EVOH/clay nanocomposites produced by melt processing

Ethylene‐vinyl alcohol copolymer(EVOH)/clay nanocomposites were prepared via a dynamic melt‐intercalation process. The phase morphology and the crystallization behavior of the nanocomposites were investigated, using DSC, DMTA, XRD and SEM. It was found that the treated clay content and dynamic processing time affect the viscosity of the EVOH/clay mixtures: higher clay contents and longer mixing times result in higher torque/viscosity levels. This is due to the increased interaction of the molten polar matrix (EVOH) with the treated organosilicate surface. Under the dynamic high shearing forces, the polymer penetrates the clay agglomerates/aggregates, intercalates within the organoclay galleries, and finally causes delaniination. Thermal analysis of the EVOH/clay nanocomposites showed that the melting temperature, crystallization temperature and heat of fusion of the EVOH matrix, sharply decrease with increasing both, the clay content and processing time. The intercalation level was characterized by X‐ray diffraction (XRD), which verified an increased gallery height. The DMTA spectra showed that longer processing times resulted in higher damping (E″ intensity) levels of the EVOH/clay composites, indicating higher fractions of the EVOH amorphous phase. However, no Tg changes were seen in spite of the high polymer/treated clay interaction levels, which may be attributed to a plasticizing effect of the low molecular weight organic cations.     

Assessing organo‐clay dispersion in polymer nanocomposites

Organo‐clay polymer nanocomposites offer improved material properties at very low filler loadings making them of immediate interest for application in body panels, claddings, and instrument panels. This improvement in properties requires that the organo‐clay be well dispersed if not completely exfoliated. Conventionally, the dispersion and exfoliation of the organo‐clay is evaluated using transmission electron microscopy (TEM) and X‐ray diffraction (XRD). Although both TEM and XRD data were found to correlate with flexural modulus of thermoplastic olefin nanocomposite materials, only TEM proved successful in quantifying the dispersion of the organo‐clay in all nanocomposite materials (exfoliated, tactoid, or agglomerated tactoid). XRD was found to be capable of detecting exfoliation and intercalation but is limited because of clay dilution, preferred orientation, mixed‐layering, and other peak broadening factors. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1110–1117, 2004     

Solvent‐assisted extrusion of polypropylene/clay nanocomposites

Polypropylene (PP) nanocomposites were prepared by a melting‐compounding process with a montmorillonite (MMT) suspension. In this process, an organically modified MMT was swollen in a polar solvent and blended with molten PP in an extruder; this was followed by solvent removal. The effect of a coswelling agent was also evaluated. The nanocomposites were characterized with X‐ray diffraction, transmission electron microscopy, differential scanning calorimetry, and scanning electron microscopy. In addition, the mechanical properties of the materials were studied. The nanocomposites prepared with the clay suspension presented a remarkable increase in the impact strength with the maintenance of their flexural modulus. The mechanical properties of the nanocomposites were found to be related to the interaction between PP and the clay. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Properties of organo‐clay/natural rubber nanocomposites: Effects of organophilic modifiers

The effect of various modifiers on the structure and properties of clay/natural rubber nanocomposites are investigated with the aim to evaluate the effect of size and structure of the modifier. Nanocomposites are prepared by melt intercalation method. Mechanical properties of the cured rubber containing nanoclay are compared with the reference compound without the filler. No improvement of mechanical properties is observed for small organic cations; however, stress and strain at break of clay/rubber nanocomposites increase with rising number of octyl chains in the interlayer spaces of organo‐clays. Concerning organo‐cations with the same number of carbon atoms, more effective are the modifiers with several shorter carbon chains compared to those with one long chain. The composites exhibit hybrid structure of nanocomposite and microcomposite as revealed by X‐ray powder diffraction (XRD), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The details of the structure are supported by DMTA and hysteresis measurements. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

The effect of maleated compatibilizers on the structure and properties of EVOH/clay nanocomposites

The effect of compatibilizers on the blending torque, crystallization behavior, intercalation level, thermal stability and morphology of EVOH/treated clay 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 as compatibilizers of EVOH with clay, in various concentrations (1, 5 and 10 wt%). The blends were processed using Brabender Plastograph and characterized by XRD, SEM, DSC, DMTA and TGA. X‐ray diffraction shows advanced intercalation within the galleries when the compatibilizers were added. Unique results were obtained for the EVOH/clay/compatibilizer systems, owing to a high level of interaction developed in these systems, which plays a major role. Thermal analysis showed that with increasing compatibilizer content, lower crystallinity levels result, until at a certain content no crystallization has taken place. Significantly higher viscosity levels were obtained for the EVOH/clay blends compared to the neat polymer, as seen by a dramatic torque increase when processed in the Brabender machine. The DMTA spectra showed lower T_g values for the compatibilized nanocomposites compared to the neat EVOH and the uncompatibilized composites. Storage modulus was higher compared to the uncompatibilized EVOH/clay blend when EVA‐g‐MA compatibilizer was added (at all concentrations), and only at low contents of LLDPE‐g‐MA. TGA results show significant improvement of the blends thermal stability compared to the neat EVOH, and to the uncompatibilized blend, indicating an advanced intercalation.     

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     

Effect of kind and content of organo‐modified clay on properties of PET nanocomposites

In this work we report the properties of nanocomposite based on PET with two different samples of organically modified montmorillonites. In particular, we studied the effect of the filler concentration on morphology, rheology, and mechanical performance, focusing our attention on the effect of the degradation phenomena of the clay modifiers. The results indicate that at low clay level the morphology achieved is mainly intercalated. On increasing the filler level, coalescence and/or bad defragmentation phenomena induce a coarser morphology, as confirmed by XRD, SEM, and TEM observations. When a more polar organic modifier is used to modify the clay, the particle adhesion and distribution is slightly better. Conversely, at the processing temperatures adopted, this organic modifier induces a strong degradation of PET, as confirmed by melt rheology and intrinsic viscosity measurements. DSC indicates, in addition, a slight increase of crystallinity likely due to the decreased molecular weight. As regards the mechanical properties, Young's modulus is not significantly changed unless high amounts of clay (10%) are used while the elongation at break drops even at the lowest clay content. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Role of silane crosslinking on the properties of melt blended metallocene polyethylene‐g‐silane/clay nanocomposites at various clay contents

A study to investigate matrix properties and their interaction with loaded nanoclay was designed under controlled clay dispersion. Metallocene polyethylene grafted vinyltriethoxy silane (mPE‐g‐silane) was served as the matrix, with or without silane crosslinking (grafting and post crosslinking with catalyst versus only grafting without catalyst), to assess the strength of commercial organoclay (20A)‐filled nanocomposites prepared via a melt mixing. According to X‐ray diffraction and transmission electron microscopy analyses, all nanocomposites achieved similar dispersion degrees at specific clay contents mainly due to the silane interaction with the dispersed clay via hydrogen bonding and/or chemical bonding. Chemical bonding of grafted silane with clay was inferred based on the slightly higher crosslinking degree with increasing clay content for crosslinked cases. For uncrosslinked cases, the crosslinking degree was virtually zero regardless of clay content. The dynamic mechanical properties revealed enhanced interaction between mPE‐g‐silane and clay with increasing clay content based on the increased glass transition temperatures. Young's modulus of nanocomposites with crosslinked cases showed higher values in comparison with uncrosslinked cases at a specific clay content, indicating the significance of matrix crosslinking effect and the effective interfacial interaction between silane and clay especially at higher clay content. To the authors' best knowledge, this is the first study which generally maintains similar clay dispersions through the effect of uncrosslinking (only grafting) and crosslinking (grafting and post crosslinking), and then probes the effect of matrix properties and interfacial interactions at the large deformation state (tensile test) and small deformation state (cutting test). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Studies on nylon‐6/EVOH/clay ternary composites

Nylon‐6 (Ny‐6)/EVOH blends are interesting host multiphase systems for incorporation of low clay contents. The Ny‐6/EVOH blend is a unique system, which tends to chemically react during melt‐mixing, affecting thermal, morphological and mechanical properties of the ternary systems containing clay. The addition of clay seems to interrupt the chemical reaction between the host polymers at certain compositions, leading to lower blending torque levels when clay is added. A competition between Ny‐6 and EVOH regarding the intercalation process takes place. Ny‐6 seems to lead to exfoliated structure, whereas EVOH forms intercalated structure, as revealed from XRD and TEM analyses, owing to thermodynamic considerations and preferential localization of the clay in Ny‐6. Hence, the ternary systems have combined intercalated and delaminated morphology or complete exfoliated morphology depending on blend composition and clay content. Selective extraction experiments (gel content) indicate the formation of chemical reaction between the Ny‐6 and EVOH, and give an indirect indication of the polymer content residing in the galleries. The thermal properties of the polymers were found to be affected by the occurrence of chemical reaction, the level of intercalation and exfoliation and plasticizing effect of the low molecular weight onium ions treating the clay. Of special interest is the increased storage modulus attained upon the addition of only 1.5 wt% clay. POLYM. COMPOS. 27:15–23, 2006. © 2005 Society of Plastics Engineers     

Starch‐based nanocomposites by reactive extrusion processing

Nanocomposites with unique material properties have been prepared from synthetic plastics and nanosilicates (nanoclay) until now, but not from biopolymers such as starch. The primary challenge in making biopolymeric nanocomposites is to achieve strong adhesion between nanoclay and polymer matrix. For the first time nanocomposites with superior properties have been successfully made from starch‐polycaprolactone (PCL) blends in the presence of montmorillonite (MMT) nanoclay. Reactive extrusion results showed that addition of a modified nanoclay at 3 % wt level increased elongation almost fourfold over that of pristine starch–PCL blends. X‐ray diffractions results showed dispersion of clay in the polymer matrix. The nanocomposites have better solvent‐resistance properties because of resistance to diffusion offered by clay platelets in the polymer matrix. Copyright © 2004 Society of Chemical Industry     

Functional copolymer/organo‐MMT nanoarchitectures. II. Dynamic mechanical behavior of poly(MA‐co‐BMA)s‐organo‐MMT clay nanocomposites

Functional copolymer/organo‐silicate [N,N′‐dimethyldodecyl ammonium cation surface modified montmorillonite (MMT)] layered nanocomposites have been synthesized by interlamellar complex‐radical copolymerization of preintercalated maleic anhydride (MA)/ organo‐MMT complex as a ‘nano‐reactor’ with n‐butyl methacrylate (BMA) as an internal plasticization comonomer in the presence of radical initiator. Synthesized copolymers and their nanocomposites were investigated by dynamic mechanic analysis, X‐ray diffraction, SEM, and TEM methods. It was found that nanocomposite dynamic mechanical properties strongly depend on the force of interfacial MA … organo‐MMT complex formation and the amount of flexible n‐butyl ester linkages. An increase in both of these parameters leads to enhanced intercalation and exfoliation in situ processes of copolymer chains and the formation of hybrid nanocomposites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Ultrasound‐aided extrusion process for preparation of polypropylene–clay nanocomposites

Two methods for the fabrication of polypropylene/clay nanocomposites using a continuous ultrasound assisted process are compared. In the first approach, a two‐stage process was implemented. The nanocomposites were prepared by using a corotating twin‐screw extruder followed by a single‐screw extruder equipped with an ultrasonic die attachment. In the second method, a single‐stage process was used. The nanocomposites were compounded by using a single‐screw extruder with mixing elements and an ultrasonic die attachment. Two regimens of feeding were realized, namely, starved and flood feeding. The gap size in the ultrasonic treatment zone was varied. Die pressure and power consumption were measured. Similarities and differences of nanocomposites obtained by these two methods are discussed on the basis of their rheological and mechanical properties and their structural characteristics. J. VINYL ADDIT. TECHNOL., 13:40–45, 2007. © 2007 Society of Plastics Engineers.     

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.     

Liquid‐crystalline copolyester/clay nanocomposites

A series of novel polymer–clay nanocomposites, that is, liquid‐crystalline copolyester/montmorillonite (MMT) nanocomposites, were synthesized by the intercalation polycondensation of terephthalic acid, p‐acetoxy benzoic acid, and 1,2‐diacetoxy benzene in the presence of different organically modified montmorillonites (OMt's). The OMt's were prepared by the ion exchange of MMT with octadecylamine hydrochloride, p‐aminobenzoic acid hydrochloride, or lysine hydrochloride. X‐ray diffraction and transmission electron microscopy studies indicated that the inorganic cations in the MMT interlayers were already exchanged by organic onium ions and that the OMt intercalated with p‐aminobenzoic acid or lysine was good for obtaining more delaminated clay nanocomposites. The glass‐transition temperature and modulus of the nanocomposites increased compared with those of the pure polymer, whereas the isotropic temperature decreased. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3155–3159, 2003     

Twin‐screw extrusion of polypropylene‐clay nanocomposites: Influence of masterbatch processing,screw rotation mode,and sequence

This work seeks to optimize the twin‐screw compounding of polymer‐clay nanocomposites (PCNs). Proportional amounts (3:1) of maleic anhydride functionalized polypropylene compatibilizer (PP‐g‐MA) and organically modified montmorillonite clay at clay loadings of 1, 3, and 5 wt% were melt‐blended with a polypropylene (PP) homopolymer using a Leistritz Micro 27 twin‐screw extruder. Three melt‐blending approaches were pursued: (1) a masterbatch of PP‐g‐MA and organoclay were blended in one pass followed by dilution with the PP resin in a second pass; (2) all three components were processed in a single pass; and (3) uncompatibilized PP and organoclay were processed twice. Both corotation and counterrotation operation were utilized to investigate the effect of screw rotation mode and sequence on organoclay exfoliation and dispersion. X‐ray diffraction was employed to characterize basal spacing; however, since rheology is known to be highly sensitive to mesoscale organoclay structure, it is an ideal tool to examine the relationship between the various processing methods and exfoliation and dispersion. A holistic analysis of rheological data demonstrates the efficacy of the masterbatch approach, particularly when compatibilizer and organoclay are blended in counterrotating mode followed by dilution with matrix polymer in corotating mode. POLYM. ENG. SCI., 47:898–911, 2007. © 2007 Society of Plastics Engineers     

Effect of the type of clay organo‐modifier on the morphology,thermal/mechanical/impact/barrier properties and biodegradation in soil of polycaprolactone/clay nanocomposites

The effect of addition of unmodified (CNa+) and modified (C30B and C20A) montmorillonites on the performance of polycaprolactone (PCL) based nanocomposites prepared by melt intercalation was studied. The study covers morphological and thermal aspects, mechanical and barrier properties and also biodegradability, which are important for packaging applications. Particular effort was made to find the main characteristics of the clays responsible for the final clay dispersion degree inside the nanocomposite. The most hydrophobic reinforcement (demonstrated by water adsorption tests) also showed the strongest thermal stability (shown by thermogravimetrical analysis) and the larger basal spacing (calculated by X‐ray diffractometry (XRD)), which were the main characteristics that led to the best clay dispersion degree inside the PCL matrix (demonstrated by XRD and Transmission Electron Microscopy (TEM)). The findings demonstrate that a biodegradable polymer/clay nanocomposite with enhanced mechanical, impact, and barrier properties was obtained. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Nanocomposite systems based on unsaturated polyester and organo‐clay

Unsaturated polyester (UP) systems give rise to numerous possible approaches in synthesizing nanocomposites. A simultaneous mixing method was used to synthesize UP‐resin/organo‐clay nanocomposites. The effects of various mixing processes, using several organically‐modified clay types, were investigated. The incorporation of these organo‐clays resulted in an intercalated structure, the extent of which depended mainly on the type of the clay organic treatment. Organo‐clays that exhibited the highest intercalation levels were further studied using a sequential mixing method. The UP‐alkyd (without styrene) was mixed with different organo‐clays. Processing parameters such as mixing modes, applied shearing levels, clay contents, and mixing‐temperatures were investigated. Prolonged high shear levels promoted the intercalation and exfoliation of the silicate layers, resulting in a better dispersion of clay particles. The high shear levels effects were achieved by vigorous mechanical mixing and were intensified by using large amounts of clay and optimized matrix viscosity. Rheological studies of the nanocomposites were found complementary and in correlation with morphological and thermal characterization. This methodological approach provides a basis for understanding the structuring processes involving the formation of the UP/clay nanocomposites and establishing materials‐processing‐structure interrelations. Polym. Eng. Sci. 45:174–186, 2005. © 2005 Society of Plastics Engineers.     

Preparation and properties of novel natural rubber/organo‐vermiculite nanocomposites

Polymer‐layered silicate nanocomposites have an attracting increasing attention over recent years because of their unique mechanical, thermal, and other properties. In this article, a new kind of natural rubber (NR)/organo‐vermiculite (OVMT) nanocomposites were investigated. The vermiculite (VMT) was intercalated by cetyltrimethylammonium bromide with ball mill method. The intercalation led to an increase of the d₍₀₀₁₎ of VMT from 1.46 nm to 4.51 nm. NR/OVMT nanocomposites were prepared via a melt process in a HAAKE mixer and were analyzed by X‐ray diffraction and scanning electron microscope observations. The mechanical properties of the vulcanized nanocomposites were tested. It was found that the tensile strength and the elongation at the breaking point of the NR/OVMT nanocomposites loading 15 phr of the OVMT reached 28.4 MPa and 623.2%, respectively. The 300% modulus, tear strength, and hardness (Shore A) of the nanocomposites increased with the increase of the OVMT loading. The thermal properties of the nanocomposites were investigated by dynamic mechanical analysis, and the results showed that the storage modulus and the glass transition temperature of the nanocomposites were increased. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Morphology and properties of SAN‐clay nanocomposites prepared principally by water‐assisted extrusion

An efficient extrusion process involving the injection of water while processing was used to prepare poly (styrene‐co‐acrylonitrile) (SAN)/clay nanocomposites with a high degree of nanoclay delamination. The usefulness of water‐assisted extrusion is highlighted here, in comparison with classical extrusion and roll mill processes. Cloisite® 30B (C30B), a montmorillonite clay organomodified with alkylammonium cations bearing 2‐hydroxyethyl chains, and pristine montmorillonite were melt blended with SAN (25 wt% AN) in a semi‐industrial scale extruder specially designed to allow water injection. XRD analysis, visual and TEM observations were used to evaluate the quality of clay dispersion. The relationship between the nanocomposite morphology and its mechanical and thermal properties was then investigated. The superiority of the SAN/C30B nanocomposite extruded with water has been evidenced by cone calorimetry tests and thermogravimetric measurements (TGA). These analyses showed a substantial improvement of the fire behavior and the thermal properties, while a 20% increase of the Young modulus was recorded. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Mechanical properties of polypropylene/clay nanocomposites: Effect of clay content,polymer/clay compatibility,and processing conditions

In this work, polypropylene/clay nanocomposites with 0.5, 1, 3, and 5 wt % of montmorillonite (MMT) (unmodified clay) were prepared by intensive mixing at 50 rpm and 10 min of mixing. For the highest clay content (5 wt %), the initial materials or the processing conditions were changed to study their independent effect. On one hand, 10 wt % of PP‐graft‐MA (PP‐g‐MA) was incorporated or MMT was replaced by organomodified clays (C10A and C30B). On the other side, for the initial system, the speed of rotation (100 and 150 rpm) and the mixing time (5 and 15 min) were altered. In all cases, the state of the clay inside the matrix (DRX), the degree of dispersion in the micro (SEM) and nano (TEM) scales, and the rheological and mechanical properties were analyzed. It was found that the stiffness increased with clay content, whereas tensile and impact strength did not significantly change. Although intercalated structures were observed in the composites with unmodified clay, in the composites with modified clay or PP‐g‐MA, improved dispersion of clay in PP was found. The mechanical properties increased accordingly. The degree of dispersion of the filler in the matrix appeared to be unaffected by the changes in the processing conditions introduced. Finally, the elastic modulus was modeled by using an effective filler‐parameter model based on Halpin–Tsai equations, which also allowed estimating the relative degree of dispersion. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009