Microstructural contributions of different polyolefins to the deformation mechanisms of their binary blends

The mixing of polymers, even structurally similar polyolefins, inevitably leads to blend systems with a phase-separated morphology. Fundamentally understanding the changes in mechanical properties and occurring deformation mechanisms of these immiscible polymer blends, is important with respect to potential mechanical recycling. This work focuses on the behavior of binary blends of linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), high-density polyethylene (HDPE), and polypropylene (PP) under tensile deformation and their related changes in crystallinity and morphology. All of these polymers plastically deform by shear yielding. When unmixed, the high crystalline polyolefins HDPE and PP both exhibit a progressive necking phenomenon. LDPE initiates a local neck before material failure, while LLDPE is characterized by a uniform deformation as well as clear strain hardening. LLDPE/LDPE and LLDPE/PP combinations both exhibit a clear-cut matrix switchover. Polymer blends LLDPE/LDPE, LDPE/HDPE, and LDPE/PP show transition forms with features of composing materials. Combining PP in an HDPE matrix causes a radical switch to brittle behavior

On the Use of Gallic Acid as a Potential Natural Antioxidant and Ultraviolet Light Stabilizer in Cast-Extruded Bio-Based High-Density Polyethylene Films

This study originally explores the use of gallic acid (GA) as a natural additive in bio-based high-density polyethylene (bio-HDPE) formulations. Thus, bio-HDPE was first melt-compounded with two different loadings of GA, namely 0.3 and 0.8 parts per hundred resin (phr) of biopolymer, by twin-screw extrusion and thereafter shaped into films using a cast-roll machine. The resultant bio-HDPE films containing GA were characterized in terms of their mechanical, morphological, and thermal performance as well as ultraviolet (UV) light stability to evaluate their potential application in food packaging. The incorporation of 0.3 and 0.8 phr of GA reduced the mechanical ductility and crystallinity of bio-HDPE, but it positively contributed to delaying the onset oxidation temperature (OOT) by 36.5 °C and nearly 44 °C, respectively. Moreover, the oxidation induction time (OIT) of bio-HDPE, measured at 210 °C, was delayed for up to approximately 56 and 240 min, respectively. Furthermore, the UV light stability of the bio-HDPE films was remarkably improved, remaining stable for an exposure time of 10 h even at the lowest GA content. The addition of the natural antioxidant slightly induced a yellow color in the bio-HDPE films and it also reduced their transparency, although a high contact transparency level was maintained. This property can be desirable in some packaging materials for light protection, especially UV radiation, which causes lipid oxidation in food products. Therefore, GA can successfully improve the thermal resistance and UV light stability of green polyolefins and will potentially promote the use of natural additives for sustainable food packaging applications

Polymer/montmorillonite nanocomposites with improved thermal properties: Part II. Thermal stability of montmorillonite nanocomposites based on different polymeric matrixes.

In previous part of this work factors influencing the thermal stability of polymer nanocomposite materials were indicated, such as chemical constitution of organic modifier, filler content, nanocomposites’ structure and the processing- dependent degree of homogenization of nanofiller, were presented. In this part the basic changes in thermal behaviour of different polymeric matrixes (e.g. polyolefins, polyamides, poly(vinyl chloride) and styrene-containing polymers) upon addition of montmorillonite have been described. Brief description of the kinetics of the decomposition process in inert and oxidative environment, as well as analysis of volatile and condensed products of degradation, have also been present

Elastomer coated filler and composites thereof comprising at least 60% by weight of a hydrated filler and an elastomer containing an acid substituent

The impact resistance of flame retardant composites, especially thermoplastic molding: compounds containing over 60% hydrated mineral filler such as Al(OH)3 or Mg(OH)2 as improved by coating the filler with 1 to 20% of an elastomer. The composite will fail by crazing or shearing rather than by brittle fracture. A well bonded elastomeric interphase resulted by utilizing acidic substituted resins such as ethyl-hexyl acrylate-acrylic acid copolymers which bond to and are cross-linked by the basic filler particles. Further improvement in impact resistance was provided by incorporating 1 to 10% of a resin fiber reinforcement such as polyvinyl alcohol fibers that decompose to yield at least 30% water when heated to decomposition temperature

MFC concept as a possible solution for closed-loop recycling of food packaging trays

Flexible plastic films from food packaging trays make up one of the largest fractions of the plastic waste stream and recycling is one of the most important actions to deal with this fraction, reducing the impact of these plastics on the environment. However, the recyclability of multi-layered films is not straightforward and in most of the cases these fractions are landfilled or incinerated. Recycling of discarded mixed polymers without previous separation often results in low mechanical properties which have lead researchers to investigate novel solutions for recycling. In this research, the concept of microfibrillar composites (MFCs) was investigated aiming to upcycle mixed polymer waste streams. A blend based on polypropylene (PP) and poly(ethylene terephthalate) (PET) at a weight ratio of 80/20 PP/PET was studied. The final step of the MFC processing was conducted using a conical twin screw extrusion. The morphological results confirmed the presence of PET microfibrils in the composites, leading to an improvement in mechanical properties such as in the tensile yield strength and strain at break. Subsequently, the MFC samples were successfully moulded into trays via thermoforming

Interfaces and interfacial effects in glass reinforced thermoplastics - Keynote Presentation

Optimization of the fibre-matrix interphase region is critical to achieving the required performance level in thermoplastic matrix composites. Due to its initial location on the fibre surface, the sizing layer is an important component in the formation and properties of the composite interphase. Consequently, any attempt to understand the science of the composite interphase must encompass an understanding of the science of sizing. In this paper the role of sizings from fibre manufacture through to performance of composite parts is reviewed. In particular the role of organosilane coupling agents and how the formation of a polysiloxane interphase is influenced by the surface properties of the fibre is examined. The influence of the sizing film former in terms of its level of interaction with the silane coupling agent is also examined. The importance of residual stresses in thermoplastic composites in the values obtained for the apparent adhesion levels in these systems is highlighted. These residual stresses are shown to play a significant role in determining the level of interfacial strength in thermoplastic composites and in particular in polyolefin matrices. By applying some of the available models for this phenomenon this analysis is extended to explore the effect of the anisotropic fibre microstructure of carbon, aramid and natural fibres on the apparent interfacial strength in thermoplastic composites

A general kinetic model for the photothermal oxidation of polypropylene

A general kinetic model for the photothermal oxidation of polypropylene has been derived from the basic auto-oxidation mechanistic scheme in which the main sources of radicals are the thermolysis and photolysis of the most unstable species, i.e hydroperoxides. Thermolysis is a uni- or bi-molecular reaction whose rate constant obeys an Arrhenius law. In contrast, photolysis is exclusively a unimolecular reaction and its rate constant is independent of temperature. According to the quantum theory, this latter is proportional to the energy absorbed by photosensitive species and thus, accounts for the impact of UV-light intensity and wavelength on the global oxidation kinetics. The validity of this model has been checked on iPP films homogeneously oxidized in air over a wide range of temperatures and UV-light sources. It gives access to the concentration changes of: (i) primary (hydroperoxides) and secondary (carbonyls) oxidation products, (ii) double bonds, (iii) chain scissions and crosslinking nodes, but also to the subsequent changes in molecular masses. These calculations are in full agreement with the photolysis results reported by Carlsson and Wiles in the 70s [1–3]. However, the model seems to be only valid for UV-light energies equivalent to about 10 suns as upper boundary, presumably because of multiphotonic excitations or chromophores photosensitization (i.e. termolecular photo-physical reactions), both enhanced at high irradiances

Multiscale Modeling of Binary Polymer Mixtures: Scale Bridging in the Athermal and Thermal Regime

Obtaining a rigorous and reliable method for linking computer simulations of polymer blends and composites at different length scales of interest is a highly desirable goal in soft matter physics. In this paper a multiscale modeling procedure is presented for the efficient calculation of the static structural properties of binary homopolymer blends. The procedure combines computer simulations of polymer chains on two different length scales, using a united atom representation for the finer structure and a highly coarse-grained approach on the meso-scale, where chains are represented as soft colloidal particles interacting through an effective potential. A method for combining the structural information by inverse mapping is discussed, allowing for the efficient calculation of partial correlation functions, which are compared with results from full united atom simulations. The structure of several polymer mixtures is obtained in an efficient manner for several mixtures in the homogeneous region of the phase diagram. The method is then extended to incorporate thermal fluctuations through an effective chi parameter. Since the approach is analytical, it is fully transferable to numerous systems.Comment: in press, 13 pages, 7 figures, 6 table

Novel functionalized polyolefins as compatibilizers in polyolefin/polyamide 6 blends and polyethylene/metal hydroxide composites

Ricinoloxazoline maleinate (OXA) was grafted by melt free radical grafting onto polyolefins and elastomers to produce new compatibilizers for polymer blends. Effects of initial monomer and peroxide concentrations on the degree of grafting, on the amount of residual monomer, and on the side reactions were investigated. Reactive compatibilizers could be prepared with a suitable choice of processing conditions and initial concentrations. These oxazoline functionalized polyolefins and elastomers were found to act as effective compatibilizers in polymer blends. Blends of polyolefins and polyamide 6 were compatibilized with two novel types of compatibilizers: oxazoline functionalized polymers prepared by grafting and functionalized polyolefins prepared by copolymerization using metallocene catalysts. Comparison was made with commercial compatibilizers. Effects of the compatibilizers on blend morphology and thermal, tensile, and impact properties were studied. All of the functionalized polyolefins were effective compatibilizers in polyethylene/polyamide 6 blends. They were able to reduce the particle size and attach the particles more firmly to the matrix. The toughness was improved, though usually at the cost of stiffness. Only functionalized polyethylenes prepared with metallocene catalysts were able to improve the stiffness and strength along with toughness. In commercial polyolefin composites, fillers are usually coated with a fatty acid to make them organophilic. Replacement of fatty acid coatings with polymeric compatibilizers was studied in polyethylene/aluminum hydroxide (PE/ATH) and polyethylene/magnesium hydroxide (PE/MH) composites. The polymeric compatibilizers were oxazoline grafted polyethylene prepared by melt free radical grafting, hydroxyl and carboxylic acid functionalized polyethylenes prepared with metallocene catalysts, and commercial functionalized polyethylenes. Adhesion fracture changed to cohesion failure when the fatty acid coating was replaced through the addition of polymeric compatibilizers. Improvement in both stiffness and toughness was achieved, and improvements in flammability properties achieved with ATH or MH were preserved when polymeric compatibilizers were used as adhesion promoters.reviewe