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.

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.

Study of the potential employment of Malvaceae Species in composites materials

The employ of vegetal fibers for textiles and composites represents a great potential in economic and social sustainable development. Some Malvaceae species are considered tropical cosmopolitans, such as from Sida genus. Several species of this genus provide excellent textile bast fibers, which are very similar in qualities to the jute textile fiber. The objective of the present study is present the physicochemical characterization of six Brazilian vegetal fibers: Sida rhombifolia L.; Sida carpinifolia L. f.; Sidastrum paniculatum (L.) Fryxell; Sida cordifolia L.; Malvastrum coromandelianum (L.) Gurck; Wissadula subpeltata (Kuntze) R.E.Fries. Respectively the two first species are from Brazilian Atlantic Forest biome and the four remaining from Brazilian Cerrado biome, despite of present in other regions of the planet. The stems of these species were retted in water at 37oC for 20 days. The fibers were tested in order to determine tensile rupture strength, tenacity, elongation, Young’s modulus, cross microscopic structure, Scanning Electronic Microscopy (SEM), regain, combustion, acid, alkali, organic solvent and cellulase effects, pH of the aqueous extract, Differential Scanning Calorimetry (DSC) and Thermogravimetric Analysis (TGA). The obtained values were compared with those from fibers of recognized applicability in the textile industry including hemp. The results are promising in terms of their employment in thermoset and thermoplastic medium resistance composites.

Pultrusion of fibre reinforced thermoplastic pre-impregnated materials

Fibre reinforced thermoplastic pre impregnated materials produced continuously by diverse methods and processing conditions were used to produce composites using pultrusion. The processing windows used to produce these materials and composites profiles were optimized by using the Taguchi / DOE (Design of Experiments) methods. Composites were manufactured by pultrusion and compression moulding and subsequently submitted to mechanical testing and microscopy analysis. The obtained results were compared with the expected theoretical ones predicted from the Rule of Mixtures (ROM) and with those of similar engineering conventional available materials. The results obtained shown that produced composites have adequate properties for applications in common and structural engineering markets.

Jute/polypropylene composites: Effect of enzymatic modification on thermo-mechanical and dynamic mechanical properties

In this study, a high-performance composite was prepared from jute fabrics and polypropylene (PP). In order to improve the compatibility of the polar fibers and the non-polar matrix, alkyl gallates with different hydrophobic groups were enzymatically grafted onto jute fabric by laccase to increase the surface hydrophobicity of the fiber. The grafting products were characterized by FTIR. The results of contact angle and wetting time showed that the hydrophobicity of the jute fabrics was improved after the surface modification. The effect of the enzymatic graft modification on the properties of the jute/PP composites was evaluated. Results showed that after the modification, tensile and dynamic mechanical properties of composites improved, and water absorption and thickness swelling clearly decreased. However, tensile properties drastically decreased after a long period of water immersion. The thermal behavior of the composites was evaluated by TGA/DTG. The fiber-matrix morphology in the modified jute/PP composites was confirmed by SEM analysis of the tensile fractured specimens.

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.

Dielectric relaxation and ferromagnetic resonance in magnetoelectric (Polyvinylidene-fluoride)/ferrite composites

In this work the dielectric properties and ferromagnetic resonance of Polyvinylidene- uoride embedded with 10 wt. % of NiFe2O4 or Ni0.5Zn0.5Fe2O4 nanoparticles are presented. The mechanisms of the dielectric relaxation in these two composites do not differ from each other. For more precise characterization of the dielectric relaxation, a two dimensional distribution of relaxation times was calculated from the temperature dependencies of the complex dielectric permittivity. The results obtained from the 2D distribution and the mean relaxation time are found to be consistent. The dynamics of the dielectric permittivity is described by the Arrhenius law. The energy and attempt time of the dielectric relaxators lie in a narrow energy and time region thus proving that the single type chains of polymer are responsible for a dispersion. The magnetic properties of the composites were investigated using the fer- romagnetic resonance. A single resonance line was observed for both samples. From the temperature dependence (100 K - 310 K) of the resonance eld and linewidth, the origin of the observed line was attributed to the NiFe2O4 and Ni0.5Zn0.5Fe2O4 superparamagnetic nanoparticles. By measuring lms at dif- ferent orientations with respect to the external magnetic eld, the angular dependence of the resonance was observed, indicating the magnetic dipolar in-plane interactions.

Synthesis, physical and magnetic properties of BaFe12O19/P(VDF-TrFE) multifunctional composites

Composite films with filler microparticles of Barium ferrite dispersed within P(VDF-TrFE) as polymeric matrix have been prepared by solvent evaporation. The lowest BaFO content of 1% wt acts as a small defect within the polymeric matrix, reducing the values of the dielectric and mechanical properties of the pure P(VDF-TrFE). For filler contents up to a 20%, the BaFO filler reinforces the matrix and measured properties increase their values. This trend is not followed by the electrical conductivity. We extended the study to fibers composed by BaFe12O19 microparticles in a PVDF matrix. Due to the big size of BaFO particles (1 micron in diameter), proper fabrication of the fiber shaped composites has not been achieved. We found that true BaFO content are always lower than nominal ones. Results are discussed in terms of the influence of size and morphology of the BaFO particles on the initial properties of the polymeric matrix.

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.

Mechanical vs. electrical hysteresis of carbon nanotube/styrene-butadiene-styrene composites and their influence in the electromechanical response

The interesting properties of thermoplastics elastomers can be combined with carbon nanotubes (CNT) for the development of large strain piezoresistive composites for sensor applications. Piezoresistive properties of the composites depend on CNT content, with the gauge factor increasing for concentrations around the percolation threshold, mechanical and electrical hysteresis. The SBS copolymer composition (butadiene/styrene ratio) influences the mechanical and electrical hysteresis of composites and, therefore, the piezoresistive response. This work reports on the electrical and mechanical response of CNT/SBS composites with 4%wt nanofiller content, due to the larger electromechanical response. C401 and C540 SBS copolymers with 80% and 60% butadiene content, respectively have been selected. The copolymer with larger amount of soft phase (C401) shows a rubber-like mechanical behavior, with mechanical hysteresis increasing linearly with strain until 100% strain. The copolymer with the larger amount of hard phase (C540) just shows rubber-like behavior for low strains. The piezoresistive sensibility is similar for both composites for low strains, with a GF≈ 5 for 5% strain. The electrical hysteresis shows opposite behavior than the mechanical hysteresis, increasing with strain for both composites, but with higher increase for softer copolymer, C401. The GF increases with increasing strain, but this increase is larger for composites with lower amounts of soft phase due to the distinct initial modulus and deformation of the soft and hard phases of the copolymer. The soft phase shows larger strain under a given stress than the harder phase and the conductive pathway rearrangements in the composites are different for both phases, the harder copolymer (C540) showing higher piezoresistive sensibility, GF≈ 18, for 20% strain.

Ion exchange dependent electroactive phase content and electrical properties of poly(vinylidene fluoride)/Na(M)Y composites

Different metal-ion exchanged NaY zeolite, Na(M)Y, were used to prepare poly(vinylidene fluoride) based composites by solvent casting and melting crystallization. The effect of different metal ion-exchanged zeolites on polymer crystallization and electrical properties was reported. Cation-framework interactions and hydration energy of the cations determined that K+ is the most efficient exchanged ion in NaY zeolite, followed by Cs+ and Li+. The electroactive phase crystallization strongly depends on the ions present in the zeolite, leading to variations of the surface energy characteristics of the Na(M)Y zeolites and the polymer chain ability of penetration in the zeolite. Thus, Na(Li)Y and NaY induces the complete electroactive -phase crystallization of the crystalline phase of PVDF, while Na(K)Y only induces it partly and Na(Cs)Y is not able to promote the crystallization of the electroactive phase. Furthermore, different ion size/weigh and different interaction with the zeolite framework results in significant variations in the electrical response of the composite. In this way, iinterfacial polarization effects in the zeolite cavities and zeolite-polymer interface, leads to strong increases of the dielectric constant on the composites with lightest ions weakly bound to the zeolite framework. Polymer composite with Na(Li)Y show the highest dielectric response, followed by NaY and Na(K)Y. Zeolite Na(Cs)Y contribute to a decrease of the dielectric constant of the composite. The results show the relevance of the materials for sensor development.

Microstructure and mechanical properties of carbon nanotube reinforced cementitious composites developed using a novel dispersion technique

The authors also acknowledge Centre for Textile Science and Technology (University of Minho) and FIBRENAMICS PLATFORMfor providing required conditions for this research. Sincere thanks are also due to Mr. Pedro Samuel Leite and Mr. Carlos Jesus for their kind help in sample preparation and testing.

Evaluation of natural fibers from brazilian malvaceae family and its potential as reinforced composites

This study compares the physicochemical characteristics of six species from Brazilian Malvaceae family with natural fibers of recognized applicability in the industry. The objective of the present study is present the physicochemical characterization of six Brazilian vegetal fibers: Sida rhombifolia L.; Sida carpinifolia L. f.; Sidastrum paniculatum (L.) Fryxell; Sida cordifolia L.; Malvastrum coromandelianum (L.) Gurck; Wissadula subpeltata (Kuntze) R.E.Fries. Respectively the two first species are from Brazilian Atlantic Forest biome and the four remaining from Brazilian Cerrado biome, despite of present in other regions of the plane

Optimization of magnetoelectric composites based on electroactive polymers for energy harvesting and sensor application

Tese de Doutoramento em Engenharia de Materiais.

Exploring the use of HPFRC and GFRP grids for the production of manhole covers

Corrosion of the steel reinforced concrete elements is one of the common pathologies that limits the long-term performance of urban infrastructures. This problem causes the loss of structural serviceability by decreasing the concrete-steel bond strength and reducing the cross section of the reinforcements. The present study introduces a new system for developing free-corrosion resistance prefabricated manhole covers for applications in the aggressive environments, i.e. wastewater collector systems, sewer systems, stormwater systems, etc. Fibre reinforced cement composites were applied in this system in order to suppress the corrodible steel mesh and maintain the structural ductility as well. Application of fibre reinforced polymer (FRP) system is adopted as the additional solution for increasing the load carrying capacity of these elements without concerns about corrosion. The effectiveness of the applied strategy in developing the manhole covers in terms of load carrying capacity and failure mode is evaluated in this research. Furthermore, this paper discusses a FEM-based simulation, aiming to address the possibility of calibrating the constitutive model parameters related to fracture modes I and II.