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.

Dispersion of graphite nanoplates during melt mixing

Artigo publicado a convite da Society for Polymer Engineers

Improvign mixing processes with the help of numerical tools

In several industrial applications, highly complex behaviour materials are used together with intricate mixing processes, which difficult the achievement of the desired properties for the produced materials. This is the case of the well-known dispersion of nano-sized fillers in a melt polymer matrix, used to improve the nanocomposite mechanical and/or electrical properties. This mixing is usually performed in twin-screw extruders, that promote complex flow patterns, and, since an in loco analysis of the material evolution and mixing is difficult to perform, numerical tools can be very useful to predict the evolution and behaviour of the material. This work presents a numerical based study to improve the understanding of mixing processes. Initial numerical studies were performed with generalized Newtonian fluids, but, due to the null relaxation time that characterize this type of fluids, the assumption of viscoelastic behavior was required. Therefore, the polymer melt was rheologically characterized, and, a six mode Phan-Thien-Tanner and Giesekus models were used to fit the rheological data. These viscoelastic rheological models were used to model the process. The conclusions obtained in this work provide additional and useful data to correlate the type and intensity of the deformation history promoted to the polymer nanocomposite and the quality of the mixing obtained.

Saloplastic membranes as green devices for soft tissue regeneration

Implantable devices must exhibit mechanical properties similar to native tissues to promote appropriate cellular behavior and regeneration. Herein, we report a new membrane manufacture method based on the synthesis of polyelectrolyte complexes (PECs) that exhibit saloplasticity, i.e. variable physical-chemistry using salt as a plasticizer. This is a Green Chemistry approach, as PECs generate structures that are stabilized solely by reversible electrostatic interactions, avoiding the use of harmful crosslinkers completely. Furthermore, natural polyelectrolytes - chitosan and alginate - were used. Upon mixing them, membranes were obtained by drying the PECs at 37ºC, yielding compact PECs without resorting to organicsolvents. The plasticizing effect of salt after synthesis was shown by measuring tensile mechanical properties, which were lower when samples were immersed in high ionic strength solutions.Salt was also used during membrane synthesis in different quan- tities (0 M, 0.15 M and 0.5 M in NaCl) yielding structures with no significant differences in morphology and degradation (around 15% after 3 months in lysozyme). However, swelling was higher (about 10x) when synthesized in the presence of salt. In vitro cell studies using L929 fibroblasts showed that cells adhered and proliferated preferentially in membranes fabricated in the presence of salt (i.e. the membranes with lower tensile strength). Structures with physical-chemical properties controlled with precision open a path to tissue engineering strategies depending on fine tuning mechanical properties and cellular adhesion simply by changing ionic strength during membrane manufacture

Recycled asphalt mixtures with foamed bitumen: an alternative to build ecofriendly road pavements

Nowadays, recycling has become a very important objective for the society in the scope of a closed loop product life cycle. In recent years, new recycling techniques have been developed in the area of road pavements that allow the incorporation of high percentages of reclaimed asphalt (RA) materials in recycled asphalt mixtures. The use of foamed bitumen for production of recycled asphalt mixtures is one of those techniques, which also allows the reduction of the mixing temperatures (warm mix technology). However, it is important to evaluate if this solution can maintain or improve the performance of the resulting mixtures. Thus, the main aim of the present study is to assess the performance of warm recycled asphalt mixtures incorporating foamed bitumen as the new binder and 50% RA, in comparison with a control mixture using conventional bitumen. Four mixtures have been produced with 50% RA, one of them at typical high mixing temperatures with a conventional bitumen (control mixture) and the other three with foamed bitumen at different production temperatures. These four mixtures were tested to evaluate their compactability and water sensitivity. The laboratory test results showed that the production of recycled mixtures with foamed bitumen can be reduced by 40ºC without changing the performance of the resulting mixtures.

Dispersion and re-agglomeration of graphite nanoplates in polypropylene melts under controlled flow conditions

The kinetics of GnP dispersion in polypropylene melt was studied using a prototype small scale modular extensional mixer. Its modular nature enabled the sequential application of a mixing step, melt relaxation, and a second mixing step. The latter could reproduce the flow conditions on the first mixing step, or generate milder flow conditions. The effect of these sequences of flow constraints upon GnP dispersion along the mixer length was studied for composites with 2 and 10 wt.% GnP. The samples collected along the first mixing zone showed a gradual decrease of number and size of GnP agglomerates, at a rate that was independent of the flow conditions imposed to the melt, but dependent on composition. The relaxation zone induced GnP re-agglomeration, and the application of a second mixing step caused variable dispersion results that were largely dependent on the hydrodynamic stresses generated.

Controlo da qualidade de betões

Dissertação de mestrado em Construção e Reabilitação Sustentáveis

Estudo do trabalho numa empresa de produção de pneus e implementação de ferramentas Lean

Dissertação de mestrado integrado em Engenharia e Gestão Industrial

Structure-property relationships in polymer nanocomposites

Tese de Doutoramento em Ciência e Engenharia de Polímeros e Compósitos

Assessing the production of jet mix columns using alkali activated waste based on mechanical and financial performance and CO2 (eq) emissions

Recent research has proved the potential of alkaline activated fly-ash for soil stabilisation. However, such studies have not focused on the link between financial, mechanical and environmental aspects of this solution, but only on their absolute mechanical properties. The present paper characterises the mechanical behaviour of a large spectrum of activator-ash-soil combinations used to build jet mixing columns, analysing also the cost and CO2 (eq) emissions. The concern with these two vectors forced a decrease in the quantity of stabilising agent added to the soil, relatively to previous research, and the effects of such low quantities have not yet been published. However, the results clearly showed a significant improve in strength, still well above the average values expected when improving the stressstrain behaviour of a weak soil. Uniaxial compressive strength tests were used to assess the effects of the fly-ash percentage, the alkalieash ratio and the water content. The carbon calculator recently developed by the European Federation of Foundation Contractors and the Deep Foundations Institute was used to quantify the CO2 (eq) emissions associated with this technique. The financial cost was estimated based on the experience of a major Portuguese contractor. For comparison purposes, soil cement mixtures were also analysed, using similar conditions and tools used for the soil-ash analysis. Results showed that the cement and ash solutions are very similar in terms of overall performance, with some advantage of the former regarding financial cost, and a significant advantage of the latter regarding the CO2 (eq) emissions. This new grout, although it is in an embryonic stage, it has the potential for broader developments in the field.

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.

Mechanical, fatigue and wear properties of sintered Carbon Nanotube-based functionally graded materials

Tese de Doutoramento Engenharia Mecânica

Measurement of the forward-backward asymmetry of electron and muon pair-production in pp collisions at s√ = 7 TeV with the ATLAS detector

This paper presents measurements from the ATLAS experiment of the forward-backward asymmetry in the reaction pp→Z/γ∗→l+l−, with l being electrons or muons, and the extraction of the effective weak mixing angle. The results are based on the full set of data collected in 2011 in pp collisions at the LHC at s√ = 7 TeV, corresponding to an integrated luminosity of 4.8 fb−1. The measured asymmetry values are found to be in agreement with the corresponding Standard Model predictions. The combination of the muon and electron channels yields a value of the effective weak mixing angle of 0.2308±0.0005(stat.)±0.0006(syst.)±0.0009(PDF), where the first uncertainty corresponds to data statistics, the second to systematic effects and the third to knowledge of the parton density functions. This result agrees with the current world average from the Particle Data Group fit.

Search for heavy Majorana neutrinos with the ATLAS detector in pp collisions at s√=8 TeV

A search for heavy Majorana neutrinos in events containing a pair of high-pT leptons of the same charge and high-pT jets is presented. The search uses 20.3fb−1 of pp collision data collected with the ATLAS detector at the CERN Large Hadron Collider with a centre-of-mass energy of s√=8 TeV. The data are found to be consistent with the background-only hypothesis based on the Standard Model expectation. In the context of a Type-I seesaw mechanism, limits are set on the production cross-section times branching ratio for production of heavy Majorana neutrinos in the mass range between 100 and 500 GeV. The limits are subsequently interpreted as limits on the mixing between the heavy Majorana neutrinos and the Standard Model neutrinos. In the context of a left-right symmetric model, limits on the production cross-section times branching ratio are set with respect to the masses of heavy Majorana neutrinos and heavy gauge bosons WR and Z′.