Study of the interaction between asphalt and plastic wastes in new polymer modified binders (PMB)

The aim of this study is evaluating the interaction between several base pen grade asphalt binders (35/50, 50/70, 70/100, 160/220) and two different plastic wastes (EVA and HDPE), for a set of new polymer modified binders produced with different amounts of both plastic wastes. After analysing the results obtained for the several polymer modified binders evaluated in this study, including a commercial modified binder, it can be concluded that the new PMBs produced with the base bitumen 70/100 and 5% of each plastic waste (HDPE or EVA) results in binders with very good performance, similar to that of the commercial modified binder.

In-line rheo-optical characterization during small-scale polymer processing and compounding

As increasingly more sophisticated materials and products are being developed and times-to-market need to be minimized, it is important to make available fast response characterization tools using small amounts of sample, capable of conveying data on the relationships between rheological response, process-induced material structure and product characteristics. For this purpose, a single / twin-screw mini-extrusion system of modular construction, with well-controlled outputs in the range 30-300 g/h, was coupled to a in- house developed rheo-optical slit die able to measure shear viscosity and normal-stress differences, as well as performing rheo-optical experiments, namely small angle light scattering (SALS) and polarized optical microscopy (POM). In addition, the mini-extruder is equipped with ports that allow sample collection, and the extrudate can be further processed into products to be tested later. Here, we present the concept and experimental set-up [1, 2]. As a typical application, we report on the characterization of the processing of a polymer blend and of the properties of extruded sheets. The morphological evolution of a PS/PMMA industrial blend along the extruder, the flow-induced structures developed and the corresponding rheological characteristics are presented, together with the mechanical and structural characteristics of produced sheets. The application of this experimental tool to other material systems will also be discussed.

Probing dispersion and re-agglomeration phenomena upon melt-mixing of polymer-functionalized graphite nanoplates

A one-step melt-mixing method is proposed to study dispersion and re-agglomeration phenomena of the as-received and functionalized graphite nanoplates in polypropylene melts. Graphite nanoplates were chemically modified via 1,3-dipolar cycloaddition of an azomethine ylide and then grafted with polypropylene-graft-maleic anhydride. The effect of surface functionalization on the dispersion kinetics, nanoparticle re-agglomeration and interface bonding with the polymer is investigated. Nanocomposites with 2 or 10 wt% of as-received and functionalized graphite nanoplates were prepared in a small-scale prototype mixer coupled to a capillary rheometer. Samples were collected along the flow axis and characterized by optical microscopy, scanning electron microscopy and electrical conductivity measurements. The as-received graphite nanoplates tend to re-agglomerate upon stress relaxation of the polymer melt. The covalent attachment of a polymer to the nanoparticle surface enhances the stability of dispersion, delaying the re-agglomeration. Surface modification also improves interfacial interactions and the resulting composites presented improved electrical conductivity.

Essential oil composition of leaf and fine stem of Aniba canelilla (Kunth) Mez from Manaus, Brazil

The essential oil of the leaves and fine stems of Aniba canelilla (Kunth) Mez collected in the city of Manaus, AM, Brazil, were obtained by hydrodistillation and analyzed by GC/MS. Forty-two components were identified, of which 1-nitro-2-phenylethane, as expected, was the major (71.2%-68.2%).

Limitations and improvements to the risk assessment process in Olive Oil Mills: the views of OSH practitioners

Although most of the accidents occurred in Olive Oil Mill (OOM) resulted from “basic” risks, there is a need to apply adequate tools to support risk decisions that can meet the specificities of this sector. This study aims to analyse the views of Occupational, Safety & Health (OSH) practitioners about the risk assessment process in OOM, identifying the key difficulties inherent to the risk assessment process in these sector, as well as identifying some improvements to the current practice. This analysis was based on a questionnaire that was developed and applied to 13 OSH practitioners working at OOM. The results showed that the time available to perform the risk assessment is the more frequent limitation. They believe that the methodologies available are not an important limitation to this process. However, a specific risk assessment methodology, that includes acceptance criteria adjusted to the OOM reality, using risk metrics supported on the frequency of accidents and workdays lost, were indicated as being also an important contributions improve the process. A semi-quantitative approach, complemented with the use of the sector accident statistics, can be a good solution for this sector. However, further strategies should also be adopted, mainly those that can lead to an easy application of the risk assessment process.

Using glass-fibre reinforced polymer composites in the production of sustainable water storage vessels

The present work focuses on the use of the life cycle assessment (LCA) and life cycle costing (LCC)methodologies to evaluate environmental and economic impacts of polymers and polymer composites materials and products. Initially a literature review is performed in order to assess the scope and limitations of existing LCA and LCC studies on these topics. Then, a case study, based on the production of a water storage glass-fibre reinforced polymer (GFRP) composite storage tank, is presented. The storage tank was evaluated via a LCA/LCC integrated model, a novel way of analysing the life cycle (LC) environmental and economic performances of structural products. The overarching conclusion of the review is that the environmental and economic performances of polymers composites in non-mobile applications are seldom assessed and never in a combined integrated way.

Effects of clove oil on the stress response of matrinxã (Brycon cephalus) subjected to transport

Fish transport is one of the most stressful procedures in aquaculture facilities. The present work evaluated the stress response of matrinxã to transportation procedures, and the use of clove oil as an alternative to reduce the stress response to transport in matrinxã (Brycon cephalus). Clove oil solutions were tested in concentrations of 0, 1, 5 and 10 mg/L during matrinxã transportation in plastic bags, supplied with water and oxygen as the usual field procedures in Brazil. Clove oil reduced some of the physiological stress responses (plasma cortisol, glucose and ions) that we measured. The high energetic cost to matrinxã cope with the transport stress was clear by the decrease of liver glycogen after transport. Our results suggest that clove oil (5 mg/l) can mitigate the stress response in matrinxã subjected to transport.

Structure-property relationships in polymer nanocomposites

Tese de Doutoramento em Ciência e Engenharia de Polímeros e Compósitos

Assessment of polymer-based nanocomposites biodegradability

The management of solid waste is a growing concern in many countries. Municipal solid waste is a major component of the total solid waste generated by society, and the composting of municipal solid waste has gained some attention even though a composting treatment for it is not yet widespread. It may not be realistic to replace large portions of these plastics with biodegradable materials, and it may be more important to separate plastics unsuitable for the composting process at the generating spots. However, for food packaging, there is still a great deal of interest in using biodegradable plastics that are difficult to sort at the generation spots. Under these circumstances, nanocomposites of biodegradable polymers as matrix and nanoparticles, that can be degraded along with organic wastes during composting could be a solution. Therefore, this chapter aims to give an overview on the biodegradability studies of bio-nanocomposites. It will focus on different polymers, nanocomposites containing different clay types and inorganic particles exposed under different environments.

Development of polymer wicks for the fabrication of bio-medical sensors

Polymer based wicking structures were fabricated by sintering powders of polycarbonate (PC), ultra-high molecular weight polyethylene and polyamide 12, aiming at selecting a suitable material for an innovative electroencephalography (EEG) bio-electrode. Preliminary experiments showed that PC based wicks displayed the best mechanical properties, therefore more detailed studies were carried out with PC to evaluate the influence of powder granulometry and processing parameters (pressure, temperature and time) on the mechanical properties, porosity, mean pore radius and permeability of the wicks. It was concluded that the mechanical properties are significantly enhanced by increasing the processing time and pressure, although at the expense of a significant decrease of porosity and mean pore diameter (and thus permeability), particularly for the highest applied pressures (74kPa). However, a good compromise between porosity/permeability and mechanical properties could be obtained by sintering PC powders of particle sizes below 500μm at 165°C for 5min, upon an applied pressure of 56kPa. Moreover, PC proved to be chemically stable in contact with an EEG common used disinfectant. Thus, wicking structures with appropriate properties for the fabrication of reusable bio-electrodes could be fabricated from the sintering of PC powders.

Dispersion of fillers in viscoelastic polymer matrices using Eulerian-Lagrangian approaches

Understanding the behavior of c omplex composite materials using mixing procedures is fundamental in several industrial processes. For instance, polymer composites are usually manufactured using dispersion of fillers in polymer melt matrices. The success of the filler dispersion depends both on the complex flow patterns generated and on the polymer melt rheological behavior. Consequently, the availability of a numerical tool that allow to model both fluid and particle would be very useful to increase the process insight. Nowadays there ar e computational tools that allow modeling the behavior of filled systems, taking into account both the behavior of the fluid (Computational Rheology) and the particles (Discrete Element Method). One example is the DPMFoam solver of the OpenFOAM ® framework where the averaged volume fraction momentum and mass conservation equations are used to describe the fluid (continuous phase) rheology, and the Newton’s second law of motion is used to compute the particles (discrete phase) movement. In this work the refer red solver is extended to take into account the elasticity of the polymer melts for the continuous phase. The solver capabilities will be illustrated by studying the effect of the fluid rheology on the filler dispersion, taking into account different fluid types (generalized Newtonian or viscoelastic) and particles volume fraction and size. The results obtained are used to evaluate the relevance of considering the fluid complex rheology for the prediction of the composites morphology

Understanding the dispersion of fillers in polymer matrices

Understanding the mixing process of complex composite materials is fundamental in several industrial processes. For instance, the dispersion of fillers in polymer melt matrices is commonly employed to manufacture polymer composites, using a twin-screw extruder. The effectiveness of the filler dispersion depends not only on the complex flow patterns generated, but also on the polymer melt rheological behavior. Therefore, the availability of a numerical tool able to predict mixing, taking into account both fluid and particles phases would be very useful to increase the process insight, and thus provide useful guidelines for its optimization. In this work, a new Eulerian-Lagrangian numerical solver is developed OpenFOAM® computational library, and used to better understand the mechanisms determining the dispersion of fillers in polymer matrices. Particular attention will be given to the effect of the rheological model used to represent the fluid behavior, on the level of dispersion obtained. For the Eulerian phase the averaged volume fraction governing equations (conservation of mass and linear momentum) are used to describe the fluid behavior. In the case of the Lagrangian phase, Newton’s second law of motion is used to compute the particles trajectories and velocity. To study the effect of fluid behavior on the filler dispersion, several systems are modeled considering different fluid types (generalized Newtonian or viscoelastic) and particles volume fraction and size. The results obtained are used to correlate the fluid and particle characteristics on the effectiveness of mixing and morphology obtained.

Cytotoxic evaluation of essential oil from Zanthoxylum rhoifolium Lam. leaves

Zanthoxylum rhoifolium Lam is a plant popularly used as antimicrobial, for malaria and inflammatory treatment. The essential oil of Z. rhoifolium was extracted and its cytotoxic effects against HeLa (human cervical carcinoma), A-549 (human lung carcinoma), HT-29 (human colon adenocarcinoma), Vero (monkey kidney) cell lines and mice macrophages were evaluated. Some of the terpenes of its essential oil (ß-caryophyllene, alpha-humulene, alpha -pinene, myrcene and linalool) were also tested to verify their possible influence in the oil cytotoxic activity. The results obtained permitted to confirm that the essential oil is cytotoxic against tumoral cells (CD50 = 82.3, 90.7 and 113.6 µg/ml for A-549, HeLa e HT-29 cell lines, respectively), while it did not show cytotoxicity against non-tumoral cells (Vero and mice macrophages). Thus, the essential oil from Z. rhoifolium leaves seems to present a possible therapeuthic role due to its selective cytotoxic activity against tumoral cell lines.

Structure-properties relationships in thermoplastic polyurethane elastomer nanocomposites: Interactions between polymer phases and nanofillers

Polyurethane thermoplastic elastomer (TPU) nanocomposites were prepared by the incorporation of 1 wt% of high-structured carbon black (HSCB), carbon nanofibers (CNF), nanosilica (NS) and nanoclays (NC), following a proper high-shear blending procedure. The TPU nanofilled mechanical properties and morphology was assessed. The nanofillers interact mainly with the TPU hard segments (HS) domains, determining their glass transition temperature, and increasing their melting temperature and enthalpy. A significant improvement upon the modulus, sustained stress levels and deformation capabilities is evidenced. The relationships between the morphology and the nanofilled TPU properties are established, evidencing the role of HS domains on the mechanical response, regardless the nanofiller type.