Ana Rita Morales

Argilas organofílicas: características, metodologias de preparação, compostos de intercalação e técnicas de caracterização

Clays are materials used since historical periods and nowadays have several applications due to their interesting properties. The surface modification of clays is one area that has received enough attention from researchers because through modification it is possible to prepare new materials and find applications. The purpose of this paper is to present a review on the use of clays for obtaining organophilic clays, especially those used in polymeric nanocomposites. Several studies have been done based on different techniques and process conditions of these materials. The review includes clays of different regions, different modification agents and applications.

Propriedades mecânicas de nanocompósitos de polipropileno e montmorilonita organofílica

Nanocomposites of polypropylene and commercial montmorillonite organophilic Cloisite 20A containing 2.5%, 5%, 7.5% and 10% of clay with polypropylene-graft-maleic anhydride as coupling agent were prepared through the melt intercalation by twin-screw extruder. The materials were characterized by x-ray diffraction, tensile and impact properties according to ASTM D638 and D256 test methods, respectively. The x-ray diffraction results showed exfoliated or intercalated structures for different concentrations of the clay. The tensile modulus improved with the increase of the amount of the clay while the impact strength showed unsatisfactory results.

Electrical percolation, morphological and dispersion properties of MWCNT/PMMA nanocomposites

Nanocomposites of poly (methyl methacrylate) (PMMA) and carbon nanotubes have a high potential for applications where conductivity and low specific weight are required. This piece of work concerns investigations of the level of dispersion and morphology on the electrical properties of in situ polymerized nanocomposites in different concentrations of multi-walled carbon nanotubes (MWCNT) in a PMMA matrix. The electrical conductivity was measured by the four point probe. The morphology and dispersion was analyzed by Transmission Electron Microscopy (TEM) and Small Angle X-ray Scattering (SAXS). The correlation between electrical conductivity and the MWCNT amount, presented a typical percolation behavior, whose electrical percolation threshold determined by power law relationship was 0.2 vol. (%) The exponent t from the percolation power law indicated the formation of a 3D network of randomly arranged MWCNT. SAXS detected that the structures are intermediate to disks or spheres indicating fractal geometry for the MWCNT aggregates instead of isolated rods. HR-TEM images allowed us to observe the MWCNT individually dispersed into the matrix, revealing their distribution without preferential space orientation and absence of significant damage to the walls. The combined results of SAXS and HR-TEM suggest that MWCNT into the polymeric matrix might present interconnected aggregates and some dispersed single structures.

PLA and Montmorilonite Nanocomposites: Properties, Biodegradation and Potential Toxicity

The concern related to solid waste increases efforts to develop products based on biodegradable materials. At present, PLA has one of the highest potentials among biopolyesters, particularly for packaging. However, its application is limited in some fields. In order to optimize PLA properties, organo-modified montmorilonites have been extensively used to obtain nanocomposites. Although PLA nanocomposites studies are widely reported in the literature, there is still few information about the influence of organoclays on de biodegradation process, which is a relevant information, since one of the main purposals related to the final disposal of biopolymers as PLA is composting. Besides, in the last years some research has been conducted in order to evaluate the potential toxicity of montmorilonite, unmodified or organo-modified. Since the use of montmorilonite is expanding in different applications, human exposure and risk assessment are important issues to be investigated. In this context, this review intends to compile available information related to common organoclays used for PLA nanocomposites, its properties, biodegradation analysis and potential toxicity evaluation of nanocomposites, focused on montmorilonite as filler. Two issues of relevance were pointed out. The first is food safety and quality, and the second consideration is the environmental effect.

Nanocompósitos de PEAD/PEBDL: avaliação da esfoliação da argila organofílica pela aplicação do modelo de Nielsen e das propriedades mecânicas, ópticas e permeabilidade

A typical high density polyethylene and linear low density polyethylene (HDPE/LLDPE) blend used in flexible packaging was modified with commercial organophylic montmorilonite clay to obtain nanocomposites with superior barrier properties. Samples with 5 and 7.5% of clay were prepared under different processing conditions. Films produced from the nanocomposites were evaluated in terms of oxygen and water vapor permeation and also by X-ray diffraction and Transmission Electron Microscopy. Tensile and optical properties were also evaluated. The clay showed to be intercalated and partially exfoliated. The oxygen permeation was mainly reduced and the vapor permeation was weakly modified. The mechanical properties and transparency did not change significantly. Nielsen’s model was applied considering the relative permeability coefficient. This method was able to give an estimate of the exfoliation state of the samples, supported by the transmission electron microscopy.

The effect of end groups on thermodynamics of immiscible polymer blends. 2. Cloud point curves

Abstract The effect of chain end groups on the thermodynamics of polymer blends is investigated by the collection of cloud point curves for low molecular weight blends of poly(isoprene) (PIP) with three different α,ω-functionally-terminated poly(dimethyl siloxane) (PDMS) materials: α,ω-trimethylsilyl PDMS (PDMS–CH3), α,ω-propylamino PDMS (PDMS–NH2) and α,ω-propylcarboxy PDMS (PDMS–COOH). The cloud point curves for these blends differ radically, demonstrating the possibility of controlling miscibility of low molecular weight blends by modification of polymer chain ends. The apparent critical points for equivalent molecular weight blends of PIP/PDMS–CH3, PIP/PDMS–COOH, and PIP/PDMS–NH2 are found at temperatures of 250, 190, and 85°C, respectively, scaling inversely with the polarity of the PDMS end group. Cloud point curves, calculated from the Flory–Huggins (F–H) rigid lattice model and a quasi-binary extension of the F–H model, are in good agreement with the experimental cloud point data, and are used to estimate the interaction parameters for PIP/PDMS–CH3 and PIP/PDMS–NH2 blends. The interaction parameters for both blend types are found to be insensitive to the molecular weight of the PDMS component and to scale inversely with the polarity of the end group. The total interaction parameters for the PDMS–NH2 blends are also calculated from the summation of binary interactions between blend components, PIP, PDMS, and end groups. Incorporation of amine end groups onto PDMS causes a decrease in the total interaction parameter calculated in this manner, consistent with the increased miscibility observed experimentally in blends containing PDMS–NH2 in comparison to those containing PDMS–CH3. In addition, the calculated binary interaction parameters show the following trend: χDMS/NH2>χIP/DMS>χIP/NH2. This suggests that the observed compatibilization effect in blends with PDMS–NH2 is driven by the repulsive nature of the interactions between the PDMS backbone and its end groups.

Life Cycle Assessment of Poly(Lactic Acid) (PLA): Comparison Between Chemical Recycling, Mechanical Recycling and Composting

This paper presents a life cycle assessment (LCA) comparing three forms of poly(lactic acid) (PLA) disposal: mechanical recycling, chemical recycling and composting. The LCA data was taken from lab scale experiments for composting and hydrolysis steps. Polymerization data in chemical recycling was obtained from computer simulation. Mechanical recycling data from lab scale were combined with the data from a plastics commercial mechanical recycling plant. The analysis considered two different product systems based on the input of the recycled PLA in the product system. Considering the categories: climate change, human toxicity and fossil depletion, the LCA showed that mechanical recycling presented the lowest environmental impact, followed by chemical recycling and composting. Among the forms of recycling, the most important input was the electricity consumption.

Biodegradation in Soil of PLA/PBAT Blends Compatibilized with Chain Extender

This paper presents a study of biodegradation, in soil, of samples of poly(butylene adipate-co-terephthalate)(PBAT), poly(lactic acid) (PLA) and blends of these materials prepared in torque rheometer with the addition of a chain extender. Film samples of these materials were buried in soil under controlled laboratory conditions. The degraded samples were regularly taken from soil and analyzed by visual inspection, size exclusion chromatography, differential scanning calorimetry and infrared spectroscopy. Respirometry biodegradation tests were conducted to assess samples mineralization degree. Blends showed higher degree of crystallinity compared to pure polymers. Crystallinity degree enhanced during the biodegradation process in all samples, being able to causing the samples to degrade slowly. The study showed the great complexity of the biodegradation process of PLA and PBAT blends when compatibilized with a chain extender. The biodegradation rate showed different results depending on the characteristic applied to evaluate it: visual, molecular weight or mineralization. The chain extender had strong influence in PBAT and blends degradation, slowing the process as observed by the variation of molecular weight and carbonyl index. Blends showed an intermediate behavior compared to the original polymers.

Polymeric biocomposites of poly (butylene adipate-co-terephthalate) reinforced with natural Munguba fibers

In this work, polymeric biocomposites of poly (butylene adipate-co-terephthalate), PBAT, were reinforced with Munguba fibers (Pseudobombax munguba). This tree is found in great abundance in the marshy areas of the Amazon forest. The motivation for using this fiber in polymer composites comes from the fact that although research for this fiber has not been reported in the scientific literature, it is commonly used by the local population because its bark is strong and flexible. Most important is that the extraction of Munguba fibers does not damage the supplier tree because as it is extracted from the bark, its regeneration starts as it is removed. The fibers were chemically treated by mercerization/acetylation and evaluated by Fourier transform infrared spectroscopy, thermogravimetric analysis and tensile tests. The Munguba fiber presented mechanical properties similar to those of other natural fibers traditionally used in composites, and the chemical treatment provided improvements of its thermal stability and stiffness. The biocomposites showed a better elastic modulus in relation to the pure PBAT. The addition of fibers caused changes in the Tg, Tm and Tc of PBAT as observed by differential scanning calorimetry analysis. The Russel, Halpin-Tsai and Maxwell models were employed to provide the theoretical elastic modulus of the biocomposites.

Morphology, Structure and Mechanical Properties of Polypropylene Modified with Organophilic Montmorillonite

The aim of this work is to study the properties of systems based on polypropylene (PP) and commercial organophilic montmorillonite, prepared by melt intercalation. Because of the non polar character of PP, the polypropylene-graft-maleic anhydride (PP-g-MA) was used as compatibilizer. Materials containing 2.5, 5, 7.5 and 10% of clay and PP, and two extra compositions containing only PP and 15 and 30% of PP-g-MA were processed using a twin-screw extruder. The level of clay dispersion was characterized by X ray diffraction, showing exfoliated/intercalated structures for different concentrations of clay. The crystallization behavior was studied by differential scanning calorimetry (DSC) and polarizing optical microscopy (POM) with hot stage. Tensile properties were also studied and presented a moderate improvement with increase in clay concentration.