Properties and morphology of nanocomposites based on styrenic polymers. Part I: Styrene-acrylonitrile copolymers

For polymer/organoclay nanocomposites formed by melt processing, interactions between the polymer, montmorillonite surface, and surfactant determine any thermodynamic driving force for dispersion of the clay in the polymer. Interactions between poly(styrene-co-acrylonitrile) (SAN) and a single organoclay were probed by varying the SAN copolymer composition. Sample preparation was accomplished by melt processing on a microcompounder followed by injection molding. The level of mechanical reinforcement was observed to increase with acrylonitrile content. Digital analyses of TEM photomicrographs of core samples suggest an optimum in the aspect ratio of the particles at ∼38 wt% acrylonitrile; montmorillonite particles are much longer and thicker for the PS-based composites indicting poor exfoliation compared to the SAN-based composites. The melt viscosity of the SAN copolymers used in this work increased with AN content; experiments showed that varying melt viscosity independent of AN content can account for some improvement in reinforcement.     

Preparation and properties of polysulfone–clay composite membranes

Porous membranes and dense films were prepared from polysulfone solutions in N‐methyl‐2‐pyrrolidone (NMP) containing different types and amounts of clay. Commercial clays supplied by Southern Clay, either unmodified (Cloisite Na) or organically modified (Cloisite 30B and Cloisite 93A), were used. The clay behavior in the organic solvent was dependent on the presence and type of the organic compatibilizer: Cloisite containing Na ions did not swell in NMP, whereas those with the organic compatibilizer swelled, though to a different degree. Electron microscopy observations were made to examine the clay dispersion in the membrane structure. At variance with Cloisite Na and Cloisite 93A formed microaggregates, Cloisite 30B yielded nanostructures composed of both single sheets and well‐ordered multilayer silicate clusters, which were characterized by an interlayer distance higher than that of the neat clay. The increase in the distance between the layers of Cloisite 30B was related to the formation of intercalated nanocomposites, whereas the presence of single sheets well distributed in the polymer matrix supported the occurrence of delaminated nanocomposites. The intercalation of the polymer into clay layers was confirmed with wide‐angle X‐ray diffractometry. The addition of Cloisite 30B to the casting solution influenced the phase‐separation process in the coagulation bath. Therefore, by the variation of the layered‐silicate concentration in the casting solution, membranes with different morphological structures and ultrafiltration properties were obtained. Cloisite 30B was also found to improve the wettability and mechanical properties of dense films. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3637–3644, 2007     

Effect of clay on the properties of poly(styrene‐co‐acrylonitrile)–clay nanocomposites

Clay‐dispersed poly(styrene‐co‐acrylonitrile) nanocomposites (PSAN) were synthesized by a free radical polymerization process. The montmorillonite (MMT) was modified by a cationic surfactant hexadecyltrimethylammonium chloride. The structures of PSAN were determined by wide‐angle X‐ray diffraction and FTIR spectroscopy. The dispersion of silicate layers in the polymer matrix was also revealed by transmission electron microscopy (TEM). It was confirmed that the clay was intercalated and exfoliated in the PSAN matrix. The increased thermal stability of PSAN with the addition of clay was observed by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The dielectric properties of PSAN were measured in the frequency range 100 Hz to 1 MHz at 35–70°C. It was found that the dielectric constant from the dipole orientation had been suppressed due to the intercalation of clay. The dielectric loss is strongly related to the residual sodium content of clay, which increases as the sodium content increases by the addition of clay. Copyright © 2004 Society of Chemical Industry     

Effects of epoxy treatment of organoclay on structure, thermo-mechanical and transport properties of poly(ethylene terephthalate-co-ethylene naphthalate)/organoclay nanocomposites

Poly(ethylene terephthalate-co-ethylene naphthalate) (PETN) nanocomposites containing two different organoclays, Cloisite 20A and 30B, were prepared by melt intercalation using an extruder. The organoclays was treated with epoxy monomer to further improve the polar interactions with PETN matrix. The morphological, thermal-mechanical, mechanical and gas barrier characteristics of the nanocomposites were evaluated using several characterization tools. It is found that the Cloisite 30B had better interactions with PETN and was more uniformly dispersed within PETN than Cloisite 20A. Epoxy treatment of Cloisite 30B organoclay resulted in improvements in d-spacing between silicate layers, thermo-mechanical and tensile properties, as well as thermal stability, processing and gas barrier characteristics of the PETN/30B nanocomposites. These results suggest that the epoxy acted as the compatibilizer as well as the chain extender, improving the chemical interactions between PETN and organoclay, while discouraging the macromolecular mobility of polymer chains in the vicinity clay particles. The implications and the mechanisms behind these observations are discussed.     

Novel blends of alternating propene-carbon monoxide copolymers and styrenic copolymers

Summary Alternating propene-carbon monoxide copolymers (P-CO) were melt-blended with polystyrene, poly(styrene-co-acrylonitrile) (SAN), and with poly(styrene-co-maleic anhydride) (SMA). P-CO forms homogeneously miscible blends with SAN containing 25 wt% AN at the investigated blend compositions. The transparent blends have single, intermediate glass transition temperatures that fit the Fox equation. The elastic properties of P-CO at room temperature disappear upon blending with SAN because the T _g is driven above RT. Polystyrene and SMA are not miscible with P-CO and form heterogeneous blends with two glass transitions. This demonstrates that both the polarity of the styrenic copolymer and the nature of the comonomer govern its phase behavior. Received: 14 January 1999/Revised version: 19 April 1999/Accepted: 19 April 1999     

Preparation and interaction characteristics of exfoliated ABS/organoclay nanocomposite

A series of poly(acrylonitrile‐co‐butadiene‐co‐styrene) (ABS)/organoclays (Cloisite10A, Cloisite25A, and Cloisite30B) nanocomposites are prepared via two different methods: one is a solution blending and the other is a two‐step process where the solution blended mixture is subsequently compounded in the melt state using a torque rheometer (SOAM method). The effect of surfactants on the surface of three different organoclays that are modified with alkylammonium salts in polymer/organoclay nanocomposites is investigated by focusing on two major aspects; Flory‐Huggins interaction parameters and physical (thermal and mechanical) properties. The d‐spacing of both neat organoclays and intercalated/exfoliated organoclays is examined by X‐ray diffraction analysis, and the microstructure of these nanocomposites is examined by FE‐TEM. Solubility parameters of both polymer and organoclays of interest are calculated according to the group contribution method. Viscoelastic behavior of the nanocomposites is also investigated by measuring rheological properties under an oscillatory shear. The increase in the onset temperature of the thermal degradation indicates the enhancement of thermal stability of ABS due to intercalation or partial exfoliation. Mechanical properties, such as, tensile strength, tensile modulus, and elongation at break of the nanocomposites are measured. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Effect of interfacial attraction on intercalation in polymer/clay nanocomposites

In order to examine the adhesive behavior of a polar polymer between hydrophilic clay layers, the so‐called glue effect, a clay intercalation by an ethylene–vinyl alcohol (EVOH) copolymer, which was capable of strong hydrogen bonding with the silicate surface of clay, was prepared by the melt intercalation technique and compared with a clay nanocomposite containing styrene–acrylonitrile (SAN) copolymer of less polar interaction energy in terms of the morphology and mechanical properties. Although initial penetration of the guest polymer into the gallery of the host clay occurred more rapidly for EVOH because of its strong hydrophilic nature, the dissociation of clay nanoplatelets was better developed for SAN with less polar interaction with clay, well evidencing the fact that the glue effect effectively affects the intercalation behavior of polymer/clay nanocomposites. However, the mechanical properties of the EVOH/clay nanocomposite were superior to those of SAN/clay nanocomposites. Although dissociation of respective silicate layers was poor for EVOH/clay nanocomposites, strong attractive energy stabilizes the interface between inorganic nanoparticles and the polymer matrix much more effectively, resulting in higher mechanical properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2749–2753, 2006     

Miscibility studies of polymer blends by viscometry methods

The intrinsic viscosities of blends of poly(vinyl chloride)/poly(ethylene-co-vinyl acetate) (PVC/EVA), poly(vinyl chloride)/poly(styrene-co-acrylonitrile) (PVC/SAN), and poly(ethylene-co-vinyl acetate)/poly(styrene-co-acrylonitrile) (EVA/SAN) have been studied in cyclohexanone as a function of blend composition. In order to predict the compatibility of polymer pairs in solution, the interaction parameter term, Δb, obtained from the modified Krigbaum and Wall theory, and the difference in the intrinsic viscosities of the polymer mixtures and the weight average intrinsic viscosities of the two polymer solutions taken separately are used. © 1994 John Wiley & Sons, Inc.     

Modeling of polymer/clay nanocomposite formation

A statistical thermodynamic modeling of the formation of polymer/clay intercalation and nanocomposites was developed. The key factor in determining intercalation was an exothermic heat of mixing between polymer chains and the organically modified silicate surface. This was found to agree with previous experimental results in the literature including halogenated polymers and acrylonitrile copolymers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1657–1663, 2006     

FTIR characterization of tropical wood–polymer composites

Wood–polymer composites (WPC) of Geronggang (Cratoxylon arborescens), a light tropical hardwood, impregnated with methyl methacrylate (MMA), methyl methacrylate-co-acrylonitrile (1 : 1; MAN), and styrene-co-acrylonitrile (3 : 2; STAN), were prepared by in situ polymerization using gamma radiation or the catalyst–heat treatment. The FTIR spectra of the three types of WPC, with polymer loadings ranging from 10 to 70%, were compared with that of the wood itself and the respective polymers. Characteristic peaks due to C?O vibration of MMA, C?N stretching of acrylonitrile, and ring stretching and bending of styrene monomers, were prominent in the samples that had higher polymer loadings. For the copolymeric systems, quantitation of the FTIR spectra of these characteristic peaks enabled calculations of incorporated acrylonitrile and styrene monomers in the composites to be made. The FTIR spectra of the residues remaining, after exhaustive extraction to remove homopolymer, showed that graft copolymerization of wood components with acrylonitrile and styrene monomers was possible, but not with MMA. Composites prepared by the two methods, gamma radiation and the catalyst–heat treatment, were shown to be chemically very similar.     

Nanostructure of EVA/organoclay nanocomposites: Effects of kinds of organoclays and grafting of maleic anhydride onto EVA

Nanostructure of poly(ethylene‐co‐vinyl acetate)/organically modified montmorillonite (MMT; EVA/organoclay) nanocomposites prepared by melt intercalation process was investigated using X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Three kinds of organoclays were used to see their influences on the nanostructure of the EVA hybrids. The effects of the polar interactions between the polymer and the silicate layers of organoclays were also investigated by grafting maleic anhydride onto EVA. It was found that the strong polar interactions between the polymer and the silicate layers of organoclays are critical to the formation of polymer‐layered silicate nanocomposites. The results also showed that increasing the mixing temperature was unfavorable to improve the dispersion of organoclays in the EVA matrix. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1901–1909, 2003     

Mechanical properties of layered silicate/starch polycaprolactone blend nanocomposites

The mechanical behavior of layered silicate/starch polycaprolactone blend nanocomposites was evaluated. Three different clays (Cloisite Na⁺, Cloisite 30B and Cloisite 10A) were used as reinforcement. Nanocomposites were prepared by melt intercalation followed by compression molding. These nanocomposites were characterized using X‐ray diffraction, scanning electron microscopy, dynamic mechanical analysis and tensile testing. X‐ray diffraction results showed that most of the clays were intercalated within the polymeric chains. In all cases, mechanical properties were improved with clay incorporation and the improvement was better as the clay content was increased. The best properties were achieved with Cloisite 10A due to their greatest compatibility with the matrix. A mechanical model, which takes into account the effective parameters of the clay, was used in order to estimate the dispersion of clay within the polymer. The highest dispersion was obtained for Cloisite 10A, which is in accordance with the experimental mechanical properties. Although dynamical‐mechanical properties improved with clay incorporation, the glass transition temperature was not affected. Copyright © 2006 Society of Chemical Industry     

Morphology and physical properties of SAN/NBR blends: The effect of AN content and melt viscosity of SAN

To study the effect of dispersed poly(butadiene-co-acrylonitrile) (NBR) rubber size on the physical properties of poly(styrene-co-acrylonitrile) (SAN)/NBR blends, SANs with various melt viscosities and acrylonitrile (AN) contents were examined. The dispersed size of NBR, whose AN content is 30 wt %, was reduced as the melt viscosity of the SAN matrix was increased or as the AN content of the SAN matrix was reduced in the range of 19–32 wt %. As the melt viscosity of the SAN matrix was increased, the damping peak of the NBR phase moved to a higher temperature, and as the AN content of SAN was reduced, the damping peak of the SAN phase moved to a lower temperature. Higher values of impact strength and elongation at break and reduced yield behavior at a low shear rate were observed at a finer dispersion of NBR. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 935–941, 1999     

Compatibility enhancement of ABS/PVC blends

The compatibilizing effect of poly(styrene-co-acrylonitrile) (SAN) whose acrylonitrile (AN) content is 25 wt % (SAN 25) in poly(acrylonitrile-co-butadiene-co-styrene) (ABS)/poly(vinyl chloride) (PVC) blend was studied when the AN content of the matrix SAN in ABS was 35 wt % (SAN 35). When some amount of matrix SAN 35 was replaced by SAN 25 in a ABS/PVC (50/50 by weight) blend, the mixed phase of SAN and PVC at the interface was thickened, and about a twofold increase of impact strength was observed. The changes in morphology, dynamic mechanical properties, and rheological properties by the compatibilizing effect of SAN 25 were observed. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 705–709, 1998     

Compatibility behavior in thermoplastic polymer blends containing poly(t-butylstyrene-co-acrylonitrile)

The phase behavior of a series of binary component polymer blends of poly(ε-caprolactone) (PCL) and poly(t-butylstyrene-co-acrylonitrile) (TBSAN) containing varying contents of acrylonitrile (AN) was examined to determine the influence of copolymer composition and PCL content on blend miscibility or immiscibility. Thermal measurements were extensively used to determine phase behavior, i.e., a single compositionally dependent glass transition temperature implies blend miscibility. Otherwise, immiscibility is assumed to dominant blend behavior. It was determined that TBSAN and PCL form miscible blends over a broad range of AN content, i.e., spanning from below 43.2 mol % (19.8 wt %) to about 66.4 mol % (39.6 wt %), a range considerably different from that found in poly(styrene-co-acrylonitrile) copolymers. TBSAN-containing blends were found to be immiscible when the AN content is less than about 43 mol % or greater than about 67 mol %. Small-angle light-scattering and polarized light microscopy was used to probe the substantial morphological changes in the miscible blends. Little change was observed in the immiscible blends. These results clarify the phase separation observed in these blend systems. © 1993 John Wiley & Sons, Inc.     

Synthesis,structure, and thermal stability of poly(methyl methacrylate)‐co‐ poly(3‐tri(methoxysilyil)propyl methacrylate)/ montmorillonite nanocomposites

The structure and the thermodegradation behavior of both poly(methyl methacrylate)‐co‐poly(3‐tri(methoxysilyil)propyl methacrylate) polymer modified with silyl groups and of intercalated poly(methyl methacrylate)‐co‐poly(3‐tri(methoxysilyil)propyl methacrylate)/Cloisite 15A? nanocomposite have been in situ probed. The structural feature were comparatively studied by Fourier transform infrared spectroscopy (FTIR), ¹³C and ²⁹Si nuclear magnetic resonance (NMR), and small angle X‐ray scattering (SAXS) measurements. The intercalation of polymer in the interlayer galleries was evidenced by the increment of the basal distance from 31 to 45 Å. The variation of this interlayer distance as function of temperature was followed by in situ SAXS. Pristine polymer decomposition pathway depends on the atmosphere, presenting two steps under air and three under N₂. The nanocomposites are more stable than polymer, and this thermal improvement is proportional to the clay loading. The experimental results indicate that clay nanoparticles play several different roles in polymer stabilization, among them, diffusion barrier, charring, and suppression of degradation steps by chemical reactions between polymer and clay. Charring is atmosphere dependent, occurring more pronounced under air. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

An approach to yielding and toughness in rubber-modified thermoplastics

An interpretation of yielding and fracture of rubber-toughened polymers is attempted, considering the fracture mechanics behavior of the matrices, with the rubber particles as stress-intensification sites. The fit of effective tensile yield stresses of composites vs. particle radii defines a stress-intensity factor K_Yc for craze yielding much smaller than the classical fracture factor K_c, values are found for polystyrene and poly(styrene-co-acrylonitrile)-based polymers. These factors are considered characteristic for craze initiation and propagation in the matrices, while K_c, in turn, would include also the craze-crack transformation contribution. K_Yc appears independent of the rubbery-phase volume fraction and characteristics, but two different values are found and discussed for poly(styrene-co-acrylonitrile)-based materials in two different particle-size ranges. A similar treatment on notched specimens' yield stress indicates the presence of a maximum in different radius ranges for polystyrene and poly(styrene-co-acrylonitrile) matrices, with higher values than their breakdown stresses. This stress increment is in relation to the minimum particle size inducing and still stabilizing crazes and preventing crack formation. This maximum seems to control the reinforcing extent of the polymer matrix conditioning the Izod fracture initiation energy.     

Preparation and characterization of poly(butylene terephthalate) nanocomposites with various organoclays

Layered‐silicate‐based polymer–clay nanocomposite materials were prepared depending on the surface modification of montmorillonite (MMT). Nanocomposites consisting of poly(butylene terephthalate) (PBT) as a matrix and dispersed inorganic clay modified with cetyl pyridinium chloride (CPC), benzyl dimethyl N‐hexadecyl ammonium chloride, and hexadecyl trimethyl ammonium bromide by direct melt intercalation were studied. The organoclay loading was varied from 1 to 5 wt %. The organoclays were characterized with X‐ray diffraction (XRD) to compute the crystallographic spacing and with thermogravimetric analysis to study the thermal stability. Detailed investigations of the mechanical and thermal properties as well as a dispersion study by XRD of the PBT/clay nanocomposites were conducted. X‐ray scattering showed that the layers of organoclay were intercalated with intercalating agents. According to the results of a differential scanning calorimetry analysis, clay acted as a nucleating agent, affecting the crystallization. The PBT nanocomposites containing clay treated with CPC showed good mechanical properties because of intercalation into the polymer matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Water uptake behavior of layered silicate/starch–polycaprolactone blend nanocomposites

The water uptake behavior of biodegradable layered silicate/starch–polycaprolactone blend nanocomposites was evaluated. Three different commercial layered silicates (Cloisite Na⁺, Cloisite 30B and Cloisite 10A) were used as reinforcement nanofillers. Tests were carried out in two different environments: 60 and 90% relative humidity using glycerol solutions. The clay/starch–polycaprolactone blend nanocomposites were obtained by melt intercalation and characterized by gravimetric measurements and tensile tests. The intercalated structure (determined by wide‐angle X‐ray diffraction) showed a decrease in water absorption as a function of clay content probably due to the decrease of the mean free path of water molecules. The diffusion coefficient decreased with clay incorporation but a further increase in the clay content did not show an important effect on this parameter. Elongation at break increased with exposure showing matrix plasticization. Mechanical properties of the nanocomposites deteriorated after exposure whereas they remained almost constant in the case of the neat matrix. Copyright © 2007 Society of Chemical Industry     

Thermoplastic elastomeric nanocomposites from poly[styrene–(ethylene‐co‐butylene)–styrene] triblock copolymer and clay: Preparation and characterization

Thermoplastic elastomer (TPE)–clay nanocomposites based on poly[styrene–(ethylene‐co‐butylene)–styrene] triblock copolymer (SEBS) were prepared. Natural sodium montmorillonite (MMT) clay was organically modified by octadecyl amine to produce an amine‐modified hydrophobic nanoclay (OC). Commercially available Cloisite 20A (CL20) and Cloisite 10A, tallow ammine modified nanoclays, were also used. The intergallery spacing of MMT increased on amine modification as suggested by the shifting of the X‐ray diffraction (XRD) peak from 7.6 to 4.5 and 3.8° in the cases of OC and CL20, respectively. The latter demonstrated no XRD peak when it was used at 2 and 4 parts phr in the SEBS system. Transmission electron microscopy studies showed the intercalation–exfoliation morphology in SEBS containing 4 parts of CL20₄–SEBS, agglomeration in SEBS having 4 parts of MMT, and mixed morphology in SEBS with 4 parts of OC systems. Locations of the clay particles were indicated by the atomic force micrographs. Mechanical and dynamic mechanical thermal analysis studies confirmed the best properties with the CL20₄–SEBS nanocomposites. Significant improvements in mechanical properties such as tensile strength, modulus, work to break, and elongation at break were achieved with the CL20₄–SEBS in polymer‐layered silicate nanocomposites. Dynamic mechanical studies further showed the affinity of the organoclays toward both segments of the TPE and a compatibilization effect with CL20 at a 4‐phr loading. Atomic force microscopy showed distinctly different morphologies in nanocomposites prepared through solution and melt processing. Comparisons of the mechanical, dynamic mechanical, and morphological properties of the nanocomposites prepared by melt and solution intercalation processes were done. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2040–2052, 2006