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.

Abstract Blends of Polystyrene (PS) and Poly(ε-caprolactone) (PCL) were twin screw extruded, two PSs, with low and high melt flow rate (MFR) were used and their feasibility within PCL investigated by means of torque rheometry, mechanical tests, heat deflection temperature (HDT) and scanning electron microscopy (SEM); predictive models were utilized to evaluate interfacial adhesion in PS/PCL blends. Results show that no decreasing was verified in torque rheometry plots suggesting thermally stable blends; elastic modulus decreased and elongation at break increased in PS/PCL blends compared to neat PS. PS/PCL blends with low MFR PS and higher PCL amount are more thermodynamically stable. Higher HDT was verified in PS/PCL blends. The trends observed applying predictive models are indicative of poor adhesion between PCL and PS, agreeing with coalescence and phase segregation as verified in SEM images. PS/PCL systems with higher MFR PS presented the best results.

Biodegradable Poly (ɛ-caprolactone) (PCL) was compounded with Brasgel PA (MMT) and Cloisite Na (CLNa), and compatibilized with maleic anhydride grafted poly(ɛ-caprolactone) (PCL-g-MA). No evidence of degradation was verified during processing, as well as particle aggregates were absent as displayed through scanning electron microscopy (SEM) images. Compatibilized compounds upon clay addition achieved higher thermal stability as visualized by thermogravimetry (TG). Montmorillonite clays acted as nucleant agent during PCL melt crystallization as evidenced by differential scanning calorimetry (DSC). Mechanical behavior of PCL was preserved, and all compounds presented Elongation higher than 350% meanwhile the heat distortion temperature (HDT) was increased by 20% in PCL compounds, which may have wider range of application and better performance.

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.

RESUMO A Poli(ɛ-caprolactona) (PCL) é um termoplástico sintético biodegradável que tem sido foco de estudos em novos “polímeros verdes”, devido principalmente as suas boas propriedades mecânicas, o que a torna competitiva com outros polímeros convencionais e biopolímeros, tais como: Poli(ácido lático) (PLA), Poli(hidroxibutirato) (PHB). O objetivo deste trabalho foi a enxertia de grupos reativos anidrido maleico (MA) na PCL para a produção de um polímero funcional biodegradável. A síntese de enxertia do anidrido maleico na PCL ocorreu em um misturador interno de laboratório, utilizando concentrações de 2,5 e 5 % de MA e de 0,3 e 0,5% do iniciador peróxido de dicumila (DCP) em duas temperaturas de processo, 110oC e 160oC. A metodologia do planejamento fatorial 23 foi usada visando à otimização dos experimentos, assim como também para avaliar a eficiência das condições reacionais empregadas para a funcionalização da PCL. Os resultados indicaram que o anidrido maléico foi enxertado na PCL usando o iniciador peróxido de dicumila. A porcentagem de anidrido maléico grafitizado (%gMA) foi obtida por titulação e comprovada por Espectroscopia na região do Infravermelho por Transformada de Fourier (FTIR). Através dos resultados obtidos pode-se inferir que um maior teor (5,0%) de MA favoreceu positivamente a enxertia. No entanto, acima de determinada quantidade, possivelmente ocorre uma saturação do sistema e a tendência é a recombinação.

ABSTRACT Poly (ɛ-caprolactone) (PCL) is a biodegradable synthetic thermoplastic that has been the focus of studies on new "green polymers", due mainly to its good mechanical properties, which makes it competitive among other conventional polymers and biopolymers, such as, Poly(lactic acid) (PLA) and Poly(hydroxybutyrene) (PHB). The objective of this work was the grafting of maleic anhydride (MA) reactive groups in PCL for the production of a functional biodegradable polymer. The grafting synthesis of the maleic anhydride in the PCL occurred in an internal lab mixer, using concentrations of 2.5 and 5.0% MA and 0.3 and 0.5% of the dicumyl peroxide initiator (DCP) at two temperatures of process, 110°C and 160°C. The methodology of factorial planning 23 was used to optimize the experiments, as well as to evaluate the efficiency of the reaction conditions employed for PCL functionalization. The results indicated that maleic anhydride was grafted onto PCL using the dicumyl peroxide initiator. The percentage of graphitized maleic anhydride (% gMA) was obtained by titration and confirmed by Fourier Transform Infra-Red (FTIR). Through the obtained results it can be inferred that higher content (5.0%) of MA positively favored the grafting. However, over certain amount, a saturation of the system may occur and the tendency is for recombination.

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.

Nanocomposites were processed using the technique of melt intercalation, starting from a concentrated polar compatibilizer/organoclay (PE-g-MA/organoclay) prepared in an internal mixer. The concentrate was incorporated into the matrix of HDPE by two methods: I) counter-rotating twin-screw extruder and II) co-rotating twin-screw extruder, using two screw profiles (ROS and 2KB90). After extrusion, the specimens of the extruded composites were injection molded. The X-ray diffraction (XRD) technique was used to analyze the degree of expansion of the prepared clays. To analyze the degree of exfoliation of obtained nanocomposites, XRD and TEM (transmission electron microscopy) were used. The influence of processing variables on mechanical properties was studied through the behavior of the modulus and tensile strength of nanocomposite systems. By XRD and TEM, it was seen that the clay was well dispersed in the matrix and the presence of intercalated and partially exfoliated hybrid structure for nanocomposites was observed when the systems were prepared in counter-rotating twin-screw extruder. A similar behavior was observed in the use of screws (2KB90 or ROS) of the nanocomposites, with a reduction in modulus and tensile strength. Although the mixing process by extruding be the most common industrial practice, and also it is the preferred strategy for the preparation of polymer nanocomposites, much of the literature was directed to the study of chemical modification of clay, type and level of compatibilizer, in order to maximize the compatibility between clay and the polymeric matrix. On the other hand, studies about the role of the processing and configurations of screws are relatively scarce. The main motivation of this work was to expand and to contribute to spread a better understanding of the effects of processing to obtain polymer nanocomposites.