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 organic modifiers and silicate type on filler dispersion,thermal, and mechanical properties of ABS‐clay nanocomposites

Acrylonitrile–butadiene–styrene (ABS)–clay composite and intercalated nanocomposites were prepared by melt processing, using Na‐montmorillonite (MMT), several chemically different organically modified MMT (OMMT) and Na‐laponite clays. The polymer–clay hybrids were characterized by WAXD, TEM, DSC, TGA, tensile, and impact tests. Intercalated nanocomposites are formed with organoclays, a composite is obtained with unmodified MMT, and the nanocomposite based on synthetic laponite is almost exfoliated. An unintercalated nanocomposite is formed by one of the organically modified clays, with similar overall stack dispersion as compared to the intercalated nanocomposites. T_g of ABS is unaffected by incorporation of the silicate filler in its matrix upto 4 wt % loading for different aspect ratios and organic modifications. A significant improvement in the onset of thermal decomposition (40–44°C at 4 wt % organoclay) is seen. The Young's modulus shows improvement, the elongation‐at‐break shows reduction, and the tensile strength shows improvement. Notched and unnotched impact strength of the intercalated MMT nanocomposites is lower as compared to that of ABS matrix. However, laponite and overexchanged organomontmorillonite clay lead to improvement in ductility. For the MMT clays, the Young's modulus (E) correlates with the intercalation change in organoclay interlayer separation (Δd₀₀₁) as influenced by the chemistry of the modifier. Although ABS‐laponite composites are exfoliated, the intercalated OMMT‐based nanocomposites show greater improvement in modulus. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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     

Influence of organic modification on mechanical properties of melt processed intercalated poly(methyl methacrylate)–organoclay nanocomposites

The influence of organic modifiers on intercalation extent, structure, thermal and mechanical properties of poly(methyl methacrylate) (PMMA)–clay nanocomposites were studied. Two different organic modifiers with varying hydrophobicity (single tallow versus ditallow) were investigated. The nanocomposites were prepared from melt processing method and characterized using wide angle X‐ray diffraction, transmission electron microscopy, thermogravimetric analysis, differential scanning calorimetry (DSC), and tensile tests. Mechanical properties such as tensile modulus (E), break stress (σ_brk), and % break strain (ε_brk) were determined for nanocomposites at various clay loadings. Extent of PMMA intercalation is sufficient and in the range 9–15 Å depending on organoclay and filler loading. Overall thermal stability of nanocomposites increases by 16–30°C. The enhancement in T_g of nanocomposite is merely by 2–4°C. With increase in clay loading, tensile modulus increases linearly while % break strain decreases. Break stress is found to increase till 4 wt % and further decreases at higher clay loadings. The overall improvement in thermal and mechanical properties was higher for the organoclay containing organic modifier with lower hydrophobicity and single tallow amine chemical structure. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

New aramid‐based nanocomposites: Synthesis and characterization

New type of nanocomposites containing various proportions of montmorillonite in aromatic polyamide was prepared via solution intercalation method. Aramid chains were synthesized by reacting 4,4′‐oxydianiline with isophthaloyl chloride in N,N′‐dimethyl acetamide. Dodecylamine was used as swelling agent to change the hydrophilic nature of montmorillonite into organophilic. Appropriate amounts of organoclay were mixed in the polymer solution using high‐speed mixer for complete dispersion of the clay. Thin films cast from these materials after evaporating the solvent were characterized by XRD, TEM, mechanical, thermal, and water absorption measurements. The structure and morphology of the nanocomposites determined by XRD and TEM revealed the formation of exfoliated and intercalated clay platelets in the aramid matrix. Mechanical data indicated improvement in the tensile strength and modulus of the nanocomposites with clay loading up to 6 wt%. The glass transition temperature increased up to 12 wt% clay content and thermal stability amplified with increasing clay loading. The water absorption reduced gradually as a function of organoclay and approached to zero with 20 wt% organoclay in the aramid. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Fracture behavior of thermoplastic polyolefin/clay nanocomposites

A thermoplastic polyolefin (TPO) containing 70 wt % styrene–ethylene–butadiene‐styrene‐g‐maleic anhydride and 30 wt % polypropylene and its nanocomposites reinforced with 0.3–1.5 wt % organoclay were prepared by melt mixing followed by injection molding. The mechanical and fracture behaviors of the TPO/clay nanocomposites were investigated. The essential work of fracture (EWF) approach was used to evaluate the tensile fracture behavior of the nanocomposites toughened with elastomer. Tensile tests showed that the stiffness and tensile strength of TPO was enhanced by the addition of low loading levels of organically modified montmorillonite. EWF measurements revealed that the fracture toughness of the TPO/clay nanocomposites increased with increasing clay content. The organoclay toughened the TPO matrix of the nanocomposites effectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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     

Effect of carbon black on properties of rubber nanocomposites

Polymer based nanocomposites were prepared using brominated poly(isobutylene‐co‐paramethylstyrene) (BIMS) rubber and octadecyl amine modified montmorillonite nanoclay. The effect of nature and loading of carbon black on these nanocomposites and the control BIMS was investigated thoroughly using X‐ray diffraction technique (XRD), Fourier transform infrared spectroscopy (FTIR), and mechanical properties. The addition of 4 parts of the modified nanoclay to 20 phr N550 carbon black filled samples increased the tensile strength by 53%. Out of the three different grades of carbon black (N330, N550, and N660), N550 showed the best effect of nanoclay. Optimum results were obtained with the 20 phr filler loading. For comparison, china clay and silica at the same loading were used. Fifty‐six and 46% improvements in tensile strength were achieved with 4 parts of nanoclay added to the silica and the china clay filled samples, respectively. N330 carbon black (20 parts) filled styrene butadiene rubber (SBR) based nanocomposite registered 20% higher tensile strength with 4 parts of the modified nanoclay. In all the above carbon black filled nanocomposites, the modulus was improved in the range of 30 to 125%. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 443–451, 2005     

Mesua ferrea L. seed oil based highly branched polyester/epoxy blends and their nanocomposites

Mesua ferrea L. seed oil based highly branched polyester and epoxy resins blends were prepared by mechanical mixing at different weight ratios. The best performing blend was used as the matrix for the preparation of nanocomposites with different dose levels of organophilic montmorillonite (OMMT) nanoclay. The prepared nanocomposites were characterized by X‐ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, and transmission electron microscopy. Data resulting from the mechanical and thermal studies of the blends and nanocomposites indicated improvements in the tensile strength and thermal stability to appreciable extents for the nanocomposites with OMMT loading. The nanocomposites were characterized as well‐dispersed, partially exfoliated structures with good interfacial interactions. From the X‐ray diffraction analysis, the absence of d₀₀₁ reflections of the OMMT clay in the cured nanocomposites indicated the development of an exfoliated clay structure, which was confirmed by transmission electron microscopy. The homogeneous morphologies of the pure polyester/epoxy blend and clay hybrid systems were ascertained with scanning electron microscopy. The tensile strength of the 5 wt % clay‐filled blend nanocomposite system was increased by 2.4 times compared to that of the pure blend resin system. The results suggest that the prepared nanocomposites have the potential to be used as active thin films for different applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of clay modification on the morphological,mechanical, and thermal properties of polyamide 6/polypropylene/montmorillonite nanocomposites

Polyamide 6/polypropylene (PA6/PP = 70/30 parts) blends containing 4 phr (parts per hundred resin) of organophilic montmorillonite (OMMT) were prepared by melt compounding. The sodium montmorillonite (Na‐MMT) was modified using three different types of alkyl ammonium salts, namely dodecylamine, 12‐aminolauric acid, and stearylamine. The effect of clay modification on the morphological and mechanical properties of PA6/PP nanocomposites was investigated using x‐ray diffraction (XRD), transmission electron microscopy (TEM), tensile, flexural, and impact tests. The thermal properties of PA6/PP nanocomposites were characterized using thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), and heat distortion temperature (HDT). XRD and TEM results indicated the formation of exfoliated structure for the PA6/PP nanocomposites prepared using stearylamine modified montmorillonite. On the other hand, a mixture of intercalated and exfoliated structures was found for the PA6/PP nanocomposites prepared using 12‐aminolauric acid and dodecylamine modified montmorillonite. Incorporation of OMMT increased the stiffness but decreased the ductility and toughness of PA6/PP blend. The PA6/PP nanocomposite containing stearylamine modified montmorillonite showed the highest tensile, flexural, and thermal properties among all nanocomposites. This could be attributed to better exfoliated structure in the PA6/PP nanocomposite containing stearylamine modified montmorillonite. The storage modulus and HDT of PA6/PP blend were increased significantly with the incorporation of both Na‐MMT and OMMT. The highest value in both storage modulus and HDT was found in the PA6/PP nanocomposite containing stearylamine modified montmorillonite due to its better exfoliated structure. POLYM. COMPOS., 31:1156–1167, 2010. © 2009 Society of Plastics Engineers     

Preparation and characterization of chitosan/montmorillonite‐K10 nanocomposites films for food packaging applications

Chitosan (CS)/montmorillonite‐K10 (MMTK‐10) clay composite films with different amounts of the clay MMTK‐10 (0.5, 1, 2.5, and 5%) were prepared using a solution‐casting method, and their properties were determined. The objective of this study is to prepare CS/clay nanocomposites and then to investigate the effects of clay content on mechanical, barrier, and thermal properties of these nanocomposites. The prepared films were characterized by Fourier transform infrared spectroscopy, X‐ray diffraction analysis, transmission electron microscopy, and scanning electron microscopy. Barrier properties (oxygen and water permeability), mechanical properties (tensile strength and elongation), and thermal behaviors (thermogravimetric analysis) were investigated and compared. The water vapor and gas permeability values of the composite films decreased significantly with increasing filler concentration. Tensile strength of the composites increased significantly with the addition of clay, and elongation at break decreased with increasing clay concentration. The tensile strength of nanocomposites is up to 34.82 MPa for 5 wt% clay content, and the tensile modulus shows a 74.63% higher value than that of neat CS. The resulting films had an opaque appearance, which depended on the amount of MMTK‐10 added. The oxygen permeability decreased with the increase in MMTK‐10. The minimum oxygen permeability (1.54 cm³/m² day atm) was recorded for film with 5% MMTK‐10. The water permeability of the composite films decreased significantly between 13 and 22% when clay was added. The dispersed clay improves the thermal stability and enhances the hardness and elastic modulus of the matrix systematically with the increased loading of clay. POLYM. COMPOS., 33:1874–1882, 2012. © 2012 Society of Plastics Engineers     

Synthesis and characterization of epoxy based nanocomposites

Epoxy‐clay nanocomposites were synthesized to examine the effects of the content and type of different clays on the structure and mechanical properties of the nanocomposites. Diglycidyl ether of bisphenol‐A (epoxy) was reinforced by 0.5–11 wt % natural (Cloisite Na⁺) and organically modified (Cloisite 30B) types of montmorillonite. SEM results showed that as the clay content increased, larger agglomerates of clay were present. Nanocomposites with Cloisite 30B exhibited better dispersion and a lower degree of agglomeration than nanocomposites with Cloisite Na⁺. X‐ray results indicated that in nanocomposites with 3 wt % Cloisite 30B, d‐spacing expanded from 18.4 Å (the initial value of the pure clay) to 38.2 Å. The glass transition temperature increased from 73°C, in the unfilled epoxy resin, to 83.5°C in the nanocomposite with 9 wt % Cloisite 30B. The tensile strength exhibited a maximum at 1 wt % modified clay loading. Addition of 0.5 wt % organically modified clay improved the impact strength of the epoxy resin by 137%; in contrast, addition of 0.5 wt % unmodified clay improved the impact strength by 72%. Tensile modulus increased with increasing clay loading in both types of nanocomposites. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1081–1086, 2005     

Alteration of the mechanical and thermal properties of nylon 6/nylon 6,6 blends by nanoclay

Nylon 6 [N(6)], nylon 6,6 [N(6,6)], and their blends at different clay loadings were prepared. The mix was melted and injected into strip‐shaped samples. Mechanical and thermal analyses were performed to investigate the effect of blending and the incorporated clay on the mechanical and thermal properties. Enhancements in the Young's modulus and hardness were obtained for all of the nanocomposites, with a 55% increase in Young's modulus after the addition of 6 wt % nanoclay, although the improvement in tensile strength depended on the blend ratio, with greatest effects on the 50% N(6)/50% N(6,6) blend with increases of 44 and 59% for 2 and 4% clay loadings, respectively. Thermogravimetric analysis showed an enhancement in the thermal properties in the 50% N(6)/50% N(6,6) blend at 2% clay loading, and the blend exhibited ductile behavior at this loading. Increases in the crystallization peak temperatures of 10–15° in N(6,6) and the two blends 30% N(6)/70% N(6,6) and 50% N(6)/50% N(6,6) were observed after the addition of the clay. The nanoclay enhanced the γ‐/β‐form crystals in N(6) and N(6,6) neat polymers and also in the blends. Fourier transform infrared spectroscopy FT‐IR revealed the formation of hydrogen bonding and the possible formation of ionic bonds between the polymers and the nanoclay, which resulted in enhancements in the mechanical properties of the blends. The distribution of the nanoclay in the blend was well dispersed, as shown by X‐ray diffraction analysis. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Bio‐based polymer nanocomposites based on layered silicates having a reactive and renewable intercalant

Soybean oil‐based polymer nanocomposites were synthesized from acrylated epoxidized soybean oil (AESO) combined with styrene monomer and montmorillonite (MMT) clay by using in situ free radical polymerization reaction. Special attention was paid to the modification of MMT clay, which was carried out by methacryl‐functionalized and quaternized derivative of methyl oleate intercalant. It was synthesized from olive oil triglyceride, as a renewable intercalant. The resultant nanocomposites were characterized by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The effect of increased nanofiller loading in thermal and mechanical properties of the nanocomposites was investigated by thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA). The nanocomposites exhibited improved thermal and dynamic mechanical properties compared with neat acrylated epoxidized soybean oil based polymer matrix. The desired exfoliated nanocomposite structure was achieved when the OrgMMT loading was 1 and 2 wt % whereas partially exfoliated nanocomposite was obtained in 3 wt % loading. It was found that about 400 and 500% increments in storage modulus at glass transition and rubbery regions, respectively were achieved at 2 wt % clay loading compared to neat polymer matrix while the lowest thermal degradation rate was gained by introducing 3 wt % clay loading. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2031–2041, 2013     

Effect of different nanoparticles on thermal,mechanical and dynamic mechanical properties of hydrogenated nitrile butadiene rubber nanocomposites

Organically modified and unmodified montmorillonite clays (Cloisite NA, Cloisite 30B and Cloisite 15A), sepiolite (Pangel B20) and nanosilica (Aerosil 300) were incorporated into hydrogenated nitrile rubber (HNBR) matrix by solution process in order to study the effect of these nanofillers on thermal, mechanical and dynamic mechanical properties of HNBR. It was found that on addition of only 4 phr of nanofiller to neat HNBR, the temperature at which maximum degradation took place (T_max) increased by 4 to 16°C, while the modulus at 100% elongation and the tensile strength were enhanced by almost 40–60% and 100–300% respectively, depending upon nature of the nanofiller. It was further observed that T_max was the highest in the case of nanosilica‐based nanocomposite with 4 phr of filler loading. The increment of storage modulus was highest for sepiolite‐HNBR and Cloisite 30B‐HNBR nanocomposites at 25°C, while the modulus at 100% elongation was found maximum for sepiolite‐HNBR nanocomposite at the same loading. A similar trend was observed in the case of another grade of HNBR having similar ACN content, but different diene level. The results were explained by x‐ray diffraction, transmission electron microscopy, and atomic force microscopy studies. The above results were further explained with the help of thermodynamics. Effect of different filler loadings (2, 4, 6, 8, and 16 phr) on the properties of HNBR nanocomposites was further investigated. Both thermal as well as mechanical properties were found to be highest at 8 phr of filler loading. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and characterization of polymer/organosilicate nanocomposites based on unmodified LDPE

Low‐density polyethylene (LDPE)/silicate nanocomposites were prepared by the melt compounding and solution blend methods using unmodified LDPE polymer and layered silicates with different aspect ratio. X‐ray diffraction (XRD) analysis performed on composites obtained by dispersing the organosilicates in molten LDPE evidenced an exfoliated or partially exfoliated structure for the low aspect ratio silicate (laponite) in contrast to the high aspect ratio silicate (montmorillonite), which led to the formation of intercalated nanocomposites. With regard to the preparation method, the melt compounding method was more effective in forming exfoliated/highly intercalated LDPE nanocomposites compared with the solution blend method (using CCl₄ as a solvent). A gradual increase in crystallization temperatures (T_c) with increasing laponite content for LDPE‐organolaponite nanocomposites was revealed by differential scanning calorimetry (DSC) measurements. Thermogravimetric analysis and tensile measurements results indicated that thermal stability and elastic modulus increment were more prevalent for nanocomposites prepared using organomontmorillonite as filler. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Dynamic mechanical,rheological, and thermal properties of intercalated polystyrene/organomontmorillonite nanocomposites: Effect of clay modification on the mechanical and morphological behaviors

Polystyrene (PS)/organomontmorillonite nanocomposites were prepared by melt processing with a twin‐screw extruder. Sodium montmorillonite was organically modified with stearyl trimethyl ammonium chloride to evaluate the effect of clay modification on the performance of the nanocomposites. A comparative account of nanocomposites prepared with the commercial clay Cloisite 20A (C20A) is presented. X‐ray diffraction studies indicated that the clay layers were completely dispersed, and a delaminated structure was formed in the case of C20A/PS and organomontmorillonite/PS nanocomposites. The dispersion characteristics of the clays within the matrix polymer were further investigated through transmission electron microscopy analysis. Mechanical tests revealed increases in the tensile, flexural, and impact strengths of 83, 55, and 74%, respectively, for C20A/PS nanocomposites at a 5% clay loading. The viscoelastic response of the nanocomposites, studied with dynamic mechanical analysis, also showed a substantial increase in the storage modulus of the nanocomposites with the incorporation of organically modified nanoclays. Furthermore, the melt‐state rheology of the organically modified nanocomposites displayed three distinct regions—glassy, plateau, and terminal—from the high‐frequency region to the low‐frequency region, with a considerable increase in the storage modulus in the glassy and terminal regions. Differential scanning calorimetry and thermogravimetric analysis were also used to evaluate the effect of the addition of nanoclays on the glass‐transition temperature and thermal stability of the PS matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The structure and properties of PA6/MMT nanocomposites prepared by melt compounding

Polyamide 6 (PA6)/organo‐montmorillonite nanocomposites prepared by melt compounding using a co‐rotating twin‐screw extruder were intercalated nanocomposites. The modulus, bending strength and heat distortion temperature of these nanocomposites increased with increasing clay content, and tensile strength increased up to 4.3 wt% and then decreased with further increases in montmorillonite content. The notched Izod impact strength decreased slightly with montmorillonite content. Nanocomposites based on the higher‐molecular‐weight PA6 yielded higher moduli, tensile strengths, and heat distortion temperatures at the same montmorillonite content. Polym. Eng. Sci. 44:2070–2074, 2004. © 2004 Society of Plastics Engineers.     

Structure and properties of phenolic resin/nanoclay composites synthesized by in situ polymerization

An in situ semibatch polymerization process for making phenolic resin/montmorillonite clay nanocomposites is developed. It is found that auxiliary mixing in phenol allows intercalation of the monomer and polymer between montmorillonite clay layers. At 2.7% clay by mass the montmorillonite is predominantly exfoliated (fully dispersed). At higher clay loading, a substantial amount of the clay remains in aggregate or intercalated form. When the montmorillonite is exfoliated, the material is mechanically superior. The composite has a tensile modulus that is 21% higher than the neat resin and has 87% improved fracture strength, 100% larger fracture energy, and strain to failure 13% above the pure resin. Thermogravimetric analysis shows the montmorillonite system maintains its thermal stability up to 200°C. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1169–1174, 2005     

New approach for preparation of dry natural rubber nanocomposites through acid‐free co‐coagulation: Effect of organoclay content

Natural rubber (NR) vulcanizates exhibit good mechanical properties compared to vulcanizates of synthetic rubbers. Incorporation of a conventional filler at higher loadings to NR enhances its modulus, while reduction in tensile strength and elongation. This paper presents a new strategy for development of a NR‐clay nanocomposite with enhanced mechanical properties by incorporation of lower loadings (2–8 phr) of cetyl trimethyl ammonium bromide modified montmorillonite clay (OMMT‐C) under acid‐free environment. The effect of OMMT‐C loading on cure characteristics, rubber‐filler interactions, crosslink density, dynamic mechanical thermal properties, and mechanical properties were evaluated. Incorporation of OMMT‐C accelerated the vulcanization process and enhanced mechanical properties. X‐ray diffraction analysis and scanning electron microscopy images revealed that the formation of intercalated clay structures at lower OMMT‐C loadings, and clay aggregates at higher loadings. A nanocomposite at OMMT‐C loading of 2 phr exhibited the best balanced mechanical properties, and was associated with highest crosslink density and rubber–filler interactions. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46502.