Use of a new natural clay to produce poly(methyl methacrylate)‐based nanocomposites

Nanocomposites of poly(methyl methacrylate) (PMMA) filled with 3 wt% of modified natural Algerian clay (AC; montmorillonite type) were prepared by either in situ polymerization of methyl methacrylate initiated by 2,2′‐azobisisobutyronitrile or a melt‐mixing process with preformed PMMA via twin‐screw extrusion. The organo‐modification of the AC montmorillonite was achieved by ion exchange of Na⁺ with octadecyldimethylhydroxyethylammonium bromide. Up to now, this AC montmorillonite has found applications only in the petroleum industry as a rheological additive for drilling muds and in water purification processes; its use as reinforcement in polymer matrices has not been reported yet. The modified clay was characterized using X‐ray diffraction (XRD), which showed an important shift of the interlayer spacing after organo‐modification. The degree of dispersion of the clay in the polymer matrix and the resulting morphology of nanocomposites were evaluated using XRD and transmission electron microscopy. The resulting intercalated PMMA nanocomposites were analysed using thermogravimetric analysis and differential scanning calorimetry. The glass transition temperature of the nanocomposites was not significantly influenced by the presence of the modified clay while the thermal stability was considerably improved compared to unfilled PMMA. This Algerian natural montmorillonite can serve as reinforcing nanofiller for polymer matrices and is of real interest for the fabrication of nanocomposite materials with improved properties. Copyright © 2009 Society of Chemical Industry     

Effect of organoclay in an immiscible poly(ethylene terephtalate) waste/poly(methyl methacrylate) blend

Blends of organically modified montmorillonite (OMMT) with poly(ethylene terephtalate) (PET) waste and poly(methyl methacrylate) (PMMA) were prepared by melt mixing. The morphology of PET/PMMA nanocomposites with different OMMT contents was characterized by transmission electron microscopy (TEM) and X‐ray diffraction (XRD). The nonisothermal crystallization temperatures of nanocomposites were also examined by DSC. TEM observations and XRD patterns revealed that silicate layers were intercalated and well dispersed in the blend. Nanocomposites displayed better mechanical properties when compared with the unfilled blend. DMA analyses also showed efficient mixing of the two immiscible polymers and changes in glass transition temperature with the presence of OMMT. DSC analysis showed an enhancement in crystallization rate of nanocomposites and a decrease in cristallinity. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Studies on synthesis and characterization of poly(methyl methacrylate)‐bentonite clay composite by emulsion polymerization and simultaneous in situ clay incorporation

Well‐dispersed poly(methyl methacrylate) (PMMA)–bentonite clay composite was synthesized by emulsion polymerization using methyl methacrylate (MMA) monomer and 3% sodium carbonate treated bentonite clay. The composite lost its transparency normally encountered with the neat PMMA. The composite was characterized by Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), vicat softening point (VSP), dynamic mechanical thermal analysis (DMTA), and tensile studies. The morphology was investigated by scanning electron microscopy (SEM) and atomic forced microscopy (AFM) as well. The crystallography was studied to estimate the changes in crystallographic planes by X‐ray diffraction (XRD) analysis. The particle size distribution was compared amongst neat bentonite clay, neat PMMA and the composite. The FTIR spectra reveal the fact that no new primary valence bond is formed between the clay and PMMA. The thermal stability of the composite is significantly improved, as indicated by the TGA and VSP studies. A substantial increase in glass transition temperature (T_g) approximately, 10°C was recorded from the DMTA as both the storage modulus and tan δ values underwent inflexion at higher temperatures in case of the composite compared with the pristine PMMA. The XRD pattern indicates increase in basal “d” spacing for the composite. The morphology from both the SEM and AFM is quite supportive to well‐dispersed exfoliation. The incorporation of nanosized activated clay particles in PMMA during its in situ polymerization from MMA led to the formation of nanocomposites. POLYM. COMPOS., 2013. © 2012 Society of Plastics Engineers     

Effect of blend composition and organoclay loading on the nanocomposite structure and properties of miscible poly(methyl methacrylate)/poly(styrene‐co‐acrylonitrile) blends

Organically‐modified montmorillonite clay nanocomposites of poly(styrene‐co‐acrylonitrile) (SAN), poly(methyl methacrylate) (PMMA) and SAN/PMMA miscible blend are investigated. Structure characteristics at the nanoscale and microscale and thermal and tensile properties are studied as a function of polymer blend composition and filler loading fraction. Blend miscibility and T_g are unaffected by up to 10% by wt. organoclay. Thermal degradation stability increases with SAN content and exhibits an optimum value of clay loading. Stiffness shows significant improvement. Tensile strength and elongation‐at‐break suffer as a result of nanocomposite formation. Modulus shows a maximum enhancement of 57% (5 ± 0.06 GPa at 10 wt% filler, 20/80 SAN/PMMA) and varies linearly with clay fraction for all compositions of matrix phase. Predictions of Halpin–Tsai composite model are in excellent agreement with the experimental behavior over full range of polymer blend composition. Fundamental aspects of a polymer blend–clay nanocomposite are clarified, such as lack of additional synergy between clay platelets and matrix, and tensile ductility reduction, compared with polymer–clay system. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Effect of clay with different cation exchange capacity on the morphology and properties of poly(methyl methacrylate)/clay nanocomposites

PMMA/clay nanocomposites were successfully prepared by in situ free‐radical polymerization with the organic modified MMT‐clay using methyl methacrylate monomer and benzoyl peroxide initiator. Two clays with different cation exchange capacity have been used to prepare and compare the several properties. The clays have been modified using Amphoterge K2 by ion exchange reaction to increase the compatibility between the clay and polymer matrices. The modified clays have been characterized by wide‐angle X‐ray diffraction pattern, Fourier transform infrared spectroscopy, and thermogravimetric analysis (TGA). The powdered X‐ray diffraction and transmission electron microscopy techniques were employed to study the morphology of the PMMA/clay nanocomposites which indicate that the modified clays are dispersed in PMMA matrix to form both exfoliated and intercalated PMMA/modified clay nanocomposites. The thermomechanical properties were examined by TGA, differential scanning calorimetry, and dynamic mechanical analysis. Gas permeability analyzer shows the excellent gas barrier property of the nanocomposites, which is in good agreement with the morphology. The optical property was measured by UV–vis spectroscopy which shows that these materials have good optical clarity and UV resistance. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

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     

Nanocomposites of poly(methyl methacrylate) and organically modified layered silicates by melt intercalation

Polymer‐layered silicate nanocomposites of poly(methyl methacrylate) (PMMA) and an organically modified silicate [tetraallkyl ditallow ammonium bentonite (B34)] system prepared via melt intercalation were studied. The saturation ratio of PMMA to B34 was 25:75 (w/w), as determined by dynamic mechanical thermal analysis, differential scanning calorimetry, and X‐ray diffraction. The interaction between PMMA and B34 was detected by Fourier transform infrared spectrometry, which showed two new absorption bands of PMMA/B34 hybrids in comparison with unannealed physical mixtures of PMMA and B34. The degradation temperature of the PMMA/B34 hybrids was 26°C higher than that of neat PMMA according to thermogravimetric analysis, the thermal stability of the hybrids having been enhanced. The glass‐transition temperature of excess PMMA remaining outside the clay galleries was about 12–19°C higher than that of neat PMMA. A structural model of the hybrid was also presented. It involves some PMMA chains diffusing into the gallery of B34 and expanding it by 6.8 Å and some penetrating and interacting with the organic chains of the modified cations. Some of the PMMA chains partly contained inside the clay layers were entangled with those remaining outside when PMMA in excess of the saturation ratio was used. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2101–2115, 2004     

Evaluation of polymethacrylic ionomer as compatibilizers for MCPA6/clay composites

The compatibilization effects provided by polymethacrylic ionomer (PMMA ionomer) on monomer‐casting polyamide6 (MCPA6)/clay (pristine sodium montmorillonite) composites were studied in this work. The PMMA ionomer used in this study was sodium polymethacrylate ionomer (PMMA Na⁺‐ionomer), which is a copolymer of methyl methacrylate and sodium methacrylate, prepared using emulsion polymerization. MCPA6/clay/PMMA Na⁺‐ionomer composites were prepared by in situ anionic ring‐opening polymerization (AROP) of ε‐caprolactam (CLA). X‐ray diffraction (XRD) and transmission electron microscopy (TEM) plus rheological measurement were used to characterize those composites. The results indicated that PMMA Na⁺‐ionomer is a good compatibilizer for this system. With increasing PMMA Na⁺‐ionomer content, a better dispersion of clay layers was successfully achieved in the MCPA6 matrix. Furthermore, differential scanning calorimetry (DSC) and XRD results indicated that well dispersed silicate layers limit the mobility of the MCPA6 molecule chains to crystallize, reduce the degree crystalline, and favor the formation of the γ‐crystalline form of the MCPA6 matrix. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermal and mechanical properties of melt processed intercalated poly(methyl methacrylate)–organoclay nanocomposites over a wide range of filler loading

BACKGROUND: Poly(methyl methacrylate) (PMMA)–organoclay nanocomposites with octadecylammonium ion‐modified montmorillonite, prepared via melt processing, over a wide range of filler loading (2–16 wt%) were investigated in detail. These hybrids were characterized for their dispersion structure, and thermal and mechanical properties, such as tensile modulus (E), break stress (σ_brk), percent break strain (ε_brk) and ductility (J), using wide‐angle X‐ray diffraction, transmission electron microscopy, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and tensile and impact tests. RESULTS: Intercalated nanocomposites were formed even in the presence of 16 wt% clay (high loading) in PMMA matrix. PMMA intercalated into the galleries of the organically modified clay, with a change in d‐spacing in the range 11–16 Å. TGA results showed improved thermal stability of the nanocomposites. The glass transition temperature (T_g) of the nanocomposites, from DSC measurements, was 2–3 °C higher than that of PMMA. The ultimate tensile strength and impact strength decreased with increasing clay fraction. Tensile modulus for the nanocomposites increased by a significant amount (113%) at the highest level of clay fraction (16 wt%) studied. CONCLUSION: We show for the first time the formation of intercalated PMMA nanocomposites with alkylammonium‐modified clays at high clay loadings (>15 wt%). Tensile modulus increases linearly with clay fraction, and the enhancement in modulus is significant. A linear correlation between tensile strength and strain‐at‐break is shown. Thermal properties are not affected appreciably. Organoclay can be dispersed well even at high clay fractions to form nanocomposites with superior bulk properties of practical interest. Copyright © 2007 Society of Chemical Industry     

Effect of organoclays on the rheological and morphological properties of poly(acrylonitrile‐butadiene‐styrene)/poly(methyl methacrylate)/ clay nanocomposites

Using the rheological measurements, the effect of three types of organoclays on the morphology and nanoclay dispersion in the poly(acrylonitrile‐butadiene‐styrene)/poly(methyl methacrylate) (ABS/PMMA) blends was investigated. For this purpose, polymers were melt blended with 2 and 4 wt% of organoclays in a twin‐screw extruder. Structural analysis of the blends and nanocomposites through the rheometery, theoretical approach, X‐ray diffraction, transmission electron microscopy, and scanning electron microscopy revealed that the clay content and interaction level between clays and the polymers dominated the morphology. While the morphology of the blends varied by PMMA content, smaller PMMA domains were observed for blends containing clay particles. Better‐interacted and intercalated nanoclays were mainly located within the interface at lower content. While, at higher content, they tended to migrate into the dispersed phase. Theoretical calculations of interfacial tensions and wetting coefficients confirmed this kind of migration. POLYM. COMPOS., 33:1893–1902, 2012. © 2012 Society of Plastics Engineers     

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     

Structure and properties of nanocomposites based on poly(butylene succinate) and organically modified montmorillonite

Poly(butylene succinate) and organically modified montmorillonite nanocomposites with there different compositions were prepared via melt blending in a twin‐screw extruder. The structure of the nanocomposites was studied with X‐ray diffraction and transmission electron microscopy, which revealed the formation of intercalated nanocomposites, regardless of the silicate loading. Dynamic mechanical analysis revealed a substantial increase in the storage modulus of the nanocomposites over the entire temperature range investigated. The tensile property measurements showed a relative increase in the stiffness with a simultaneous decrease in the yield strength in comparison with that of neat poly(butylene succinate). The oxygen gas barrier property of neat poly(butylene succinate) improved after nanocomposite preparation with organically modified montmorillonite. The effect of the layered‐silicate loading on the melt‐state linear viscoelastic behavior of the intercalated nanocomposites was also investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 777–785, 2006     

Poly(m‐xylene adipamide)–kaolinite and poly(m‐xylene adipamide)–montmorillonite nanocomposites

Two clay compounds, montmorillonite (Cloisite 30B) and kaolinite, were dispersed in a poly(m‐xylene adipamide) resin at loading levels of 2 wt % clay. The samples were melt‐compounded and extruded. The extruded samples were injection‐molded into preforms and then blow‐molded into multilayer bottles. Rheology, calorimetry, electron microscopy, and gas‐transport measurements were performed. Both clays were nucleating agents, giving crystallite sizes that did not cause haze. Kaolinite was more difficult to exfoliate than montmorillonite, and under similar processing conditions, kaolinite resulted in a higher degree of crystallinity. Both nanocomposites exhibited improved gas‐barrier properties over the neat resin. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1377–1381, 2007     

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     

Synthesis and properties of poly(ethylene terephthalate)/clay nanocomposites by in situ polymerization

Poly(ethylene terephthalate) (PET)/clay nanocomposites (PCNs) with N‐methyl diethanol amine (MDEA)‐based organoclays are synthesized by using in situ polymerization. Four kinds of MDEA‐based materials are prepared and used as organifiers of pristine montmorillonite. The clay treated with the organifiers has a d‐spacing range that is about 14–21 Å. The PCNs with these organoclays are characterized by using wide‐angle X‐ray diffraction, scanning and transmission electron microscopy, atomic force microscopy, capillary rheometry, and tensile and barrier testing. The PCNs form an intercalated and delaminated structure. The well‐stacked nanoclays are broken down into small pieces in the PET matrix and the thickness of the clay bundle decreases to 20 nm. The melt viscosity and tensile strength of these PCNs increases with only 0.5 wt % clay. In oxygen barrier testing, the PCN with 1 wt % well‐dispersed organoclay shows a twofold higher barrier property than pure PET. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1262–1271, 2007     

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     

Synthesis and properties of poly(methyl methacrylate)/montmorillonite (PMMA/MMT) nanocomposites

PMMA/MMT nanocomposites were successfully synthesized via in situ intercalative polymerization, and characterized by means of wide‐angle X‐ray diffractometry, transmission electron microscopy, thermal gravimetric analysis, dynamic mechanical analysis and Fourier‐transform infrared analysis. The nanocomposites possess partially exfoliated and partially intercalated structure, in which the silicate layers are exfoliated into nanometre secondary particles with thickness of less than 20 nm and uniformly dispersed in the polymer matrix. In comparison with pure PMMA, the thermal stability, glass transition temperature, and mechanical properties of the polymer are notably improved by the presence of the nanometric silicate layers. It was found that part of the PMMA chains in the nanocomposites are well immobilized inside and/or onto the layered silicates and, therefore, the unique properties of the nanocomposites result from the strong interactions between the nanometric silicate layers and the polymer chains. Copyright © 2003 Society of Chemical Industry     

Preparation of polyethylene‐octene elastomer/clay nanocomposite and microcellular foam processed in supercritical carbon dioxide

Polyethylene‐octene elastomer (POE)/organoclay nanocomposite was prepared by melt mixing of the POE with an organoclay (Cloisite 20A) in an internal mixer, using poly[ethylene‐co‐(methyl acrylate)‐co‐(glycidyl methacrylate)] copolymer (E‐MG‐GMA) as a compatibilizer. X‐ray diffraction and transmission electron microscopy analysis revealed that an intercalated nanocomposite was formed and the silicate layers of the clay were uniformly dispersed at a nanometre scale in the POE matrix. The nanocomposite exhibited greatly enhanced tensile and dynamic mechanical properties compared with the POE/clay composite without the compatibilizer. The POE/E‐MA‐GMA/clay nanocomposite was used to produce foams by a batch process in an autoclave, with supercritical carbon dioxide as a foaming agent. The nanocomposite produced a microcellular foam with average cell size as small as 3.4 µm and cell density as high as 2 × 10¹¹ cells cm^?3. Copyright © 2005 Society of Chemical Industry     

Solid‐state linear viscoelastic properties of intercalated poly(L‐lactide)/organo‐modified montmorillonite hybrids

Hybrids of poly(L ‐lactide)/organophilic clay (PLACHs) have been prepared by a melt‐compounding process using poly(L ‐lactide) (PLLA) and different contents of surface‐treated montmorillonite modified with a dimethyl dioctadecyl ammonium salt. The dispersion structures of clay particles in PLACHs were investigated using wide‐angle X‐ray diffraction and transmission electron microscopy. The solid‐state linear viscoelastic properties for these PLACHs were examined as functions of temperature and frequency. The incorporation of organo‐modified silicate into PLLA matrix enhanced significantly both storage moduli (E′) and loss moduli (E″). The strong enhancement observed in dynamic moduli of PLACHs could be attributed to uniformly dispersed state of the clay particles with high aspect ratio (= length/thickness of clay) and the intercalation of the PLLA chains between silicate layers. Copyright © 2006 Society of Chemical Industry     

Poly(methyl methacrylate)/clay nanocomposites by photoinitiated free radical polymerization using intercalated monomer

A series of poly(methyl methacrylate)/montmorillonite (PMMA/MMT) nanocomposite were prepared by successfully dispersing the inorganic nanolayers of MMT clay in an organic PMMA matrix via in situ photoinitiated free radical polymerization. Methyl methacrylate monomer was first intercalated into the interlayer regions of organophilic clay hosts by “click” chemistry followed by a typical photoinitiated free radical polymerization. The intercalated monomer was characterized by FT-IR spectroscopy, elemental analysis and thermogravimetric analysis methods. The intercalation ability of the modified monomer and exfoliated nanocomposite structure were confirmed by X-ray diffraction spectroscopy (XRD), transmission electron microscopy (TEM) and atomic force microscopy (AFM). Thermal stability of PMMA/MMT nanocomposites was also studied by both differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA).