Influence of the compatibilizer polarity and molar mass on the morphology and the gas barrier properties of polyethylene/clay nanocomposites

In this study, different modified polyethylenes with different molar masses and different modification rates were examined as compatibilizers to prepare high density polyethylene/organoclay nanocomposites. Nanocomposites having 5 wt % organo-modified clay and 20 wt % interfacial agent were prepared by melt blending. The effect of compatibilizer molar mass and polarity was investigated on the clay dispersion and on the gas barrier properties. It was observed that the amount of large and dense fillers aggregates was considerably reduced by introduction of an interfacial agent. The nanocomposite final morphology was governed by a diffusion/shear mechanism. A high degree of clay delamination was obtained with the high molar mass compatibilizers, whereas highly swollen clay aggregates resulted from the incorporation of the low molar mass interfacial agents. In the investigated nanocomposites series, the barrier properties could not be directly related to the clay dispersion state but resulted also from the matrix/clay interfacial interactions. A gas transport mechanism based on these both parameters was proposed to explain the barrier properties evolution in these low polar nanocomposites series. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2593–2604, 2008     

Shear‐induced clay dispersion in HDPE/PEgMA/organoclay composites as studied via real‐time rheological method

In current study, a real‐time rheological method was used to investigate the intercalation and exfoliation process of clay in high‐density polyethylene/organoclay (HDPE/OMMT) nanocomposites using maleic anhydride grafted polyethylene (PEgMA) as compatibilizer. To do this, a steady shear was applied to the original nonintercalated or slightly intercalated composites prepared via simple mixing. The moduli of the composites were recorded as a function of time. The effect of matrix molecular weight and the content of compatibilizer on the modulus were studied. The role of the compatibilizer is to enhance the interaction between OMMT and polymer matrix, which facilitates the dispersion, intercalation, and exfoliation of OMMT. The matrix molecular weight determines the melt viscosity and affects the shear stress applied to OMMT platelets. Based on the experimental results, different exfoliation processes of OMMT in composites with different matrix molecular weight were demonstrated. The slippage of OMMT layers is suggested in low‐molecular weight matrix, whereas a gradual intercalation process under shear is suggested in high‐molecular weight matrix. Current study demonstrates that real‐time rheological measurement is an effective way to investigate the dispersion, intercalation, and exfoliation of OMMT as well as the structural change of the matrix. Moreover, it also provides a deep understanding for the role of polymer matrix and compatibilizer in the clay intercalation process. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 302–312, 2010     

Atomic force microscopy study on blend morphology and clay dispersion in polyamide‐6/polypropylene/organoclay systems

The phase structure and clay dispersion in polyamide‐6(PA6)/polypropylene(PP)/organoclay (70/30/4) systems with and without an additional 5 parts of maleated polypropylene (MAH‐g‐PP) as a compatibilizer were studied with atomic force microscopy (AFM). AFM scans were taken from the polished surface of specimens that were chemically and physically etched with formic acid and argon ion bombardment, respectively. The latter technique proved to be very sensitive to the blend morphology, as PP was far more resistant to ion bombardment than PA6. In the absence of the MAH‐g‐PP compatibilizer, the organoclay is located in the PA6 phase; this finding is in line with transmission electron microscopic results. Further, the PP is coarsely dispersed in PA6 and the adhesion between PA6 and PP is poor. The addition of MAH‐g‐PP resulted in a markedly finer PP dispersion and good interfacial bonding between PA6 and PP. In this blend, the organoclay was likely dispersed in the PA6‐grafted PP phase. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43:1198–1204, 2005     

Gas barrier properties of poly(ε‐caprolactone)/clay nanocomposites: Influence of the morphology and polymer/clay interactions

Poly(ε‐caprolactone)/montmorillonite nanocomposites were prepared maintaining a constant inorganic content with three means: melt blending of poly(ε‐caprolactone) with natural or organomodified clays, in situ polymerization of ε‐caprolactone in the presence of organomodified clays, and initiation of ε‐caprolactone polymerization from the silicate layer with appropriate organomodified montmorillonites and activator. In this last case, the polymer chains were grafted to the silicate layers and it was possible to tune up the grafting density. The presence of clays did not modify the polymer crystallinity. It was shown that the in situ polymerization process from the clay surface improved the clay dispersion. The gas barrier properties of the different composite systems were discussed both as a function of the clay dispersion and of the matrix/clay interactions. The highest barrier properties were obtained for an exfoliated morphology and the highest grafting density. Similar evolution of the permeability and the diffusion coefficients was observed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 205–214, 2005     

Assessing crystalline lamellae orientation impact on the properties of semi‐crystalline polymer‐clay nanocomposites

Semi‐crystalline polymer‐clay nanocomposite properties are often considered only by their clay dispersion state. The purpose of this work is to highlight texture effects on semi crystalline polymer‐clay properties. Maleic anhydride‐grafted polyethylene nanocomposites with two different processing techniques (Blown Extrusion and Compression) were studied. The processing was shown to induce different crystalline lamellae orientation in the films but with no significant changes in the crystalline lamellae long period, degree of crystallinity, clay particle orientation morphology and dispersion. The impact of these specific textures on the nanocomposites barrier and tensile properties were reported. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1966–1975, 2008     

Synthesis and characterization of polyethylene/clay–silica nanocomposites: A montmorillonite/silica‐hybrid‐supported catalyst and in situ polymerization

A novel approach to the preparation of polyethylene (PE) nanocomposites, with montmorillonite/silica hybrid (MT‐Si) supported catalyst, was developed. MT‐Si was prepared by depositing silica nanoparticles between galleries of the MT. A common zirconocene catalyst [bis(cyclopentadienyl)zirconium dichloride/methylaluminoxane] was fixed on the MT‐Si surface by a simple method. After ethylene polymerization, two classes of nanofillers (clay layers and silica nanoparticles) were dispersed concurrently in the PE matrix and PE/clay–silica nanocomposites were obtained. Exfoliation of the clay layers and dispersion of the silica nanoparticles were examined with transmission electron microscopy. Physical properties of the nanocomposites were characterized by tensile tests, dynamic mechanical analysis, and DSC. The nanocomposites with a low nanofiller loading (<10 wt %) exhibited good mechanical properties. The nanocomposite powder produced with the supported catalyst had a granular morphology and a high bulk density, typical of a heterogeneous catalyst system. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 941–949, 2004     

Polypropylene/organoclay nanocomposites compatibilized with hydroxyl‐functional polypropylenes

The properties of polypropylene composites can be tailored through the use of nanoclay fillers. The effectiveness of a metallocene‐catalyzed hydroxyl‐functional polypropylene in the compatibilization of polypropylene layered nanosilicate composites was studied, and the results were compared with those for a commercial maleic anhydride functionalized polypropylene. Polypropylene/organoclay nanocomposites were prepared by melt blending, and two polypropylene/compatibilizer/organoclay ratios, 90/5/5 and 70/20/10, were characterized. The organomodification of the clay was carried out with octadecylamine and N‐methylundecenylamine. The structure of the layered silicate was studied by transmission electron microscopy, wide‐angle X‐ray scattering, and small‐angle X‐ray scattering. The fracture surfaces of the composites and thus the efficiency of the compatibilizers to penetrate the galleries of the organoclays were characterized by scanning electron microscopy, and the melt viscosity was studied by stress‐controlled rotational rheometry. The nanostructure was observed with both alkyl amines used for intercalation. The fillers facilitated the processability of all the composites, consisting of equal amounts of compatibilizer and organoclay filler and, in some of the composites, containing twice as much compatibilizer as organoclay filler. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1892–1903, 2005     

Morphology and properties of polypropylene/ethylene–octene copolymer/clay nanocomposites with double compatibilizers

The influence of nanoclay on the morphology and properties of the polypropylene (PP)/ethylene–octene block copolymer (EOC) blend with double compatibilizers of maleated PP (PP‐g‐MA) and maleated EOC (EOC‐g‐MA) was investigated and compared with the nanocomposites containing either PP‐g‐MA or EOC‐g‐MA as a compatibilizer. X‐ray diffraction, transmission electron microscopy, and scanning electron microscopy were utilized for morphological characterization in conjunction with dynamic mechanical thermal analysis, mechanical testing, and rheological evaluation of these nanocomposites. The results suggested that in the nanocomposite including both compatibilizers of PP‐g‐MA and EOC‐g‐MA, clay was dispersed as a mixed structure of intercalation and exfoliation in both phases of the polymer blend. Comparing the mechanical properties of the studied nanocomposite with nanocomposites of PP/EOC/PP‐g‐MA/clay and PP/EOC/EOC‐g‐MA/clay also indicated that the nanocomposite containing mixed compatibilizers displayed higher tensile modulus, tensile strength, and complex viscosity because of the better dispersion of clay in both phases. The results also confirmed the increased structural stability and reduced dispersed phase size of PP/EOC/PP‐g‐MA/EOC‐g‐MA blend in the presence of clay that proposed the compatibilization role of clay in this nanocomposite. Copyright © 2014 John Wiley & Sons, Ltd.     

Thermal properties and microhardness of HDPE/clay nanocomposites compatibilized by different functionalized polyethylenes

The calorimetric characteristics, the flammability, the thermal stability and the microhardness of polyethylene high density/clay nanocomposites (HDPE/clay) have been studied by differential scanning calorimetry, thermogravimetry, determination of limiting oxygen index and microhardness tests. The nanocomposites have been compatibilized by ethylene–acrylic acid copolymer (EAA), acrylic acid grafted HDPE (HDAA) and maleic anhydride grafted HDPE (HDMA). The clay was montmorillonite Cloisite 15A. The influence of the presence and the type of the compatibilizers on the properties of the nanocomposites has been evaluated. The results have shown that the thermal stability, the reduction of the flammability and the microhardness of HDPE/clay nanocomposites, compatibilized by HDAA and HDMA are higher than those for nanocomposite compatibilized by EAA. Moreover, the presence and the type of compatibilizer have negligible effect on the characteristics of the HDPE phase transitions. These results have been interpreted by the better clay dispersion and higher level of clay exfoliation in the presence of compatibilizers HDAA and HDMA, than those in the presence of EAA compatibilizer.     

Combined effects of clay modifications and compatibilizers on the formation and physical properties of melt‐mixed polypropylene/clay nanocomposites

The melt mixing technique was used to prepare various polypropylene (PP)‐based (nano)composites. Two commercial organoclays (denoted 20A and 30B) served as the fillers for the PP matrix, and two different maleated (so‐called) compatibilizers (denoted PP‐MA and SMA) were employed as the third component. The results from X‐ray diffraction (XRD) and transmission electron microscope (TEM) experiments revealed that 190 °C was an adequate temperature for preparing the nanocomposites. Nanocomposites were achieved only if specific pairs of organoclay and compatibilizer were simultaneously incorporated in the PP matrix. For example, PP/20A(5 wt %)/PP‐MA(10 wt %) and PP/30B(5 wt %)/SMA(5 wt %) composites exhibited nanoscaled dispersion of 20A or 30B in the PP matrix. Differential scanning calorimetry (DSC) results indicated that the organoclays served as nucleation agents for the PP matrix. Generally, their nucleation effectiveness increased with the addition of compatibilizers. The thermal stability enhancement of PP after adding 20A was confirmed with thermogravimetric analysis (TGA). The enhancement became more evident as a suitable compatibilizer was further added. However, for the 30B‐included composites, thermal stability enhancement was not evident. The dynamic mechanical properties (i.e., storage modulus and loss modulus) of PP increased as the nanocomposites were formed; the properties increment corresponded to the organoclay dispersion status in the matrix. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4139–4150, 2004     

Preparation of the polymer–clay nanocomposites in exfoliated state by interface stabilization

To suppress the repulsive interfacial energy between hydrophilic clay and a hydrophobic polymer matrix for polymer–clay nanocomposites, a third component of amphiphilic nature such as poly(?‐caprolactone) (PCL) was introduced into the styrene–acrylonitrile copolymers (SAN)/Na‐montmorillonite system. Once ?‐caprolactone was polymerized in the presence of Na‐montmorillonite, the successful ring‐opening polymerization of ?‐caprolactone and the well‐developed exfoliated structure of PCL/Na‐montmorillonite mixture were confirmed. Thereafter, SAN was melt‐mixed with PCL/Na‐montmorillonite nanocomposite, and the SAN matrix and PCL fraction were completely miscible to form a homogeneous mixture with retention of the exfoliated state of Na‐montmorillonite, exhibiting that PCL effectively stabilizes the repulsive polymer–clay interface and contributes to the improvement of the mechanical properties of nanocomposites. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 246–252, 2004     

Phase behavior of modified montmorillonite– poly(ϵ‐caprolactone) nanocomposites

The thermal behavior and overall isothermal crystallization kinetics of a series of organophilic modified montmorillonite–poly(?‐caprolactone) nanocomposites were investigated. In general, the thermal behavior was influenced more by the type of dispersion than by the clay content. For nanocomposites in which silicate platelets were predominantly dispersed in the polymer matrix to give exfoliated structures, the thermal properties were improved with respect to those of neat poly(?‐caprolactone), whereas in those cases in which simply intercalated structures were attained, the thermal properties regularly decayed as the clay content increased. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1321–1332, 2004     

Compatibilization of polyethylene/polyamide 6 blends with functionalized polyethylenes prepared with metallocene catalyst

Metallocene catalyst technology was utilized to prepare functionalized polyethylenes, which were used as compatibilizers in polyethylene/polyamide 6 (40/60) blends. Polymerization of ethylene with 10-undecen-1-ol, 10-undecenoic acid, or N-methyl-10-undecenylamine resulted in ethylene copolymers with a small amount (0.2–1.2 mol %) of functionalized side chains. The blends were prepared in a twin-screw midiextruder, and injection molded with a mini-injection molding machine. The effect of the new compatibilizers on morphology and mechanical and thermal properties was studied. Toughness as well as stiffness and strength increased significantly with an addition of 10 wt % compatibilizer. Morphology became much more uniform, and crystallization and melting behavior changed. The Molau test with FTIR analysis was used to determine that the desired reactions between the compatibilizer and polyamide had actually taken place. The results showed functionalized polyethylenes prepared with metallocene catalysts to act as effective compatibilizers in polyethylene/polyamide 6 blends. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3099–3108, 1999     

Preparation of bimodal HDPEs with metallocene on Cr‐montmorillonite support

Previously described Cr‐montmorillonite (Cr‐MMT) was found to retain reactivity in the ethylene polymerization reaction regardless of which alkyl‐metal was used for workup in the preparation process, as long as alkylaluminium was used as a cocatalyst in the actual polymerization reaction. Introduction of hydrogen pressure was found to regulate the polymerization to give the product polymer with a narrower weight distribution, albeit with a somewhat smaller average molecular weight. Supporting metallocene onto Cr‐MMT produced a binuclear catalyst system which gave rise to bimodal polyethylene (PE). Polymer composition of the produced high density polyethylenes (HDPEs) could be controlled by changing factors such as the polymerization conditions and the identity of the metallocene compounds. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3722–3728, 2010     

“Structure and mechanical properties of blown films of ionomer-compatibilized LDPE nanocomposites”

Blown films based on low density polyethylene (LDPE) organoclay nanocomposites (NCs) were obtained by melt extrusion followed by film blowing, using a zinc ionomer of poly(ethylene-co-methacrylic acid) (Pema-Zn) as a compatibilizer. The parameters studied were the compatibilizer and the montmorillonite (MMT) contents that ranged from 0 to 20% and from 0 to 5%, respectively. The presence of clay hindered Pema-Zn crystallization indicating the existence of interaction between the Pema-Zn and the clay. Analysis of the nanostructure showed that the MMT was found inside microscopic domains of Pema-Zn distributed throughout the LDPE matrix. The addition of Pema-Zn improved the dispersion of the clay in LDPE films resulting in synergistic improvements in the mechanical properties. These improvements occur both in the machine and transverse directions. Thus, the presence of Pema-Zn is a determining factor in biaxiality and can clearly be attributed to the bidimensional laminar structure of clays such as MMT.     

Thermal decomposition of amide and imide derivatives of maleated polyethylene

The thermal decomposition behavior of six derivatives of maleated polyethylene was investigated by high‐resolution pyrolysis gas chromatography–mass spectrometry. The results revealed that substituents attached to maleated polyethylene as amides formed from secondary amines were significantly less stable than imides formed from primary amines. Morpholine amide and N‐methylaniline amide derivatives of maleated polyethylene underwent significant decomposition at 160 °C and substantial decomposition at 200 °C. In contrast, the imide derivatives of maleated polyethylene were stable for long periods of time at elevated temperatures. Following 2 min of heating, the first traces of decomposition were detected at 200 °C for the 2‐aminoanthrancene imide derivative, at 255 °C for the 2‐phenethylamine imide, and at 280 °C for the 9‐aminomethylphenanthrene imide. With the exception of the 9‐aminomethylphenanthrene imide, all other derivatives decomposed to form the corresponding amine as the single most significant volatile product. The most likely explanation for this result is that the polymer contained small amounts of succinamic acid that did not close to form the imide. We concluded that the imide was stable even to 315 °C and that the amine was lost from β‐carboxyamide groups present in the sample. In the 9‐aminomethylphenanthrene imide derivative, we observed no loss of amine. Instead, we observed an alternative fragmentation process yielding 9‐methyl phenanthrene. The dependence of the thermal stability of these various derivatives of maleated polyethylene has important implications for the design of reactive‐blending strategies for polyolefins with other functional polymers. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 730–740, 2000     

Structure–property relationships of polymer blend/clay nanocomposites: Compatibilized and noncompatibilized polystyrene/propylene/clay

Polymer blends represent an important class of materials in engineering applications. The incorporation of clay nanofiller may provide new opportunities for this type of materials to enhance their applications. This article reports on the effects of clay on the structure and properties of compatibilized and noncompatibilized polymer blends and presents a detailed process for quantitative analysis of the elastic moduli of polymer blend/clay nanocomposites, based on immiscible polystyrene/polypropylene (PS/PP) blends with or without maleated PP as the compatibilizer. The results show that in the noncompatibilized PS/PP/clay nanocomposite clay locates solely in the PS phase, whereas in the compatibilized nanocomposite clay disperses in both phases. The addition of clay to both polymer blends reduces the domain size significantly, modifies the crystallinity and improves the stiffness. The Mori–Tanaka and Christensen's models offer a reasonably good prediction of the elastic moduli of both types of nanocomposites. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Nanocomposites of polyurethane with various organoclays: Thermomechanical properties,morphology, and gas permeability*

The properties of polyurethane (PU) nanocomposites with three different organoclays were compared in terms of their thermal stabilities, mechanical properties, morphologies, and gas permeabilities. Hexadecylamine–montmorillonite, dodecyltrimethyl ammonium–montmorillonite, and Cloisite 25A were used as organoclays for making PU hybrid films. The properties were examined as a function of the organoclay content in a matrix polymer. Transmission electron microscopy photographs showed that most clay layers were dispersed homogeneously into the matrix polymer on the nanoscale, although some particles of clay were agglomerated. Moreover, the addition of only a small amount of organoclay was enough to improve the thermal stabilities and mechanical properties of PU hybrid films, whereas gas permeability was reduced. Even polymers with low organoclay contents (3–4 wt %) showed much higher strength and modulus values than pure PU. Gas permeability was reduced linearly with an increasing amount of organoclay in the PU matrix. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 670–677, 2002; DOI 10.1002/polb.10124     

Long‐lived layered silicates‐immobilized 2,6‐bis(imino)pyridyl iron (II) catalysts for hybrid polyethylene nanocomposites by in situ polymerization: Effect of aryl ligand and silicate modification

Heterogeneous‐layered silicate‐immobilized 2,6‐bis(imino)pyridyl iron (II) dichloride/MMAO catalysts, in which the active polymerization species are intercalated within sodium‐ and organomodified‐layered silicate galleries, were prepared for producing hybrid exfoliated polyethylene (PE) nanocomposites by means of in situ polymerization. The inorganic filler was first treated with modified‐methylaluminoxane (MMAO) to produce a supported cocatalyst: MMAO reacts with silicates replacing most of the organic surfactant, thus modifying the original crystallographic clay order. MMAO anchored to the nanoclay was able to activate polymerization iron complexes initiating the polymer growth directly from the filler lamellae interlayer. The polymerization mechanism taking place in between the montmorillonite lamellae separates the layers, thus promoting deagglomeration and effective clay dispersion. Transmission electron microscopy revealed that in situ polymerization by catalytically active iron complexes intercalated within the lower organomodified clay led to fine dispersion and high exfoliation extent. The intercalated clay catalysts displayed a longer polymerization life‐time and brought about ethylene polymerization more efficiently than analogous homogeneous systems. PEs having higher molecular masses were obtained. These benefits resulted to be dependent more on the filler nature than on the ligand environment around the iron metal center and the experimental synthetic route. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 548–564, 2009     

Polypeptide‐based nanocomposite: Structure and properties of poly(L‐lysine)/Na+‐montmorillonite

The feasibility of constructing polymer/clay nanocomposites with polypeptides as the matrix material is shown. Cationic poly‐L‐lysine · HBr (PLL) was reinforced by sodium montmorillonite clay. The PLL/clay nanocomposites were made via the solution‐intercalation film‐casting technique. X‐ray diffraction and transmission electron microscopy data indicated that montmorillonite layers intercalated with PLL chains coexist with exfoliated layers over a wide range of relative PLL/clay compositions. Differential scanning calorimetry suggests that the presence of clay suppresses crystal formation in PLL relative to the neat polypeptide and slightly decreases the PLL melting temperature. Despite lower crystallinity, dynamic mechanical analysis revealed a significant increase in the storage modulus of PLL with an increase in clay loading producing storage modulus magnitudes on par with traditional engineering thermoplastics. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2579–2586, 2002