subjected to a sudden imposition of constant shear stress or constant electric field

Experimental transient results in the nonlinear region are reported for a commercial polyisobutylene subjected to sudden imposition of either a constant shear stress or a constant electric field. Some steady-state results, eventually obtained in different types of experiments, are also considered. In both cases, a model analysis is presented that accounts for the nonlinear effects through changes in the free volume depending upon the applied stress. The good comparison between theoretical predictions and experimental results seems to indicate that the phenomenological approach advanced here is very promising.

Mechanisms of polymer crystallization from flowing solutions

The recent experimental results on flow-induced crystallization by Pennings and coworkers show that extremely rigid polyethylene fibers can be obtained in a shear flow. On the other hand, the mechanism by which these flow-induced crystals are produced is still open to investigation. In this work a few aspects of fibrous crystal growth are theoretically investigated. The molecular dynamics of chains partly attached to the crystal and partly immersed in the solution is considered. The influence of temperature and of geometrical factors is also discussed.

Dynamic-mechanical and dielectric measurements have been performed with some polycarbonate samples. In one set of experiments care was taken to avoid any absorption of moisture. In other sets of experiments, samples were exposed to atmospheric humidity and to boiling water. The glass transition temperature was found to be highly affected by the absorption of water and by the test conditions. Dynamisch-mechanische und dielektrische Messungen wurden an Polycarbonatproben durchgefuhrt. In einer Versuchsserie wurde die Absorption von Wasser vollstandig vermieden, in weitern Versuchen wurden die Proben der Luftfeuchte bzw. kochendem Wasser ausgesetzt. Die Glasubergangstemperatur wurde durch das …

SHEAR BEHAVIOUR OF MOLTEN LINEAR LOW DENSITY POLYETHYLENE.

The rheological behaviour of molten polyethylene has been widely studied especially with respect to the different structure of the high density and low density samplesI–I0. In particular it is well known that the presence in the LDPE of long chain branching alters dramatically the whole flow curve, the activation energy, the die-swell, the instability phenomena, etc.

Rheological Behaviour, Mechanical Properties and Processability of Biodegradable Polymer Systems for Film Blowing

Films for agricultural or packaging applications are typically made of low density polyethylene (LDPE). They are produced through the film blowing process, which requires the use of polymers with suitable rheological properties. Furthermore, the short shelf-life which is often related to many packed products leads to huge amounts of plastic-based wastes. This suggests the use of biodegradable and/or compostable polymers in replacement for traditional ones. To this regard, only few data exist on the rheological properties of biodegradable polymers undergoing film blowing processing. In this work, a detailed investigation on the rheological, mechanical and processability behaviour of some bio…

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 structu…

Morphology and Rheology of HDPE/LCP Blends Compatibilized by a Novel PE-g-LCP Copolymer

A novel graft copolymer (PE-g-LCP) consisting of polyethylene (PE) backbones and liquid crystalline polymer (LCP) branches was synthesized via reactive blending of an acrylic acid-functionalized PE (Escor 5000 by Exxon) with a semiflexible LCP (SBH 1 : 1 : 2 by Eniricerche S.p.A.). The crude reactive blending product (COP) was shown by investigation of the fractions soluble in boiling toluene and xylene and of the residue to contain unreacted Escor and SBH, together with the graft copolymer forming the interphase. The compatibilizing activity of COP for PE/SBH blends, compared to that of pure Escor, was investigated using two PE grades. The COP addition into 80/20 PE/SBH blends caused a muc…

Elongational behavior of low density/linear low density polyethylenes

Rheological data have been collected in isothermal elongational flow for three different types of blends, made from one low density polyethylene and three linear low density samples. In addition to the transient curves, elongation at break data are also reported. The influence of the composition and of the molecular weight of the linear low density polyethylene is discussed.

Recycling of dry and wet polyamide 6

Recycling of polycondensation polymers can give rise to secondary materials with good mechanical properties only if a careful drying is carried out before the melt reprocessing operations. The presence of humidity provokes the hydrolytic chain scission of the macromolecules and the consequent decrease of molecular weight and properties. In this work, the drying step was substituted by the addition of an antioxidant that is able to protect the macromolecules because it is the autioxidant is more prone to hydrolysis, thus removing the water from the melt. The mechanical properties of polyamide 6 reprocessed more times in wet conditions and in the presence of this stabilizer are even better th…

Selective localization of organoclay and effects on the morphology and mechanical properties of LDPE/PA11 blends with distributed and co-continuous morphology

A study was made on the effect of small amounts of organically modified clay on the morphology and mechanical properties of blends of low-density polyethylene and polyamide 11 at different compositions. The influence of the filler on the blend morphology was investigated using wide angle X-ray diffractometry, scanning and transmission electron microscopy and selective extraction experiments. The filler was found to locate predominantly in the more hydrophilic polyamide phase. Although such uneven distribution does not have a significant effect on the onset of phase co-continuity of the polymer components, it brings about a drastic refinement of the microstructure for the blends both with dr…

Effect of the orientation on the photooxidation behaviour of polymer films

Abstract The effect of the orientation on the photooxidation of polymers is quite controversial. Both improvement of the photo-resistance along the oriented direction and worsening of the photooxidation kinetic have been reported. In this work the effect of the orientation has been investigated on films of PE, PP and PET with different degree of orientation and crystallinity. The results show that the photo-stability, measured from the decay of the elongation at break curve as a function of the irradiation time, improves in the more oriented direction, but this is more and more relevant with increasing the crystallinity degree. It has been hypothesized that the reinforcing action of the ori…

EFFECT OF DRAWING ON THE STRUCTURE AND THE DYNAMIC-MECHANICAL BEHAVIOR OF SALTED POLYCAPROAMIDE.

Abstract Structural determinations, obtained through density, birefringence, and WAXS measurements, are reported for nylon 6/inorganic salt fiber samples as a function of draw ratio. They confirm the possibility of achieving very high amorphous orientation in these systems. Dynamic-mechanical data have also been collected which allow determination of glass transition temperatures. These are also discussed in terms of structural parameters.

Green composites of organic materials and recycled post-consumer polyethylene

International audience; Addition of organic fillers to post‐consumer recycled plastics can give rise to several advantages. First of all, the cost of these fillers is usually very low, the organic fillers are biodegradable contributing to an improved environmental impact and, last but not least, some mechanical and thermomechanical properties can be enhanced. Organic fillers are not widely used in the plastic industry although their use is increasing. Bad dispersion into the polymer matrix at high‐level content and poor adhesion with the matrix are the more important obstacles to this approach. In this work various organic fillers have been used with a post‐consumer plastic material origina…

Morphology and properties of compatibilized PP/PET melt spun fibers

This work provides a study on the influence of a rubbery compatibilizer on the morphology and on the physical properties of polypropylene (PP)/polyethylenetherephthalate(PET) melt spun fibers at different hot draw ratios. In particular, a sample of SEBS copolymer grafted with maleic anhydride was used as compatibilizer. Both the uncompatibilized PP/PET blend and the compatibilized one were prepared by melt compounding in a counter-rotating twin-screw extruder. The materials have been characterized from a rheological, morphological and mechanical point of view. The addition of the compatibilizer increased the viscosity in shear flow of the uncompatibilized blend, and significantly improved t…

Dielectric and dynamic-mechanical behaviour of ethylene-vinyl alcohol copolymers

Abstract Dynamic-mechanical and dielectric measurements on ethylene-vinyl alcohol copolymers with two different vinyl alcohol contents and, for comparison on polyvinylalcohol and low density polyethylene, have been carried out in order to clarify the nature of the relaxation peak. The relaxation peak observable in the dielectric loss curves of the copolymers has been assigned to the interfacial polarization, MWS type, occurring between hydrogen bonded hydroxyl groups and the apolar polyethylene segments. The shoulder also present in the e″-T curves of the copolymers seems to correspond to the glass transition peak which is hidden since the dielectric loss curve increases quickly because of …

On the modification of the nitrile groups of acrylonitrile/butadiene/styrene into oxazoline in the melt

Oxazoline functionality is well known to be highly reactive toward a lot of other functional groups like carboxyls, hydroxyls, mercaptans, and amines. In this work we report the possibility to modify the nitrile groups of an acrylonitrile/butadiene/styrene (ABS) copolymer into oxazoline in the molten state in the presence of aminoethanol as modifier agent and zinc acetate as a catalyst. The reaction has been carried out in a batch mixer and in a corotating twin screw extruder. The conversion of the nitrile groups into oxazoline has been verified by infrared spectroscopy, NMR analysis microanalysis and confirmed by thermomechanical characterization. The results indicate that the kinetic of g…

Shear and nonisothermal elongational characterization of a liquid crystalline polymer

A commercial liquid crystalline polymer (LCP) sample was characterized both in shear and in nonisothermal elongational flow over a wide range of temperatures (240–350°C). The LCP sample employed was a copolyesteramide of 2,6 hydroxynaphthoic acid, terephthalic acid, and aminophenol manufactured by Celanese and commercially known as Vectra B950. The viscosity decreases dramatically at temperatures above the crystal-nematic transition of the polymer. At lower temperatures, the extrusion of the sample is mainly due to plastic flow. Die-swell values are very small and contraction of the extrudate is also revealed, but the sample shows high elasticity. The polymer is not spinnable at very low te…

Thermal stability of PP with acetylated sisal fiber: Romero Garc�a kinetic method

This work deals the effect of acetylated and non-acetylated sisal fiber 011 thermal degradation of polypropylene. Applying the R-G method at constant conversion levels of 0.1, 0.3, 0.5, 0.7 and 0.9 to thermograms of the ”PP/untreated sisal fiber” blend, E, values of 99, 213, 224, 187, and 145 kJ/mol were obtained, whereas they were 99, 299, 255, 205, 154 kJ/mol for the “PP/treated sisal fiber” blend. On the other hand, with the R-G method at constant temperature, activation energies within the range of 156-417 kJ/mol were obtained for the “PP/treated sisal fiber” blend and within the range of 126-344 kJ/mol for the “PP/untreated sisal fiber” blend. Additionally, the method establishes as do…

Non linear viscoelasticity of polymeric liquids interpreted by means of a stress dependence of free volume

Several existing data of non-linear viscoelasticity of amorphous polymers aboveT g are here interpreted by assuming that the free volume changes during the motion. Equations of a stress-temperature equivalence are suggested which favorably compare with the data. It is also shown that the volume variations are sufficiently small to have escaped observation.

Competition between chain scission and branching formation in the processing of high-density polyethylene: effect of processing parameters and of stabilizers

Two samples of high-density polyethylene with different molecular weight were processed in a batch mixer and the rheological and structural properties were investigated. In particular, the effect of different processing parameters and the eventual presence of different stabilizers were evaluated. Actually, two reactions may occur during processing: branching/crosslinking or chain scission. The results indicate that when the processing conditions promote a scarce mobility of the macromolecular chains (lower temperatures, lower mixing speed, and higher molecular weight), branching is more favored than chain scission. On increasing the mobility of the chain (higher temperature, higher mixing s…

Model analysis of uniaxial and biaxial stretching of polymer melts

The biaxial extension results byDenson et al. are compared with the predictions of a model of non-linear viscoelasticity. Date of uniaxial extension on the same material (a commercial polyisobutylene) are taken for extending the comparison. The model used seems to adequately describe both types of elongational flow with the same value of the single adjustable parameter.

Photo-re-stabilisation of recycled post-consumer films from greenhouses

The photo-oxidation behaviour of recycled post-consumer films from greenhouses has been studied in order to evaluate the environmental resistance of these secondary materials and the effect of some stabilising agents. The presence of the UV absorber slows down the weathering of the post-consumer materials. After about 1000 h of accelerated weathering the unstabilised post-consumer material becomes brittle, while the re-stabilised post-consumer film becomes fragile only after about 1500 h. A synergistic effect is observed when an antioxidant and an UV stabiliser are added. Indeed, in this case, the recycled material is not brittle even after more than 1700 h. These last results can be probab…

Rheological properties and morphology in LLDPE and PC based blends

Abstract During an interlaboratory project on polymer blends (Technical Working Party-Polymer Blends-VAMAS), the rheological characteristics of some samples of blends of polycarbonate with linear low density polyethylene have been evaluated with the aid of a capillary rheometer. Some morphological observations on the extruded samples have also been performed through SEM and an attempt has been made to correlate the macroscopic and microscopic results.

Thermomechanical degradation of polyethylene/polyamide 6 blend-clay nanocomposites

Abstract Polymer nanocomposites are gaining a growing interest both in the academia and in the industrial field, because of some specific properties they can assure. However, the rise in the attention from the industry is also leading to concerns about their processing, which can involve issues which are not present in traditional polymers processing; furthermore, additional issues can arise when nanocomposites are based on a polymer blend rather than a single polymer. In this work, a systematic study on thermomechanical degradation and reprocessing behaviour of LDPE/PA6/Cloisite 15A systems has been performed. The characterization was based on rheological, mechanical and morphological anal…

Effect of Hot Drawing on the Mechanical Properties of Biodegradable Fibers

The use of biodegradable polymers is increasingly attracting interest over the last years, since they can reduce the environmental effects related to disposal of traditional plastics and, in general, the use of fossil, non-renewable resources. One of the most promising applications is represented by fibers production. However, the orientation and the crystallinity degrees can significantly affect the mechanical properties. Therefore, it is of interest to investigate on the optimum processing conditions, in order to improve the mechanical properties. In particular, while crystallinity can be slightly modified by the processing, orientation can be significantly improved. In this work, the eff…

Characterization of a fiber-reinforced new fully aromatic liquid crystalline polymer

A new rigid liquid crystalline polymer that demonstrates good mechanical and thermomechanical properties and acceptable processing temperature has been recently synthesized and characterized. The melting temperature and some thermomechanical properties do not seem, however, suitable for use in some applications at high temperature or in the presence of aggressive fluids. The use of appropriate inorganic fillers can overcome these shortcomings. In this work the new LCP, polymerized in a bench-scale apparatus, and the same sample filled with carbon fibers are characterized. The properties of the carbon fiber filled LCP are compared with those of another filled wholly aromatic commercial LCP,…

Processing and Properties of Biopolymer/Polyhydroxyalkanoates Blends

In this paper, the processability and the performance of a biodegradable polymer, Mater-Bi, and of its blends with either a sample of poly (hydroxy alkanoates) (PHA) or with bacterial biomass containing PHAs were compared. Adding PHA or directly the biomass containing it allows improving the processability of the matrix. Moreover, the mechanical behaviour of the systems was compared considering two different preparation methods, namely compression and injection moulding. The injection moulded samples show poorer mechanical performances than those of the compression moulded systems. The impact strength significantly improves when PHA is added while it reduces when bacterial biomass is used i…

Constant stretching rate experiments on low density polyethylene

A simple apparatus for elongational test of molten polymers is presented. Its realiability is demonstrated by means of stress growth in constant stretching rate experiments and relaxation test on a low density polyethylene sample.

Improvement of photo-stability of LLDPE-based nanocomposites

LLDPE-based nanocomposites undergo faster photo-oxidation than the unfilled matrix and the extent of their physical properties deterioration, namely elongation at break and tensile strength, is dependent on the organo-nanoclay loading. The observed acceleration is not due to faster photo-oxidation but rather due to a reduction of the oxidation induction time. The presence in the organoclays of trace amounts of metal ions may be promoting catalytic photodegradation. While UV absorbers provide useful protection, use of a metal deactivator has been found to greatly enhance the photo-stability of the LLDPE-based nanocomposites. Combinations of a metal deactivator and UV absorber yield synergist…

Structure and dynamics of polyethylene/clay films

The relationships between structure and rheology of polyethylene/clay hybrid composite blown films were investigated through rheological tests both in shear and elongational flow. Two polymer matrices (low density polyethylene, LDPE and linear low density polyethylene, LLDPE) with different relaxation kinetics were used. Independently from the matrix, morphological analyses (TEM, XRD, and SEM) indicate that the hybrid structures are similarly constituted of delaminated platelets or tactoids having a relevant degree of orientation along the draw direction. This strongly affects the rheological behavior of materials. However, despite the similarities emerged from morphological analyses, both …

The viscoelastic behavior of nylon 6/lithium halides mixtures

Stress-relaxation experiments in the limit of small deformations have been carried out in a wide range of temperatures for pure nylon 6 and its mixtures with LiBr and/or LiCl. Master curves have been constructed, by allowing horizontal shifts only, showing the shape typical for semicrystalline polymers in the case of pure nylon and that of essentially amorphous polymers in the case of salted samples. The glass transition temperatures determined from the plot logaT− 1/T is increased when in the presence of salts. All such effects are considered to reflect the binding action of Li+ and Br− ions.

Effect of the processing techniques on the properties of ecocomposites based on vegetable oil-derived Mater-Bi® and wood flour

Polymer composites based on biodegradable polymers and natural-organic fillers are becoming more and more important because of their interesting properties in terms of environmental impact, manufacturing cost, and esthetic features. In particular, the use of biodegradable polymer matrices allows obtaining a full biodegradability. One of the most interesting biodegradable polymer families is the Mater-Bi® one. In this work, we investigated the processability, the influence of different processing techniques, and the influence of the filler particle size on the properties of Mater-Bi/wood flour composites. Injection molding caused a partial degradation of the macromolecular chains, whereas si…

Non-isothermal elongational flow of polymer nanocomposites

The elongational flow is a very important flow involved in important processing operations, like spinning, film blowing, etc. In these processing operations, the molten polymer is subject to the elongational flow and at the same time is cooled (non-isothermal elongational flow). The response to the non-isothermal elongational flow of the melt is then the critical parameter to process the polymer in these processing operations. MS (melt strength) and BSR (breaking stretching ratio) are to two values measured during the non-isothermal flow and depend mainly on the molecular structure of the polymer. In biphasic systems, the adhesion and the shape of the dispersed particles play a very importa…

Physicochemical characterisation of thermally aged anodic films on magnetron sputtered niobium

The influence of thermal aging, at intermediate temperature (1h at 250°C) and in different environments, on the electronic and solid-state properties of stabilized 160 nm thick amorphous anodic niobia, grown on magnetron sputtered niobium metal, has been studied. A detailed physicochemical characterisation of the a-Nb2O5/0.5M H2SO4 electrolyte junction has been carried out by means of photocurrent and electrochemical impedance spectroscopy as well by differential admittance measurements. A change in the optical band gap (3.45 eV) of niobia film has been observed after aging (3.30 eV) at 250°C in air for 1 hour. A cathodic shift (0.15-0.2 Volt) in the flat band potential of the junction has …

Degradation of polymer blends: A brief review

Abstract The usefulness of any material, including polymer blends, depends on its degradability and durability. The blend composition can significantly affect the degradative behavior of a polymer blend and can differ from the degradation routes of the pure components since the interactions among different species in the blends during degradation, and among the degradation products, can occur. These reactions can lead either to an acceleration of the degradation rate or to a stabilizing effect in comparison with the pure components. Thus, the additive rule cannot be often applied in case of degradation of polymer blends and, therefore, it is difficult to predict the degradative behavior of …

Effect of Processing Conditions on the Degradation and on the Recycling of Polycarbonate

Polycarbonate, like other polycondensation polymers, can be easily recycled without significant loss of properties only with careful drying. Indeed, the presence of humidity strongly decreases the molecular weight of the polymer by hydrolytic chain scission. In this paper, the degradation and the recycling of an extrusion grade polycarbonate sample has been investigated considering mainly the effect of the humidity. Some degradation is observed also for the material reprocessed in dry conditions and due to the thermomechanical stress acting on the melt. The chain scission is strongly reduced if the processing is carried out under nitrogen flow. In these conditions less degradation effects …

The rheological behaviour of HDPE/LDPE blends. II. Die swell and normal stresses

Die swell data are presented for different high-density/low-density polyethylene blends. The data relating to samples with frozen-in stresses are represented, collected as a function of the usual operational parameters (L/D ratio, flow rate, temperature). Data obtained with annealed samples are used to derive, through a theoretical approach, normal stresses. Die Strahlaufweitung wurde fur verschiedene Mischungen aus Polyethylenen hoher und niedriger Dichte gemessen. Die an Proben mit eingefrorenen Spannungen erhaltenen Werte wurden in Abhangigkeit von technologischen Parametern (Lange/Durchmesser-Verhaltnis, Fliesgeschwindigkeit, Temperatur) dargestellt. An getemperten Proben gemessene Wert…

Prediction of the flow curves of thermoplastic polymer/clay systems from torque data

Abstract The aim of this work was to determine some relevant rheological parameters of polymer/clay systems using mixing torque and mixing speed data obtained during processing in an internal mixer. The method used was originally proposed by Marquez et al. for monophase polymers, and is here applied to polymer/clay systems for the first time. Several clay-containing composites based on different polymer matrices (i.e., LDPE, HDPE, PA6, EVA) were used to verify the effectiveness of the method for measuring the flow curves of these polymer/clay systems. The results indicated that, for all the systems at low clay level, the rheological curves calculated with the Marquez method fit quite well t…

Recycling of degraded polyethylene: Blends with nylon 6

Abstract Recycled polyethylene can be used for blending with nylon to obtain blends with mechanical properties better than those of blends with virgin polyethylene. Moreover, the mechanical properties of these blends are very close to and, in some cases, better than those of the pure nylon and those of blends made with functionalized polyolefines. The carbonyl groups of the photo-oxidized polyethylene react with amino end-groups of nylon 6, giving rise to graft copolymers which act as interfacial agents between the two incompatible phases. Large degrees of photo-oxidation of the polyethylene and intense mixing improve the properties of the blends.

Rheological Behavior Under Shear and Non-Isothermal Elongational Flow of Biodegradable Polymers for Foam Extrusion

The production of many items, in particular for food packaging applications, is based on foam extrusion and thermoforming. These operations require the use of polymers which can grant some specific rheological properties, both under shear and elongational flow. In this work, the behavior of some biodegradable polymers [Mater-Bi® and poly(lactic acid)] under shear and non-isothermal elongational flow was investigated and compared with a traditional, non-biodegradable polymer, in order to assess their suitability for industrial-scale foam extrusion and thermoforming. The rheological characterization evidenced the differences between the different biodegradable polymers and the reference polys…

Effect of the orientation and rheological behaviour of biodegradable polymer nanocomposites

Abstract The recent increasing interest towards biodegradable polymers has favoured the investigation on these systems, showing also their limits. On the other hand, the success achieved by nanocomposites has fostered the search for new systems where the polymer matrix is biodegradable. The final properties can depend on a number of factors, including the biodegradable polymer used as well as the nanosized filler, their mutual compatibility, the filler dispersion and the processing conditions. In this work, nanocomposites based on a starch-derived matrix and three different lamellar silicates were prepared, and the effects of the elongational flow on the dispersion, the improvement of inter…

Theoretical study on the decomposition mechanism of bisphenol A polycarbonate induced by the combined effect of humidity and UV irradiation.

Polycarbonate (PC) is a good material for covering and protecting cultural heritage sites because of its durability, mechanical properties, and transparency. When bisphenol A polycarbonate is subjected to weathering conditions this polymer shows several degradation processes depending on the irradiation wavelength, humidity and temperature. In particular, the combined effects of humidity and UV irradiation speed up the PC molecular weight reduction. In this work, the decomposition mechanisms associated to the hydrolysis process are scrutinized and the effects of UV irradiation on the hydrolysis process are evaluated throughout the Density Functional Theory (DFT) approach. It was found that …

Extensional flow of HDPE/LDPE blends

Elongational viscosity data, obtained through the converging flow analysis by Cogswell, are presented for two types of HDPE/LDPE blends at various compositions and different temperatures. The results relative to the homopolymer parents compare favourably with literature data obtained also with different and more sophisticated techniques. Those relative to blends show peculiar features for the two cases: when the newtonian viscosity of the LDPE is higher all the blends show a behaviour typical of the LDPE with a maximum in η el /η0 enhanced at small percentage of HDPE; when the newtonian viscosity of the LDPE is similar to that of the HDPE there is only a gradual change in the properties.

Thermomechanical degradation of PLA-based nanobiocomposite

Nanobiocomposites are a new class of biodegradable polymer materials with nanometric dispersion of inert particles in a biodegradable polymer matrix that show very interesting properties often very different from those of conventional- filled polymers and also biodegradability. An important issue in the applications of the biodegradable polymers is their easy degradability during processing due to the thermomechanical stress or to the presence of humidity. In this work, the thermomechanical degradation behavior of a nanobiocomposite made by a PLA-based blend and an organomodified montmorillonite has been investigated. The degradation kinetics has been followed by means of rheological, mecha…

Shear viscosity of polybutyleneterephthalate/liquid crystal polymer blends

Viscosity measurements have been carried out on blends of polybuty-leneterephthalate (PBT) and a liquid crystalline copolyesteramide (LCP). The flow curves of the blends with LCP content larger than 20%, show a behavior similar to that of the pure LCP, with a rapid rise of the viscosity at low shear rates. The viscosity-composition curves exhibit a deep minimum at low LCP content which may be mainly attributed to the lack of interactions between the two phases.

Photooxidation and Stabilization of Photooxidized Polyethylene and of its Monopolymer Blends

The increasing use of products from recycled polymers, or from blends with recycled polymers exposed to the outdoors, implies the need for good weathering resistance. This is particularly important when the recycled material comes, in turn, from products exposed during their lifetime to the sun. In this case the presence of C=O groups in the macromolecular chains strongly increases the photooxidative degradation kinetics of these secondary materials. In this work the change of the photooxidative degradation of blends of virgin and photooxidized polyethylene was evaluated as a function of the C=O content present in the material. As expected, the presence of the C=O groups strongly increases …

Effect of the processing on the properties of biopolymer based composites filled with wood flour

Wood-polymer composites (WPCs) are well known today in the field of industrial applications, because of several advantages they can grant if compared with mineral filler-polymer composites. These advantages regard the low cost of wood based fillers, the reduced specific weight, the lower hazards for production workers in case of inhalation, the special aesthetic features, environmental issues. The scientific literature reports studies regarding polymer matrices like, for instance, polyethylene and polypropylene, in combination with several natural-organic fillers. However, a limit of these composites is represented by the fact that there is not a full biodegradability: this, in fact, regard…

Effect of a filler on the dielectric properties of an epoxy resin

The effect of aluminum hydroxide upon the dielectric properties of an epoxy resin has been studied in a wide frequency and temperature range. An interfacial polarization effect, known as the Maxwell–Wagner–Sillars polarization is evidenced for the filled resin, which shows a higher permittivity, a higher dielectric loss, and a β transition with a larger relaxation time. The glass transition temperature is, on the contrary, mostly unaffected by the presence of the filler.

Photo-oxidative behavior of PP/GnP nanocomposites

In this work the photo-oxidative behavior of neat polypropylene (PP) and PP based nanocomposites incorporating graphene nanoplatelets (GnP) was studied. In particular, the influence of the amount of incorporated GnP was evaluated. The photo-oxidation has been followed by monitoring the change of the rheological, mechanical and spectroscopic properties upon artificial exposure to UV-B light. The results revealed that the presence of GnP reduced the rate of photooxidation of the PP matrix and, in the investigated composition range, the photo-stabilizing action improved with increasing the GnP content.

A procedure is described for the preparation of a block copolymer with A-B-A sequences in which ω-ω′-dihydroxy-poly-(ethylene glycol) is inserted between two polymeric monoacidic chains of polycaproamide and bonded to them by means of ester links. The resulting material was characterized. The copolymer is isomorphous with the polycaproamide. Thermal treatments induce a crystalline transition γ α as in polycaproamide. The influence of the moisture content on the glass transition temperature and on the storage modulus is discussed. Ein Verfahren zur Herstellung eines Blockcopolymers mit A-B-A-Sequenzen wird beschrieben. In dem Copolymer ist ω-ω′-Dihydroxy-polyethylenglycol uber Esterbindungen…

The non-isothermal rheological behaviour of molten polymers: Shear and elongational stress growth of polyisobutylene under heating

Data of stress growth under both shear and elongational kinematics have been taken in presence of heating temperature ramps on a commerical polyisobutylene.

THERMOTROPIC HOMOPOLYESTERS. IV. STUDY OF FIBER FORMATION.

We report a melt spinning and viscosity study of two semiflexible homopolyesters containing both rigid and flexible segments in the repeating unit. Single filaments of the polyesters formed from 4,4′-diacetoxybiphenyl and azelaic acid (PB7) and sebacic acid (PB8), and from 4′-hydroxyphenyl-4-hydroxycinnamate and azelaic acid (C7), were spun at temperatures between 205 and 255°C. The temperature dependence of the Newtonian melt viscosity of PB7 and C7 was investigated, and a range of molecular weights was studied for PB7. The spinning parameters, fiber characteristics, and viscosity-temperature behavior are related to the type of mesophase formed. The mechanical properties of fibers spun fro…

Influence of long chain branching on the elongational behaviour of different polyethylenes and their blends

Elongational data on a series of polyethylenes with different structure and on their blends are presented in order to correlate the extensional behaviour with the long chain branching degree.

Flow properties of low density/linear low density polyethylenes

Rheological data have been collected both in shear and non-isothermal elongational flow on three different types of blends, made from one low density polyethylene sample and three linear low density polyethylene samples. In addition to the flow curves, data are presented on the extrudate-swell phenomenon, on the instability arising in capillary flow and on the tensile behavior in the molten state.

Influence of molecular weight on the creep behavior of undiluted polyisobutylenes

The elongational behavior in constant force experiments has been considered for three samples of commercial polyisobutylene. The results compare favorably with the predictions of two existing non-linear theories as long as the samples deform homogeneously. Some qualitative observations have been made with reference to the “failure point”, i.e., the point where a non-homogeneous deformation begins.

Synthesis and Characterization of a New Fully Aromatic LCP

Abstract Liquid crystal polymers (LCP)are a relatively new class of polymers with very interesting and unusual properties. In particular, easy processability and outstanding mechanical and barrier properties make them very attractive. Unfortunately the high stiffness of their chains often leads to compounds having very high melting points and consequently to unprocessable materials. By adding a flexible segments in the chain backbone the LCPs become processable at lower temperatures but lower properties are displayed. A new rigid liquid crystalline polymer, having excellent physical properties, good processing temperature and a good cost/performance compromise, is described in this work. Th…

Non-Isothermal Effects in the Elongational Flow of Polymer Melts

Non-isothermal histories occur in almost all polymer processing, and however only a few experimental and theoretical studies have been devoted to the rheological response of the polymeric fluids under non-isothermal conditions. A systematic study, which cannot however be considered exhaustive, has been recently carried out in this field by Bogue and coworkers1–3.

Dielectric properties of a filled epoxy resin: Effect of thermal treatments

Dielectric measurements have been performed at several frequencies on samples of a cycloaliphatic epoxy resin filled with aluminum hydroxide. The samples were thermally treated at three different temperatures for times up to 2,000 hours. At low aging temperatures and times an improvement of the characteristics is observed due perhaps to an assessment of the bulk of the polymer and more precisely to a change in the free volume. At high temperatures and times a thermo-oxidation involving layers deeper and deeper becomes the predominant mechanism responsible of the decrease in the properties with respect to the virgin material.

Preparation and mechanical characterization of fibres from a new copoly(ether-ester-amide) are reported. The mechanical characteristics are slightly lower than those of polyamide 6, but satisfactory for textile use, and the fibres have larger moisture absorption. This gives rise to more comfortable fibres preventing the accumulation of electrostatic charges. Die Herstellung und mechanische Charakterisierung von Fasern aus einem neuen Copoly(ether-ester-amid) werden beschrieben. Die mechanischen Eigenschaften sind etwas schlechter als die von Polyamid 6, aber ausreichend fur textile Anwendungen. Die Fasern weisen eine grosere Feuchtigkeitsabsorption auf. Dies fuhrt zu einem angenehmeren Verh…

Influence of processing conditions on some properties of anionically synthesized polycaprolactam in presence of lithium chloride

Nylon 6–LiCl systems of various concentrations were prepared by anionic polymerization of caprolactam in the presence of salt. A depression of both crystallization rate and melting temperature was evidenced through x-ray, density, and DSC analyses. Such a preliminary characterization allowed for choosing the proper conditions in order to obtain amorphous fibers from a spinning operation which was performed at a temperature lower than the pure polymer melting point. These results are of technological relevance, especially in view of obtaining, as in similar cases, large amorphous orientations through a spinning–drawing process and high-modulus fibers after subsequent crystallization. Also, t…

Structure-properties relationships in melt reprocessed PLA/hydrotalcites nanocomposites

In this work the effect of multiple reprocessing was studied on molecular structure, morphology and properties of poly(lactic acid)/hydrotalcites (PLA/HT) nanocomposites compared to neat PLA. In addition, the influence of two different kinds of HT – organically modified (OM-HT) and unmodified (U-HT) – was evaluated. Thermo-mechanical degradation was induced by means of five subsequent extrusion cycles. The performance of the recycled materials was investigated by mechanical and rheological tests, differential scanning calorimetry (DSC), intrinsic viscosity measurements and SEM observation. The results indicated that the best morphology was achieved in the systems incorporating OM-HT. On inc…

Durability of a strach-based biodegradable polymer

Abstract The photo-oxidation and the photo-stabilization of a commercial biodegradable polymer have been investigated in order to establish the possibility of using this polymer as raw material for films for agriculture. The degradation has been followed by measuring the mechanical properties as a function of photo-oxidation time and in particular by following the elongation at break. The virgin polymer, made from maize starch and a synthetic biodegradable polyester, shows poor resistance to the UV irradiation as observed by the fast decay of the elongation at break, but the presence of small amounts of conventional UV stabilizers strongly improves the durability of this polymer. The UV sta…

Using organoclay to promote morphology refinement and co-continuity in high-density polyethylene/polyamide 6 blends – Effect of filler content and polymer matrix composition

We investigate the gradual changes of the microstructure of two blends of high-density polyethylene (HOPE) and polyamide 6 (PA6) at opposite composition filled with increasing amounts of an organo-modified clay. The filler locates preferentially inside the polyamide phase, bringing about radical alterations in the micron-scale arrangement of the polymer phases. When the host polyamide represents the major constituent, a sudden reduction of the average sizes of the polyethylene droplets was observed upon addition of even low amounts of organoclay. A morphology refinement was also noticed at low filler contents when the particles distributes inside the minor phase. In this case, however, keep…

Cyclophosphazenes as versatile substrates in polymer chemistry

In this article we present the synthesis of new cyclophosphazenes and their use as chain extenders, polymers compatibilizers, and monomers.

Characterization of a fiber reinforced semirigid liquid crystalline polymer

In this work, samples of a semirigid Liquid crystalline polymer reinforced with carbon and glass fibers has been characterized. Semirigid liquid crystalline polymers (LCPs) show some advantages with respect to rigid LCPs: in particular lower processing temperatures, and better compatibility with flexible thermoplastics, but also some disadvantages: lower mechanical properties and poor thermomechanical resistance. Both properties can be improved by adding inorganic fillers. Although elastic modulus and tensile strength of the glass fiber filled LCP improve remarkably with increasing the filler content, the same properties for the carbon fiber-filled samples do not increase with increasing ti…

Processing and characterization of blends of fluoroelastomers with semirigid liquid crystal polymers

Fluoroelastomers (FEs) usually have working temperatures above 150°C and a great resistance to aggressive agents such as oils, fuels, aliphatic and aromatic solvents, steam, moderate acid, and basic environments. Liquid crystal polymers (LCPs) can be effective processing aids and reinforcing agents for elastomers. These characteristics are very attractive to lower melt viscosity and to stiffen and strengthen the final product through a simple blending. Among the LCPs, the semirigid LCPs seem the most appealing for blending with flexible thermoplastics (FTs) because their processing temperatures can be arranged to be in the same processing temperature range of FTs and because the presence of…

Thermomechanical degradation of filled polypropylene

The main problem in post-consumer plastics recycling is due to the thermomechanical stress acting on the melt during the reprocessing operations. The macromolecules break because of the temperature and of the mechanical stress. The extent of degradation is then correlated to the level of mechanical stress which, in turn, is proportional to the viscosity of the melt. The presence of fillers increases the viscosity of the polymers and then it is expected that the level of thermomechanical degradation of these systems is larger than that of the unfilled material. In this work the thermomechanical degradation kinetic of a polypropylene sample is investigated as a function of the calcium carbona…

Reprocessing and Properties of Homopolymer Blends of Virgin and Recycled Polymers

The blends of the same virgin and recycled polymer, (homopolymer or “monopolymer” blends), show rheological and mechanical properties in most cases between those of the two components athough, in general, lower than those expected on the basis of additivity rules. In some cases, however, a minimum observed in some property versus composition curves is correlated with the change of the crystalline morphology induced by structural differences of the two components and due to different molecular weights and, in particular, the presence of oxygenated groups. In this chapter, the main properties of some homopolymer blends will be reviewed by considering, in particular, the influence of compositi…

Recycling of heterogeneous plastics wastes. II—The role of modifier agents

Abstract Recycling of mixed plastics waste, mainly composed of PEs, PET and PVC has been carried out by blending with recycled polyethylene. Although the extrusion of these blends has been carried out at high temperatures, the degradation of the PVC was modest due to the short residence times. The mechanical properties of these secondary materials, up to about 30% of mixed plastics waste, are very similar to those of the recycled polyethylene, except for the elongation to break. By adding some modifier agents, the elongation at break and especially the impact strength can be further improved.

Accelerated weathering of PP based nanocomposites: Effect of the presence of maleic anhydryde grafted polypropylene

Polymer nanocomposites are currently a topic of great interest. The increasing importance they are gaining also in the standpoint of industrial applications, is giving concerns regarding their environmental stability and, in general, their behaviour in outdoor applications, under direct solar irradiation. Papers available in the literature have highlighted the different influences of different nanosized fillers, in particular clay-based nanofillers; however, few data are available regarding other nanosized fillers. Furthermore, the research on polymer nanocomposites has clearly pointed out that the use of compatibilizers is required to improve the mechanical performance and the dispersion o…

UV-stabilisation of polystyrene-based nanocomposites provided by polyhedral oligomeric silsesquioxanes (POSS)

Abstract The photo-ageing behaviour of Polyhedral Oligomeric SilSequioxane (POSS)-polystyrene (PS) nanocomposites has been investigated for the first time. POSS having different inorganic framework and pendant organic groups have been used in the PS nanocomposite preparation and the formulated films were subjected to accelerated weathering. Compared to pristine PS, the POSS-containing PS developed a lower level of carbonyl and hydroxyl groups as a function of the exposure time, indicating a significantly improved resistance of the nanocomposites to photo-degradation. The results suggest that all of the investigated POSS molecules play a protective role and may extend the in-use lifetime of …

Photooxidation and photostabilization of EVA and cross-linked EVA

Abstract Cross-linked EVA copolymers are widely used as encapsulant material for photovoltaic modules in order to protect the solar cell from the dangerous and degrading environmental factors like moisture and UV radiations. The protection of these modules from photooxidation is the main important objective in their production. In this work, samples of cured EVA in presence of different types of stabilizers have been photooxidized to better understand the photooxidation behavior and the effects of these stabilizers on the mechanical properties. All the results obtained on the cross-linked samples have been compared with those obtained in the same conditions and with the same formulations wi…

In-line monitoring of the photooxidation behaviour of a PP/clay nanocomposite through creep measurements

Abstract The photooxidation behaviour of a polypropylene/organomodified clay nanocomposite sample has been monitored by means of a new apparatus through the record of the creep curves measured while the sample is subjected to the contemporary action of temperature, tensile strength and UV radiation. The creep curves of the irradiated samples are higher than those of the non-irradiated samples and the curves diverge when the molecular weight begins to decrease because of the degradation. At the same the formation of carbonyl groups is observed. The creep curves of the non-irradiated and irradiated samples give, then, an immediate evaluation of the begin and of the development of the photooxi…

Recycling of compatibilized and uncompatibilized nylon/polypropylene blends

The recycling of compatibilized and uncompatibilized nylon6/polypropylene blends has been carried out by repetitive extrusions. The change of the properties of the blends is a function not only of the number of reprocessing steps but also of the type of compatibilizer. The worsening of the mechanical properties is small and, indeed, some improvement can be observed after one or two extrusion steps for some blends. It is hypothesised that the decrease of the molecular weight, the typical effect occurring during this thermomechanical treatment, is counterbalanced and overcome by the possible formation of new copolymers that act as bridges between the two phases. This behaviour is displayed by…

Waste polymers as bitumen additive: characterization and properties

Influence of small amounts of polyvinylchloride on the recycling of polyethyleneterephthalate

Abstract Polyethylene terephthalate (PET), and polyvinyl chloride (PVC), are commonly encountered in plastics stream coming from separate collections of plastic bottles. The presence of PVC in the recycled PET is very dangerous because of the chain scission provoked by the hydrogen chloride evolved from the macromolecules during degradation of PVC. Recycled PET must be free of PVC; contents of PVC as little as 100 ppm can induce degradation and discoloration of the polyester. PET, in its turn, is degraded when the processing is carried out in the presence of water. In previous work, however, the degradation of PET was eliminated and rather an increase of the molecular weight has been measur…

Liquid crystal polymer-based blends: “Universal grade” polymers?

Polymeric materials can be easily processed with different processing operations thanks to suitable rheological properties. Melt flow index, or grade, which is a measure of the fluidity of the polymers, is the most commonly parameter used to characterize the polymers from the point of view of their melt viscosity. Injection molding requires high grade materials, whereas low grade values are best suited for extrusion. Of course, it would be no doubt of interest if single “universal grade” materials could be used for all processing operations. In this paper it is demonstrated that the blends of low grade polymers with small amounts of liquid crystal polymers can be conveniently used for all p…

Photo-oxidation of polypropylene/graphene nanoplatelets composites

Abstract The photo-oxidation behaviour of polymer nanocomposites depends not only on the photo-oxidation behaviour of the matrix, but also on the chemical composition, on the physical properties of the nanoparticles and on the possible interactions between the two phases. In the case of nanocomposites with carbonaceous particles, the main effect is a photo-stabilization due to the absorption of the UV energy and the radical scavenging action. In this work we investigated the effect of the presence of graphene nanoplatelets on the photo-oxidation behaviour of the polypropylene. The presence of the graphene nanoplatelets improves the photo-resistance of the polypropylene and this effect incre…

Effect of graphene nanoplatelets on the photo-oxidative behavior of PP based nanocomposites

The photo-oxidation behavior of polymer nanocomposites depends not only on the photo-oxidation behavior of the matrix, but also on the chemical composition and on the physical properties of the nanoparticles and on the possible interactions between the two phases. Graphene nanoplatelets (GnP) are short stacks of individual layers of graphite that, even at low contents, strongly affects many properties of the thermoplastic matrix. Indeed, by GnP adding, also at low filler concentration (< 5 wt.%), the mechanical, heat-resistance, thermal and electrical properties of the polymer matrix can be surprisingly modified. Of course, the effects of these nanoparticles on the properties of the poly…

Effect of the Orientation on the Properties of Compatibilized Polypropylene/Liquid Crystal Polymer Blends

Abstract Blends of polypropylene and a semirigid liquid crystal polymer have been compatibilized with an acrylic acid modified polypropylene and with an ad-hoc synthesized graft copolymer made from polypropylene and from the monomers of the liquid crystal polymer. The two compatibilizers improve the adhesion and the mechanical properties of the two incompatible phases. The two compatibilizers give about the same results. The effect of the compatibilization improve also the orientation of the liquid crystalline polymer particles and the mechanical properties.

Crystallization kinetics of LDPE/Ny6 blends

The crystallization behaviour of low density polyethylene/nylon 6 blends has been investigated as a function of the composition. The melting points of the polymers are almost uninfluenced by the presence of the other homopolymers except for blends with a nylon content of 75–90%. Blends with 10% nylon content do not exhibit the crystallization peak during the cooling step probably because of the low concentration and high viscosity of the low density polyethylene matrix. The crystallinity degree of the polyethylene is independent of the composition, while some variations are shown by the polyamide. Finally the rate of nucleation is strongly affected by the composition, in particular for the …

Photo-oxidation behaviour of polyethylene/multi-wall carbon nanotube composite films

Abstract The resistance to accelerated photo-oxidation of polyethylene/multi-walled carbon nanotubes (MW-CNTs) composite films was compared with the photo-oxidation behaviour of pristine polyethylene film. The polyethylene/MW-CNTs films containing different CNTs loading were subjected to accelerated UV-B exposure. At short exposure time, i.e. under 200 h, the rates of carbonyl formation are very similar to that observed for pristine polyethylene film but at longer irradiation times the carbonyl formation increases for lower MW-CNTs contents (0.1, 0.2 and 0.5% wt./wt.), and decreases for higher MW-CNTs contents (1 and 2% wt./wt.). By adding a UV-stabilizer to the films their photo-oxidation …

Photo-oxidation behaviour of polyethylene/polyamide 6 blends filled with organomodified clay: Improvement of the photo-resistance through morphology modification

Abstract The impact of small amounts of organomodified clay (OMMT) on the photo-degradation behaviour of two blends obtained by mixing either low-density polyethylene (LDPE) or high density polyethylene (HDPE) with polyamide 6 (PA6) (LDPE/PA6 and HDPE/PA6 75/25 wt-%) was studied. The complex photo-degradation behaviour was followed by monitoring the main physical–mechanical properties of the blends. In particular, mechanical and spectroscopic tests were performed in conditions of accelerated artificial aging. An accurate mechanical and morphological characterization was previously carried out. The presence of the OMMT promotes the unexpected formation of a co-continuous morphology for the H…

Recycling of a starch-based biodegradable polymer

A new starch-based polymeric system, ZI1OU from Novamont, mainly composed of starch and polycaprolactone, was reprocessed several times in an extruder to investigate the recyclability of this biodegradable polymer. A previous investigation of the thermomechanical degradation in a mixer has been also done. The degradation is mostly due to the thermal stress but the presence of the mechanical stress strongly increases the degradation kinetic. During melt processing two concurrent processes take place: the first is the degradation, i.e. the breaking and shortening of polymeric chains, mostly occurring in the PCL phase; the second is the formation of some crosslinked structure in the starch pha…

Blends of polypropylene and nylon 6: Influence of the compatibilizer, molecular weight, and processing conditions

The aim of this work is to study the influence of different types of compatibilizing agents, different processing conditions, and the molecular weight of the two components on the properties of immiscible blends of polypropylene and nylon 6. Increasing the content of the functional group of the modified polypropylene and the content of nylon in the blend, the effectiveness of the compatibilization improves. The same effect is observed by decreasing the molecular weight of the two components, in particular, that of the polyamide. The influence of the processing conditions is slight provided no degradation takes place during processing. © 1993 John Wiley & Sons, Inc.

Rheological behaviour, filmability and mechanical properties of biodegradable polymer films

The rheological properties in shear flow and non isothermal elongational flow of two biodegradable polymers, belonging to two different classes of materials, have been measured and compared with those of a film blowing grade high density polyethylene in order to assess the filmability of these polymers. The mechanical properties of isotropic and anisotropic samples have been also reported.

The role of organoclay in promoting co-continuous morphology in high-density poly(ethylene)/poly(amide) 6 blends

The effect of organically modified clay on the morphology, rheology and mechanical properties of high-density polyethylene (HDPE) and polyamide 6 (PA6) blends (HDPE/PA6 ¼ 75/25 parts) is studied. Virgin and filled blends were prepared by melt compounding the constituents using a twin-screw extruder. The influence of the organoclay on the morphology of the hybrid was deeply investigated by means of wide-angle X-ray diffractometry, transmission and scanning electron microscopies and quantitative extraction experiments. It has been found that the organoclay exclusively places inside the more hydrophilic polyamide phase during the melt compounding. The extrusion process promotes the formation o…

DEGRADATION OF MATER-BI /WOOD FLOUR BIOCOMPOSITES IN ACTIVE SEWAGE SLUDGE

The mechanical properties of Mater-Bi® are, in general, not adequate for certain applications and the addition of a filler is therefore necessary. Among the different fillers, natural fibres are particularly interesting because they potentially allow improving the performance of the material without compromising its biodegradability. In order to improve the basic mechanical properties of a Mater-Bi grade and to obtain a new, fully biodegradable material, wood flour based composites were prepared by different processing methods. To simulate actual and not laboratory bacterial attack on the prepared materials, in this work we studied the biodegradation of the composites in a real active sewag…

Thermo- and photo-oxidative stability and improved processability of polyamide stabilized with a new functional additive

During processing polyamides can undergo thermo-mechanical degradation due to the mechanical stress and to the high temperature applied to the melt. Degradation can occur also during the polyamides lifetime due to many driving forces, like temperature, ultraviolet radiations, etc. The mechanisms of degradation are not well understood and the stabilization with usual stabilizers, like phenol antioxidants, is not so efficient as for other classes of polymers. The aim of this work is the study of the effects of the addition of a new multifunctional additive on the processing and on the thermo- and photo-stabilization of polyamide-6. This additive is able to prevent the thermo-mechanical degrad…

Morphology and properties of blends of polyethylene with a semiflexible liquid crystalline polymer

Blends of three polyethylene (PE) samples (two HDPE grades and LLDPE) with an experimental sample of a semiflexible liquid crystalline polymer (SBH 1 :1 :2 by Eniricerche) have been prepared in a Brabender compounder. The processing-aid effect of the LCP has been demonstrated by the decreased energy required for extruding the blends, as compared to that needed for neat PE. The thermal properties, as studied by differential scanning calorimetry (DSC), have shown that the two components of the blends are immiscible. However, the dispersed SBH phase has been found to act as a nucleating agent for the crystallization of LLDPE, whereas no such effect was observed for HDPE. This has been taken as…

Filmability and properties of compatibilized PA6/LDPE blends

Blends of low density polyethylene (LDPE) and polyamide 6 (PA6), compatibilized with an ethylene-acrylic acid copolymer (EAA), either alone or combined with a low molar mass bis-oxazoline compound (PBO), have been processed in film blowing operations and the properties of the films have been investigated. Without of compatibilization, the filmability of the blend was very poor and no significant specimen was collected. As a result of the reactive compatibilization, the blends with EAA and even more with the EAA-PBO, were processed successfully in film blowing. The films of the quaternary blends were shown to possess satisfactory mechanical properties as a result of fine and stable morpholog…

Optimization of spinning, drawing, and annealing conditions in the production of highly oriented fibers from the polycaprolactam/3.7% LiCl system

A polycaprolactam/3.7% w/w LiCl system, obtained by anionic polymerization of caprolactam directly in the presence of salt, has been employed for the production of highly oriented fibers. More particularly, an optimization of spinning, drawing, and annealing conditions has been performed, finally obtaining fibers which shows very satisfactory mechanical results. Namely, average moduli values up to 12 GPa and strength values up to 1 GPa when fracture is far from clamps, have been observed.

Melt spinning and mechanical properties of semirigid liquid-crystal copolyesters

Melt-spinning and mechanical properties of fibers of a new class of semirigid thermotropic liquid-crystal polymers are presented. These copolyesters are synthesized from 4-4′-dihydroxybiphenyl (B), 4-hydroxybenzoic acid (H), and flexible units provided by aliphatic diacids. The flexible units depress the melting temperature without strongly depressing the mechanical properties. These liquid-crystal polymers can be easily spun at high draw ratios. Indeed, unlike rigid liquid-crystal polymers, relatively high draw ratios are needed to attain high mechanical strength. Tensile moduli of about 28 GPa and tensile strengths of about 350 MPa are obtained. © 1993 John Wiley & Sons, Inc.

Melt stabilisation of high-density film-grade polyethylene

The thermoxidative degradation of a high-density polyethylene stabilised either with standard and novel kinds of antioxidants was examined at many different temperatures. The aim of this work was to investigate the degradation response (crosslinking or chain-breakage) on the polyolefin molecular structure in terms of low shear rate melt viscosity increment and oxidation induction time both studied through steady and dynamic shear flow tests performed in a rotational rheometer. Lactone type antioxidants, especially the one containing P-EPQ phosphite component, exhibit the lowest thermoxidative degradation at high temperatures. Vitamine E, used in blend with a phosphite, appears to be a good …

An experimental investigation of the shear behaviour of polyethylenes with different structures

Rheological properties in shear flow are presented for four different polyethylene samples: a high density, a linear low density and two low density polyethylenes manufactured using different techniques. Tests have been performed with the aid of capillary types of instrument equipped with capillaries of various lengths at three different temperatures. End correction factors have been determined and true flow curves obtained. Swelling ratios for both unannealed and annealed samples have been determined as well as the shear rate and shear stress at which irregularities begin. In some cases generalized plots have been prepared and in all cases the rheological response is discussed in terms of …

Environmental degradation of polymers for cultural heritage

Plastic materials are used both for the protection of cultural heritage and as material for artworks. As for other materials, the durability and the maintenance of their initial properties are fundamental for the use of these materials. For the protection of the cultural heritage (particularly for stone artworks) the main important properties are the hydrophobicity, the UV transparency and the water vapour permeability that must be maintained even after a long exposure to the environmental conditions (UV irradiation, rain, temperature variations, etc.). When the polymers are used for the production of an artwork, the most important characteristics are the maintenance of the aesthetical appe…

Effects of filler type and mixing method on the physical properties of a reinforced semirigid liquid crystal polymer

Semirigid liquid crystalline polymers (LCPs) show some advantages with respect to rigid LCP: in particular lower processing temperatures, better compatibility with flexible thermoplastics, but also some disadvantages. Thermal resistance of rigid LCPs is much better and the maximum working temperature is, in general, very high. The thermomechanical properties can be improved by adding inorganic fillers. In this work processing, mechanical and thermomechanical properties of a filled semirigid liquid crystal copolyester are reported. Several inorganic fillers have been used in order to put in evidence the influence of shape and dimensions of the particles on the properties of the filled materi…

Injection moldability and properties of compatibilized PA6/LDPE blends

An ethylene-acrylic acid copolymer (EAA), either alone or combined with a low molar mass bis-oxazoline compound (PBO), has been used as a compatibilization promoter for blends of polyamide-6 (PA6) with low-density polyethylene (LDPE). The effect of compatibilization on blend processability in injection molding operations and on the properties of the molded specimens has been studied. In the absence of compatibilization, the injection molded articles were shown to have low-quality surface appearance and poor mechanical properties. Both these characteristics were appreciably improved as a result of reactive compatibilization of the blends with EAA and, even more, with the EAA-PBO couple. In f…

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 understan…

Ultimate tensile properties and dart impact behaviour of coextruded films of LDPE and LLDPE were compared with those of films made from blends of the same resins. The effect of composition and of both blow up ratio and axial draw ratio of the blowing process on film properties was explored. The results indicate that, at least for semicompatible systems like that considered here, films made from blends and coextruded ones have mechanical properties very close to each other. Die Festigkeitseigenschaf ten und das Verhalten beim Kugelfalltest von coextrudiertcn Filmen aus LDPE und LLDPE wurden mit den entsprechenden Eigenschaften von aus Mischungen dieser Polymere hergestellten Filmen vergliche…

Processing and characterization of highly oriented fibres of biodegradable nanocomposites

Abstract Biodegradable polymeric materials are becoming day by day ever more important in packaging, agriculture, single-use cutleries and other large consumer applications. The major part of those materials is used under the form of film, i.e. subjected to elongational flow, but the main problem is that they often offer poor mechanical properties. Adding nanofillers, like Multi Walled Carbon Nanotubes (MWCNTs) may solve this problem but only if there is a full control of their orientation inside the material. Aim of this work is to investigate the processing-properties-morphology relationships for a system prepared under elongation flow of MaterBi and commercial MWCNTs. The materials were …

Effetto del flusso elongazionale su nanocompositi a base di miscele polimeriche.

Scopo di questo lavoro è stato, pertanto, quello di studiare l’effetto del flusso elongazionale su nanocompositi a base di miscele poliammide/polietilene al fine di valutare come questo possa influenzare e modificare le principali proprietà. In particolare, si è osservato come variano le proprietà meccaniche fra il materiale isotropo (piastrine ottenute per stampaggio a compressione) e il materiale orientato ottenuto per filmatura in bolla.

Mechanical behaviour of Mater-Bi/wood flour composites: a statistical approach

Interest in biocomposites (lignocellulosic filled biopolymers) started in the 90s, due to environmental advantages, related to the full biodegradability of both matrix and filler, economical issues (organic fillers usually come from sawmill or agriculture wastes) and aesthetical issues (wood filled biopolymers could be particularly pleasant if used for indoor furnishing and automotive interior). In this work, a method for a systematic study of the properties of Mater-Bi®/wood flour composites is presented. A two-level full factorial model was built. It allows investigating the effects of multiple operative variables on the observed properties, their contributions, their optimal combinations…

Effect of the Components Molar Mass and of the Mixing Conditions on the Compatibilization of PE/LCP Blends by PE-g-LCP Copolymers

The rheology, morphology, and mechanical properties of blends of high-density polyethylene (HDPE) with a semiflexible liquid crystalline copolyester (SBH) were studied in order to assess the compatibilizing ability of added PE-g-SBH copolymers, and its dependence on the molar mass of the PE matrix, and on the technique used for blend preparation. The PE-g-SBH copolymers were synthesized as described in previous articles, either by the polycondensation of the SBH monomers in the presence of a functionalized PE sample containing free carboxyl groups, or by reactive blending of the latter polymer with preformed SBH. Two samples of HDPE having different molar masses, and two samples of SBH with…

A Biodegradable, Bio-Based Polymer for the Production of Tools for Aquaculture: Processing, Properties and Biodegradation in Sea Water

Bio-based, biodegradable polymers can dramatically reduce the carbon dioxide released into the environment by substituting fossil-derived polymers in some applications. In this work, prototypes of trays for aquaculture applications were produced via injection molding by using a biodegradable polymer, Mater-Bi®. A characterization carried out via calorimetric, rheological and mechanical tests revealed that the polymer employed shows properties suitable for the production of tools to be used in aquaculture applications. Moreover, the samples were subjected to a biodegradation test in conditions that simulate the marine environment. The as-treated samples were characterized from gravimetrical,…

Amorphous semiconducting passive film-electrolyte junctions revisited. The influence of a non homogeneous density of state on the differential admittance behaviour of anodic a-Nb2O5

Abstract An analysis of the electronic properties of amorphous semiconductor-electrolyte junction is reported for passive films grown on Nb in alkaline solution and in a large range of thickness (~20nm ÷ ~250nm). A modelling of electronic density of state (DOS) has been carried out by fitting EIS spectra, at different potentials and in a range of frequencies (0.1 Hz ≤ f ≤100 kHz), and differential admittance (DA) data of a-Nb 2 O 5 /El interface. The fitting of EIS and DA curves was performed by using the theory of amorphous semiconductor Schottky barrier and a non-homogeneous DOS distribution.

The role of organoclay and matrix type in photo-oxidation of polyolefin/clay nanocomposite films

Abstract In this paper the photo-oxidation behaviour of polyolefin/clay nanocomposite films was studied; in particular, the effect of the amount of organo-modifier and the matrix polarity on the photo-oxidation was investigated. Two different organo-modified clays and compositions of LDPE/EVA blend films were used and the photo-oxidation was followed by mechanical and spectroscopic analyses. The organoclay and matrix type strongly influence the photo-oxidative behaviour of nanocomposite films. The films filled with CL15A show a faster loss of mechanical performance and higher carbonyl formation with respect to the films filled with the CL20A. Additionally, the LDPE based nanocomposite under…

Liquid crystal polymers (LCP) as processing aids and reinforcing agents. A study of nylon 6/LCP blends

Influence de petites quantites d'un copolyesteramide thermotropique sur les proprietes mecaniques et la mise en œuvre du polyamide 6

Effect of annealing below the glass transition on the loss peak of glassy polycarbonate

Effect of kind and content of organo-modified clay on properties of PET nanocomposites

In this work we report the properties of nanocomposite based on PET with two different samples of organically modified montmorillonites. In particular, we studied the effect of the filler concentration on morphology, rheology, and mechanical performance, focusing our attention on the effect of the degradation phenomena of the clay modifiers. The results indicate that at low clay level the morphology achieved is mainly intercalated. On increasing the filler level, coalescence and/or bad defragmentation phenomena induce a coarser morphology, as confirmed by XRD, SEM, and TEM observations. When a more polar organic modifier is used to modify the clay, the particle adhesion and distribution is …

Thermomechanical degradation of PP based nanocomposites filled with graphene nanoplatelets

Graphitic nanofillers have extensively used to prepare nanocomposites based on both conventional petroleum based plastics and bio-based polymers . Among them, graphene or graphite nanoplatelets (GnP), also called graphite nanosheets or nanoflakes, are a relatively new carbon nanomaterial composed of stacked 2D graphene sheets with outstanding electrical, thermal and mechanical properties. Indeed, by adding GnP, also at low filler concentration (< 5 wt.%), the mechanical, heat-resistance, thermal and electrical properties of the polymer matrix can surprisingly enhance due to unique properties of these nanofillers. However, the characteristics of these multiphase systems certainly depend o…

The Amorphous Semiconductor Schottky Barrier Approach to Study the Electronic Properties of Anodic Films on Ti

A detailed study of the electronic properties of thin (>20 nm) anodic TiO2 potentiostatically grown on titanium in two different solutions is presented. The results show that the nature of the anodizing solution affects the electronic properties of the anodic film and, more specifically, the density of electronic states (DOS) distribution. Different DOS were derived from the experimental data analyzed according to the theory of amorphous semiconductor (a-SC) Schottky barrier. It is shown that the usual non-linear and frequency dependent Mott-Schottky plots are in agreement with expected theoretical behavior of a-SC Schottky barrier.

Compatibilization of a polyethylene/polyamide 6 blend nanocomposite

Polymer blends of incompatible components need to be compatibilized to give rise to a blend with good properties. At the same way, polymer/clay nanocomposites show the same problem because of different chemical nature of the polymer matrix and of the clay. Compatibilization is then necessary if an incompatible polymer blend is filled with an organomodified clay. In this work a polyethylene/polyamide 6 blend filled with an organomodified clay has been compatibilized with a maleic anyhidride grafted SEBS (styrene-ethylene-butylene-styrene) copolymer and a glicidylmethacrylate-ethylene copolymer. The results show that compatibilization improves the mechanical properties in terms of elongation …

Dielectric behaviour of a γ-irradiated polycarbonate

Dielectric measurements on a γ-irradiated polycarbonate in a dose range 0–20 Mrad and at test frequencies of 103 and 104 Hz have been carried out. The glass transition temperature shows a maximum at 3.5 Mrad and then decreases at larger doses. This result is in line with other experiments (intrinsic viscosity, dynamic-mechanical measurements, etc) already reported: the Tg values are however larger in the present results. This is probably due to the plasticizing action of the absorbed moisture present in the previous tests. A Tg vs 1/[n]2 plot (1/[n]2 is proportional to 1/m ) allows to find the value of the glass transition point at an infinite molecular weight and the dependency of Tg on mo…

Electromechanical coupling in anodic niobium oxide: Electric field-induced strain, internal stress, and dielectric response

Seemingly, contradictory results have been reported so far for electrostriction in anodic oxides. Furthermore, no definitive agreement could be obtained with theory. In this paper, in situ techniques are combined to elucidate electrostriction in anodic niobium oxide. The dependence of strain, internal stress, and dielectric constant on the electric field is measured by, respectively, spectroscopic ellipsometry, curvature, and impedance measurements. The through-thickness strain is tensile and proportional to the square of the electric field. The in-plane internal stress is compressive and proportional to the square of the electric field at low field values. The internal stress is predicted …

Low-density polyethylene/polyamide/clay blend nanocomposites: Effect of morphology of clay on their photooxidation resistance

The photooxidation behaviour of low-density polyethylene (LDPE)/polyamide (PA) blends, containing polyamide 11 (PA11) or polyamide 6 (PA6), has been investigated in the absence and presence of a small amount of commercial organomodified clay (OMMT). The polymer blends LDPE/PA11 and LDPE/PA6 at 75/25 wt./wt.%, with and without OMMT, have been prepared by a two-step procedure: extrusion and sheet formulation. The formulated complex systems have been subjected to accurate morphological analysis in order to evaluate the effect of the OMMT presence on the refinement of the blend morphology. Furthermore, the produced sheets have been subjected to arterial UVB exposure and the variations of the me…

Recycling of inside upholstery of end-of-life cars

A model study for the recycling of the interior upholstery plastic parts of end-of-life cars has been carried out by reprocessing the homogenized scraps of an upholstery farm in the presence of different compatibilizer precursors, such as an ethylene-glycidylmethacrylate copolymer (EGMA), a maleic anhydride functionalized thermoplastic elastomer (SEBS-MA), etc. The investigated scraps contained recycled polyethylene (from agricultural uses) and poly(ethylene terephthalate), as the main components, plus minor proportions of polypropylene, polyamide-6, and other additives, including an ethylene copolymer (EC), probably an ethylene-acrylic acid copolymer, which is used to compatibilize the car…

Testing of a constitutive equation with free volume dependent relaxation spectrum

A model of non-linear viscoelasticity with relaxation times dependent upon free volume is here proposed. The free volume is related to the isotropic part of the stress tensor by means of a simple differential equation. The model predictions are compared with a large amount of experimental results taken on polymeric melts or concentrated solutions and reported in the literature. The single parameter of the model is determined, within each set of data, by fitting of the viscosity curve. A satisfactory agreement is obtained with data taken under both elongation and shear for which also the relaxation behavior after single and double strain steps is considered.

Influence of processing conditions on rheological and mechanical properties of polycarbonate/polypropylene blends

Abstract Rheological and mechanical data on polycarbonate/polypropylene blends are reported as a function of the blend preparation. Both kinds of properties depend on the properties of the homopolymers and on the processing conditions. In the molten state the blends are compatible at low content of polypropylene and incompatible at high content. The blends with intermediate compositions can be called semicompatible. Also in the solid state the blends with low content of polypropylene are compatible, while all other blends are incompatible.

Effect of small amounts of poly(lactic acid) on the recycling of poly(ethylene terephthalate) bottles

Abstract Poly(ethylene terephthalate) (PET) is one of the most used commodity polymers, especially for food and beverage applications, and its recycling is of great importance because of the possible use in the textile and construction industries. On the other hand, the interest in biodegradable polymers has led, in recent years, to the use of materials such as poly(lactic acid) (PLA) also in the food and beverage industry. The presence of small amounts of PLA in the PET waste can significantly affect the post-consumer recycling process. In this work, the effect of the presence of small amounts of PLA on the recycling of PET bottles is investigated by rheological, mechanical, morphological …

Thermomechanical degradation of compatibilized and uncompatibilized nylon 6/polypropylene blends

The thermomechanical degradation of compatibilized and uncompatibilized nylon 6/polypropylene blends has been followed to investigate the changes of structure, morphology and properties of these blends as a function of the type of compatibilizer and of the processing time. The degradation of the blends mostly depends on the type of functional group of the polypropylene. Indeed, the thermolability of an acrylic acid-functionalized polypropylene gives rise to a continuous decrease of the compatibilization efficiency and the properties of the blend with this polypropylene sample much worse than that observed for the blend with a maleic anhydride-functionalized polypropylene.

Chemical Modification of Nitrile to Oxazoline Functionality on a Styrene-Acrylonitrile Copolymer in the Melt

Oxazoline is a very interesting functionality for reactive extrusion and other applications. In this paper, we report the possibility of chemically transforming nitrile group attached to a copolymer of styrene and acrylonitrile (SAN) to oxazoline group using 2-amino-ethanol (AE). The chemical modification of SAN with AE was done in the molten state. Among various catalysts tested, zinc acetate turned out to be the most efficient. The effects of the catalyst concentration, temperature and mixing on the overall kinetics were studied. The formation of the expected oxazoline functionality was confirmed by infrared spectroscopy and by reacting with 1-naphthylacetic acid. The reaction between the…

Polypropylene/graphene nanoplatelets nanocomposites subjected to elongational flow

In this work the effect of the presence of graphene nanoplatelets (GnP) on the morphology and mechanical properties of polypropylene/GnP nanocomposites has been investigated when these polymer systems are subjected to non-isothermal elongational flow in a melt spinning operation. The presence of the GnP magnifies the effect of the elongational flow. Indeed, the elastic modulus and the tensile strength increases with the orientation more than that observed for the pure matrix.

Effect of heating of organo-montmorillonites under different atmospheres

Abstract We studied the influence of heating on the behaviour of two organo-montmorillonites paying particular attention to the possible degradation effects of the organic modifier under different atmospheres. Hoffmann elimination and anucleophilic substitution on the nitrogen led to rapid degradation of the modifier. As confirmed by deconvoluted FTIR spectra, the presence of oxygen accelerated the degradation rate. The degradation products of the modifier (α-olefins transforming into various carboxyl compounds if oxygen is present) initially increased the basal spacing, followed by a collapse of the particle layers when the decomposition products migrated toward the surface and eventually …

EFFECT OF MOISTURE ON THE BULK PROPERTIES OF SALTED POLY(CAPROAMIDE).

The glass-transition temperature (Tg) and the elastic modulus of nylon-6 and its mixtures with 4% w/w LiCl and with 2% LiCl+3% LiBr were investigated. In one set of experiments care was taken to avoid absorption of moisture during the measurements. In another set of experiments, samples were exposed to atmospheric humidity for different lengths of time. Both unoriented and oriented specimens were investigated. The presence of 4% LiCl almost doubles the amount of moisture absorbed at equilibrium by nylon-6. The Tg was found to be greatly affected by the moisture content and by salt type. When strict precautions to exclude moisture are taken, the addition of 4% LiCl raises the Tg of nylon-6 b…

Processing – morphology – property relationships of polyamide 6/polyethylene blend–clay nanocomposites

In this work, we studied the effect of the method of preparation and of reprocessing on the morphology and, con- sequently, on the physical properties of polyamide 6 (PA6)/ high density polyethylene (HDPE)-clay nanocomposite blends in the presence of different compatibilizers. In particular, the nanocomposites were obtained by melt mixing using a co- rotating twin screw extruder (E1). The blends thus obtained were re-extruded (E2) under the same operating conditions. Moreover, blends with the same final composition were produced using a masterbatch of the compatibilizer with the clay prepared in a separated stage in a batch mixer (MB). All the materials were characterized by scanning electr…

Green composites: A brief review

The rising concern towards environmental issues and, on the other hand, the need for more versatile polymer-based materials has led to increasing interest about polymer composites filled with natural-organic fillers, i.e. fillers coming from renewable sources and biodegradable. The composites, usually referred to as "green", can find several industrial applications. On the other hand, some problems exist, such as worse processability and reduction of the ductility. The use of adhesion promoters, additives or chemical modification of the filler can help in overcoming many of these limitations. These composites can be further environment-friendly when the polymer matrix is biodegradable and c…

Thermomechanical degradation of PLA-based nanobiocomposite

Nanobiocomposites are a new class of biodegradable polymer materials with nanometric dispersion of inert particles in a biodegradable polymer matrix that show very interesting properties often very different from those of conventional- filled polymers and also biodegradability. An important issue in the applications of the biodegradable polymers is their easy degradability during processing due to the thermomechanical stress or to the presence of humidity. In this work, the thermomechanical degradation behavior of a nanobiocomposite made by a PLA-based blend and an organomodified montmorillonite has been investigated. The degradation kinetics has been followed by means of rheological, mecha…

Characterization of monopolymer blend of virgin and recycled polyamide 6

It is a common industrial practice to blend virgin polymer with the same recycled polymer coming from plastic scraps that, in general, has not undergone relevant degradation. In this work, the characteristics of blends of virgin and recycled polyamide have been considered by changing the amount of recycled polymer and the presence of humidity and a stabilizer. Neither dry nor wet stabilized recycled polyamide samples show significant variations of the molecular weight, but the melt Newtonian viscosity of the blends are slightly different from that predicted by an additive rule, despite the same chemical nature of the two components. This holds true even more for the humid unstabilized sampl…

Increasing the elastic modulus of polyamides

A comprehensive experimental study of the rheological behaviour of HDPE.

Extensional properties of four high density polyethylenes with different molecular weights and molecular weight distributions are presented. The samples have already been well characterized in shear and non-isothermal extensional flow. The data were collected at 180 °C for elongational rates between 3 · 10−1 and 10−4s−1. Some qualitative and quantitative generalizations of the results are given.

Biopolymer based nanocomposites reinforced with graphene nanoplatelets

In this work, biopolymer based nanocomposites filled with graphene nanoplatelets (GnP) were prepared by melt compounding in a batch mixer. The polymer used as matrix was a commercial biodegradable polymer-blend of PLA and a copolyester (BioFlex®). The prepared materials were characterized by scanning electron microscopy (SEM), rheological and mechanical measurements. Moreover, the effect of the GnP amount on the investigated properties was evaluated. The results indicated that the incorporation of GnP increased the stiffness of the biopolymeric matrix.

Melt Strength and Extensibility of High-Density Polyethylene

The extensional flow of polymer melts has been extensively studied because of its importance in many technological processing operations and, from a more fundamental point of view, because the tensile properties of the polymer melts cannot be correlated directly with shear viscosity behavior.1–5

Influence of molecular parameters on the elongational behaviour of different polyethylenes and their blends

Elongational data on a large number of polyethylene samples with different structures and their blends are presented in order to evaluate the influence of the molecular weight and molecular weight distribution for a given degree of long chain branching. The elongational viscosity rises with the number of branch points and also with molecular weight and molecular weight distribution. Simple relationships between elongational viscosity at a given deformation and molecular parameters are presented.

The rheological behaviour of HDPE/LDPE blends

The rheological behaviour of three types of HDPE/LDPE blends at several compositions (various weight percentages of LDPE) has been studied with the aid of a capillary rheometer and three different capillaries.

Physicochemical characterization of passive films on niobium by admittance and electrochemical impedance spectroscopy studies

An analysis of the electronic properties of amorphous semiconductor-electrolyte junction is reported for thin (D ox < 20 nm) passive film grown on Nb in acidic electrolyte. It will be shown that the theory of amorphous semiconductor-electrolyte junction (a-SC/EI) both in the low band-bending and high band-bending regime is able to explain the admittance data of a-Nb 2 O 5 /El interface in a large range (10 Hz-10 kHz) of frequency and electrode potential values. A modelling of experimental EIS data at different potentials and in the frequency range of 0.1 Hz-100 kHz is presented based on the theory of amorphous semiconductor and compared with the results of the fitting of the admittance data…

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…

Accelerated weathering of polypropylene/wood flour composites

Abstract Wood–plastic composites (WPCs) have received increasing attention during the last decades, because of many advantages related to their use. Some of their main applications are represented by outdoor furnishing and decking; therefore, it is important to assess their behaviour under UV exposure. In this work, polypropylene/wood flour composites were prepared and their resistance to photooxidation investigated. The composites were prepared by extrusion and compression moulding, and were subjected to mechanical tests, FTIR analysis and molecular weight measurements. The results showed that the composites retained a higher fraction of the original mechanical properties after accelerated…

The Role of Elongational Flow in Morphology Modification of Polyethylene/OMMt Nanocomposite System

The formulation of high-performance polymer based nanocomposites depend on many factors, such as polymeric matrix type, nanoparticle type, loading and morphology, affinity between the polymeric matrix and nanoparticles, presence of compatibilizer and processing conditions [1-4]. During the industrial processing the polymer based systems are subjected to two different processing flows, i.e. the shear and elongational flow. The shear flow plays a significant role in polyethylene/OMMt manufacture processing but it is not able to change the system morphology, while, the elongational flow, involved in spinning and film-blowing processing operations, can induce considerably clay morphology variat…

Compatibilization of polyethylene/polyamide 6 blend nanocomposite films

Polymer blends of incompatible components need to undergo compatibilization, in order to give rise to a blend with good physical properties. At the same way, polymer/clay nanocomposites show this problem because of different chemical nature of the polymer matrix and of the clay. Compatibilization is therefore more necessary if an incompatible polymer blend is filled with an organomodified clay in order to give a final material with good properties. In this work, a polyethylene/polyamide 6 blend filled with an organomodified clay has been compatibilized with a maleic anhydride grafted SEBS (styrene-ethylene-butylene-styrene) copolymer and a glicidylmethacrylate-ethylene copolymer. The result…

EVA Copolymer Based Nanocomposites

Nanocomposites are a new class of polymer material with an ultrafine phase dispersion of the order of a few nanometers that shows very interesting properties often very different from those of conventional filled polymers. In this work the mechanical and optical properties of Poly-[ethylene-co-(vinyl acetate)] (EVA copolymer) based nanocomposites have been investigated to evaluate its possible use in several applications. For example, films for covering greenhouse effect. Mechanical properties, and the rigidity in particular, are, on the contrary, quite low. Nanocomposites should avoid this shortcoming if optical properties and processability are not unfavorably effected. EVA copolymer base…

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, …

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…

Shear behaviour of undiluted polyisobutylenes

Some new data in shear flow are presented for two commercial polyisobutylene samples, namely Vistanex LMMH and L 100. In particular beyond a few steady state results, the tangential stress build-up after a sudden imposition of a shear rate and the decay after cessation of steady shear flow have been collected. The data are used to further test a constitutive equation already advanced by some of the authors. The comparison seems to confirm the validity of the proposed model, whose single adjustable parameter is shown to be independent of molecular weight.

The role of the disposition of the recycled polymer on the properties of films for greenhouses coverage

Multilayer films, by using postconsumer materials in the central layer, i.e., multilayer composition: virgin polyethylene/postconsumer polymer/virgin polyethylene, allows to get a film for greenhouses coverage with good mechanical properties and photo-oxidation resistance, similar to that of the films made from virgin material and certainly better than the photo-oxidation resistance of the film made melt blending the virgin polyethylene and the postconsumer polymer. Moreover, the disposition of the postconsumer polymer containing oxygenated groups only in the central layer determines a significant slowdown of the photo-oxidation process of the multilayer film although faster than of the pri…

Rheological behavior of a semirigid liquid crystal polymer

The rheological behavior of liquid crystal polymers is still far from completely clarified from both experimental and theoretical points of view. In this paper, the shear flow and the non-isothermal elongation flow behavior of a semi-rigid liquid crystal copolyester is discussed. The viscosity strongly decreases when the test temperature is increased above the crystal-nematic transition temperature; below this temperature the viscosity is very high. The thermal history strongly affects the shear viscosity. The elongational flow behavior depends also on temperature. Above the crystal-nematic transition temperature and the mesophase is easily spinnable, whereas below this temperature, the spi…

The rheological behavior of HDPE/LDPE blends 4. Instability phenomena in capillary flow

Experimental data, relative to instability phenomena in capillary flow, have been collected for HDPE/LDPE blends already characterized from a rheological viewpoint. The data comprise morphological observations as well as the determination of critical parameters as a function of the blend composition and of the processing conditions.

The antioxidant effect in controlling thermal degradation of a low density polyethylene blown film

Abstract It is well known that antioxidants are widely used to prevent thermal degradation of high density and linear low density polyethylene. Antioxidants are not always present in low density polyethylene and only small amounts are usually added to these resins. In this work the effect of an antioxidant system on a low density resin having MFI (190 °C/2.16 kg)=2 g/10′ and density 0.9230 g/cm3 has been studied. Its effect on melt viscosity has been studied by means of a batch mixer and the torque vs time behaviour has been analysed. The results show that a maximum in the torque vs time curve can be seen for the material containing antioxidant. In contrast, the material without antioxidant…

A new equipment to measure the combined effect of humidity, temperature, mechanical stress and UV exposure on the creep behaviour of polymers

To be able to study and predict the physical properties of a polymeric material under different environmental conditions is very important. Moisture, UV irradiation, thermal and mechanical stresses can dramatically change the characteristics of the material and hinder some specific applications. In this work, a new equipment able to perform creep tests under different environmental conditions (temperature, humidity, stress) is presented. Some preliminary results are also presented using a sample of polyamide 6. As this polymer is sensitive to all these variables, it is appropriate to verify the effectiveness of the new instrument.

Testing of a model for the non linear electric behavior of polymeric materials

Some experimental results relative to a molten polymer (a commercial polyisobutylene) in d.c. and a.c. tests are presented.

Reprocessing of Poly(Vinyl Chloride), Polycarbonate and Polyethyleneterephthalate

Poly ethyleneterephthalate — PET- and Poly(vinyl chloride) — PVC — are two of the most frequently encountered polymers in post-consumer plastics. In particular, these polymers can be used for manufacturing the same products (bottles, for example) and therefore are often found in the same stream, even when the collection is done with separation. The recycling of PET and PVC is usually carried out by separating them and reprocessing the two homogeneous polymers. Indeed, the heterogeneous recycling of two polymers is at present almost impossible because of many problems: as their melting points are very different, at the processing temperature of PET severe degradation phenomena of PVC take pl…

Effect of elongational flow on morphology and properties of polymer/CNTs nanocomposite fibers

Carbon nanotubes (CNTs) have been attracting increasing interest for the fabrication of polymer-based nanocomposites because of their excellent properties. Traditional methods for the preparation of polymer/CNTs nanocomposites are in situ polymerization, solution blending, and melt mixing. The achievement of a good CNT dispersion and a percolation network is important in order to obtain better mechanical and electrical properties. However, the rheological behavior of polymer/CNTs systems, in particular regarding the extensional flow, has not been much investigated so far. In this work we present, for the first time, rheological data in non-isothermal extensional flow and an investigation on…

Reactive blending of a functionalized polyethylene with a semiflexible liquid crystalline copolyester

Reactive blends (50/50 w/w) of a low molar mass polyethylene containing free carboxylic groups (PEox) and a semiflexible liquid crystalline polyester (SBH 1 : 1 : 2, by Eniricerche) have been prepared at 240 degrees C in a Brabender mixer, in the presence of Ti(OBu)(4) catalyst, for different mixing times (15, 60, and 120 min). In order to prove the formation of a PE-g-SBH copolymer, the blends have been fractionated by successive extractions with boiling toluene and xylene. The soluble fractions and the residues have been analyzed by Fourier transform infrared (FTIR) spectroscopy, thermogravimetry (TG and DTG), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM)…

Effect of Elongational Flow and Polarity of Organomodified Clay on Morphology and Mechanical Properties of a PLA Based Nanobiocomposite

Abstract In biodegradable polymer world nanobiocomposites represent a new group of materials filled with inert nanoparticles that shows very interesting properties and the biodegradability of the matrix. In this work we have studied the effect of the polarity of the organomodified montmorillonite and of the elongational flow on the morphology and the rheological and mechanical properties of a new nanobiocomposite with a matrix of biodegradable PLA based blend. The elastic modulus enhances in presence of the nanofiller and this increase is larger and larger with the increment of the orientation. The tensile strength does not show any significant change at the same level of orientation. Moreo…

Rheology-morphology relationships in nylon 6/liquid-crystalline polymer blends

Extrusion measurements have been carried out on blends of nylon 6 and a liquid-crystalline copolyesteramide (LCP). The flow curves at low temperature show a behavior similar to that of pure LCP with a rapid rise of the viscosity at low shear rates. At high shear rates the viscosity is lower than that for each of the two components. This minimum has been attributed to the lack of interactions between the two phases and to the formation of fibrils of the LCP phase. The SEM analysis shows, indeed, that fibrils of the LCP phase are produced in the convergent flow at the inlet of the capillary at high shear rates. These fibrils are lost during the flow in the long capillary.

EVA copolymer based nanocomposites: rheological behavior under shear and isothermal and non-isothermal elongational flow

Abstract Nanocomposites are a very promising new class of polymer composites that exhibit an interesting combination of chemical, physical and mechanical properties. Only small amounts of nanofiller are sufficient to generate great variation of many properties. This work focuses on the rheological properties of poly[ethylene- co -(vinyl acetate)] (EVA copolymer) based nanocomposites in shear and in isothermal and non-isothermal elongational flow. The nanocomposites, at two different filler contents, were prepared in two different extruders and intercalates were obtained for all the samples. The twin-screw compounder is more efficient. The change of rheological properties, both in shear and …

Creep response of a LDPE-based nanocomposite

Polymer nanocomposites and their behavior have been widely investigated by several paths, including mechanical, rheological, and permeability tests, finding that several parameters (such as the polymer matrix, the nanofiller, their amounts, the presence of compatibilizers, processing parameters, etc.) can influence the main properties. However, less information is available regarding the creep response of polymer nanocomposites; in particular, few or no data are reported about the combined effect of different loads and different temperatures. In this article, the creep behavior of a low density polyethylene/organomodified clay nanocomposite has been investigated. The characterization of vis…

Improvement of the mechanical properties of photo-oxidized films after recycling

Mechanical recycling of post-consumer plastics gives rise, in most cases, to secondary materials with mechanical properties worse than those of the reclaimed polymer. This is mostly due to the thermomechanical treatment undergone during the melt reprocessing operations. In this work, low density polyethylene films have been photo-oxidized in artificial accelerated ageing conditions and then the brittle films have been melt reprocessed. It is shown that the secondary material, after reprocessing, shows mechanical properties, in particular elongation at break, better than those of the photo-oxidized films. This behaviour has been attributed to the fact that the melt reprocessing has the effec…

Blends of nylon 6 with a polyethylene functionalized by photooxidation

An easy and cheap method to prepare functionalized polyethylene is reported in which polyethylene is photooxidized and then melt-blended with nylon. Structural, rheological, and mechanical modifications indicate that carbonyl, formed during photooxidation, and amine groups react giving rise to copolymers which stabilize the blends. Photooxidized polyethylene from waste could be very effective in preparing polyethylene/polyamide blends with improved properties. This new approach improves over current methods in which compatibilization of polyolefines and polyamides is mostly performed by reacting functionalized polyolefines with polyamides in molten state. The functionalization is achieved b…

Reactive melt blending of functionalized-MW/CNTs with polyolefin

Adding nanotube adding into a polymeric matrix leads to the formulation of nanocomposites with enhanced macroscopical performances, and, moreover, the use of functionalized MW-CNTs leads to the nanocomposite formulation with even better properties. Furthermore, the reactive melt blending can be considered as a powerful processing method, i.e. reasonably simple and ecologically friendly, in order to formulate polymer based nanocomposite with good performance. In this work, the reactive melt blending between an ethylene-acrylic acid co-polymer, bis-oxazoline and functionalized MW-CNTs was performed and the rheological properties of the formulated systems were investigated.

TI: Compatibilization of PA6/rubber blends by using an oxazoline functionalized rubber

The compatibilization of blends of polyamide 6 with a nitrile butadiene rubber has been investigated. The procedure consists of two steps: modification of the nitrile groups of the rubber into oxazoline in the melt through condensation of ethanolamine with formation of a molecule of ammonia, followed by use of the modified rubber as a compatibilizing precursor which is melt mixed with the polyamide to produce the compatibilized blend. The modification reaction has been detected by NMR analysis and a rheological, mechanical and thermomechanical characterization has been carried out on the all the blends. The results indicate that the modification reaction occurs but the conversion of nitrile…

The glass transition behaviour of salted nylon 6

Glass transition measurements of nylon-6/lithium halides mixtures have been carried out in wide range of frequency with the aid of different experimental techniques. The results show an increase of the glass transition temperature when the salt is present and prove the larger effectiveness of lithium chloride with respect of lithium bromide. This effect, in line with the large reduction of the specific volume caused by the salt, is due to the formation of a pseudo-cross-linking between lithium ions and the carbonyl-oxygen groups of the polyamide.

Formulation, Characterization and Optimization of the Processing Conditions of Blends of Recycled Polyethylene and Ground Tyre Rubbers: Mechanical and Rheological Analysis

Abstract Recycling represents a valid alternative to the disposal of post-consumer plastics in common landfills if it is possible to obtain new materials with good final properties compatible with practical application and, above all, by using cheap methods. In this work the possibility to produce secondary materials by blending recycled polyethylene (RPE) coming from greenhouses and post-consumer ground tyre rubber (GTR) has been studied. In particular, the preparation of these blends has been carried out in a common industrial twin screw extruder. RPE pellets and GTR powder were fed to the extruder without any other additive. Temperature, processing speed, mixing procedure and composition…

Effect of adding new phosphazene compounds to poly(butylene terephthalate)/polyamide blends. I: Preliminary study in a batch mixer

Abstract Poly(butylene terephthalate) (PBT) and a sample of polyamide have been melt processed in the presence of two new phosphazene compounds, namely 2,2-dichloro-4,4,6,6-bis[spiro(2′,2″dioxy-1′,1″biphenyl)]cyclotriphosphazene (2Cl-CP) and 2,2-bis-(2-methoxy-4-methyleneoxy-phenoxy)-4,4,6,6,-bis[spiro(2′,2″dioxy-1′,1″biphenyl)]cyclophosphazene (CP-2EPOX). The blends were prepared by using polyamide 6 (PA6) at 25/75 w/w and 75/25 w/w composition. In order to perform a preliminary analysis on the behaviour of the blends, the materials were prepared in a batch mixer. The materials have been completely characterized from a rheological, morphological, mechanical point of view. The results indic…

Theoretical predictions from a non-linear model based on the free volume concept, which were previously tested only with a molten polymer, are presented and compared with literature data of solid polyethylene. The agreement is good both when a steady state is reached in the experimentally explored times and when, on the contrary, the data do not show it. Theoretische Berechnungen des elektrischen Verhaltens von Polymeren anhand eines nichtlinearen Modells, die auf dem Konzept des freien Volumens basieren und bisher lediglich an einem geschmolzenen Polymer getestet wurden, werden vorgestellt und mit Literaturdaten von festem Polyethylen verglichen. Die Ubereinstimmung ist gut, wenn in den ex…

A simple method to interpret the rheological behaviour of intercalated polymer nanocomposites

Abstract Nanocomposites are a new class of polymer composites that exhibit an interesting combination of chemical, physical, thermal and mechanical properties. Only small amounts of nanofiller are sufficient to generate great variations of many properties. This work focuses on the rheological behaviour of the intercalated polymer nanocomposites in shear flow. The increase of the viscosity and the more pronounced non-Newtonian behaviour is interpreted simply considering the increase of volume of the inert phase caused by the intercalation of the macromolecules. Indeed, the volume of the intercalated tactoids increases with increasing the interlayer distance. On the other hand, the interlayer…

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…

Effect of different dispersing additives on the morphology and the properties of polyethylene-based nanocomposite films

In this work, the use of a polar wax, e.g. amphiphilic Tegomer ® E 525 (TEG) is investigated with the aim of mod- ifying, and possibly improving, the dispersion of an organically modified nanoclay (OMMT), loaded at 5 wt%, in a poly- ethylene matrix (PE) at relatively low loading levels. We have indeed found that the incorporation of low loadings, e.g. 0.5 wt%, of TEG, an amphiphilic block co-polymer, into a PE/OMMT sample results in a substantial improvement of the clay dispersion in the nanocomposite and, consequently, of the mechanical and thermomechanical properties of the films. The achieved results are comparable to those obtained for systems containing traditional dispersing agents su…

Rheological characterization of polycaprolactam anionically synthesized in the presence of lithium chloride

Melt viscosity and dynamic-mechanical data are reported for samples obtained by anionic polymerization of caprolactam, in the presence of LiCl. The full body of results is essentially in line with those previously reported relative to mixtures of inorganic salts and commercial nylon 6, In particular a drastic-decrease of the melting point and of the rate of crystallization is confirmed as well as an increase of the glass transition temperature and of the melt viscosity. Some quantitative differences exist, which may be attributed to the different molecular weight distribution in the polymers employed in the present work.

Effect of the elongational flow on morphology and properties of polypropylene/graphene nanoplatelets nanocomposites

Abstract In this work the effect of the presence of graphene nanoplatelets (GnP) on the morphology and mechanical properties of polypropylene/GnP nanocomposites has been investigated when these polymer systems are subjected to non-isothermal elongational flow in a melt spinning operation. The presence of the GnP magnifies the effect of the elongational flow. Indeed, the elastic modulus and the tensile strength of nanocomposites increases with the orientation more than that observed for the pure matrix. Moreover, the elongation at break increases at low values of the draw ratio for the nanocomposites, while, the matrix shows the expected decrease in deformability. These effects have been cor…

Effect of adding new phosphazene compounds to poly(butylene terephthalate)/polyamide blends. II: Effect of different polyamides on the properties of extruded samples

Poly(butylene terephthalate) (PBT) and a sample of polyamide have been melt processed in the presence of two new phosphazene compounds, namely 2,2-dichloro-4,4,6,6-bis[spyro(2',2"-dioxy-1',1"-biphenyl)]cyclotriphosphazene (2Cl-CP) and 2,2-bis(2-methoxy-4-methyleneoxy-phenoxy)-4,4,6,6-bis[spyro(2',2"-dioxy-1',1"-biphenyl)]cyclophosphazene (CP-2EPOX). The blends were prepared by using polyamide 6 (PA6) and polyamide 6,6 (PA66) in 25/75 and 75/25 w/w compositions by using a co-rotating twin-screw extruder. The materials have been completely characterized from a mechanical, rheological, and morphological point of view. The results indicate that the additives used cause an increase of the ruptur…

Effect of the additive level and of the processing temperature on the re-building of post consumer pipes from polyethylene blends

Abstract One of the main shortcomings of the mechanical recycling is that the properties of the secondary materials are generally sensibly inferior with respect to the virgin ones. This feature implies, for sure, that they cannot be used for the same technological application but also other uses of the secondary material are impossible. The aim of this work is to study the re-building of recycled post-consumer pipes, made of a blend of different polyethylenes, by re-processing in the presence of a nitroxyl compound as radical generator. The processing temperature and the additive concentration have been varied in order to study the effect of these parameters on the final properties. The mec…

On the mechanism of compatibilization of polyolefin/liquid crystalline polymer blends with graft copolymers

The compatibilization mechanism of some compatibilizers for blends of polyolefins with a liquid crystalline polymer (LCP) was studied. Polyethylene (PE) and polypropylene (PP) were blended with a semirigid LCP (SBH) in a batch mixer, either with and without compatibilizers. The latter were two commercially available samples of functionalized polyolefins, that is, a PE-g-MA (HDM) and a PP-g-AA (Polybond 1001) copolymer and some purposely synthesized PE-g-LCP and PP-g-LCP copolymers. Microtomed films of the binary and the ternary blends were annealed at 240°C on the hot stage of a polarizing microscope and the changes undergone by their morphology were recorded as a function of time. The resu…

On the effectiveness of different additives and concentrations on the re-building of the molecular structure of degraded polyethylene

Mechanical recycling is an easy and economic way to re-use plastic waste as secondary materials, but, in general, their properties are worse with respect to the reclaimed materials and the virgin polymer. The aim of this work was to study the effect of concentration and reaction kinetics of two additives, an ethylene-co-glycidyl methacrylate (Lotader) and a hydroxylamine derivative (CGX), in the re-building of a degraded polyethylene. CGX is a nitroxyl radical generator able to form branching in polyolefins while the epoxy groups of Lotader can react with the functional groups present in the recycled polyethylene. The results indicate that the CGX has a higher reaction rate than Lotader, pr…

Preparation and characterization of polyamide 6/polyethylene blend-clay nanocomposites in the presence of compatibilisers and stabilizing system

Abstract Several compatibilising systems were added to high-density polyethylene (HDPE) and polyamide 6 (PA6) blends in the presence of an organically modified montmorillonite (OMM). All the blends were prepared by using a co-rotating twin-screw extruder and characterized by SEM, TEM and XRD analyses. In addition, the rheological behaviour and the mechanical properties – tensile and impact – were evaluated. The presence of OMM affects the dimensions of the polymeric phases in the blend but not their mutual adhesion, granted only by the compatibilisers. TEM, SEM and XRD analyses indicated that there is a strict correlation between the compatibilisation level and the final interlayer distance…

Processing and mechanical properties of organic filer-polypropylene composites

The addition of organic fillers into thermoplastic polymers is an interesting issue, which has had growing consideration and experimentation during the last years. It can give rise to several advantages. First, the cost of these fillers is usually very low. Also, the organic fillers are biodegradable (thus contributing to an improved environmental impact), and finally, some mechanical and thermomechanical properties can be enhanced. In this study, the effect of the addition of different organic fillers on the mechanical properties and processability of an extrusion-grade polypropylene were investigated. The organic fillers came from natural sources (wood, kenaf, and sago) and were compared …

A Study of Polycarbonate-Liquid Crystal Polymer Blends

BThe morphologican and mechanical properties of blends of bisphenol-A polycarbonate (PC) with a wholly aromatic liquid crystal copolyesteramide (Vectra-B) are discussed with reference to the conditions used for their preparation. The blends made by extrusion behave as mixtures of incompatible polymers. THe behaviour of the blends prepared in a batch mixer depends strongly on mixing time. A slight decrease in the mechanical properties accompanies the morphological changes associated with a progressive improvement in the compatibility of the two polymers

Improving the properties of polypropylene–wood flour composites by utilization of maleated adhesion promoters

Polymer composites filled with natural organic fillers have gained a significant interest during the last few years, because of several advantages they can offer compared with properties of inorganic-mineral fillers. However, these composites (based, in most cases, on polyolefins) often show a reduction in some mechanical properties. This is mainly due to the problems regarding dispersion of the polar filler particles in the non-polar polymer matrix and their interfacial adhesion with polymer chains. In this work, polypropylene-wood flour composites were prepared and the effect of the addition of a maleated polypropylene was investigated. The two materials were compounded by an industrial c…

Effect of extrusion and photoxidation on polyethylene/clay nanocomposites

Polyethylene (a 1:1 blend of m-LLDPE and z-LLDPE) double layer silicate clay nanocomposites were prepared by melt extrusion using a twin screw extruder. Maleic anhydride grafted polyethylene (PEgMA) was used as a compatibiliser to enhance the dispersion of two organically modified monmorilonite clays (OMMT): Closite 15A (CL15) and nanofill SE 3000 (NF), and natural montmorillonite (NaMMT). The clay dispersion and morphology obtained in the extruded nanocomposite samples were fully characterised both after processing and during photo-oxidation by a number of complementary analytical techniques. The effects of the compatibiliser, the organoclay modifier (quartenary alkyl ammonium surfactant) …

“Effect of Filler Type and Processing Apparatus on the Properties of the Recycled “Light Fraction” from Municipal Post-Consumer Plastics”

Plastic waste or scraps are generated from two main sources: industrial wastes and post-consumer wastes. By using the flotation method, generally two fractions are obtained from municipal post-consumer wastes: a light fraction, floating on water, and a heavy fraction. The former is essentially made of low and high density polyethylene—LDPE, HDPE—and polypropylene—PP; the heavy fraction is formed by poly(vinyl chloride)—PVC—and poly(ethylene terephthalate)—PET. In this work, the recycling of a light fraction from municipal post-consumer plastics has been studied, considering also the effect of filler type—glass fibres, calcium carbonate and wood fibres—and processing apparatus—discountinous …

Nonisothermal elongational behavior of blends with liquid crystalline polymers

Measurements of melt strength and breaking stretching ratio of several blends of thermoplastic polymers with liquid crystalline polymers are presented. The melt strength behavior depends not only on the viscosity of the blends but also on the temperature dependence of the viscosity. In particular, even if the viscosities of the blends are, at the extrusion temperature, lower than that of the thermoplastic matrices, the melt strength can be larger than that of the pure thermoplastics if its viscosity-temperature curve exceeds that of the matrices far from the solidification temperature. This behavior allows one to spin or film blow these blends despite the low viscosity.

Effect of adding wood flour to the physical properties of a biodegradable polymer

Wood flour/polymer composites (WPC) gained a significant interest during the last decades, due to several advantages related to the use of a natural-organic filler rather than an inorganic-mineral one. However, most of the studies have been performed on composites based on polyolefin matrices. A further step is the use of biodegradable polymers instead of traditional ones. In this work, wood flour (WF), under the form of short fibers, with two different sizes (coarse and fine) was added to a corn starch based biodegradable polymer of the Mater-Bi family. The effect of WF size, WF content, thermal treatment on the mechanical properties was investigated. The tensile mechanical tests showed an…

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 me…

Long-term thermomechanical degradation of molten polystyrene

Abstract Rheological data on polystyrene samples processed for long periods under various mechanical stresses are presented. The data indicate that thermomechanical degradation occurs and that the rate of thermal degradation is increased by the applied stress. Moreover degradation does not reach a limiting value even at high processing times.

Melt stabilization of wet polyamide 6

Abstract Melt processing of polycondensate polymers must be carried out after careful drying in order to avoid any hydrolytic chain scission caused by the presence of water or other small molecules. In this work, the effect of two different antioxidants on the processing and flow properties of a polyamide 6 sample not dried before processing operations has been studied. One of these stabilizers seems to protect the wet polymer from hydrolytic chain scission. This action has been interpreted considering that the stabilizer hydrolyses instead of the polyamide macromolecules.

Quarry limestone dust as fine aggregate for concrete

In quarrying activities, rock is extracted and transformed into aggregate of various sizes for civil engineering applications. In this process waste fine aggregates (dust waste) are generated. The disposal of this type of waste is a further cost in the extraction process, but also a possible cause of environmental pollution (e.g. leaching into water reserves, atmospheric pollution as a result of small particles causing respiratory diseases or deposited on plants disrupting photosynthesis, affecting aquatic habitats, etc.). A strategy for the effective recycling of quarry dust does not only reduce waste generation and disposal, but also addresses protection of the environment. The Italian qu…

Reprocessing of PLA based nanocomposites: Effect of nanofiller

Several studies investigated the effect of the reprocessing on the properties of PLA. However, recycling of PLA-based nanocomposites was not been investigated in depth so far. PLA is susceptible to thermo-degradation during melt processing operations. For this purpose, the study of thermo-mechanical degradative phenomena associated to its re-processing is of great concern in order to assess the possibility of recycling PLA-based nanocomposites. This work aims to evaluate the effect of reprocessing on morphology and properties of PLA reinforced with different nanofillers, i.e. hydrotalcites (HT) and graphene nanoplatelets (GnPs), pointing out on the role of the nanofiller.

Recent advances on physico-chemical characterization of passive films by EIS and differential admittance techniques

Abstract Thin Nb2O5 anodic films (∼20 nm thick) grown in phosphoric acid solution have been characterised by EIS and differential admittance study in a large range of potential and frequency. The overall electrical behaviour has been interpreted by means of the theory of amorphous semiconductor Schottky barrier in presence of a non-constant density of states (DOS). A comparison of DOS for films grown in different electrolytes is reported.

Reprocessing and restabilization of greenhouse films

From the ecological and economical points of view, reprocessing of polyethylene greenhouse films is a promising solution to reduce discarded materials and to produce useful, or potentially useful, objects for service. Films exposed outdoors, however, show inferior mechanical properties and the melt processing worsens these properties. The addition of stabilizers and antioxidants to recycled plastic products prevents inherent thermal instabilities from occurring within the time frame of proper processing. In this study, we attempt to explore ways for improving product performance by the addition of four different additives when the recycled films undergo intensive shear processing. The proce…

Rheological behavior and thermal stability of poly(phenylene sulfide)/vectra-B950 blends

Blends of polyphenylene sulfide (PPS) with a commercial, wholly aromatic, liquid crystalline polymer (LCP), Vectra-B950, have been prepared by melt-blending. Their rheological behavior has been studied in order to determine if the LCP displays a processing aid ability, and under what conditions it gives rise to potentially reinforcing fibrils dispersed in the PPS matrix. The problem of the thermal stability of PPS/LCP blends, which has been considered by some authors as the main obstacle to the production of usable materials due to the evolution of gaseous substances during processing, has been discussed. © 1994 John Wiley & Sons, Inc.

Stress relaxation of a polyisobutylene under large strains

Stress relaxation data after single and double elongational strain “steps” were collected on a commercial polyisobutylene, Oppanol B 50. Analogously to other cases a separability of deformation and time effects was observed over an extended time region for the relaxation after single “steps”. Moreover, by comparing the results after double with those after single steps, it was noted that any rheological equation of integral type having a rigorously constant memory function is not able to describe accurately the full body of results presented here. On the other hand the data were favorably compared with the predictions of a model proposed earlier.

Mechanical properties of recycled polyethylene ecocomposites filled with natural organic fillers

The use of natural organic fillers in addition to postconsumer recycled polymers is getting a growing interest during the last years; this is due to many advantages they can provide in terms of cost, aesthetic properties, environmental impact. In this work, several types of wood flour (differing each other with regard to production source and particle size) were added to a recycled polyethylene coming from films for greenhouses and the effects of filler type, content, and size were investigated. Investigation was then focused on the improvement of mechanical properties, through the addition of polar copolymers (ethylene-co-acrylic acid, ethylene-vinyl acetate) and a maleic anhydride-grafted…

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 modi…