Effect of clay orientation on the tensile modulus of polypropylene-nanoclay composites

We present an experimental investigation of the effect of clay orientation, as produced by melt extrusion, on the tensile modulus of compatibilized and uncompatibilized syndiotactic polypropylene nanoclay composites. The orientation of the clay tactoids in extruded tape samples was quantified using 2D X-ray diffraction data. It was found that in the case of the tapes made from compatibilized nanocomposites the orientation of the clay tactoids increased with extrusion shear rate, while in the case of tapes extruded from uncompatibilized hybrids the clay orientation was independent of the shear rate. Tensile modulus of the extruded tapes along the flow direction was measured and was found to correlate well with the average orientation of the clay tactoids. In the case of the compatibilized hybrids the modulus increased with the extrusion shear rate until a saturation value, whereas for the uncompatibilized hybrids the modulus was nearly independent of the shear rate. Semi-quantitative predictions of the effect of clay orientation on the tensile modulus of the compatibilized tape samples were obtained using a micromechanical model.     

Orientation of montmorillonite clay in dicyclopentadiene/organically modified clay dispersions and nanocomposites

Highly delaminated dispersions of the organically modified clay I‐28 (Nanocor, Inc.) in liquid dicyclopentadiene (DCPD) were prepared. In situ ring‐opening metathesis polymerization of I‐28/DCPD nanodispersions generated I‐28/poly(DCPD) nanocomposites. When clay/DCPD dispersions were cured under shear, alignment of clay platelets, tactoids, and small particles was captured. This orientation was confirmed by X‐ray diffraction and transmission electron microscopy. The Herman's orientation parameters were calculated for the oriented nanocomposites. Viscosities of these liquid nanodispersions exhibited thixotropic flow behavior, prior to curing. The time‐dependent viscosity effects became more pronounced with an increase in delamination. Initial viscosities increased with progressive clay platelet generation during delamination and nanodispersion within the liquid monomer. Viscosity can be used to follow clay exfoliation/delamination. Etching the surface of a 2 wt % I‐28 clay/poly(DCPD) nanocomposite with oxygen plasma eroded the matrix, exposing clay tactoids protruding from the surface. These surfaces were examined by SEM and energy dispersive X‐ray spectroscopy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2743–2751, 2006     

Water-assisted extrusion of polypropylene/clay nanocomposites: A comprehensive study

Water-assisted extrusion process has been used to successfully prepare polypropylene (PP)/clay nanocomposites with high degree of clay delamination and markedly improved rheological, thermal and mechanical properties. PP-graft-maleic anhydride (PP-g-MA)-based nanocomposites and masterbatches were synthesized from untreated clay and organoclay, respectively, and fully characterized. The effects of using high-shear rates and water injection during the melt-compounding were examined. A mechanism explaining the formation of such nanocomposites is then proposed. The best clay dispersion and properties improvements of PP-g-MA/organoclay nanocomposites and masterbatches were obtained using high-shear rates and water injection (synergy effect). PP-based nanocomposites were then synthesized by dilution of PP-g-MA-based masterbatches into neat PP. For comparison, nanocomposites were also prepared by a one-pot process where PP, PP-g-MA and organoclay are directly melt-blended with or without water injection. The nanocomposites prepared by dilution into PP of a masterbatch prepared through water-assisted extrusion showed the highest clay dispersion and consequently the best thermal, mechanical and rheological properties.     

A new elaboration concept of polypropylene/unmodified Montmorillonite nanocomposites by reactive extrusion based on direct injection of polypropylene aqueous suspensions

Nanocomposites based on polypropylene (PP) and unmodified Montmorillonite were prepared using a novel elaboration route based on a water‐assisted extrusion process. Unmodified Montmorillonite, high shear compounding together with injection of aqueous suspension and reactive processing technology were used. Different aqueous suspensions containing cationic or anionic surfactants, and a compatibilizer (PP‐g‐MA) were injected during extrusion to promote clay dispersion. For a comparison purpose, a commercial PP/clay masterbatch was melt mixed to PP. Structural, morphological, and rheological characterizations indicate clearly that the cationic suspensions ease the dispersion of clay platelets in the PP matrix. No full exfoliation is, however, obtained, and the system remains still less homogeneous than the nanocomposite based on the commercial masterbatch. Nevertheless, mechanical and thermal characterizations of the nanocomposites based on cationic surfactants demonstrate the efficiency to disperse clay in the polymer matrix, and the effect on the ductility compared to usual PP nanocomposites is promising. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Preparation of extruded melt‐mixed polypropylene/montmorillonite nanocomposites with inline monitoring

This article advances the use of an inline optical detector to monitor the disaggregation of the montmorillonite (MMT) clay tactoids during the preparation of polypropylene (PP)/MMT nanocomposites via polymer melt compounding. During the exfoliation of the tactoids their size are reduced below the minimum particle size to produce light extinction and so, the signal of the inline detector reduces as the nanosize composite is formed. The measurement is done at the transient state with the MMT clay added as a pulse with constant weight into the PP extrusion melt flow and followed by the optical detector. The data comes out as the common residence time distribution curves having its maximum intensity related to the tactoids average particle size, keeping all other variables constants. The light extinction was measured for composites with different clays (Cloisite® 15A, 30B, Na⁺, and Sintered 20A) using the same PP grafted with maleic anhydride compatibilizer. The dissaglomeration/exfoliation efficiency increases as: ‘‘Sintered 20A’’ < ‘‘Na+ clay’’ < ‘‘organo‐modified clay’’ < ‘‘organo‐modified clay + compatibilizer’’. The best result is obtained using Cloisite® 15A and Cloisite® 20A following the expected reduction of the particle size obtained during a nanocomposite melt processing. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Exfoliation of organic montmorillonite in iPP free of compatibilizer through the multistage stretching extrusion

Polypropylene (PP)/organic montmorillonite (OMMT) nanocomposites were first prepared through twin-screw extruder and then subjected to multistage stretching extrusion with an assembly of laminating-multiplying elements (LMEs, which divide and recombine polymer melts). The exfoliated efficiency of LMEs on OMMT dispersed in PP matrix was investigated by optical microscopy, scanning electron microscope, transmission electron microscopy and X-ray diffraction. Because of the absence of compatibilizer, molecular chains of PP were not intercalated into the galleries of OMMT during the multistage stretching extrusion. The exfoliation of OMMT was induced by the strong force occurred in LMEs, which can destruct van der Waal’s interaction between the laminate OMMT platelets. The exfoliation degree of OMMT has been improved with the increase of number of LMEs used. The dispersion morphology of OMMT was thermodynamically stable after secondary melt processing. As a result, the mechanical properties of composites have been enhanced with increasing LME number. We realized the exfoliation of OMMT by the function of strong shear field without the incorporation of compatibilizer.     

Polycarbonate nanocomposites. Part 1. Effect of organoclay structure on morphology and properties

Polycarbonate nanocomposites were prepared by melt processing from a series of organoclays based on sodium montmorillonite exchanged with various amine surfactants. To explore the effects of matrix molecular weight on dispersion, an organoclay was melt-mixed with a medium molecular weight polycarbonate (MMW-PC) and a high molecular weight polycarbonate (HMW-PC) using a twin screw extruder. The effects of surfactant chemical structure on the morphology and physical properties were explored for nanocomposites formed from HMW-PC. Wide angle X-ray scattering, transmission electron microscopy, and stress-strain behavior were employed to investigate the nanocomposite morphology and physical properties. The modulus enhancement is greater for nanocomposites formed from HMW-PC than MMW-PC. This trend is attributed to the higher shear stress generated during melt processing. A surfactant having both polyoxyethylene and octadecyl tails shows the most significant improvement in modulus with some of the clay platelets fully exfoliated. However, the nanocomposites formed from a range of other organoclays contained both intercalated tactoids and collapsed clay particles with few, if any, exfoliated platelets.     

The effect of clay dispersion on the properties of LLDPE/LLDPE‐g‐MAH/montmorillonite nanocomposites

In this work, three coupling agents presenting different grafting contents and molecular weights were used to prepare linear low density polyethylene (LLDPE)/linear low density polyethylene grafted with maleic anhydride (LLDPE‐g‐MAH)/montmorillonite nanocomposites with various morphologies. The clay dispersion was analyzed at the micrometric level by scanning electron microscopy and at the nanometric level by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). It was found that coupling agents having intermediate molecular weights led to the highest exfoliation extents, whereas the coupling agent presenting the highest molecular weight led to a poor delamination of the clay platelets. The properties of the nanocomposites produced and of their LLDPE/LLDPE‐g‐MAH reference blends were analyzed. It was shown that the best improvements in mechanical and barrier properties are not necessarily achieved for the nanocomposites, exhibiting the highest exfoliation extents. The length of the tactoids also plays a crucial role on the macroscopic properties. In addition, a high level of delamination could result in a loss of reinforcement effect, due to the inherent flexibility of the individual clay platelets. Finally, the strength of the clay/polymer interface, which was evaluated through surface tension measurements, seems to play a significant role on the properties of the nanocomposites. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers.     

Effects of organoclay modification on microstructure and properties of polypropylene–organoclay nanocomposites

We prepared polypropylene nanocomposites based on a modified organoclay with isobutyl trimethoxysilane to investigate the effects of such modifications of organoclay on the microstructure and properties of the nanocomposite. The organoclay was preliminarily intercalated with distearyldimethylammonium bromide via an ion exchange before being grafted with silane. The morphology of the polypropylene–organoclay nanocomposites was characterized by wide‐angle X‐ray diffraction analyses and transmission electron microscopy. The modification of the edges of clay platelets with organic silane resulted in a more uniform dispersion of nonagglomerated tactoids, which consisted of several intercalated clay platelets. However, the unmodified organoclay led to a mixed morphology with both agglomerated and nonagglomerated tactoids. The grafting of the clay edges with organic silane also affected the linear viscoelastic properties of the nanocomposites in the melt state, which was shown to be sensitive to the interaction between the edges of clay platelets as well as to the interaction of the polymer with the platelet edges. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1752–1759, 2006     

Batch and continuous processing of polymer layered organoclay nanocomposites

The generation of nanocomposites upon intercalation and exfoliation of clay tactoids using melt compounding is a difficult process. In this study various polymeric binders were melt compounded with organophilic clay particles using myriad methods, including sonication, batch mixing, and twin screw extrusion. The characterization of the compounded samples employing X‐ray diffraction (XRD) and transmission electron microscopy (TEM) revealed that there is little intercalation and exfoliation when nonpolar poly(dimethyl siloxane) (PDMS) and poly(propylene) (PP) binders were used, resulting in no significant changes in the dynamic properties of the suspensions upon small‐amplitude oscillatory shearing. On the other hand, when polar polymeric binders, i.e., silanol terminated poly(dimethyl siloxane) and maleic anhydride modified PP were used for compounding with organoclays, TEM and XRD revealed intercalation with some partial exfoliation, resulting in increases in the dynamic properties, along with sensitivity to the thermomechanical history during processing. These results reinforce earlier findings, which suggest that the interfacial properties between the organoclays and the polymeric binders need to be tailored properly to enable the generation of nanocomposites of organoclays using melt compounding technologies. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1391–1398, 2007     

Orientation Effect of Clay Platelets in Transfer Molded Polymer Nanocomposites

Transfer molding has been increasingly used to process polymer composites with various shaped nanoparticles, including platelet type nanoparticles. Platelet nanoparticles exhibit high aspect ratios (length to thickness); therefore their distributions in polymer matrix can be greatly affected by the flow trajectories in the mold. In present study, the clay platelet-polyethylene nanocomposite was prepared by transfer molding. The orientation of clay platelets developed during molding process was analyzed and measured with wide angle X-ray diffraction. Due to large velocity and shear stress gradients in the mold, the platelets caught in surface regions were rotated towards the flow direction and formed the oriented morphologies. With weaker shear stresses at the central region, the platelets were mostly randomly distributed. The shear stresses may be amplified locally at regions near the mold walls, which can further lead to or accelerate the orientations of clay particles. The orientation distribution was found to depend upon the clay fraction and sample size. The oriented platelets can be re-randomized through the annealing process. The orientation of clay platelets enhanced the orientation of polyethylene lamellae and caused shear band formation in composites when deformed.     

Structure and melt rheology of long‐chain branching polypropylene/clay nanocomposites

Long‐chain branching polypropylene (LCB‐PP)/clay nanocomposites were prepared by melt blending in a twin‐screw extruder. The microstructure and melt rheology of these nanocomposites were investigated using x‐ray diffraction, transmission electron microscopy, oscillatory shear rheology, and melt elongation testing. The results show that, the clay layers are intercalated by polymer molecular chains and exfoliate well in LCB‐PP matrix in the presence of maleic anhydride grafted PP. Rheological characteristics, such as higher storage modulus at low‐frequency and solid‐like plateau in tan‐ω curve, indicate that a compact and stable filler network structure is formed when clay is loaded at 4 phr (parts per hundred parts of) or higher. The response of the nanocomposite under melt extension reveals an initial decrease in the melt strength and elongational viscosity with increasing clay concentration up to 6 phr. Later, the melt strength and elongational viscosity show slight increases with further increasing clay concentration. These results might be caused by a reduction in the molecular weight of the LCB‐PP matrix and by the intercalation of LCB‐PP molecular chains into the clay layers. Increases in the melt strength and elongational viscosity for the nanocomposites with decreasing extrusion temperature are also observed, which is due to flow‐induced crystallization under lower extrusion temperature. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Melt rheology of organoclay and fumed silica nanocomposites

The objective of the present work is to investigate, from the open literature, the recent developments in the rheology of silica and organoclay nanocomposites. In particular, this paper focuses on general trends of the linear viscoelastic behaviour of such nanocomposites. Hence, the variations of the equilibrium shear modulus and critical strain (limit of linearity), which depend on power laws of the volume fraction of particles, are discussed as filler fractal structure. In the third section, the strong nonlinearity behaviour (Payne effect) of filled polymers has been discussed in terms of filler nature. Typically two mechanisms arise to depict the linear solid-like behaviour and the Payne effect: particle–particle interactions is the dominant mechanism in fumed silica nanocomposites whereas particle–polymer interaction is the dominant one in colloidal silica nanocomposites at identical filler concentrations. However, these interactions are balanced in each nanocomposite systems by the silica surface treatments (chain grafting, silane modification) and the molecular weight of the matrix. Finally, we aim to unify the main findings of the literature on this subject, at least from a qualitative point of view.We finally report on the thixotropy and modulus recovery after a large deformation in steady and dynamic shear conditions. Following this, the nonlinear rheological properties of nanocomposite materials have been discussed. The discussion is particularly focused on the effect of flow history (transient shear experiments) on the orientation–disorientation of clay platelets. Actually, the linear and nonlinear rheological properties are consistent with a network structure of a weakly agglomerated tactoids. As far as exfoliated clay nanocomposites are concerned, the inter-particle interaction is the dominant effect in the nonlinearity effect.     

Solid‐state mechanical properties of polypropylene/nylon 6/clay nanocomposites

The mechanical and thermomechanical properties as well as microstructures of polypropylene/nylon 6/clay nanocomposites prepared by varying the loading of PP‐MA compatibilizer and organoclay (OMMT) were investigated. The compatibilizer PP‐MA was used to improve the adhesion between the phases of polymers and the dispersion of OMMT in polymer matrix. Improvement of interfacial adhesion between the PP and PA6 phases occurred after the addition of PP‐MA as confirmed by SEM micrographs. Moreover, as shown by the DSC thermograms and XRD results, the degree of crystallinity of PA6 decreased in the presence of PP‐MA. The presence of OMMT increased the tensile modulus as a function of OMMT loading due to the good dispersion of OMMT in the matrix. The insertion of polymer chains between clay platelets was verified by both XRD and TEM techniques. The viscosity of the nanocomposites decreased as PP‐MA loading increased due to the change in sizes of PA6 dispersed phase, and the viscosity increased as OMMT loading increased due to the interaction between the clay platelets and polymer chains. The clay platelets were located at the interface between PP and PA6 as confirmed by both SEM and TEM. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Improvement of toughness in polypropylene nanocomposite with the addition of organoclay/silicone copolymer masterbatch

Polypropylene nanocomposites were prepared with organic‐modified montmorillonite, by blending the polymer and the organoclay (direct addition), or by blending the polymer with an organoclay/silicone copolymer masterbatch. The effect of the organoclay/silicone copolymer masterbatch on the morphology and properties of polypropylene was compared with that nanocomposite obtained with the direct organoclay addition. The results showed that the morphology of both polypropylene nanocomposites is constituted by clay tactoids together with some few individual platelets and clay aggregates. Smaller tactoids were observed for the nanocomposite prepared with the masterbatch, in which the silicone copolymer remained intercalated in the clay or adjacent to tactoids. The introduction of the organoclay in the polymer matrix resulted only in an increase in the Young's modulus (28%), while yielding stress, elongation at break and Izod impact strength remained practically unchanged. On the other hand, the incorporation of organoclay by using the masterbatch resulted in a marked improvement (111%) in the elongation at break and in Izod impact strength (85%). The improvement in the elongation at break came with the reduction of the modulus and the yielding stress, by 25 and 15%, respectively. POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

Natural rubber-clay nanocomposites: Mechanical and structural properties

The mechanical properties of non-vulcanized natural rubber and dialyzed natural rubber-clay nanocomposites have been studied by uniaxial deformations to evaluate the reinforcement efficiency of the clay. We show that while non-rubber molecules contribute to auto-reinforcement, removal of these molecules improves significantly the performance of clay as reinforcement agent. These mechanical properties are discussed in relation to morphological aspects of the clay characterized by TEM and SANS. The nanocomposites prepared by “latex-mixing” with aqueous dispersions of clay are found to contain completely exfoliated clay lamellae in co-existence with tactoids. Improved mechanical properties of the nanocomposites can be modeled by the high aspect ratio of exfoliated clay platelets coupled with immobilized rubber matrix. Interestingly, presence of tactoids does not appear to compromise the excellent reinforcement properties of the exfoliated platelets. At high deformations, strain-induced alignment of the clay exhibits anisotropic scattering, with anisotropy increasing with clay concentration and stretching.     

Crystal structure and orientation of uniaxially and biaxially oriented PLA and PP nanoclay composite films

Cast films of poly(lactic acid) (PLA) and polypropylene (PP) with 2.5 and 5 wt % organo modified nanoclay were prepared and then uniaxially and biaxially hot drawn at T = 90 and 155°C, respectively, using a biaxial stretcher. The orientation of PLA and PP crystal unit cells, alignment of clay platelets, as well as the extent of intercalation and exfoliation were studied using wide angle X‐ray diffraction (WAXD). The measurement of d‐spacing of the 001 plane (normal to platelets plane) of the clay tactoids indicated the intercalation of the silicate layers for the PLA nanocomposite films, whereas the PP nanofilled films showed only dispersion of the nanoparticles (i.e., neither intercalation nor exfoliation were observed). The intercalation level of the clay platelets in PLA was almost identical for the uniaxially and biaxially drawn films. Our finding showed that the crystallite unit cell alignments are appreciably dependent on uniaxial and biaxial stretching. Moreover, the incorporation of clay to some extent influenced the orientation of the crystal unit cell axes (a, b, and c) of the oriented films. The silicate layers revealed a much higher orientation into the flow direction in the uniaxially stretched films compared to the biaxially drawn samples. In addition, the orientation of the 001 plane of nanoclays was significantly greater in the PLA compared to the PP nanoclay composite films probably due to a better intercalation and stress transfer in the former. Morphological pictograms illustrating the effects of uniaxial and biaxial stretching on the clay orientation are proposed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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     

Assessing organo-clay dispersion in polymer layered silicate nanocomposites: A SAXS approach

A SAXS method for the quantitative assessment of the morphology of polymer layered silicate nanocomposites is proposed. Fitting the SAXS patterns, the number of clay layers, the periodicity of the layers in the tactoids, the thickness of the regions interposed between the clay platelets and their distributions can be measured. A good agreement with TEM data was obtained, avoiding the inconsistencies with microscopical observations often reported in the literature.     

Morphology and properties of polymer/organoclay nanocomposites based on poly(ethylene terephthalate) and sulfopolyester blends

Poly(ethylene terephthalate) (PET) nanocomposite films containing two different organoclays, Cloisite 30B^® (C30B) and Nanomer I.28E^® (N28E), were prepared by melt blending. In order to increase the gallery spacing of the clay particles, a sulfopolyester (PET ionomer or PETi) was added to the nanocomposites via a master‐batch approach. The morphological, thermal and gas barrier characteristics of the nanocomposite films were studied using several characterization techniques such as scanning electron microscopy, transmission electron microscopy, X‐ray diffraction, differential scanning calorimetry, dynamic mechanical analysis, rheometry and oxygen permeability. PET and PETi were found to form immiscible polymer blends and the nanoparticles were preferentially located in the PETi dispersed phase. A better dispersion of clay was obtained for nanocomposites containing N28E with PETi. On the contrary, for nanocomposites containing C30B and PETi, the number of tactoids increased and the clay distribution and dispersion became worse than for C30B alone. Overall, the best properties were obtained for the PET/C30B nanocomposite without PETi. Higher crystallinity was found for all nanocomposite films in comparison to that of neat PET. © 2012 Society of Chemical Industry