Composites from Brazilian natural fibers with polypropylene: mechanical and thermal properties

Brazil has a well established ethanol production program based on sugarcane. Sugarcane bagasse and straw are the main by-products that may be used as reinforcement in natural fiber composites. Current work evaluated the influence of fiber insertion within a polypropylene (PP) matrix by tensile, TGA and DSC measurements. Thus, the mechanical properties, weight loss, degradation, melting and crystallization temperatures, heat of melting and crystallization and percentage of crystallinity were attained. Fiber insertion in the matrix improved the tensile modulus and changed the thermal stability of composites (intermediary between neat fibers and PP). The incorporation of natural fibers in PP promoted also apparent T(c) and Delta H(c) increases. As a Conclusion, the fibers added to polypropylene increased the nucleating ability, accelerating the crystallization process, improving the mechanical properties and consequently the fiber/matrix interaction.

Characterization of dimethacrylate polymeric networks: A study of the crosslinked structure formed by monomers used in dental composites

The resin phase of dental composites is mainly composed of combinations of dimethacrylate comonomers, with final polymeric network structure defined by monomer type/reactivity and degree of conversion. This fundamental study evaluates how increasing concentrations of the flexible triethylene glycol dimethacrylate (TEGDMA) influences void formation in bisphenol A diglycidyl dimethacrylate (BisGMA) co-polymerizations and correlates this aspect of network structure with reaction kinetic parameters and macroscopic volumetric shrinkage. Photopolymerization kinetics was followed in real-time by a near-infrared (NIR) spectroscopic technique, viscosity was assessed with a viscometer, volumetric shrinkage was followed with a linometer, free volume formation was determined by positron annihilation lifetime spectroscopy (PALS) and the sol-gel composition was determined by extraction with dichloromethane followed by (1)H NMR analysis. Results show that, as expected, volumetric shrinkage increases with TEGDMA concentration and monomer conversion. Extraction/(1)H NMR studies show increasing participation of the more flexible TEGDMA towards the limiting stages of conversion/crosslinking development. As the conversion progresses, either based on longer irradiation times or greater TEGDMA concentrations, the network becomes more dense, which is evidenced by the decrease in free volume and weight loss after extraction in these situations. For the same composition (BisGMA/TEGDMA 60-40 mol%) light-cured for increasing periods of time (from 10 to 600 s), free volume decreased and volumetric shrinkage increased, in a linear relationship with conversion. However, the correlation between free volume and macroscopic volumetric shrinkage was shown to be rather complex for variable compositions exposed for the same time (600 s). The addition of TEGDMA decreases free-volume up to 40 mol% (due to increased conversion), but above that concentration, in spite of the increase in conversion/crosslinking, free volume pore size increases due to the high concentration of the more flexible monomer. In those cases, the increase in volumetric shrinkage was due to higher functional group concentration, in spite of the greater free volume. Therefore, through the application of the PALS model, this study elucidates the network formation in dimethacrylates commonly used in dental materials. (C) 2010 Elsevier Ltd. All rights reserved.

Innovative manufacturing process for hybrid pultruded products based on cork and polymeric pre-shapes

Pultruded products are being targeted by a growing demand due to its excellent mechanical properties and low chemical reactivity, ensuring a low level of maintenance operations and allowing an easier assembly operation process than equivalent steel bars. In order to improve the mechanical drawing process and solve some acoustic and thermal insulation problems, pultruded pipes of glass fibre reinforced plastics (GFRF) can be filled with special products that increase their performance regarding the issues previously referred. The great challenge of this work was drawing a new equipment able to produce pultruded pipes filled with cork or polymeric pre-shaped bars as a continuous process. The project was carried out successfully and the new equipment was built and integrated in the pultrusion equipment already existing, allowing to obtain news products with higher added-value in the market, covering some needs previously identified in the field of civil construction.

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.

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

Tese de Doutoramento Engenharia Mecânica

Ethylene-Propylene-Diene Terpolymer/Hexafluoropropylene-Vinylidinefluoride Elastomeric Composites: Thermal, Mechanical and Microwave Properties

In the present study, an attempt has been made to prepare composites by incorporating expanded graphite fillers in insulating elastomer matrices and to study its DC electrical conductivity, dielectric properties and electromagnetic shielding characteristics, in addition to evaluating the mechanical properties. Recently, electronic devices and components have been rapidly developing and advancing. Thus, with increased usage of electronic devices, electromagnetic waves generated by electronic systems can potentially create serious problems such as malfunctions of medical apparatus and industry robots and can even cause harm to the human body. Therefore, in this work the applicable utility of the prepared composites as electromagnetic interference (EMI) shielding material are also investigated. The dissertation includes nine chapters

Effect of Carbon Black on the Mechanical and Dielectric Properties of Rubber Ferrite Composites Containing Barium Ferrite

Fine particles of barium ferrite (BaFe12O19) were synthesized by the conventional ceramic technique. These materials were then characterized by the X-ray diffraction method and incorporated in the natural rubber matrix according to a specific receipe for various loadings of ferrite. The rubber ferrite composites (RFC) thus obtained have several applications, and have the advantage of molding into complex shapes. For applications such as microwave absorbers, these composites should have an appropriate dielectric strength with the required mechanical and magnetic properties. The N330 (HAF) carbon black has been added to these RFCs for various loadings to modify the dielectric and mechanical properties. In this article we report the effect of carbon black on the mechanical and dielectric properties of these RFCs. Both the mechanical and dielectric properties can be enhanced by the addition of an appropriate amount of carbon black

Synthesis, Characterization and Applications of Hybrid Nanocomposites of TiO2 With Conducting Polymers

A nanocomposite is a multiphase solid material where one of the phases has one, two or three dimensions of less than 100 nanometers (nm), or structures having nano-scale repeat distances between the different phases that make up the material. In the broadest sense this definition can include porous media, colloids, gels and copolymers, but is more usually taken to mean the solid combination of a bulk matrix and nano-dimensional phase(s) differing in properties due to dissimilarities in structure and chemistry. The mechanical, electrical, thermal, optical, electrochemical, catalytic properties of the nanocomposite will differ markedly from that of the component materials. Size limits for these effects have been proposed, <5 nm for catalytic activity, <20 nm for making a hard magnetic material soft, <50 nm for refractive index changes, and <100 nm for achieving superparamagnetism, mechanical strengthening or restricting matrix dislocation movement. Conducting polymers have attracted much attention due to high electrical conductivity, ease of preparation, good environmental stability and wide variety of applications in light-emitting, biosensor chemical sensor, separation membrane and electronic devices. The most widely studied conducting polymers are polypyrrole, polyaniline, polythiophene etc. Conducting polymers provide tremendous scope for tuning of their electrical conductivity from semiconducting to metallic region by way of doping and are organic electro chromic materials with chemically active surface. But they are chemically very sensitive and have poor mechanical properties and thus possessing a processibility problem. Nanomaterial shows the presence of more sites for surface reactivity, they possess good mechanical properties and good dispersant too. Thus nanocomposites formed by combining conducting polymers and inorganic oxide nanoparticles possess the good properties of both the constituents and thus enhanced their utility. The properties of such type of nanocomposite are strongly depending on concentration of nanomaterials to be added. Conducting polymer composites is some suitable composition of a conducting polymer with one or more inorganic nanoparticles so that their desirable properties are combined successfully. The composites of core shell metal oxide particles-conducting polymer combine the electrical properties of the polymer shell and the magnetic, optical, electrical or catalytic characteristics of the metal oxide core, which could greatly widen their applicability in the fields of catalysis, electronics and optics. Moreover nanocomposite material composed of conducting polymers & oxides have open more field of application such as drug delivery, conductive paints, rechargeable batteries, toners in photocopying, smart windows, etc.The present work is mainly focussed on the synthesis, characterization and various application studies of conducting polymer modified TiO2 nanocomposites. The conclusions of the present work are outlined below, Mesoporous TiO2 was prepared by the cationic surfactant P123 assisted hydrothermal synthesis route and conducting polymer modified TiO2 nanocomposites were also prepared via the same technique. All the prepared systems show XRD pattern corresponding to anatase phase of TiO2, which means that there is no phase change occurring even after conducting polymer modification. Raman spectroscopy gives supporting evidence for the XRD results. It also confirms the incorporation of the polymer. The mesoporous nature and surface area of the prepared samples were analysed by N2 adsorption desorption studies and the mesoporous ordering can be confirmed by low angle XRD measurementThe morphology of the prepared samples was obtained from both SEM & TEM. The elemental analysis of the samples was performed by EDX analysisThe hybrid composite formation is confirmed by FT-IR spectroscopy and X-ray photoelectron spectroscopyAll the prepared samples have been used for the photocatalytic degradation of dyes, antibiotic, endocrine disruptors and some other organic pollutants. Photocatalytic antibacterial activity studies were also performed using the prepared systemsAll the prepared samples have been used for the photocatalytic degradation of dyes, antibiotic, endocrine disruptors and some other organic pollutants. Photocatalytic antibacterial activity studies were also performed using the prepared systems Polyaniline modified TiO2 nanocomposite systems were found to have good antibacterial activity. Thermal diffusivity studies of the polyaniline modified systems were carried out using thermal lens technique. It is observed that as the amount of polyaniline in the composite increases the thermal diffusivity also increases. The prepared systems can be used as an excellent coolant in various industrial purposes. Nonlinear optical properties (3rd order nonlinearity) of the polyaniline modified systems were studied using Z scan technique. The prepared materials can be used for optical limiting Applications. Lasing studies of polyaniline modified TiO2 systems were carried out and the studies reveal that TiO2 - Polyaniline composite is a potential dye laser gain medium.

Envelhecimento ambiental em compósitos poliméricos à base de tecidos de reforços híbridos

The utilization of synthetic fibers for plastic reinforcement is more and more frequent and this growing interest requires that their mechanic behavior under the most variable conditions of structural applications be known. The use of such materials in the open and exposed to the elements is one of them. In this case, it becomes extremely necessary to study their mechanical properties (strength, stiffness) and the mechanism of fracture by which the environment aging them out. In order to do that, the material must be submitted to hot steam and ultraviolet radiation exposure cycles, according to periods of time determined by the norms. This study proposal deals with the investigation of accelerated environmental aging in two laminated polymeric composites reinforced by hybrid woven made up of synthetic fibers. The configurations of the laminated composites are defined as: one laminate reinforced with hybrid woven of glass fibers/E and Kevlar fibers/49 (LHVK) and the other laminate is reinforced with hybrid tissue of glass fibers/E and of carbon fibers AS4 (LHVC). The woven are plane and bidirectional. Both laminates are impregnated with a thermofix resin called Derakane 470-300 Epoxy Vinyl-Ester and they form a total of four layers. The laminates were industrially manufactured and were made through the process of hand-lay-up. Comparative analyses were carried out between their mechanical properties by submitting specimen to uniaxial loading tractions and three-point flexion. The specimen were tested both from their original state, that is, without being environmentally aging out, and after environmental aging. This last state was reached by using the environmental aging chamber

Thermal and mechanical behaviour of sisal/phenolic composites

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

SURFACE MODIFICATION of SUGARCANE BAGASSE CELLULOSE and ITS EFFECT on MECHANICAL and WATER ABSORPTION PROPERTIES of SUGARCANE BAGASSE CELLULOSE HDPE COMPOSITES

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Effect of addition of MTES on the structure of siloxane-PPG nanocomposites

Hybrid transparent and flexible siloxane-polypropyleneglycol (PPG) materials with covalent bonds between the inorganic (siloxane) and organic (polymeric) phases were prepared by sol-gel process. In order to improve the quality of the mechanical properties of these materials, different amounts of methyltriethoxysilane (MTES) were added to the initial sol. The effect of MTES addition on the structure of the composites was studied by Small-Angle X-Ray Scattering (SAXS) and Si-29 Nuclear Magnetic Resonance (Si-29 NMR). In absence of MTES, SAXS spectra exhibit a peak that is assigned to spatial correlation due to short range order between the siloxane clusters embedded in the polymeric phase. The experimental results indicate that, for low MTES concentrations ([MTES]/[O] less than or equal to 0.8, O: ether-type oxygen of PPG), the silicon species resulting from hydrolysis and condensation of MTES fill the open spaces between polymeric chains, interacting with the ether-type oxygens. For larger MTES content ([MTES]/[O] greater than or equal to 0.8), the number of free ether-type oxygen sites avalaible for reaction with such silicon species is not large enough. Consequently, a fraction of silicon species resulting from MTES addition graft to siloxane clusters formed by hydrolysis and condensation of the hybrid precursor. For all MTES concentrations the condensation degree of the siloxane phase, determined from Si-29 NMR spectroscopy, is high (> 69%), as expected under neutral pH synthesis conditions.

Study of the thermo-mechanical and electrical properties of conducting composites containing natural rubber and carbon black

This work shows the preparation and characterization of composites obtained by mixing natural rubber (NR) and carbon black (CB) in different percentages aiming suitable mechanical properties, processability and electrical conductivity for future applications as transducers in pressure sensors. The composites NR/CB are characterized through dc conductivity, thermal analysis using differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMA), thermogravimetry (TGA) and stress-strain test. The electrical conductivity changed from 10-9 to 10 Sm-1 depending on the percentage of CB in the composite. Besides, it was found a linear (and reversible) dependence of the conductivity on the applied pressure in the range from 0 to 1.6 MPa for the sample 80/20 (NR/CB wt%).

Development and characterization of non-oxide ceramic composites for mechanical and tribological applications

The main reasons for the attention focused on ceramics as possible structural materials are their wear resistance and the ability to operate with limited oxidation and ablation at temperatures above 2000°C. Hence, this work is devoted to the study of two classes of materials which can satisfy these requirements: silicon carbide -based ceramics (SiC) for wear applications and borides and carbides of transition metals for ultra-high temperatures applications (UHTCs). SiC-based materials: Silicon carbide is a hard ceramic, which finds applications in many industrial sectors, from heat production, to automotive engineering and metals processing. In view of new fields of uses, SiC-based ceramics were produced with addition of 10-30 vol% of MoSi2, in order to obtain electro conductive ceramics. MoSi2, indeed, is an intermetallic compound which possesses high temperature oxidation resistance, high electrical conductivity (21·10-6 Ω·cm), relatively low density (6.31 g/cm3), high melting point (2030°C) and high stiffness (440 GPa). The SiC-based ceramics were hot pressed at 1900°C with addition of Al2O3-Y2O3 or Y2O3-AlN as sintering additives. The microstructure of the composites and of the reference materials, SiC and MoSi2, were studied by means of conventional analytical techniques, such as X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (SEM-EDS). The composites showed a homogeneous microstructure, with good dispersion of the secondary phases and low residual porosity. The following thermo-mechanical properties of the SiC-based materials were measured: Vickers hardness (HV), Young’s modulus (E), fracture toughness (KIc) and room to high temperature flexural strength (σ). The mechanical properties of the composites were compared to those of two monolithic SiC and MoSi2 materials and resulted in a higher stiffness, fracture toughness and slightly higher flexural resistance. Tribological tests were also performed in two configurations disco-on-pin and slideron cylinder, aiming at studying the wear behaviour of SiC-MoSi2 composites with Al2O3 as counterfacing materials. The tests pointed out that the addition of MoSi2 was detrimental owing to a lower hardness in comparison with the pure SiC matrix. On the contrary, electrical measurements revealed that the addition of 30 vol% of MoSi2, rendered the composite electroconductive, lowering the electrical resistance of three orders of magnitude. Ultra High Temperature Ceramics: Carbides, borides and nitrides of transition metals (Ti, Zr, Hf, Ta, Nb, Mo) possess very high melting points and interesting engineering properties, such as high hardness (20-25 GPa), high stiffness (400-500 GPa), flexural strengths which remain unaltered from room temperature to 1500°C and excellent corrosion resistance in aggressive environment. All these properties place the UHTCs as potential candidates for the development of manoeuvrable hypersonic flight vehicles with sharp leading edges. To this scope Zr- and Hf- carbide and boride materials were produced with addition of 5-20 vol% of MoSi2. This secondary phase enabled the achievement of full dense composites at temperature lower than 2000°C and without the application of pressure. Besides the conventional microstructure analyses XRD and SEM-EDS, transmission electron microscopy (TEM) was employed to explore the microstructure on a small length scale to disclose the effective densification mechanisms. A thorough literature analysis revealed that neither detailed TEM work nor reports on densification mechanisms are available for this class of materials, which however are essential to optimize the sintering aids utilized and the processing parameters applied. Microstructural analyses, along with thermodynamics and crystallographic considerations, led to disclose of the effective role of MoSi2 during sintering of Zrand Hf- carbides and borides. Among the investigated mechanical properties (HV, E, KIc, σ from room temperature to 1500°C), the high temperature flexural strength was improved due to the protective and sealing effect of a silica-based glassy phase, especially for the borides. Nanoindentation tests were also performed on HfC-MoSi2 composites in order to extract hardness and elastic modulus of the single phases. Finally, arc jet tests on HfC- and HfB2-based composites confirmed the excellent oxidation behaviour of these materials under temperature exceeding 2000°C; no cracking or spallation occurred and the modified layer was only 80-90 μm thick.

Mechanical behaviour of laminated functionally graded fibre-reinforced self-compacting cementitious composites

El hormigón autocompactante (HAC) es una nueva tipología de hormigón o material compuesto base cemento que se caracteriza por ser capaz de fluir en el interior del encofrado o molde, llenándolo de forma natural, pasando entre las barras de armadura y consolidándose únicamente bajo la acción de su peso propio, sin ayuda de medios de compactación externos, y sin que se produzca segregación de sus componentes. Debido a sus propiedades frescas (capacidad de relleno, capacidad de paso, y resistencia a la segregación), el HAC contribuye de forma significativa a mejorar la calidad de las estructuras así como a abrir nuevos campos de aplicación del hormigón. Por otra parte, la utilidad del hormigón reforzado con fibras de acero (HRFA) es hoy en día incuestionable debido a la mejora significativa de sus propiedades mecánicas tales como resistencia a tracción, tenacidad, resistencia al impacto o su capacidad para absorber energía. Comparado con el HRFA, el hormigón autocompactante reforzado con fibras de acero (HACRFA) presenta como ventaja una mayor fluidez y cohesión ofreciendo, además de unas buenas propiedades mecánicas, importantes ventajas en relación con su puesta en obra. El objetivo global de esta tesis doctoral es el desarrollo de nuevas soluciones estructurales utilizando materiales compuestos base cemento autocompactantes reforzados con fibras de acero. La tesis presenta una nueva forma de resolver el problema basándose en el concepto de los materiales gradiente funcionales (MGF) o materiales con función gradiente (MFG) con el fin de distribuir de forma eficiente las fibras en la sección estructural. Para ello, parte del HAC se sustituye por HACRFA formando capas que presentan una transición gradual entre las mismas con el fin de obtener secciones robustas y exentas de tensiones entre capas con el fin de aplicar el concepto “MGF-laminados” a elementos estructurales tales como vigas, columnas, losas, etc. El proceso incluye asimismo el propio método de fabricación que, basado en la tecnología HAC, permite el desarrollo de interfases delgadas y robustas entre capas (1-3 mm) gracias a las propiedades reológicas del material. Para alcanzar dichos objetivos se ha llevado a cabo un amplio programa experimental cuyas etapas principales son las siguientes: • Definir y desarrollar un método de diseño que permita caracterizar de forma adecuada las propiedades mecánicas de la “interfase”. Esta primera fase experimental incluye: o las consideraciones generales del propio método de fabricación basado en el concepto de fabricación de materiales gradiente funcionales denominado “reología y gravedad”, o las consideraciones específicas del método de caracterización, o la caracterización de la “interfase”. • Estudiar el comportamiento mecánico sobre elementos estructurales, utilizando distintas configuraciones de MGF-laminado frente a acciones tanto estáticas como dinámicas con el fin de comprobar la viabilidad del material para ser usado en elementos estructurales tales como vigas, placas, pilares, etc. Los resultados indican la viabilidad de la metodología de fabricación adoptada, así como, las ventajas tanto estructurales como en reducción de costes de las soluciones laminadas propuestas. Es importante destacar la mejora en términos de resistencia a flexión, compresión o impacto del hormigón autocompactante gradiente funcional en comparación con soluciones de HACRFA monolíticos inclusos con un volumen neto de fibras (Vf) doble o superior. Self-compacting concrete (SCC) is an important advance in the concrete technology in the last decades. It is a new type of high performance concrete with the ability of flowing under its own weight and without the need of vibrations. Due to its specific fresh or rheological properties, such as filling ability, passing ability and segregation resistance, SCC may contribute to a significant improvement of the quality of concrete structures and open up new field for the application of concrete. On the other hand, the usefulness of steel fibre-reinforced concrete (SFRC) in civil engineering applications is unquestionable. SFRC can improve significantly the hardened mechanical properties such as tensile strength, impact resistance, toughness and energy absorption capacity. Compared to SFRC, self-compacting steel fibre-reinforced concrete (SCSFRC) is a relatively new type of concrete with high flowability and good cohesiveness. SCSFRC offers very attractive economical and technical benefits thanks to SCC rheological properties, which can be further extended, when combined with SFRC for improving their mechanical characteristics. However, for the different concrete structural elements, a single concrete mix is selected without an attempt to adapt the diverse fibre-reinforced concretes to the stress-strain sectional properly. This thesis focused on the development of high performance cement-based structural composites made of SCC with and without steel fibres, and their applications for enhanced mechanical properties in front of different types of load and pattern configurations. It presents a new direction for tackling the mechanical problem. The approach adopted is based on the concept of functionally graded cementitious composite (FGCC) where part of the plain SCC is strategically replaced by SCSFRC in order to obtain laminated functionally graded self-compacting cementitious composites, laminated-FGSCC, in single structural elements as beams, columns, slabs, etc. The approach also involves a most suitable casting method, which uses SCC technology to eliminate the potential sharp interlayer while easily forming a robust and regular reproducible graded interlayer of 1-3 mm by controlling the rheology of the mixes and using gravity at the same time to encourage the use of the powerful concept for designing more performance suitable and cost-efficient structural systems. To reach the challenging aim, a wide experimental programme has been carried out involving two main steps: • The definition and development of a novel methodology designed for the characterization of the main parameter associated to the interface- or laminated-FGSCC solutions: the graded interlayer. Work of this first part includes: o the design considerations of the innovative (in the field of concrete) production method based on “rheology and gravity” for producing FG-SCSFRC or as named in the thesis FGSCC, casting process and elements, o the design of a specific testing methodology, o the characterization of the interface-FGSCC by using the so designed testing methodology. • The characterization of the different medium size FGSCC samples under different static and dynamic loads patterns for exploring their possibilities to be used for structural elements as beams, columns, slabs, etc. The results revealed the efficiency of the manufacturing methodology, which allow creating robust structural sections, as well as the feasibility and cost effectiveness of the proposed FGSCC solutions for different structural uses. It is noticeable to say the improvement in terms of flexural, compressive or impact loads’ responses of the different FGSCC in front of equal strength class SCSFRC bulk elements with at least the double of overall net fibre volume fraction (Vf).