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.

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.

Structure-property relationships in polymer nanocomposites

Tese de Doutoramento em Ciência e Engenharia de Polímeros e Compósitos

Bacterial cellulose as a novel substrate for retinal pigment epithelium cells transplantation in age-related macular degeneration

Tese de Doutoramento em Engenharia Química e Biológica.

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.

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.

Thermal characterization of polyhydroxyalkanoates and poly(lactic acid) blends obtained by injection molding

In this work we present the thermal characterization of the full scope of polyhydroxyalcanoate and poly(lactic acid) blends obtain by injection molding. Blends of polyhydroxyalcanoate and poly(lactic acid) (PHA/PLA) were prepared in different compositions ranging from 0–100% in steps of 10%. The blends were injection molded and then characterized by differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and wide angle X-ray diffraction (WAXD). The increment of PHA fraction increased the degree of crystallinity of the blend and the miscibility of the base polymers as verified by the Fox model. The WAXD analysis indicates that the presence of PHA hindered the PLA crystallization. The crystallization evolution trough PHA weight fraction (wf) shows a phase inversion around 50-60%. SEM analyses confirmed that the miscibility of PHA/PLA blends increased with the incorporation of PHA and became total for values of PHA higher that 50%.

High performance electromechanical actuators based on ionic liquid/poly(vinylidene fluoride)

Due to the increasing need of low voltage actuators, independent from electrochemical processes, electroactive actuators based on poly(vinylidene fluoride) composites with 10, 25 and 40 % of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C2mim] [NTf2], ionic liquid are prepared by solvent casting and melting. We show that the charge structure of [C2mim] [NTf2] induces the complete piezoelectric -phase crystallization of the PVDF within the composite and decreases its crystallinity fraction significantly. [C2mim] [NTf2] also works as a plasticizer of PVDF, reducing the elastic modulus down to 12 % of the initial value. Moreover, the composites show significant displacement and bending under applied voltages of 2, 5 and 10 Vpp. The displacement and bending of the composite membranes are also evaluated as a function of [C2mim] [NTf2] content and sample thickness. Increasing amounts of ionic liquid result in larger deformations independently of the applied voltage.

Tailored magnetic and magnetoelectric responses of polymer-based composites

The manipulation of electric ordering with applied magnetic fields has been realized on magnetoelectric (ME) materials, however, their ME switching is often accompanied by significant hysteresis and coercivity that represents, for some applications, a severe weakness. To overcome this obstacle, this work focus on the development of a new type of ME polymer nanocomposites that exhibits tailored ME response at room temperature. The multiferroic nanocomposites are based on three different ferrite nanoparticles, Zn0.2Mn0.8Fe2O4 (ZMFO), CoFe2O4 (CFO) and Fe3O4 (FO), dispersed in a piezoelectric co-polymer poly(vinylindene fluoride-trifluoroethylene), P(VDF-TrFE), matrix. No substantial differences were detected on the time-stable piezoelectric response of the composites (≈ -28 pC.N−1) with distinct ferrite fillers and for the same ferrite content of 10wt.%. Magnetic hysteresis loops from pure ferrite nanopowders showed different magnetic responses. ME results of the nanocomposite films with 10wt.% ferrite content revealed that the ME induced voltage increases with increasing DC magnetic field until a maximum of 6.5 mV∙cm−1∙Oe−1, at an optimum magnetic field of 0.26 T, and 0.8 mV∙cm−1∙Oe−1, at an optimum magnetic field of 0.15T, for the CFO/P(VDF-TrFE) and FO/P(VDF-TrFE) composites, respectively. On the contrary, the ME response of the ZMFO/P(VDF-TrFE) exposed no hysteresis and high dependence on the ZMFO filler content. Possible innovative applications such as memories and information storage, signal processing, ME sensors and oscillators have been addressed for such ferrite/PVDF nanocomposites.

Poly(vinylidene fluoride-co-chlorotrifluoroethylene) (PVDF-CTFE) lithium-ion battery separator membranes prepared by phase inversion

Separator membranes based on poly(vinylidene fluoride-co-chlorotrifluoroethylene) (PVDF-CTFE) were prepared by solvent casting technique based on its phase diagram in N,Ndimethylformamide (DMF) solvent. The microstructure of the PVDF-CTFE separator membranes depends on the initial position (temperature and concentration) of the solution in the phase diagram of the PVDF-CTFE/DMF system. A porous microstructure is achieved for PVDF-CTFE membranes with solvent evaporation temperature up to 50 ºC for a polymer/solvent relative concentration of 20 wt%. The ionic conductivity of the separator depends on the degree of porosity and electrolyte uptake, the highest room temperature value being 1.5 mS.cm-1 for the sample with 20 wt% of polymer concentration and solvent evaporation temperature at 25 ºC saturated with 1 mol L-1 lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) in propylene carbonate (PC). This PVDF-CTFE separator membrane in Li/C-LiFePO4 half-cell shows good cyclability and rate capability, showing a discharge value after 50 cycles of 92 mAh.g-1 at 2 C, which is still 55% of the theoretical value. PVDF-CTFE separators are thus excellent candidates for high-power and safety lithium-ion batteries applications.

High-temperature polymer based magnetoelectric nanocomposites

The use of polymer based magnetoelectric materials for sensing and actuation applications has been the subject of increasing scientific and technological interest. One of the drawbacks to be overcome in this field is to increase the temperature range of application above 100 ºC. In this way, a nanocomposite material composed by a mixture of two aromatic diamines, 1,3-Bis-2-cyano-3-(3 aminophenoxy)phenoxybenzene (diamine 2CN) and 1,3-Bis(3-aminophenoxy)benzene (diamine 0CN) and CoFe2O4 (CFO) nanoparticles was designed, fabricated and successfully tested for high temperature magnetoelectric applications. Results revealed that CFO nanoparticles are well distributed within the 0CN2CN polymer matrix and that the addition of CFO nanoparticles does not significantly alter the polyimides structure. The magnetization response of the composite is determined by the CFO nanoparticle content. The piezoelectric response of the 0CN2CN polymer matrix (≈11 pC.N-1) and the maximum α33 value (0.8mV.cm-1.Oe-1) are stable over time and decrease only when the composite is subjected to temperatures above 130 ºC. Strategies to further improve the ME response are also discussed.