Abstract Researches of polymer blends based on biological and biodegradable polymers appear as a viable alternative to develop environmentally friendly materials. Therefore, the aim of this research was to produce compounds made with biological polyethylene, i.e., Biopolyethylene, Bio-PE, added to the biodegradable Polycaprolactone (PCL) and functionalized by the copolymer of polyethylene grafted with acrylic acid (PEgAA), to obtain better mechanical properties and toughen Bio-PE. Compounds were processed in a co-rotating twin screw extruder and sample tests were injection molded. The compositions investigated were: Bio-PE/PCL at 90/10, 80/20 and 70/30 wt.% without compatibilizer and upon addition of 10 phr (parts per hundred of resin) of PEgAA. The blends were characterized by X-ray diffraction (XRD), impact strength, heat deflection temperature (HDT) and scanning electron microscopy (SEM). Through XRD, it was observed that addition of PCL and PEgAA did not significantly change Bio-PE diffraction patterns. Impact strength data showed that the blends presented a tougher behavior upon addition of PCL and PEgAA. The HDT of compatibilized blend with 20wt.% of PCL was slightly higher. SEM images of compatibilized blends showed lower average particle diameters as well as absence of coalescence and aggregates.

In this work, compounds based on two grades of polypropylene (PP), i.e., PP H503 or PP H103 with residues of Big bag fabrics (RBB) were processed in a corrotational twin screw extruder with RBB content ranging from 10% to 50% of the weight. Then, their thermal properties were investigated through Differential Scanning Calorimetry (DSC) and Thermogravimetry (TG); mechanical by tensile and impact; thermomechanic by heat deflection temperature (HDT); and their morphology by Scanning Electron Microscopy (SEM). With the aim to add maximum RBB content without considerable damage to the properties of neat PPs, it was observed that addition of 10%, 30% and 50% of RBB did not significantly interfere in the PP matrices, being the compound PP + 30% RBB which one presented more successful properties, leading to reused compounds with higher performance and lower costs at same time.

Abstract In this work, blends based on environmentally friend polymers such as Biopolyethylene (Bio-PE), Polycaprolactone (PCL) and Polyethylene graft maleic anhydride (PEgMA) added as compatibilizer agent were produced by conventional extrusion, aiming to produce bio-blends with synergic properties at low processing cost, being at same time non-polluting and therefore contributing to the environment preservation. Differential scanning calorimetry (DSC) showed that blending does not significantly interfere on the melting and crystallization behaviors of neat polymers, suggesting being low miscibility compounds. Mechanical properties were observed changing with blend composition as the impact strength significantly increased reaching values higher than 130% when compared to neat Bio-PE. Scanning electron microscopy (SEM) images showed honeycomb morphology in Bio-PE/PCL blends, and the addition of PEgMA decreased the coalescence contributing to obtain more stable and synergic compounds. Bio-PE/PCL/PEgMA at 80/20/10 contents presented the best properties and may be used for packaging materials (food containers, film wrapping), and hygiene products.

Abstract The vulcanized rubber waste from the shoe industry causes environmental damage when it is incinerated or inappropriately discarded, turning this into a problem of major concern. Therefore, this study had as the main objective the Polystyrene (PS) toughening using different contents of white vulcanized styrene-butadiene rubber (SBRr) waste produced in the shoe industry. The mixtures were initially prepared in a co-rotational double screw extruder and, thereafter, the extruded granules were injection molded. Analyzed were the rheological, mechanical, thermomechanical properties and morphology of the produced blends. The rheological results showed a viscosity increase as the SBRr concentration was augmented, leading to a higher stability when compared to pure Polystyrene. Verified was an increase of impact resistance of 189% to the blend that contained 50% of SBR rather than pure Polystyrene. On the other hand, the traction properties, hardness Shore D, thermal deflection temperature (HDT) and Vicat softening temperature of the blends tended to decrease when compared to pure Polystyrene results. However, as this SBR waste is made up of a complex mixture of SBR, filler, processing additions, curing agents and stabilizers, it probably acted in the sense of not causing such a drastic reduction of the properties, even using a high concentration of SBRr waste. The morphologies obtained with the SEM method (Scanning Electronic Microscope) were quite different and typical of immiscible blends. The results show that it is possible to obtain a new material with good properties, valuing a discarded industrial waste and avoiding environment aggression.

Photodegradation of PCL was performed exposing injected specimens to ultraviolet radiation (UV-B) up to 9 weeks. Photodegradated PCL specimens were tested by Differential Scanning Calorimetry (DSC), Infrared Spectroscopy (FTIR), mechanical properties, Optical Microscopy (MO) and Scanning Electron Microscopy (SEM).Upon exposure decrease in elongation at break and increase of elastic modulus were verified, higher degree of crystallinity was observed for longer exposure what can be due to the chemi-crystallization mechanism. From IR spectra new carbonyl group (C=O) peaks were observed. Presence of micro cracks on specimens’ surface was identified by MO. From morphological analyses is suggested that the photodegradation in PCL takes place by bulk erosion mechanism.

Biodegradable compounds of poly(ε-caprolactone) (PCL)/ cotton linter were melting mixed with filling content ranging from 1% to 5% w/w. Cotton linter is an important byproduct of textile industry; in this work it was used in raw state and after acid hydrolysis. According to the results of torque rheometry no decaying of viscosity took place during compounding, evidencing absence of breaking down in molecular weight. The thermal stability increased by 20% as observed in HDT for PCL/cotton nanolinter compounds. Adding cotton linter to PCL didn't change its crystalline character as showed by XRD; however an increase in degree of crystallinity was observed by means of DSC. From mechanical tests in tension was observed an increase in ductility of PCL, and from mechanical tests in flexion an increase in elastic modulus upon addition of cotton linter, whereas impact strength presented lower values for PCL/cotton linter and PCL/cotton nanolinter compounds. SEM images showed that PCL presents plastic fracture and cotton linter has an interlacing fibril structure with high L/D ratio, which are in agreement with matrix/fibril morphology observed for PCL/cotton linter compounds. PCL/cotton linter compounds made in this work cost less than neat PCL matrix and presented improved properties making feasible its commercial use.

RESUMO O reômetro de torque é um equipamento que reproduz em escala laboratorial o processamento de polímeros. Neste equipamento, a velocidade de rotação dos rotores, temperatura e tempo de processamento são parâmetros predeterminados e impostos ao sistema investigado; avalia-se o torque necessário para a fusão, mistura e homogeneização da amostra. Através do gráfico do torque em função do tempo e do gráfico da temperatura em função do tempo de processamento, cujos valores estão relacionados com as propriedades reológicas, estrutura e massa molar das amostras, é possível obter informações sobre o comportamento dos polímeros em fluxo, ou seja, durante o processamento. Neste trabalho, foi investigado o efeito do polietileno graftizado com ácido acrílico (PEgAA) e do polietileno graftizado com anidrido maléico (PEgMA) no biopolietileno (Bio-PE) e no poli(ε-caprolactona) (PCL) por reometria de torque. Foi verificado que o PEgAA e o PEgMA promoveram aumento no torque dos sistemas Bio-PE/PEgAA, Bio-PE/PEgMA, PCL/PEgAA e PCL/PEgMA, possivelmente resultante de interações e/ou reações químicas ocorridas nesses sistemas poliméricos. Espectros de FTIR evidenciaram possíveis interações e/ou reações químicas entre os grupos funcionais dos polímeros grafitizados e o Bio-PE e o PCL. Valores de torque mais altos foram observados nos sistemas com parâmetros de solubilidade (δ) mais próximos, corroborando com os cálculos propostos por Hansen.

ABSTRACT The torque rheometer is equipment that enables to simulate the polymer processing in a laboratory scale. A set of parameters, i.e., rotor speed, temperature and processing time are predefined and imposed to the compounds under analysis. The necessary torque for melting and mixing the compound is measured. Through the plots of torque as a function of time and temperature, which are linked to the rheological properties, microstructure and molar weight of the samples, it is possible to acquire information regarding the flow behavior of polymers, meaning during processing. In this work, the effect of acrylic acid-grafted polyethylene (PEgAA) and maleic anhydride-grafted polyethylene (PEgMA) in bio-polyethylene (Bio-PE) and in poly(ε-caprolactone) (PCL) was performed by torque rheometry. PEgAA and PEgMA increased the torque rheometry values of the polymeric systems under investigation, i.e, Bio-PE/PEgAA, Bio-PE/PEgMA, PCL/PEgAA and PCL/PEgMA, possibly due to chemical interaction and/or reactions occurred during the processing. FTIR spectra presented possible interactions and/or chemical reactions between the functional groups of grafted polymers and Bio-PE and PCL. Higher torques were observed for the systems with similar solubility parameters agreeing with the mathematical calculations provided by Hansen.

Poly(Ɛ-caprolactone)/montmorillonite (PCL/MMT) and Poly(Ɛ-caprolactone)/organo-modified montmorillonite (PCL/OMMT) compounds at 3% w/w clay content were prepared by melting mixing. The effect of MMT and OMMT on the degradability of PCL injected specimens was investigated in vacuum at 40oC for up to 45 days and in aqueous medium at 40oC for up to 45 days. Selected specimens were collected after 15, 30 and 45 days of exposure. Microstructural changes were monitored during the degradation experiment by means of melt flow rate (MFR), weight loss, X ray diffraction (XRD), mechanical properties, and scanning electron microscopy (SEM). PCL and its compounds revealed not to be prone to hydrolytic degradation with similar results for MFR of samples exposed in vacuum and water. Gain and loss of weight were observed during experiments, probably due to swelling mechanism taking place in two stages, with the amorphous phase being the first to be swelled followed by the crystalline one. By XRD a new peak corresponding to (002) plane was evident for PCL/OMMT. PCL proved to be resistant to degradation since experiments carried out in vacuum or in aqueous medium for up to 45 days were not enough to affect the mechanical integrity of PCL samples.

A mistura de polímeros diferentes possibilita a obtenção de novos materiais com propriedades, na maioria das vezes superiores às dos componentes puros. Essa mistura vem sendo utilizada e aplicada na obtenção de membranas com intuito de melhorar as propriedades de barreira para que se possa separar duas fases restringindo total ou parcialmente o transporte de uma ou várias espécies químicas presentes. Neste trabalho, membranas poliméricas foram obtidas a partir de blendas de poliamida 6 (PA6), polipropileno (PP) e compatibilizantes pelo método de inversão de fases, com a finalidade de serem utilizadas em processos de separação, purificação, fracionamento e contração. Estas foram estudadas por difração de Raios-X (DRX), calorimetria exploratória diferencial (DSC) e microscopia eletrônica de varredura (MEV). Os resultados de DRX evidenciaram a presença dos picos característicos de reflexão da PA6, PP e dos compatibilizantes. Por DSC, observou-se que a presença do compatibilizante não promoveu alterações significativas na cristalinidade da PA6. Por meio das fotomicrografias de MEV, visualizou-se a obtenção de membranas microporosas assimétricas, como também percebeu-se que a presença da segunda fase na PA6 modificou a morfologia das membranas.

The mixture of different polymers enables obtaining new materials with properties most often superior to those of the pure components. This mixture is being used and applied in obtaining membranes with a view to improving the barrier properties, so that it can separate two phases wholly or partially, restricting the transport of one or more chemical species. In this work, polymer membranes were obtained from blends of polyamide 6 (PA6) and polypropylene (PP), compatibilizing by the method of phase inversion, for being used in processes of separation, purification, fractionation and contraction. These were studied by X-ray diffraction (XRD), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). XRD results showed the presence of peaks characteristic of PA6, PP and compatibilizers. For DSC, it was observed that the presence of the compatibilizer did not cause significant changes in crystallinity of PA6. Through the SEM photomicrographs is confirmed the production of asymmetric microporous membranes and the presence of the second modified PA6 phase in the morphology of the membranes is also noted.