Estudos de dispersão de nanografite em polipropileno

Dissertação de mestrado integrado em Engenharia de Materiais

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

Thermal and mechanical characteristics of polyurethane/curaua fiber composites

Polyurethane composites reinforced with curaua fiber at 5, 10 and 20% mass/mass proportions were prepared by using the conventional melt-mixing method. The influence of curaua fibers on the thermal behavior and polymer cohesiveness in polyurethane matrix was evaluated by dynamic mechanical thermal analysis (DMTA) and by differential scanning calorimetry (DSC). This specific interaction between the fibers and the hard segment domain was influenced by the behavior of the storage modulus E` and the loss modulus EaEuro(3) curves. The polyurethane PU80 is much stiffer and resistant than the other composites at low temperatures up to 70A degrees C. All samples were thermoplastic and presented a rubbery plateau over a wide temperature range above the glass transition temperature and a thermoplastic flow around 170A degrees C.

Linear viscoelasticity of styrenic block copolymers-clay nanocomposites

In this work, the rheological behavior of block copolymers with different morphologies (lamellar, cylindrical, spherical, and disordered) and their clay-containing nanocomposites was studied using small amplitude oscillatory shear. The copolymers studied were one asymmetric starblock styrene-butadiene-styrene copolymer and four styrene-ethylene/butylenes-styrene copolymers with different molecular architectures, one of them being modified with maleic anhydride. The nanocomposites of those copolymers were prepared by adding organophilic clay using three different preparation techniques: melt mixing, solution casting, and a hybrid melt mixing-solution technique. The nanocomposites were characterized by X-ray diffraction and transmission electron microscopy, and their viscoelastic properties were evaluated and compared to the ones of the pure copolymers. The influence of copolymer morphology and presence of clay on the storage modulus (G`) curves was studied by the evaluation of the changes in the low frequency slope of log G` x log omega (omega: frequency) curves upon variation of temperature and clay addition. This slope may be related to the degree of liquid- or solid-like behavior of a material. It was observed that at temperatures corresponding to the ordered state, the rheological behavior of the nanocomposites depended mainly on the viscoelasticity of each type of ordered phase and the variation of the slope due to the addition of clay was small. For temperatures corresponding to the disordered state, however, the rheological behavior of the copolymer nanocomposites was dictated mostly by the degree of clay dispersion: When the clay was well dispersed, a strong solid-like behavior corresponding to large G` slope variations was observed.

In-line rheo-optical characterization during small-scale polymer processing and compounding

As increasingly more sophisticated materials and products are being developed and times-to-market need to be minimized, it is important to make available fast response characterization tools using small amounts of sample, capable of conveying data on the relationships between rheological response, process-induced material structure and product characteristics. For this purpose, a single / twin-screw mini-extrusion system of modular construction, with well-controlled outputs in the range 30-300 g/h, was coupled to a in- house developed rheo-optical slit die able to measure shear viscosity and normal-stress differences, as well as performing rheo-optical experiments, namely small angle light scattering (SALS) and polarized optical microscopy (POM). In addition, the mini-extruder is equipped with ports that allow sample collection, and the extrudate can be further processed into products to be tested later. Here, we present the concept and experimental set-up [1, 2]. As a typical application, we report on the characterization of the processing of a polymer blend and of the properties of extruded sheets. The morphological evolution of a PS/PMMA industrial blend along the extruder, the flow-induced structures developed and the corresponding rheological characteristics are presented, together with the mechanical and structural characteristics of produced sheets. The application of this experimental tool to other material systems will also be discussed.

Modification of Polypropylene/Glass Fiber Composites with Nanosilica

Poly(propylene) (PP) reinforced with short glass fiber was modified with precipitated nanosilica (pnS) by melt mixing. The weight of the glass fiber was varied by keeping the pnS at optimum level. The properties of the composites were studied using universal testing machine, dynamic mechanic analyser (DMA), differential Scanning calorimetry (DSC) and thermo gravimetric analyser (TGA). The amount of the glass fiber required for a particular modulus could be reduced by the addition of nanosilica.

Studies on the fracture behaviour of polymer blends with special reference to PP/HDPE and PS/HIPS blends

Investigations on the fracture behaviour of polymer blends is the topic of this thesis. The blends selected are PP/HDPE and PS/HIPS. PP/HDPE blend is chosen due to its commercial importance and PS/HIPS blend is selected to study the transition from brittle fracture to ductile fracture.PP/HDPE blends were prepared at different compositions by melt blending at 180°C and fracture failure process was investigated by conducting notch sensitivity test and tensile test at different strain rates. The effects of two types of modifiers (particulate and elastomer) on the fracture behaviour and notch sensitivity of PP/HDPE blends were studied. The modifiers used are calcium carbonate, a hard particulate filler commonly used in plastics and Ethylene Propylene Diene Monomer (EPDM). They were added in 2%, 4% and 6% by weight of the blends.The study shows that the mechanical properties of PP/HDPE blends can be optimized by selecting proper blend compositions. The selected modifiers are found to alter and improve the fracture behaviour and notch sensitivity of the blends. Particulate fillers like calcium carbonate can be used for making the mechanical behaviour more stable at the various blend compositions. The resistance to notch sensitivity of the blends is found to be marginally lower in the presence of calcium carbonate. The elastomeric modifier EPDM produces a better stability of the mechanical behaviour. A low concentration of EPDM is sufficient to effect such a change. EPDM significantly improves the resistance to notch sensitivity of the blends. The study shows that judicious selection of modifiers can improve the fracture behaviour and notch sensitivity of PP/HDPE blends and help these materials to be used for critical applications.For investigating the transition in fracture behaviour and failure modes, PS/HIPS blends were selected. The blends were prepared by melt mixing followed by injection moulding to prepare the specimens for conducting tensile, impact and flexure tests. These tests were used to simulate the various conditions which promote failure.The tensile behaviour of unnotched and notched PS/HIPS blend samples were evaluated at slow speeds. Tensile strengths and moduli were found to increase at the higher testing speed for all the blend combinations whereas maximum strain at break was found to decrease. For a particular speed of testing, the tensile strength and modulus show only a very slight decrease as HIPS content is increased up to about 40%. However, there is a drastic decrease on increasing the HIPS content thereafter.The maximum strain at break shows only a very slight change up to about 40% HIPS content and thereafter shows a remarkable increase. The notched specimens also follow a comparable trend even though the notch sensitivity is seen high for PS rich blends containing up to 40% HIPS. The notch sensitivity marginally decreases with increase in HIPS content. At the same time, it is found to increase with the increase in strain rate. It is observed that blends containing more than 40% HIPS fail in ductile mode.The impact characteristics of PSIHIPS blends studied were impact strength, the energy absorbed by the test specimen and impact toughness. Remarkable increase in impact strength is observed as HIPS content in the blend exceeds 40%. The energy absorbed by the test specimens and the impact toughness also show a comparable trend.Flexural testing which helps to characterize the load bearing capacity was conducted on PS/HIPS blend samples at the two different testing speeds of 5mmlmin and 10 mm/min. The flexural strength increases with increase in testing speed for all the blend compositions. At both the speeds, remarkable reduction in flexural strength is observed as HIPS content in the blend exceeds 40%. The flexural strain and flexural energy absorbed by the specimens are found to increase with increase in HIPS content. At both the testing speeds, brittle fracture is observed for PS rich blends whereas HIPS rich blends show ductile mode of failure.Photoelastic investigations were conducted on PS/HIPS blend samples to analyze their failure modes. A plane polariscope with a broad source of light was utilized for the study. The coloured isochromatic fringes formed indicate the presence of residual stress concentration in the blend samples. The coverage made by the fringes on the test specimens varies with the blend composition and it shows a reducing trend with the increase in HIPS content. This indicates that the presence of residual stress is a contributing factor leading to brittle fracture in PS rich blends and this tendency gradually falls with increase in HIPS content and leads to their ductile mode of failure.

Short Nylon-6 Fibre/Rubber-Toughened Polystyrene Composites

The thesis describes studies on development of short Nylon-6 fibre composites based on rubber-toughened polystyrene (PS). Toughening was done using natural rubber (NR), styrene-butadiene rubber (SBR) and whole tyre reclaim (WTR). The composites were prepared by melt mixing in an internal mixer at 170 oC. It was found that the optimum blend ratio was 85/15 for PS/NR, 90/10 for PS/SBR and 90/22 for PS/WTR blends. The effect of dynamic vulcanisation on 85/15 PS/NR and 90/10 PS/SBR blends using dicumyl peroxide (DCP) at various concentrations were also studied. The dynamic crosslinking improved the tensile properties, flexural properties, impact strength and dynamic mechanical properties of both the blends. The effect of unmodified and resorcinol formaldehyde latex (RFL)-coated short Nylon-6 fibres on the mechanical properties, morphology and dynamic mechanical properties of 85/15 PS/NR, 90/10 PS/SBR and 90/22 PS/WTR blends were studied. Fibre loading was varied from 0 to 3 wt.%. For 85/15 PS/NR blend, there was a significant enhancement in tensile properties, flexural properties and impact strength with 1 wt.% of both unmodified and RFL-coated fibres. Dynamic mechanical analysis revealed that the storage modulus at room temperature was maximum at 1 wt.% fiber loading for both composites. The surface functionality of the fiber was improved by giving alkali treatment. Maleic anhydride-grafted-polystyrene (MA-g-PS) was prepared and used as a compatibiliser. The effect of MA-g-PS on the composites was investigated with respect to mechanical properties, morphology and dynamic mechanical properties. The compatibiliser loading was varied from 0 to 2 wt.%. The properties were enhanced significantly in the case of treated and untreated fibre composites at a compatibiliser loading of 0.75 wt.%. SEM analysis confirmed better bonding between the fibre and the matrix. Dynamic mechanical studies showed that the storage modulus at room temperature improved for treated fibre composites in the presence of compatibiliser. In the case of 90/10 PS/SBR composites, the addition of short Nylon-6 fibres at 1 wt.% loading improved the tensile modulus, flexural properties and impact strength while the tensile strength was marginally reduced. The surface treated fibers along with compatibiliser at 0.5 wt.% improved the tensile properties, flexural properties and impact strength. DMA reveale that the storage modulus at room temperature was better for composites containing untreated fibre and the compatibiliser. In the case of 90/22 PS/WTR blends, 1 wt.% unmodified fibre and 0.5 wt.% RFL-coated fibres improved tensile modulus, flexural properties and impact strength. Tensile strength was improved marginally. The surface treatment of Nylon fibre and the addition of compatibiliser at 0.5 wt.% enhanced the tensile properties, flexural properties and impact strength. The dynamic mechanical analysis showed that the storage modulus at room temperature was better for untreated fibre composites in conjunction with the compatibiliser. The thermal stability of PS/NR was studied by TGA. Thermal stability of the blends improved with dynamic vulcanisation and with the incorporation of RFL-coated Nylon fibres. The untreated and partially hydrolyzed fibre composites in conjunction with the compatibiliser enhanced the thermal stability. Kinetic studies showed that the degradation of the blends and the composites followed first order kinetics.

Polypropylene/metal oxide nanocomposites: fiber spinning and evaluation”

PP has been getting much attention over the years because it is a very durable polymer commonly used in aggressive environments including automotive battery casings, fuel containers etc. They are used to make bottles, fibers for clothing, components in cars etc. However, it has some shortcomings such as low dimensional and thermal stability. Materials such as metal oxides with sizes of the order 1–50 nm have received a great deal of attention because of their versatile applications in polymer/ inorganic nanocomposites, optoelectronic devices, biomedical materials, and other areas. They are stable under harsh process conditions and also regarded as safe materials to human beings and animals. In the present investigation, PP is modified by incorporating metal oxide nanoparticles such as ZnO and TiO2 by simple melt mixing method. Melt spinning method was used to prepare PP/metal oxide nanocomposite fibers. Various studies have been carried out on these composites and fibers. In the first part of the study, ZnO nanoparticles were prepared from ZnCl2 and NaOH in presence of chitosan, PVA, ethanol and starch. This is a simple and inexpensive method compared to other methods. Change in morphology and particle size of ZnO were studied. Least particle size was obtained in chitosan medium. The particles were characterized by using XRD, SEM, TEM, TGA and EDAX. Antibacterial properties of ZnO prepared in chitosan medium (NZO) and commercial zinc oxide (CZO) were evaluated using a gram positive and a gram negative bacteria

Utilization of waste expanded polystyrene: Blends with silica-filled natural rubber

Expanded polystyrene (EPS) constitutes a considerable part of thermoplastic waste in the environment in terms of volume. In this study, this waste material has been utilized for blending with silica-reinforced natural rubber (NR). The NR/EPS (35/5) blends were prepared by melt mixing in a Brabender Plasticorder. Since NR and EPS are incompatible and immiscible a method has been devised to improve compatibility. For this, EPS and NR were initially grafted with maleic anhydride (MA) using dicumyl peroxide (DCP) to give a graft copolymer. Grafting was confirmed by Fourier Transform Infrared Spectroscopy (FTIR) spectroscopy. This grafted blend was subsequently blended with more of NR during mill compounding. Morphological studies using Scanning Electron Microscopy (SEM) showed better dispersion of EPS in the compatibilized blend compared to the noncompatibilized blend. By this technique, the tensile strength, elongation at break, modulus, tear strength, compression set and hardness of the blend were found to be either at par with or better than that of virgin silica filled NR compound. It is also noted that the thermal properties of the blends are equivalent with that of virgin NR. The study establishes the potential of this method for utilising waste EPS

Desevolvimento de nanocompósitos de poli(metacrilato de metila)/argila processados por mistura no estado fundido

Poly(methyl methacrylate)/clay nanocomposites were prepared by melt mixing using a montmorillonite-rich clay (MMT). The clay in natura was treated with acrylic acid to facilitate the dispersion in the polymer matrix. A masterbatch of PMMA/clay was prepared and combined with the pure PMMA and then subjected to extrusion process using singlescrew and twin-screw extruders followed by injection. Nanocomposites were processed with clay contents of 1, 3, 5 and 8 wt.%. The effect of shear processing on the morphology of the nanocomposites was evaluated by XRD, SEM and TEM. Thermal and mechanical properties of the nanocomposites were investigated through TGA, DSC, HDT, VICAT, tensile and impact tests, to evaluate the effect of the addition of clay to the PMMA matrix. Flammability tests were also conducted to investigate the effect of the addition of clay on the flame retardation properties. SEM images of the nanocomposites indicated the presence of clay agglomerates, which resulted in the reduction of properties such as thermal stability, mechanical strength and impact resistance, and increased the rate of burning for materials processed by both extrusion routes

Obtenção e caracterização de compósitos nanoestruturados de poli(sulfeto de fenileno) reforçados com nanotubos de carbono

Pós-graduação em Engenharia Mecânica - FEG

Electrical and Thermal study of carbon nanotubes reinforced poly (phenylene sulfide) nanostructured composites

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Estudo da cinética de decomposição de compósitos nanoestruturados de poli (sulfeto de fenileno) reforçados com nanotubos de carbono

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)