Development of a new U 200 pultrusion die to produce GRP composite profiles using different thermosetting resins

In this work, a steel heated pultrusion die was designed, developed and manufactured to produce U200 glass fibre reinforced thermosetting matrix (GRP) profiles. The finite element analysis (FEA) was used to predict and optimise the developed die heating by using cylindrical electrical powered cartridges. To assess the new die performance it was mounted in the 120 kN pultrusion line of the Portuguese company Vidropol SA and used to produce continuously U200 profiles able to meet all requirements specified for the E23 grade accordingly to the European Standard EN 13706: 2002. After setting up the type, orientation and sequence of layers in laminate, orthophthalic, isophthalic and bisphenolic unsaturated polyester as well as vinylester resins were used to produce glass fibre reinforced U 200 composite profiles. An appropriated catalyst system was selected and the processing variables optimised for each case, namely, pultrusion pull-speed and die temperature. Finally, the produced U200 profiles were submitted to visual inspection, calcination and mechanical tests, namely, flexural, tensional and interlaminar shear strength (ILSS) tests, to assess their accomplishment with the EN 13706 requirements.

Using a new developed die and different types of thermosetting resins to produce U200 profiles by pultrusion

In this work, a new steel heated pultrusion die was designed, developed and manufactured to produce U200 glass fibre reinforced thermosetting matrix (GRP) profiles. The finite element analysis (FEA) was used to predict and optimise the developed die heating by using cylindrical electrical powered cartridges. To assess the new die performance it was mounted in the 120 kN pultrusion line of the Portuguese company Vidropol SA and used to produce continuously U200 profiles able to meet all requirements specified for the E23 grade accordingly to the European Standard EN 13706: 2002. After setting up the type, orientation and sequence of layers in the U 200 laminate, different types of thermosetting resins were used in its production. Orthophthalic, isophthalic and bisphenolic unsaturated polyester as well as vinylester resins were used to produce glass fibre reinforced U 200 composite profiles. All applied resins were submitted to SPI gel tests in order to select the more appropriated catalyst system and optimise the processing variables to be used in each case, namely, pultrusion pull-speed and die temperature. The best pultrusion operational conditions were selected by varying and monitoring the pull-speed and die temperature and, at the same time, measuring the temperature on the manufactured U 200 profile during processing. Finally, the produced U200 profiles were submitted to visual inspection, calcination and mechanical tests, namely, flexural, tensional and interlaminar shear strength (ILSS) tests, to assess their accomplishment with the EN 13706 requirements.

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%.

Effect of ionic liquid anion and cation on the physico-chemical properties of poly(vinylidene fluoride)/ionic liquid blends

Poly(vinylidene fluoride), PVDF, has been blended with different ionic liquids (IL) in order to evaluate the effect of the different IL anions and cations on the electroative -phase, thermal, mechanical and electrical properties of the polymer blend. [C2MIM][Cl], [C6MIM][Cl], [C10MIM][Cl], [C2MIM][NTf2], [C6MIM][NTf2], [C10MIM][NTf2] have been selected and were introduced in the polymer at a weight percentage of 40 wt%. It was found that the incorporation of ILs into the PVDF matrix leads to an increase of the -phase content due to the strong electrostatic interactions between the dipolar moments of PVDF and the ILs. Further, the incorporation of ILs into PVDF strongly decreases the elastic modulus and increases the electrical conductivity of the blend with respect to the pure polymer matrix, all these effects being accompanied by a modification of the crystallization kinetics, as indicated by the modified spherulitic microstructure. Thus, novel PVDF/IL blends films with high transparency, excellent antistatic properties, and highly polar crystal form fraction were successfully achieved.

Polymer composites and blends for battery separators: State of the art, challenges and future trends

In lithium ion battery systems, the separator plays a key role with respect to device performance. Polymer composites and polymer blends have been frequently used as battery separators due to their suitable properties. This review presents the main issues, developments and characteristics of these polymer composites and blends for battery separator membrane applications. This review is divided into two sections regarding the composition of the materials: polymer composite materials, subdivided according to filler type, and polymer blend materials. For each category the electrolyte solutions, ionic conductivity and other relevant physical-chemical characteristics are described. This review shows the recent advances and opportunities in this area and identifies future trends and challenges.

Produtos têxteis inteligentes incorporando filamentos compósitos com nanotubos de carbono

Programa Doutoral em Engenharia Têxtil.

Advances in thermoplastic pultruded composites

Pultrusion is a versatile continuous high speed production technology allowing the production of fibre reinforced complex profiles. Thermosetting resins are normally used as matrices in the production of structural constant cross section profiles. Although only recently thermoplastic matrices have been used in long and continuous fibre reinforced composites replacing with success thermosetting matrices, the number of their applications is increasing due to their better ecological and mechanical performance. Composites with thermoplastic matrices offers increased fracture toughness, higher impact tolerance, short processing cycle time and excellent environmental stability. They are recyclable, post-formable and can be joined by welding. The use of long/continuous fibre reinforced thermoplastic matrix composites involves, however, great technological and scientific challenges since thermoplastics present much higher viscosity than thermosettings, which makes much difficult and complex the impregnation of reinforcements and consolidation tasks. In this work continuous fibres reinforced thermoplastic matrix towpregs were produced using equipment developed by the Institute for Polymers and Composites (IPC). The processing of the towpregs was made by pultrusion, in a developed prototype equipment existing in the Engineering School of the Polytechnic Institute of Porto (ISEP). Different thermoplastic matrices and fibres raw-materials were used in this study to manufacture pultruded composites for commercial applications (glass and carbon fibre/ polypropylene) and for advanced markets (carbon fibre/Primospire®). To improve the temperature distribution profile in heating die, different modifications were performed. In order to optimize both processes, towpregs production and pultruded composites profiles were analysed to determine the influence of the most relevant processing arameters in the final properties. The final pultruded composite profiles were submitted to mechanical tests to obtain the relevant properties.

Phase morphology and crystallinity of poly(vinylidene fluoride)/poly(ethylene oxide) piezoelectric blend membranes

Polymer blends based on poly(vinylidene fluoride), PVDF and poly(ethylene oxide), PEO, with varying compositions have been prepared by solvent casting, the polymer blend films being obtained from solutions in dimethyl formamide at 70ºC. Under these conditions PVDF crystallizes from solution while PEO remains in the molten state. Then, PEO crystallizes from the melt confined by PVDF crystalls during cooling to room temperature. PVDF crystallized from DMF solutions adopt predominantly the electroactive β-phase (85%). Nevertheless when PEO is introduced in the polymer blend the β-phase content decreases slightly to 70%. The piezoelectric coefficient (d33) in pristine PVDF is -5 pC/N and decreases with increasing PEO content in the PVDF/PEO blends. Blend morphology, observed by electron and atomic force microscopy, shows the confinement of PEO between the already formed PVDF crystals. On the other hand the sample contraction when PEO is extracted from the blend with water (which is not a solvent for PVDF) allows proving the co-continuity of both phases in the blend. PEO crystallization kinetics have been characterized by DSC both in isothermal and cooling scans experiments showing important differences in crystalline fraction and crystallization rate with sample composition.

Effect of the degree of porosity on the performance of poly(vinylidene fluoride-trifluoroethylene)/poly(ethylene oxide) blend membranes for lithium-ion battery separators

Porous polymer membranes based on poly(vinylidene fluoride-trifluoroethylene)/poly(ethylene oxide) copolymers, P(VDF-TrFE)/PEO, are prepared through the, from partial to total, elimination of PEO, leading to interconnected micropores in the polymer blends. Electrolyte uptake, thermal and mechanical properties depend on the amount of PEO present in the polymer blend. Further, the degree of crystallinity of PEO and the elastic modulus (E´) of the polymer blend decrease with increasing PEO removal. Electrical properties of the polymer blend membranes are influenced by the porosity and are dominated by diffusion. The temperature dependence of ionic conductivity follows the Arrhenius behavior. It is the highest for the membranes with a volume fraction of pores of 44% (i.e, 90% PEO removal), reaching a value of 0.54 mS.cm-1 at room temperature. Battery performance was determined by assembling Li/C-LiFePO4 swagelok cells. The polymer blends with 90% PEO removal exhibit rate (124 mAhg-1 at C/5 and 47 mAhg-1 at 2C) and cycling capabilities suitable for lithium ion battery applications.

Chitosan-based scaffolds for tissue regeneration: preparation and microstructure characterization

Scaffolds are porous three-dimensional supports, designed to mimic the extracellular environment and remain temporarily integrated into the host tissue while stimulating, at the molecular level, specific cellular responses to each type of body tissues. The major goal of the research work entertained herein was to study the microstructure of scaffolds made from chitosan (Ch), blends of chitosan and sodium alginate (Ch/NaAlg), blends of chitosan, sodium alginate and calcium chloride (Ch/NaAlg/CaCl2) and blends of chitosan, sodium alginate and hydroxyapatite (Ch/NaAlg/HA). Scaffolds possessing ideal physicochemical properties facilitate cell proliferation and greatly increase the rate of recovery of a damaged organ tissue. Using CT three-dimensional images of the scaffolds, it was observed that all scaffolds had a porosity in the range 64%-92%, a radius of maximum pore occurrence in the range 95m-260m and a permeability in the range 1×10-10-18×10-10 m2. From the results obtained, the scaffolds based on Ch, Ch/NaAlg and Ch/NaAlg/CaCl2 would be most appropriate both for the growth of osteoid and for bone tissue regeneration, while the scaffold made with a blend of Ch/NaAlg/HA, by possessing larger pores size, might be used as a support for fibrovascular tissue.

Materiais compósitos com incorporação de cânhamo industrial

Projeto de Investigação integrado de mestrado Internacional em Sustentabilidade do Ambiente Construído

Bacterial nanocellulose as a structured platform for conductive biopolymers

[Exert] Since the discovery that polyacetylene could be doped to the metallic state more than 3 decades ago, an ever-growing body of a multidisciplinary approach to material design, synthesis, and system integration has been evidenced. The present chapter will primarily review the emerging field of intrinsically conducting polymer and conductive polymer blends, with polyaniline and polypyrrole as the major representatives of conducting polymers. This survey will also address some of the potential areas for applications of such conductive polymer blends. Also, current results concerning the chemical polymerization of conducting polymers on bacterial nanocellulose (BNC) will be presented, including brief remarks on the rationale for the use of conductive BNC blends. This will be followed by a discussion on their properties and potential applications (...).

In-line rheo-optical microstructural characterization of complex polymer systems

Tese de Doutoramento em Ciência e Engenharia de Polímeros e Compósitos.