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     

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     

Synthesis and characterization of novel oligomeric poly(styrene‐co‐acrylonitrile)–clay complexes

Oligomeric poly(styrene‐co‐acrylonitrile) quaternary ammonium salts were prepared through reactions of trimethylamine with corresponding poly(styrene–acrylonitrile–vinyl benzyl chloride)s, which were synthesized by the free‐radical polymerization of a mixture of styrene, acrylonitrile, and vinyl benzyl chloride. Then, oligomeric poly(styrene‐co‐acrylonitrile)‐modified clays were prepared through the cation exchange of the sodium ions in the clay with the corresponding poly(styrene‐co‐acrylonitrile) quaternary ammonium salts. The poly(styrene–acrylonitrile–vinyl benzyl chloride)s, poly(styrene‐co‐acrylonitrile) quaternary ammonium salts, and their clay complexes were characterized with infrared spectroscopy, gel permeation chromatography, thermogravimetric analysis, proton nuclear magnetic resonance, X‐ray diffraction, and transmission electron microscopy. X‐ray diffraction and transmission electron microscopy studies showed that these novel clay complexes were well intercalated. Furthermore, thermogravimetric analysis data indicated that this series of polymerically modified clays had high enough thermal stability for nanocomposites by melt blending. The thermal treatment of one of these novel clays at 250°C under nitrogen was also conducted. Solubility and infrared studies of this thermally treated clay complex revealed that a novel polyimine/enamine structure clay complex had been formed in the gallery of the clay. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Phase separation behavior and morphologies of PMMA/poly(styrene‐co‐acrylonitrile)/clay nanocomposites prepared by solution mixing

Nanocomposites of blends of PMMA and poly(styrene‐co‐acrylonitrile) (SAN) with natural (PM) or organically modified montmorillonite clays (Cloisite 30B, 25A, and 15A) were prepared by solution mixing and the effect of clay on the phase separation behavior along with morphologies of nanocomposites was investigated. Nanocomposites containing clay C30B prepared from methyl ethyl ketone showed the noticeable decrease in the cloud points. None of the other nanocomposites showed the increase in the cloud point. Location of clay particles in the phase separated matrix is observed to be different depending on the type of clays and solvents. The lowest cloud point of nanocomposites containing C30B may arise from the good dispersion of C30B where Clay C30B may act as the nucleating agent inducing phase separation. Dynamic mechanical and thermal analyses support above observations. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and dynamic mechanical properties of poly(styrene‐b‐butadiene)‐modified clay nanocomposites

Polybutyl acrylate (PBA) was intercalated into clay by the method of multistep exchange reactions and diffusion polymerization. The clay interlayer surface is modified, and obtaining the modified clay. The structures of the clay‐PBA, clay‐GA (glutamic acid), and the clay‐DMSO (dimethyl sulfoxide) were characterized using X‐ray diffraction (XRD). The new hybrid nanocomposite thermoplastic elastomers were prepared by the clay‐PBA with poly(styrene‐b‐butadiene) block copolymer (SBS) through direct melt intercalation. The dynamic mechanical analysis (DMA) curves of the SBS/modified clay nanocomposites show that partial polystyrene segments of the SBS have intercalated into the modified clay interlayer and exhibited a new glass transition at about 157°C (T_g3). The glass transition temperature of polybutadiene segments (T_g1) and polystyrene segments out of the modified clay interlayer (T_g2) are about ?76 and 94°C, respectively, comparied with about ?79 and 100°C of the neat SBS, and they are basically unchanged. The T_g2 intensity of the SBS‐modified clay decreases with increasing the amounts of the modified clay, and the T_g3 intensity of the SBS‐modified clay decreases with increasing the amounts of the modified clay up to about 8.0 wt %. When the contents of the modified clay are less than about 8.0 wt %, the SBS‐modified clay nanocomposites are homogeneous and transparent. The T_gb and T_gs of the SBS‐clay (mass ratio = 98.0/2.0) are ?78.39 and 98.29°C, respectively. This result shows that the unmodified clay does not essentially affect the T_gb and T_gs of the SBS, and no interactions occur between the SBS and the unmodified clay. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1499–1503, 2002; DOI 10.1002/app.10353     

Organo‐soluble polyimde (ODA–BSAA)/montmorillonite nanocomposite materials prepared by solution dispersion technique

A series of polymer–clay nanocomposite materials, consisting of organo‐soluble polyimide (ODA‐BSAA) matrix and dispersed nanolayers of inorganic montmorillonite clay, were successfully prepared by solution dispersion technique and subsequently characterized by FTIR, powder X‐ray diffraction patterns, transmission electron microscopy, and atomic force microscopy. Effects of the materials composition on the corrosion protection performance, gas barrier, and optical properties, in the form of both coating and film, were also studied by electrochemical corrosion measurements (e.g., corrosion potential, polarization resistance, corrosion current, impedance spectroscopy), gas permeability analysis, and UV–visible transmission spectroscopy, respectively. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1082–1090, 2005     

Extrusion Foaming of Poly(styrene‐co‐acrylonitrile)/Clay Nanocomposites Using Supercritical CO2

Supercritical CO₂ has been used as a blowing agent to foam poly(styrene‐co‐acrylonitrile)‐based materials in a single screw extruder specially adapted to allow fluid injection. The cellular morphology depends on foaming temperature, more regular cells being obtained with decreasing extrusion temperature. In a second step, a natural and an organomodified nanoclay have been added for the purpose of imparting some flame resistance to the foamed material. The filler efficiency in reducing sample combustion rate appeared to be dependent on its delamination level inside the matrix and better results were obtained when the organomodified clay was first delaminated in the polymer in an efficient twin screw extruder using water assistance, prior to foaming in the single screw extruder.

     

Preparation and structure and mechanical properties of poly(styrene‐b‐butadiene)/clay nanocomposites

Star‐shaped and linear block thermoplastic poly(styrene‐b‐butadiene) copolymer (SBS)/organophilic montmorillonite clays (OMMT) were prepared by a solution approach. The intercalation spacing in the nanocomposites and the degree of dispersion of nanocomposites were investigated by X‐ray diffraction (XRD) and transmission electron microscopy (TEM), respectively. The mechanical properties, dynamic mechanical properties, and thermal stability of these nanocomposites were determined. Results showed that SBS chains were well intercalated into the clay galleries and an intercalated nanocomposite was obtained. The mechanical strength of nanocomposites with the star‐shaped SBS/OMMT were significantly increased. The addition of OMMT also gave an increase of the elongation, the dynamic storage modulus, the dynamic loss modulus, and the thermal stability of nanocomposites. The increase of the elongation of nanocomposites indicates that SBS has retained good elasticity. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3430–3434, 2004     

Isothermal crystallization of poly(ethylene‐co‐glycidyl methacrylate)/clay nanocomposites

Poly(ethylene‐co‐glycidyl methacrylate) (PEGMA)/clay nanocomposites with clay concentrations of 1, 3, or 5 wt % were prepared via y melt blending in a twin‐screw extruder. Wide‐angle X‐ray diffraction showed that the clay layers were intercalated by PEGMA. Differential scanning calorimetry was used to analyze the isothermal crystallization, and the equilibrium melting temperature was determined with the Hoffman–Weeks method. The Avrami, Tobin, Malkin, and Urbanovici–Segal models were applied to describe the kinetics of crystallization from the melt state under isothermal conditions. The crystallization kinetics showed that the addition of clay facilitated the crystallization of PEGMA, with the clay functioning as a heterophase nucleating agent; at higher concentrations, however, the physical hindrance of the clay layers to the motion of PEGMA chains retarded the crystallization process. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1051–1064, 2005     

Compatibilization of polymer blends from poly(styrene‐co‐acrylonitrile) and polycarbonate by oxazoline modification of poly(styrene‐co‐acrylonitrile) in the melt

A good way of achieving compatibility in polymer blends of poly(styrene‐co‐acrylonitrile) (S/AN) and bisphenol A polycarbonate (PC) is the chemical modification of S/AN in the melt. A catalyzed reaction of the nitrile groups with a substituted 2‐amino alcohol or 2‐amino phenol resulted in a conversion of nitrile groups of 55–75% in 60 min. The introduced heterocyclic structures were ethyl hydroxymethyl oxazoline (EHMOXA) and benzoxazole (BenzOXA), respectively. The use of dibutyltin oxide as a catalyst led to the highest efficiency. The modified polymer was characterized by Fourier transform infrared and NMR spectroscopy, elemental analysis, and reactions with organic acids and anhydrides. The modified S/AN showed good technical compatibility (single glass‐transition temperature) with PC in blends made from solution and from the melt. All blends were characterized with oscillating rheometry and differential scanning calorimetry. Rheological measurements showed that EHMOXA–S/AN reacted with PC and had crosslinked structures, whereas BenzOXA–S/AN showed compatibilization without any (crosslinking) reaction. The melt blends of BenzOXA–S/AN and PC showed a downward shift in the complex viscosity due to the influence of the BenzOXA group. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2322–2332, 2003     

PTCR characteristics of poly(styrene‐co‐acrylonitrile) copolymer/stainless steel powder composites

Positive temperature coefficient of resistivity (PTCR) characteristics of poly(styrene‐co‐acrylonitrile) copolymer (SAN)/stainless steel (SS) powder (80 wt %) composites prepared by melt‐mixing method has been investigated with reference to SAN/carbon black (CB) composites. The SAN/CB (10 wt %) composites showed a sudden rise in resistivity (PTC trip) at 125°C, above the glass transition temperature (T_g) of SAN (T_g ≈ 107°C). However, the PTC trip temperature of SAN/SS (80 wt %) composites appeared at 94°C, well below the T_g of SAN. Addition of 1 phr of nanoclay increased the PTC trip temperature of SAN/CB (10 wt %) composites to 130°C, while SAN/SS (80 wt %)/clay (1 phr) nanocomposites showed the PTC trip at 101°C. We proposed that the mismatch in coefficient of thermal expansion (CTE) between SAN and SS played a key role that led to a disruption in continuous network structure of SS even at a temperature below the T_g of SAN. The dielectric properties study of SAN/SS (80 wt %) composites indicated possible use of the PTC composites as dielectric material. DMA results showed higher storage modulus of SAN/SS composites than the SAN/CB composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Properties of poly(ethylene terephthalate)–poly(ethylene naphthalene 2,6‐dicarboxylate) blends with montmorillonite clay

The production and properties of blends of poly(ethylene terephthalate) (PET) and poly(ethylene naphthalene 2,6‐dicarboxylate) (PEN) with three modified clays are reported. Octadecylammonium chloride and maleic anhydride (MAH) are used to modify the surface of the montmorillonite–Na⁺ clay particles (clay–Na⁺) to produce clay–C18 and clay–MAH, respectively, before they are mixed with the PET/PEN system. The transesterification degree, hydrophobicity and the effect of the clays on the mechanical, rheological and thermal properties are analysed. The PET–PEN/clay–C18 system does not show any improvements in the mechanical properties, which is attributed to poor exfoliation. On the other hand, in the PET–PEN/clay–MAH blends, the modified clay restricts crystallization of the matrix, as evidenced in the low value of the crystallization enthalpy. The process‐induced PET–PEN transesterification reaction is affected by the clay particles. Clay–C18 induces the largest proportion of naphthalate–ethylene–terephthalate (NET) blocks, as opposed to clay–Na⁺ which renders the lowest proportion. The clay readily incorporates in the bulk polymer, but receding contact‐angle measurements reveal a small influence of the particles on the surface properties of the sample. The clay–Na⁺ blend shows a predominant solid‐like behaviour, as evidenced by the magnitude of the storage modulus in the low‐frequency range, which reflects a high entanglement density and a substantial degree of polymer–particle interactions. Copyright © 2005 Society of Chemical Industry     

Studies on the poly(styrene‐b‐butadiene‐b‐styrene)/clay nanocomposites prepared by melt intercalation

Two types of SBS/OMMT composites are prepared by melt blending using a twin‐screw extruder. An X‐ray diffractometer indicates that polymer chains have intercalated into the gallery of the clay. It is shown in TEM photos that the thickness of the layer aggregate in the SBS1301 matrix is approximately 200 Å, but in the SBS4402 matrix the size of the filler particle is in micrometers. When SBS1301 is intermingled into SBS4402/OMMT, the particle size is reduced obviously. The tensile strength and elongation at break of the nanocomposite, SBS1301/OMMT, increase with the addition of OMMT; and when addition is 5phr, they achieve maximum. A small content of OMMT (less than 5phr) can prevent the deterioration of the mechanical properties of the SBS1301/MMT. In addition, a small content of SBS4402 (less than 20 wt %) can improve the mechanical properties of the SBS1301/OMMT composites. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 146–152, 2005     

Kinetics of phase separation of poly(styrene‐co‐methyl methacrylate) and poly(styrene‐co‐acrylonitrile) blends

The phase behavior and kinetics of phase separation for blends of the random copolymer poly(styrene‐co‐methyl methacrylate) (SMMA) and poly(styrene‐co‐acrylonitrile) (SAN) were studied by using small‐angle laser light scattering. The partially miscible SMMA/SAN blends undergo spinodal decomposition (SD) and subsequent domain coarsening when quenched inside the unstable region. For blends of SMMA and SAN, the early stages of the phase separation process could be observed, unlike a number of other blends where the earliest stages are not visible by light scattering. The process was described in terms of the Cahn–Hilliard linear theory. Subsequently, a coarsening process was detected and the time evolution of q_m at the beginning of the late stages of phase separation followed the relationship q_m∝t^?1/3, corresponding to an evaporation–condensation mechanism. Self‐similar growth of the phase‐separated structures at different timescales was observed for the late stage. Copyright © 2004 Society of Chemical Industry     

Effect of organomodified clay on the reaction kinetics,properties and thermal degradation of nanocomposites based on poly(styrene‐co‐ethyl methacrylate)

In this research, synthesis of novel nanocomposites based on a poly(styrene‐co‐ethyl methacrylate) copolymer matrix was investigated with different types and amounts of organomodified montmorillonite (MMT) clays. The in situ polymerization technique was selected with dispersion of the MMT nanoparticles into the comonomer mixture and subsequent bulk radical polymerization. Reaction kinetics was measured gravimetrically and it was found that the existence of rigid phenyl rings in the organomodifier may result in a hindered reaction rate especially at high clay loadings. Structural characteristics of the nanocomposites formed were verified with XRD and Fourier transform infrared analysis and mainly intercalated/partially exfoliated structures were verified; their glass transition temperature was measured with DSC, and their molecular weight distribution and average molecular weights were measured with gel permeation chromatography. The latter was also used to measure the variation of the copolymer average molecular weight with conversion. Slightly higher average molecular weight and T_g values for the copolymer in the nanocomposites were measured, compared with neat copolymer. The thermal stability of the nanocomposites was measured with TGA and found to be significantly improved. One‐step degradation revealed the existence of macromolecular chains without defective structures. Finally, pyrolysis of the nanocomposite copolymers resulted in the production of both comonomers in high amounts, followed by some dimers or trimers. © 2013 Society of Chemical Industry     

Synthesis and characterization of poly(glycidyl methacrylate)/Na‐montmorillonite nanocomposites

Poly(glycidyl methacrylate)/Na–montmorillonite nanocomposites were synthesized by free‐radical polymerization of glycidyl methacrylate containing dispersed montmorillonite. By changing the concentration of glycidyl methacrylate several polymer–clay nanocomposites were prepared and the resulting nanocomposites were characterized by X‐ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and thermogravimetric analysis. The results indicated that the properties of the composite were significantly improved. The thermogravimetric analysis results revealed that the degradation temperatures of nanocomposites were higher than that of pure polymer and the thermal degradation rates decreased. Examination of these materials by scanning electron microscopy showed that the clay layers are dispersed homogenously in the polymer matrix and the formation of intercalation nanostructure. Furthermore, adsorptive, moisture regain, and water uptake properties of nanocomposites were also investigated. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1532–1538, 2004     

Influence of granulometry and organic treatment of a Brazilian montmorillonite on the properties of poly(styrene‐co‐n‐butyl acrylate)/layered silicate nanocomposites prepared by miniemulsion polymerization

The influence of granulometry and organic treatment of a Brazilian montmorillonite (MMT) clay on the synthesis and properties of poly(styrene‐co‐n‐butyl acrylate)/layered silicate nanocomposites was studied. Hybrid latexes of poly(styrene‐co‐butyl acrylate)/MMT were synthesized via miniemulsion polymerization using either sodium or organically modified MMT. Five clay granulometries ranging from clay particles smaller than 75 μm to colloidal size were selected. The size of the clay particles was evaluated by specific surface area measurements (BET). Cetyl trimethyl ammonium chloride was used as an organic modifier to enhance the clay compatibility with the monomer phase before polymerization and to improve the clay distribution and dispersion within the polymeric matrix after polymerization. The sodium and organically modified natural clays as well as the composites were characterized by X‐ray diffraction analysis. The latexes were characterized by dynamic light scattering. The mechanical, thermal, and rheological properties of the composites obtained were characterized by dynamical‐mechanical analysis, thermogravimetry, and small amplitude oscillatory shear tests, respectively. The results showed that smaller the size of the organically modified MMT, the higher the degree of exfoliation of nanoplatelets. Hybrid latexes in presence of Na‐MMT resulted in materials with intercalated structures. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Study on flammability of montmorillonite/styrene‐butadiene rubber (SBR) nanocomposites

The flammability of montmorillonite (MMT)/SBR nanocomposites, prepared by the technique of cocoagulating rubber latex and clay aqueous suspension, was investigated. Flammability studies, performed on the cone calorimeter, showed that the maximum heat release rate (HRR) of SBR decreased from 1987 to 1442 kw/m² with the introduction of nanoclay (20 phr). This nanocomposite had the lowest mass loss rate and the largest amount of char upon combustion compared with conventional SBR composites with the same clay loading and pure SBR. The permeability properties of MMT/SBR composites were also measured. It was deduced that the lowered permeability was responsible for the reduced mass loss rate and hence the lower HRR. Unfortunately, the oxygen index (OI) of the nanocomposites was not as high as expected. Combination of Mg(OH)₂ and clay was effective for the improvement of both mechanical properties and OI. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 844–849, 2005     

Enhanced corrosion prevention effect of polysulfone–clay nanocomposite materials prepared by solution dispersion

A series of polymer–clay nanocomposite (PCN) materials containing polysulfone (PSF) and layered MMT clay were successfully prepared by effectively dispersing inorganic nanolayers of MMT clay in an organic PSF matrix via a solution dispersion technique. The synthesized PCN materials were subsequently investigated with a series of characterization techniques, including Fourier transform infrared (FTIR) spectroscopy, wide‐angle powder X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The prepared PCN coatings with low clay loading (1 wt %) on cold‐rolled steel (CRS) were found to be superior in corrosion prevention to those of bulk PSF, based on a series of electrochemical measurements of corrosion potential, polarization resistance, corrosion current and electrochemical impedance spectroscopy (EIS) in a 5 wt % aqueous NaCl electrolyte. The effects of material composition on the molecular barrier, mechanical strength and optical clarity of PSF and PCN materials, in the form of membranes, was also studied by molecular permeability analysis (GPA), dynamic mechanical analysis (DMA) and UV‐Visible transmission spectra, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 631–637, 2004     

Comparative studies of the properties of poly(methyl methacrylate)–clay nanocomposite materials prepared by in situ emulsion polymerization and solution dispersion

A series of polymer–clay nanocomposite (PCN) materials consisting of organic poly(methyl methacrylate) (PMMA) and inorganic montmorillonite (MMT) clay platelets were prepared successfully by the effective dispersion of nanolayers of the MMT clay in the PMMA framework through both in situ emulsion polymerization and solution dispersion. The as‐prepared PCN materials obtained with both approaches were subsequently characterized with wide‐angle powder X‐ray diffraction and transmission electron microscopy. For a comparison of the anticorrosion performance, a PCN material (e.g., 3 wt % clay loading) prepared by in situ emulsion polymerization, showing better dispersion of the clay platelets in the polymer matrix, exhibited better corrosion protection in the form of a coating on a cold‐rolled steel coupon than that prepared by solution dispersion, which showed a poor dispersion of the clay nanolayers according to a series of electrochemical corrosion measurements. Comparative studies of the optical clarity, molecular barrier properties, and thermal stability of samples prepared in both ways, as membranes and fine powders, were also performed with ultraviolet–visible transmission spectroscopy, molecular permeability analysis, thermogravimetric analysis, and differential scanning calorimetry. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1936–1946, 2004