Polymer Nanocomposites with Different Types of Nanofiller

The development of polymer nanocomposites has been an area of high scientific and industrial interest in the recent years, due to several improvements achieved in these materials, as a result of the combination of a polymeric matrix and, usually, an inorganic nanomaterial. The improved performance of those materials can include mechanical strength, toughness and stiffness, electrical and thermal conductivity, superior flame retardancy and higher barrier to moisture and gases. Nanocomposites can also show unique design possibilities, which offer excellent advantages in creating functional materials with desired properties for specific applications. The possibility of using natural resources and the fact of being environmentally friendly have also offered new opportunities for applications. This chapter aims to review the main topics and recent progresses related to polymer nanocomposites, such as techniques of characterization, methods of production, structures, compatibilization and applications. First, the most important concepts about nanocomposites will be presented. Additionally, an approach on the different types of filler that can be used as reinforcement in polymeric matrices will be made. After that, sections about methods of production and structures of nanocomposites will be detailed. Finally, some properties and potential applications that have been achieved in polymer nanocomposites will be highlighted

Structural characterization and optical monitoring of the crystallization of high density polyethylene nanocomposites with different particles during injection molding

The main objectives of this project were to study the morphology, the crystallization kinetics and to monitor on-line the crystallization during the injection molding process using an optical system of nanocomposites of high density polyethylene (HDPE) with three different inorganic particles: montmorillonite nanoclay, halloysite nanotubes and faujasite type zeolite. The optical system allowed analyzing the crystallization process by the changes of the optical properties during the solidification of the materials. The nanocomposites were prepared by melt intercalation in a twin-screw extruder. The resultant structures were characterized by transmission electron microscopy (TEM) and rheological properties. The extruded nanocomposites developed intercalated and well distributed structures. Crystallization kinetics studies were done by differential scanning calorimetry (DSC) and rheological measurements. It was concluded that the nanoparticles in quiescent conditions accelerated the overall crystallization of HDPE, acting as nucleating agents. The nucleating effect of these particles was predominant over the HDPE crystallization and they also modified the nucleation mechanism and the crystal morphology in some conditions. From the studies of flow induced crystallization, it was observed again that the nanoparticles accelerated the crystal growth rate. In this case it was attributed to the weak forces between the polymer chains and the surface of the nanoparticles. Finally, the nanocomposites’ crystallization was monitored during the injection molding process. The optical system showed that the nanoparticles accelerated the crystallization of HDPE; the optical results were correlated with the morphology of the injection molded samples.Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Neste projeto estudou-se a morfologia e a cinética de cristalização quiescente e induzida por fluxo de nanocompósitos de polietileno de alta densidade (HDPE) contendo nanocargas com diferentes geometrias: nanotubos de haloisita, lamelas de montmorilonita e nanocubos de zeólita do tipo faujasita. Utilizando-se um teor de nanocarga fixo e avaliando-se, em menor escala, a influência da presença ou não de tratamento orgânico superficial, nanocompósitos posteriormente preparados em uma extrusora de rosca dupla corrotacional foram caracterizados por microscopia eletrônica de transmissão (MET), calorimetria exploratória diferencial (DSC) e propriedades reológicas. Em seguida, estes nanocompósitos foram injetados em diferentes condições de processamento, variando- se a vazão de injeção, a temperatura do molde e a pressão de empacotamento; ao mesmo tempo em que a cinética de cristalização foi monitorada “on-line” através de um sistema ótico que permitiu a análise da cinética de cristalização através das mudanças de propriedades óticas desses materiais durante a solidificação. Após a moldagem por injeção, as amostras foram caracterizadas. Observou-se que as nanopartículas, em condições quiescentes, aceleraram a cristalização global do HDPE, agindo como agentes de nucleação, e modificaram também o mecanismo de nucleação e a morfologia dos cristais. Sob a presença de fluxos cisalhantes, as nanocargas também mostraram uma tendência em antecipar a formação de núcleos, através da orientação molecular, uma vez que as interações entre os componentes dos nanocompósitos foram bastante fracas. O sistema ótico, por sua vez, permitiu concluir o efeito acelerador da cristalização global das nanopartículas, e as posteriores análises de difração de raios-x de baixo ângulo (SAXS) permitiram observar as diferentes orientações preferenciais das lamelas cristalinas em função dos parâmetros de injeção e da influência das nanopartículas

Rheological characterization of nanocomposites for a blown film extrusion process

In this work, the use of rheological measurements in substitution or complementation to methods normally employed in the characterization of nanocomposites, such as X-ray diffraction (WAXS) and transmission electron microscopy (TEM), was evaluated. Two polymeric matrices with different chemical structures and polarities and two organophilic nanoclays modified with organic surfactants, which were compatible with the respective polymer matrix, were used. Thus, polyamide 6 (PA6) and high density polyethylene (HDPE) nanocomposites were obtained by melt mixing and blown as films. WAXS measurements showed intercalated structures in the HDPE nanocomposites and exfoliated structures in the PA6 nanocomposites. Shear oscillatory rheological experiments were done to evaluate the clay dispersion and distribution in the polymer matrices, which indicated the presence of a poor dispersion in the HDPE nanocomposites, differently of the PA6 nanocomposites. Shear steady and transient rheological measurements indicated that higher interactions between PA6 and the nanoclay modified with a polar surfactant and inside the EVA masterbatches occurred. From the rheological, morphological, mechanical and transport analysis it was found that the addition of clay modified the interfacial interactions between HDPE and EVA, increasing the system compatibility. In both systems, there was an increase in elastic modulus, yielding and rupture behaviors and barrier properties. In conclusion, the rheological characterization of nanocomposites provides further information about the nanoclay dispersion and distribution in the polymer matrix, in addition to quantify the interactions between the components. However, it can not substitute the usual methods of characterization of the nanocomposites, such as WAXS and TEM.Universidade Federal de Minas GeraisNeste trabalho avaliou-se o uso de medidas de propriedades reológicas na substituição ou complementação de métodos geralmente empregados na caracterização das estruturas de nanocompósitos, tais como a difração de raios-x de alto ângulo (WAXS) e a microscopia eletrônica de transmissão (MET). Para tanto, foram utilizadas duas matrizes poliméricas com diferentes polaridades e duas argilas organofílicas tratadas com surfatantes compatíveis com a respectiva matriz polimérica. Assim, nanocompósitos de poliamida 6 (PA6) e de polietileno de alta densidade (HDPE), este último compatibilizado com um copolímero aleatório de etileno e acetato de vinila (EVA), foram produzidos através de mistura no estado fundido e posteriormente conformados na forma de filmes tubulares. Observou-se por WAXS que os nanocompósitos de HDPE possuíam estrutura intercalada enquanto que os de PA6 possuíam uma estrutura esfoliada. Para verificar o estado de dispersão e de distribuição das argilas nas matrizes poliméricas foram realizados ensaios reológicos em regime oscilatório de cisalhamento juntamente com análises de MET, os quais mostraram para os nanocompósitos de HDPE um baixo nível de dispersão, diferentemente do observado nos nanocompósitos de PA6. Já os ensaios reológicos em regime permanente de cisalhamento e também no regime transiente mostraram que as interações entre polímero e argila eram mais fortes nos nanocompósitos de PA6 e nos concentrados de EVA do que nos nanocompósitos de HDPE. Através das analises reológicas, morfológicas e das propriedades mecânicas e de permeação, concluiu-se que a adição de argila promoveu uma significativa alteração nas interações interfaciais da blenda HDPE/EVA, que era a matriz dos nanocompósitos de HDPE, levando a uma maior compatibilização do sistema. Em ambos os sistemas houve uma melhora no módulo elástico, no comportamento de escoamento e de ruptura, além de melhores propriedades de barreira. Por fim, concluiu-se que as medidas das propriedades reológicas de nanocompósitos podem fornecer informações complementares a respeito do estado de dispersão e de distribuição da nanocarga na matriz polimérica, além de quantificar as interações existentes entre os componentes; mas que elas não podem substituir completamente as análises de WAXS e MET

Nanocomposites of polyamide 6/residual monomer with organic-modified montmorillonite and their nanofibers produced by electrospinning

Nanocomposites of an organic-modified montmorillonite (MMT) and polyamide 6 (PA6) with a residual monomer were produced by melt mixing in a torque rheometer. By wide angle X-rays diffraction (WAXD), intercalated/exfoliated structures were observed in the PA6/MMT nanocomposites with 3 and 5 wt. (%) of MMT; on the other hand, when 7 wt. (%) of MMT was added, a nanocomposite with exfoliated structures was obtained due to the predominant linking reactions between the residual monomer and the "nanoclays" organic surfactant. Solutions of these PA6/MMT nanocomposites at 15, 17 and 20 wt. (%) in formic acid were prepared. The 3 and 5 wt. (%) nanocomposites were successfully electrospun; however, electrospinning of the 7 wt. (%) nanocomposite was not possible. WAXD, scanning and transmission electron microscopy results showed that the 3 and 5 wt. (%) nanofibers with average diameter between 80-250 nm had exfoliated structures. These results indicate that the high elongational forces developed during the electrospinning process changed the initial intercalated/exfoliated structure of the nanocomposites to an exfoliated one

Non-Isothermal Crystallization Kinetics of Injection Grade PHBV and PHBV/Carbon Nanotubes Nanocomposites Using Isoconversional Method

Carbon nanotubes (CNT)-reinforced polymeric composites are being studied as promising materials due to their enhanced properties. However, understanding the behavior of polymers during non-isothermal crystallization is important once the degree of crystallinity and crystallization processes are affected when nanoparticles are added to matrices. Usually, crystallization kinetics studies are performed using a model-fitting method, though the isoconversional method allows to obtain the kinetics parameter without assuming a crystallization model. Therefore, in this work, CNTs were oxidized (CNT-Ox) and functionalized with gamma-aminobutyric acid (GABA) (CNT-GB) and incorporated into a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) matrix. The influence of the addition and functionalization of CNT in the crystallization kinetics of PHBV was evaluated using the isoconversional method with differential scanning calorimetry (DSC), and by polarized light optical microscopy (PLOM) and Shore D hardness. The incorporation and functionalization of CNT into PHBV matrix did not change the Šesták and Berggren crystallization model; however, the lowest activation energy was obtained for the composite produced with CNT-GB, suggesting a better dispersion into the PHBV matrix. PLOM and Shore D hardness confirmed the results obtained in the kinetics study, showing the smallest crystallite size for CNT-containing nanocomposites and the highest hardness value for the composite produced with CNT-GB

Polyethylene cellulose nanofibrils nanocomposites

International audienceThis paper investigates the use of an aqueous dispersion of polyethylene copolymer with a relatively high content of acrylic acid as a compatibilizer and as an alternative medium to obtain polyethylene CNF nanocomposites. The CNF content was varied from 1 to 90 wt% and the appearance, optical, thermal, mechanical and rheological properties, as well the morphology of the films were evaluated. The PE/CNF films are transparent up to 20 wt% of NFC indicating a good dispersion of CNF, but a poor distribution, with PE-rich and CNF-rich regions observed by SEM. Improved mechanical properties were achieved, with a 100% and 15,900% increase in the Young’s modulus with 1 wt% and 90 wt% NFC, respectively. The rheological behavior indicated good melt processability. According to these results, aqueous polyolefin dispersions seem to be a promising, easy and relatively fast route for obtaining cellulose/polyolefins nanocomposites with low to high contents of cellulose nanofibrils