Structure and properties of poly(lactic acid)/poly(ε‐caprolactone) nanocomposites with kinetically induced nanoclay location

Poly(lactic acid)/poly(ε‐caprolactone)/organically modified montmorillonite (PLA/PCL/OMMT) nanocomposites were melt‐processed in a twin‐screw extruder under high shear conditions. As a result of the processing conditions employed, the OMMT layers located in the less compatible PCL phase in all the ternary nanocomposites. The morphology of the PLA/PCL blend evolved from “sea‐island” to co‐continuous upon the addition of OMMT. Both the X‐ray diffraction (XRD) and viscoelastic characterization suggested similar OMMT dispersion in the reference PLA binary and in the PLA/PCL ternary nanocomposites, regardless of its location in the PLA and PCL phase, respectively. The reinforcing effect of the organoclay was also similar. The addition of OMMT to the PLA/PCL blend fully compensated the loss in stiffness and oxygen barrier performance produced by PCL in PLA; the nanocomposite with 3% OMMT showed the same modulus and permeability values as those of pure PLA. Moreover, the ductile behavior (elongation at break > 80%) of the PLA/PCL blend remained constant even in the nanocomposite containing 5% OMMT. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43815.     

Preparation of poly(lactic acid)/poly(ethylene glycol)/organoclay nanocomposites by melt compounding

Poly(lactic acid) (PLA)/organoclay nanocomposites were prepared by melt compounding in a co‐rotating twin screw extruder. Two types of commercialized organoclay (dimethyl benzyl stearyl ammonium ion and dimethyl distearyl ammonium ion intercalated between clay platelets named as Clay A and Clay B, respectively) and two grades of poly(ethylene glycol) (PEG) with different molecular weight (M_w = 2,000 and 300,000–500,000 named as PEG2k and PEG500k, respectively) were used in this study. The Young's modulus improved by the addition of organoclay to PLA matrix. The Young's modulus decreased with the addition of PEG to PLA/organoclay nanocomposites. The tensile strength and elongation of PLA/Clay B nanocomposites increased with the addition of PEG2k. The effect of the addition of PEG on d‐spacing of PLA/organoclay nanocomposites is dependent upon the kind of organoclay. The sizes of clay agglomerations in PLA/PEG/organoclay nanocomposites are larger than those of PLA/organoclay ones in the same organoclay. Addition of PEG to PLA/organoclay nanocomposites during melt compounding will not be useful for the preparation of PLA/organoclay having fully exfoliated clay platelets. The shear thinning properties of the nanocomposites are independent of the addition of PEG. On the whole, PEG2k is good plasticizer for PLA/organoclay nanocomposites. POLYM. COMPOS. 27:256–263, 2006. © 2006 Society of Plastics Engineers     

Study on dispersion and intercalation of organoclay in PP and PP‐g‐MA matrices

Understanding the complex mechanism of dispersion and intercalation of the clay tactoids can allow us to control the final morphology, homogeneity, and the macroscopic properties of clay nanocomposites. The objective of this work is a multiscale study of the dispersion state of PP/organoclay and PP‐g‐MA/organoclay composite. The microscopic investigation, WAXS diffractograms, rheological analysis, and mechanical properties were used to characterize the dispersion of organoclay in PP and PP‐g‐MA matrices during melt blending in two different shear rates. The morphological results show a system of aggregating intercalated clay particles which disperse by increasing mixing time with a strain‐controlled process and a very quick intercalation process in early mixing times for PP‐g‐MA/organoclay nanocomposite, while PP/organoclay samples only form microcomposites. The relative network modulus of these intercalated particles as a function of mixing time was obtained; and the tensile modulus of nanocomposite samples were compared with Halpin‐Tsai model prediction. POLYM. COMPOS., 2009. © 2009 Society of Plastics Engineers     

Evaluation of toughening mechanisms of polypropylene/ethylene–octene copolymer/maleic anhydride‐grafted poly(ethylene‐co‐octene)/clay nanocomposite

The toughness of a polypropylene (PP)/ethylene‐octene copolymer (EOC)/maleic anhydride‐grafted poly(ethylene‐co‐octene) (EOC‐g‐MA)/clay nanocomposite and blends of PP/EOC and PP/EOC/EOC‐g‐MA was investigated using Charpy impact and single‐edge‐notch tensile (SENT) tests. In order to understand the toughening mechanisms, impact fracture surfaces and damage zones of single‐edge‐notch samples were studied with scanning electron microscopy and transmission optical microscopy, respectively. It was observed that the addition of EOC‐g‐MA to PP/EOC blend led to improvements in both impact strength and fracture energy of SENT tests because of the enhanced compatibility of the blend, which resulted from reduced EOC particle size and improved interfacial adhesion, and the decreased crystallinity of PP. The incorporation of clay to PP/EOC/EOC‐g‐MA blend caused a further increase of the toughness, owing to the greater decrease in the size of elastomer particles, to the presence of clay tactoids inside the elastomer phase and presumably to debonding of clay layers during the low‐speed SENT tests. The results of microscopic observations showed that the main toughening mechanism in PP/EOC/EOC‐g‐MA blend and PP/EOC/EOC‐g‐MA/clay nanocomposite is crazing. Copyright © 2012 Society of Chemical Industry     

Extrusion of linear polypropylene–clay nanocomposite foams

This work presents new results on using organoclay with an appropriate polymeric compatibilizer as rheology‐modifying additives for extrusion foaming of a linear polypropylene (PP), which by itself does not display strain hardening in extensional flow of the melt. The uniaxial melt‐extensional viscosity behavior of several nanocomposites prepared with varying ratio of bound maleic anhydride to clay as well as varying compatibilizer molecular weight was investigated. A chemical‐blowing agent was used at a fixed concentration for foaming these nanocomposites in a single‐screw extruder. Among nanocomposites with similar levels of clay dispersion or intercalation, the ones that displayed significant strain hardening in the melt state along with slower crystallization led to extruded PP nanocomposite foams with smaller cell sizes and greater cell density by reducing cell coalescence. This was achieved with as little as 3 wt% organoclay and a high‐molecular weight PP‐g‐MA compatibilizer in linear PP. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Effects of the ethylene–propylene–diene monomer microstructural parameters and interfacial compatibilizer upon the EPDM/montmorillonite nanocomposites microstructure: Rheology/permeability correlation

Attempts have been made to investigate the effects of ethylene–propylene–diene monomer (EPDM) rubber structural parameters on the developed microstructure, mechanical properties, rheology, and oxygen gas permeability of EPDM/organically modified montmorillonite (O‐MMT) nanocomposite samples prepared via melt mixing. Maleic anhydride grafted EPDM (EPDM‐g‐MAH) has been employed as an interfacial compatibilizer. The influence of the EPDM melt viscosity and chain linearity on the extent of exfoliation of the clay nanolayers has been evaluated through the calculation of the nanolayer aspect ratio (length/thickness) with the Halpin–Tsai model. The results are consistent with the X‐ray diffraction patterns of the samples. The flocculation of the clay nanolayers has been found to be more probable when O‐MMT is mixed with highly branched, low‐molecular‐weight EPDM. More exfoliation occurs when EPDM rubber with a high molecular weight but low branching is used. This has been confirmed by more nonlinear melt rheology behavior and broadening of the retardation time spectra. Maleated EPDM has been shown to be effective in enhancing the molecular intercalation of the clay nanolayers and the prevention of flocculation in both low‐molecular‐weight and high‐molecular‐weight EPDM matrices. Dynamic melt rheology measurements have revealed nonterminal behavior within the low‐frequency range by interfacially compatibilized molten samples with an EPDM‐g‐MAH/clay ratio of 3, regardless of the matrix molecular weight and chain linearity. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Enhanced impact strength of compatibilized poly(lactic acid)/polyamide 11 blends by a crosslinking agent

Maleated poly(lactic acid) (PLA-g-MA) was prepared through melt grafting of maleic anhydride onto a PLA backbone with the aid of a radical initiator. PLA-g-MA thus formed was incorporated into PLA/polyamide 11 (PA11) blends as a reactive compatibilizer. By morphological observation, it was assessed that PLA-g-MA lowered the interfacial energy and strengthened the interface between PLA and PA11. However, the compatibilized PLA/PA11 blends did not show significant improvement of impact strength compared with noncompatibilized PLA/PA11 blends. Measurements of the molecular weight and impact strength of PLAs compounded with various amounts of radical initiators revealed that decreased molecular weight of PLA by the radical initiator used for the preparation of PLA-g-MA is responsible for this unexpected result. To compensate the decrease of the molecular weight, a crosslinking agent was incorporated in the preparation step of PLA-g-MA. It was found that the crosslinking agent is effective in preventing the molecular weight reduction. As a result, the impact strength of the PLA/PA11 blend was enhanced to a great extent by the PLA-g-MA prepared with the crosslinking agent.     

An investigation of melt rheology and thermal stability of poly(lactic acid)/ poly(butylene succinate) nanocomposites

A systematic investigation of the rheological and thermal properties of nanocomposites prepared with poly(lactic acid) (PLA), poly(butylene succinate) (PBS), and organically modified layered silicate was carried out. PLA/PBS/Cloisite 30BX (organically modified MMT) clay nanocomposites were prepared by using simple melt extrusion process. Composition of PLA and PBS polymers were fixed at a ratio of 80 to 20 by wt % for all the nanocomposites. Rheological investigations showed that high clay (> 3 wt %) contents strongly improved the viscoelastic behavior of the nanocomposites. Percolation threshold region was attained between 3 and 5 wt % of clay loadings. With the addition of clay content for these nanocomposites, liquid‐like behavior of PLA/PBS blend gradually changed to solid‐like behavior as shown by dynamic rheology. Steady shear showed that shear viscosity for the nanocomposites decreased with increasing shear rates, exhibiting shear‐thinning non‐Newtonian behavior. At higher clay concentrations, pseudo‐plastic behavior was dominant, whereas pure blend showed almost Newtonian behavior. Thermogravimetric analysis revealed that both initial degradation temperature (at a 2% weight loss) and activation energy of thermal decomposition nanocomposite containing 3 wt % of C30BX were superior to those of other nanocomposites as well as to those of PLA/PBS blend. Nanocomposite having 1 wt % of C30BX did not achieve expected level of thermal stability due to the thermal instability of the surfactant present in the organoclay. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of the molecular weight of maleated polypropylenes on the melt compounding of polypropylene/organoclay nanocomposites

Maleic anhydride grafted polypropylene (PP‐g‐MA) and organically modified clay composites were prepared in a plasticorder. PP‐g‐MAs, including Polybond PB3150, Polybond PB3200, Polybond PB3000, and Epolene E43, with a wide range of maleic anhydride (MA) concentrations and molecular weights were used. The structure was investigated with X‐ray diffraction (XRD) and transmission electron microscopy (TEM). PP‐g‐MA compatibilizers gave rise to similar degrees of dispersion beyond the weight ratio of 3/1, with the exception of E43, which had the highest MA content and the lowest molecular weight. The thermal instability and high melt index were responsible for the ineffective modification by E43. Furthermore, PP‐g‐MA with a lower molecular weight and a higher melt index had to be compounded at a lower mixing temperature to achieve a reasonable level of torque for clay dispersion. Polypropylene/organoclay nanocomposites were then modified with different levels of PP‐g‐MA compatibilizers with a twin‐screw extruder. The polypropylene/E43/clay system, as shown by XRD patterns and TEM observations, yielded the poorest clay dispersion of the compatibilizers under investigation. The curves of the relative complex viscosity also revealed a systematic trend with the extent of exfoliation and showed promise for quantifying the hybrid structure of the nanocomposites. The mechanical properties and thermal stability were determined by dynamical mechanical analysis and thermogravimetric analysis, respectively. Although PP‐g‐MA with a lower molecular weight led to better clay dispersion in the polypropylene nanocomposites, it caused deterioration in both the mechanical and thermal properties of the hybrid systems. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1667–1680, 2005     

Melt processing and characterization of multicomponent polymeric nanocomposites containing organoclay

Nylon 6 (Ny)/polypropylene (PP)/maleated polypropylene (PP‐g‐MA)/organoclay/wollastonite composites were prepared by melt processing. The polymers' composition was kept constant ([70PP/30Ny]/4PP‐g‐MA). Melt compounding was conducted using a twin‐screw extruder in three different methods: (1) simultaneous incorporation of the components into the compounding equipment, (2) preparation of [Ny6/clay] concentrate, and then in a second step, mixing the other components with the concentrate, and (3) mixing of PP with wollastonite and clay followed by the addition of Ny6 and PP‐g‐MA in the second step. Injection‐molded specimens were characterized in tension, scanning electron microscopy, X‐ray diffraction (XRD), and differential scanning calorimetry. The sequence of component addition greatly influences the structure and properties of the composites. Enhanced mechanical properties were achieved when the two‐step mixing procedure was used for the PP/Ny6/PP‐g‐MA/clay system (method 2) and also for the PP/Ny6/PP‐g‐MA/clay/wollastonite system (method 3). The XRD pattern of the PP/Ny6/PP‐g‐MA/clay nanocomposites produced by the two‐step mixing method does not show a characteristic basal reflection of the pristine organoclay, indicating a predominately exfoliated structure of clay. POLYM. COMPOS., 28:417–424, 2007. © 2007 Society of Plastics Engineers     

Exfoliation targeted toughness enhancement in polypropylene‐blend‐ montmorillonite nanocomposites

BACKGROUND: Both exfoliated and toughened polypropylene‐blend‐montmorillonite (PP/MMT) nanocomposites were prepared by melt extrusion in a twin‐screw extruder. Special attention was paid to the enhancement of clay exfoliation and toughness properties of PP by the introduction of a rubber in the form of compatibilizer toughener: ethylene propylene diene‐based rubber grafted with maleic anhydride (EPDM‐g‐MA). RESULTS: The resultant nanocomposites were characterized using X‐ray diffraction, atomic force microscopy, scanning electron microscopy, thermogravimetric analysis, dynamic mechanical analysis and Izod impact testing methods. It was found that the desired exfoliated nanocomposite structure could be achieved for all compatibilizer to organoclay ratios as well as clay loadings. Moreover, a mechanism involving a decreased size of rubber domains surrounded with nanolayers as well as exfoliation of the nanolayers in the PP matrix was found to be responsible for a dramatic increase in impact resistance of the nanocomposites. CONCLUSION: Improved thermal and dynamic mechanical properties of the resultant nanocomposites promise to open the way for highly toughened super PPs via nanocomposite assemblies even with very low degrees of loading. Copyright © 2008 Society of Chemical Industry     

A New Method for Producing High Melt Strength Poly(propylene) with a Reactive Extrusion

Summary: A new class of melt blend material was prepared by extruding a mixture of 3‐aminopropyltriethoxysilane (APTES), maleic anhydride‐grafted poly(propylene) (PP‐g‐MA) with different molecular weight and MA content and poly(propylene) powder produced with a TiCl₃‐based catalyst (PP‐A). A suitable selection of PP‐g‐MA provided extremely high melt strength (MS) of resultant blend materials. Such a superior melt property was caused by the synergy between the present melt reaction and the higher molecular weight portion containing PP‐A. The gel content measurements of typical blend materials and PP‐g‐MA/APTES blends indicated that an excessive amount of inert PP suppresses the formation of gels. The reaction between PP‐g‐MA and APTES was then investigated by analyzing crystalline polymer fractions separated from the atactic PP/PP‐g‐MA/APTES and atactic PP/PP‐g‐MA blends. The FT‐IR analysis of the fractions revealed that the NH₂ group in APTES readily reacts with MA grafted on PP and the reaction leads to the formation of imide linkage. Moreover, the GPC analysis of the fraction showed that higher molecular weight polymers were formed in the presence of APTES. Since a trace amount of water surely produces in the vicinity of active silyltriethoxy groups during the reactive extrusion, such polymers were formed by the condensation between hydrolyzed APTES‐grafted polymer chains. These results led us to the conclusion that long‐chain‐branched PP (LCB‐PP) was certainly produced and its formation is essential for the increase in MS of the present blend materials.

Relationship between log(MS) and log(MFR) for PP/PP‐g‐MA/APTES and commercial PP resins.     

Structural,thermal, and gas transport properties of HDPE/LLDPE blend‐based nanocomposites using a mixture of HDPE‐g‐MA and LLDPE‐g‐MA as compatibilizer

Nanocomposites based on high density polyethylene (HDPE)/linear low density polyethylene (LLDPE) blend were prepared by melt compounding in a twin‐screw extruder using organoclay (montmorillonite) as nano‐filler and a 50/50 wt% mixture of maleic anhydride functionalized high density polyethylene (HDPE‐g‐MA) and linear low density polyethylene (LLDPE‐g‐MA) as the compatibilizing system. The addition of a maleated polyethylene‐based compatibilizing system was required to improve the organoclay dispersion in the HDPE/LLDPE blend‐based nanocomposite. In this work, the relationships between thermal properties, gas transport properties, and morphology were correlated. The compatibilized nanocomposite exhibited an intercalated morphology with a small number of individual platelets dispersed in the HDPE/LLDPE matrix, leading to an significant decrease in the oxygen permeation coefficient of the nanocomposites. A decrease in the carbon dioxide permeability and oxygen permeability with increase of nanoclay was observed for the compatibilized nanocomposites. The carbon dioxide permeability of the compatibilized nanocomposites was lower than the carbon dioxide permeability of the uncompatibilized nanocomposites even with the low intrinsic barrier properties of the compatibilizer. These effects were attributed to a good dispersion of the inorganic filler, good wettability of the filler by the polymer matrix, and strong interactions at the interface that increased the tortuous path for diffusion. Theoretical permeability models were used to estimate the final aspect ratio of nanoclay in the nanocomposite and showed good agreement with the aspect ratio obtained directly from TEM images. POLYM. ENG. SCI., 56:765–775, 2016. © 2016 Society of Plastics Engineers     

Morphology development,melt linear viscoelastic properties and crystallinity of polylactide/polyethylene/organoclay blend nanocomposites

Polylactide/polyethylene blends (PLA/PE) and their nanocomposites were prepared via the melt blending process. The effects of organoclay, compatibilizer (PE‐g‐MA), and PE content on morphology, linear viscoelastic properties of the melt and cold crystallization of the samples have been studied. The Palierne model is applied to predict the rheological behavior of unfilled blends. It implies that there is a quantitative agreement between model and experimental data for low PE content blend. From WAXD and the rheological behavior, it is shown that organoclay exhibits a higher extent of intercalation and dispersion in PLA/PE/organoclay nanocomposite than in PLA/organoclay nanocomposite. The DSC results present that the addition of compatibilizer into blend nanocomposite increases cold crystallization temperature of PLA by about 3°C. This can be explained by the role of compatibilizer in transfer of a part of organoclay from PLA matrix to droplets resulting in increase of PLA chain mobility and, therefore, slightly greater cold crystallization temperature. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41300.     

Effects of molecular weight and grafted maleic anhydride of functionalized polylactic acid used in reactive compatibilized binary and ternary blends of polylactic acid and thermoplastic cassava starch

Polylactic acid (PLA) was reactively functionalized with maleic anhydride (MA) and 2,5‐bis(tert‐butylperoxy)?2,5‐dimethylhexane (Luperox 101 or L101) using a twin screw extruder (TSE). The effects of functionality (grafted MA level) and/or number average molecular weight of functionalized PLA (PLA‐g‐MA) as the reactive polymer pairs (binary blends) and reactive compatibilizer (ternary blends) were investigated. Due to the dominant side reaction during melt free radical grafting, polymer degradation or chain scission, PLA‐g‐MA having a higher grafted MA had lower molecular weights and intrinsic viscosity as well as broader molecular weight distribution values. The thermal, physical, mechanical, and morphological properties of binary blends produced by using the TSE and injection molding at a ratio of 70 wt % PLA‐g‐MA and 30 wt % thermoplastic cassava starch (TPCS) were analyzed. The reactive blends having grafted MA more than 0.4 wt % had poor tensile strength and elongation at break. Similar trends in morphology and tensile properties were observed in the reactive ternary blends. The use of PLA‐g‐MA strongly impacted the elongation at break but not the modulus or tensile strength. An increase of PLA‐g‐MA's number average molecular weight ( or M_n) improved the tensile properties of the blends. The reactive ternary blend having 0.1 wt % grafted MA on PLA and PLA‐g‐MA basis and PLA‐g‐MA's M_n of 45 kDa offered the highest elongation at break. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42230.     

Rheology‐morphology correlation in PET/PP blends: Influence of type of compatibilizer

Rheological and morphological properties of melt processed poly(ethylene terephthalate) (PET)/polypropylene (PP) blends are presented. Two types of compatibilizer namely, PP‐g‐MA <MA= maleic anhydtide> and Elvaloy PTW, an n‐butyl acrylate glycidyl methacrylate ethylene terpolymers, were incorporated at different levels to the PET/PP blend system. Scanning electron microscopy revealed that the dispersed particle sizes were smaller in PET‐rich blends than PP‐rich blends. With increasing compatibilizer level, the refinement of morphology was observed in both the systems. However, the blends compatibilized with PTW showed a more refined (smaller) particle size, and at high PTW content (10 wt%), the morphology changed towards monophasic. The significant changes in morphology were attributed to the highly reactive nature of PTW. Investigation of rheological properties revealed that the viscosity of the PET/PP blends followed typical trends based on mixing rule, which calculates the properties of blends based on a linear average. Incorporation of PP‐g‐MA into the blends resulted in a negative deviation in the viscosity of the system with respect to that of the neat blend. With increasing PP‐g‐MA level, the deviation became more pronounced. Although incorporation of the compatibilizer into the PET/PP blends refined the morphology, it led to a drastic drop of viscosity, which could be attributed to inherently lower molecular weight of the compatibilizer. In the case of the blends compatibilized by PTW, a strong positive deviation in rheological properties was observed that confirmed the stronger interaction between the blend components due to reactive compatibilization process, which led to the more refined morphology in this series of blends. J. VINYL ADDIT. TECHNOL., 19:25–30, 2013. © 2013 Society of Plastics Engineers     

Experimental and computational investigation of EVOH/clay nanocomposites

Ethylene–vinyl alcohol copolymer (EVOH)/organoclay nanocomposites were prepared via a dynamic melt‐intercalation process. The effect of compatibilizers on the melt blending torque, intercalation level, and morphology of EVOH/organoclay systems was investigated. Maleic anhydride grafted ethylene vinyl acetate (EVA‐g‐ MA), or maleic anhydride grafted linear low‐density polyethylene (LLDPE‐g‐MA), were used to compatibilize EVOH with clay, at various concentrations (1, 5, and 10 wt %). Computer‐simulation techniques are used to predict structural properties and interactions of EVOH with compatibilizers in the presence and absence of clay. The simulation results strongly support the experimental findings and their interpretation. X‐ray diffraction shows enhanced intercalation within the galleries when the compatibilizers were added. Interestingly, results were obtained for the EVOH/clay/compatibilizer systems, owing to a high level of interaction developed in these systems. Thermal analysis shows that, upon increasing the compatibilizer content, lower crystallinity levels result, until at a certain compatibilizer content no crystallization is taking place. Significantly higher mixing viscosity levels were obtained for the EVOH/organoclay blends compared with the neat EVOH polymer. The storage modulus was higher compared with the uncompatibilized EVOH/organoclay blend in the presence of EVA‐g‐MA compatibilizer (at all concentrations), and only at low contents of LLDPE‐g‐MA. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2060–2066, 2005     

Effects of the compatibilizer structural parameters on microstructural formation in ethylene–propylene–diene monomer rubber/ethylene–propylene–diene monomer rubber‐g‐maleic anhydride/organoclay nanocomposites

Nanocomposite vulcanizates based on ethylene–propylene–diene monomer rubber (EPDM) and organically modified montmorillonite with improved mechanical and barrier properties were prepared via a melt‐mixing process in the presence of maleic anhydride grafted ethylene–propylene–diene monomer rubber (EPDM‐g‐MAH) as an interfacial compatibilizer. The effects of the EPDM Mooney viscosity as the matrix and also the compatibilizer molecular weight and its maleation degree on the developed microstructure were also studied. The annealing of the vulcanized nanocomposites based on a low‐Mooney‐viscosity EPDM matrix and low‐Mooney‐viscosity EPDM‐g‐MAH enhanced the flocculation of the dispersed clay platelets; this implied that the flocculated structure for the clay nanolayers was more thermodynamically preferred in these nanocomposites. This was verified by the decrease in the oxygen permeability of the nanocomposite vulcanizates with increasing annealing time. The tendency of the clay nanosilicate layers to flocculate within the matrix of EPDM was found to be influenced by the clay volume fraction, the maleation degree, and also, the Mooney viscosity of the compatibilizer. Interfacially compatibilized nanocomposites based on high‐molecular‐weight EPDM exhibited a more disordered dispersion of the clay nanolayers, with a broadened relaxation time spectra; this was attributed to the higher shearing subjected to the mix during the melt‐blending process. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Reactive extrusion of polycaprolactone compounds containing wood flour and lignin

Biodegradable polycaprolactone (PCL) was melt‐compounded in a Werner & Pfleiderer twin‐screw extruder (ZSK25) together with wood flour (WF) and lignin with maleic anhydride‐grafted polycaprolactone (PCL‐g‐MA) used as a compatibilizer. The grafting of maleic anhydride onto PCL was achieved with reactive extrusion in the presence of 2,5‐dimethyl‐2,5‐di‐(t‐butylperoxy)hexane as an initiator. The graft copolymers were analyzed with size exclusion chromatography and titration. As a function of the initiator and maleic anhydride addition, the grafted maleic anhydride content varied from 1.4 to 3.1 wt %. Compounds compatibilized with PCL‐g‐MA exhibited improved mechanical properties: a compatibilized PCL compound containing 40 wt % WF gave a Young's modulus of 2300 MPa with respect to 400 MPa for neat PCL and a 100% increase in yield stress. The content of WF, lignin, and PCL‐g‐MA was varied systematically to examine stress–strain and impact behavior. Low contents of grafted maleic anhydride and PCL‐g‐MA were required to improve both mechanical properties and interfacial adhesion. Biodegradation was investigated. Lignin addition was found to retard biodegradation. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1972–1984, 2001     

Isothermal crystallization kinetics of biodegradable poly(lactic acid)/poly(ε‐caprolactone) blends compatibilized with low‐molecular weight block copolymers

The isothermal crystallization kinetics of biodegradable blends made of poly(lactic acid) (PLA) and poly(ε‐caprolactone) (PCL) compatibilized with two different low molecular weight block copolymers, that is, ε‐caprolactone/tetramethylene ether glycol and ε‐caprolactone/aliphatic polycarbonate (CB), was done. Blends were prepared by melt mixing in an extruder, while isothermal crystallization kinetics and morphologies were investigated by thermal (differential scanning calorimetry) and thermo‐optical (quantitative polarized light optical microscopy [qPLOM]) quantitative methods. Data were analyzed using the Avrami equation, revealing 2D and 3D growth and simultaneous heterogeneous nucleation. The presence of low molecular weight compatibilizers, that is, 2,000 g mol^?1, accelerated the PLA crystallization rate by two to threefold when compared with neat PLA, with high degrees of crystallinity (40–43%) as confirmed by PLOM images. The activation energy (E_a) showed that PCL inhibits PLA crystallization; however, the addition of block copolymers used as compatibilizers of the blends reduced E_a values, increasing the chain mobility of PLA and thus increasing the crystallization rate. POLYM. ENG. SCI., 59:E161–E169, 2019. © 2018 Society of Plastics Engineers