Effect of exfoliation and dispersion on the yield behavior of melt‐compounded polyethylene–montmorillonite nanocomposites

The yield behavior of melt‐mixed nanocomposites containing 5 wt % organically modified montmorillonite in matrices of a linear low‐density polyethylene (LLDPE) or a modified polyethylene was studied as a function of the temperature and strain rate. In the melt‐mixed LLDPE nanocomposite, the montmorillonite showed a slight increase in the clay spacing, which suggested that the clay was at best intercalated. Transmission electron microscopy (TEM) images showed that the dispersion in this nanocomposite was poor. The use of the modified polyethylene promoted exfoliation of the clay tactoids in the nanocomposite, as assessed by X‐ray diffraction and TEM. In both nanocomposites, the yield mechanisms were insensitive to the addition of the organoclay, even though modest increases in the modulus were produced. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3044–3049, 2006     

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     

Studies on nylon 6/clay nanocomposites by melt‐intercalation process

The preparation of nylon 6/clay nanocomposites by a melt‐intercalation process is proposed. X‐ray diffraction and DSC results show that the crystal structure and crystallization behaviors of the nanocomposites are different from those of nylon 6. Mechanical and thermal testing shows that the properties of the nanocomposites are superior to nylon 6 in terms of the heat‐distortion temperature, strength, and modulus without sacrificing their impact strength. This is due to the nanoscale effects and the strong interaction between the nylon 6 matrix and the clay interface, as revealed by X‐ray diffraction, transmission electron microscopy, and Molau testing. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1133–1138, 1999     

PP/clay nanocomposites: Effect of clay treatment on morphology and dynamic mechanical properties

The morphology and properties of polypropylene (PP)/clay nanocomposites are described. The melt intercalation of organophilic clay was carried out with a single‐screw extruder. The effects of two kinds of treatments of clay are discussed. Maleic anhydride (MAH)‐grafted PP was used as a compatibilizer. The expansion of the intergallery distance of the clay was governed by the interaction between the clay treatment and the compatibilizer. In one case, the composites exhibited significantly reduced intensities of diffraction peaks, suggesting partial exfoliation of the clay layers, whereas for the second clay sample, expansion of the gallery height was noted. The mechanical properties of the PP/clay composites showed significant enhancement in their mechanical and thermal properties. About a 35% increase in the tensile modulus and about a 10% increase in the tensile strength were observed. The thermal degradation temperature increased from 270 to about 400°C as a result of the incorporation of clay, and the extent depended on the dispersion of clay in the composite. The most interesting outcome of this study was the changes in morphology for PP/clay composites, which are reported here for the first time. An optical microscopic study revealed that the PP/clay composites could be crystallized at higher temperatures than pure PP and that the morphology was remarkably altered because of the presence of layers of clay. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1786–1792, 2001     

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     

Influence of organically modified nanoclay on the performance of pineapple leaf fiber‐reinforced polypropylene nanocomposites

Polypropylene/Pine apple leaf fiber (PP/PALF)‐reinforced nanocomposites were fabricated using melt blending technique in a twin‐screw extruder (Haake Rheocord 9000). Variation in mechanical properties, crystallization behavior, water absorption, and thermal stability with the addition of nanoclay in PP/PALF composites were investigated. It was observed that the tensile, flexural, and impact properties of PP increase with the increase in fiber loading from 10 to 30 wt %. Composites prepared using 30 wt % PALF and 5 wt % MA‐g‐PP exhibited optimum mechanical performance with an increase in tensile strength to 31%, flexural strength to 45% when compared with virgin PP. Addition of nanoclay results in a further increase in tensile and flexural strength of PP/PALF composites to 20 and 24.3%, which shows intercalated morphology. However, addition of nanoclay does not show any substantial increase in impact strength when compared with PP/PALF composites. Dynamic mechanical analysis tests revealed an increase in storage modulus (E′) and damping factor (tan δ), confirming a strong influence between the fiber/nanoclay and MA‐g‐PP. Differential scanning calorimetry, thermogravimetric analysis thermograms also showed improved thermal properties when compared with the virgin matrix. TEM micrographs also showed few layers of agglomerated clay galleries along with mixed nanomorphology in the nanocomposites. Wide angle X‐ray diffraction studies indicated an increase in d‐spacing from 22.4 Å in Cloisite 20A to 40.1 Å in PP/PALF nanocomposite because of improved intercalated morphology. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The role of crystallinity and reinforcement in the mechanical behavior of polyamide‐6/clay nanocomposites

The mechanical behavior of compression‐molded polyamide‐6 (PA6) reinforced with 2 wt% of organo‐nanoclay (montmorillonite intercalated with ω‐amino dodecanoic acid) has been studied and compared to that of PA6. The tensile strength and the Young's modulus of the PA6/clay were 15% higher than those of PA6. Differential scanning calorimetry, Fourier transform infrared spectroscopy, and X‐ray diffraction showed that the crystalline structures of PA6 and PA6/clay differed considerably. A crystallinity of 25% with a dual structure composed of the γ and α forms was obtained in PA6/clay, while a crystallinity of 31% with the α form as the dominant crystalline structure was obtained in PA6. To understand the role of the crystalline structure of PA6, the molding process was modified to obtain PA6 specimens with different levels of crystallinity and different crystalline forms. Quenching molten PA6 at a cooling rate sufficiently high to prevent crystallization gave a material that was predominantly amorphous (crystallinity of 7%) with traces of the mesomorphic β or γ* form. Annealing this material at 80°C considerably increased crystallinity to 21%, which was also of the mesomorphic β or γ* form. PA6 with a predominant crystalline γ form could not be generated. Comparisons with PA6/clay in terms of crystallinity and mechanical behavior lead to the conclusion that the improvements in rigidity and strength observed when montmorillonite is added to PA6 are related to the reinforcing filler and not to a modification of the crystalline structure.     

Interfacial,dynamic mechanical,and thermal fiber reinforced behavior of MAPE treated sisal fiber reinforced HDPE composites

The present article summarizes an experimental study on the mechanical and dynamic mechanical behavior of sisal fiber reinforced HDPE composites. Variations in mechanical strength, storage modulus (E′), loss modulus (E″), and damping parameter (tan δ) with the addition of fibers and coupling agents were investigated. It was observed that the tensile, flexural, and impact strengths increased with the increase in fiber loading up to 30%, above which there was a significant deterioration in the mechanical strength. Further, the composites treated with MAPE showed improved properties in comparison with the untreated composites. Dynamic mechanical analysis data also showed an increase in the storage modulus of the treated composites The tan δ spectra presented a strong influence of fiber content and coupling agent on the α and γ relaxation process of HDPE. The thermal behavior of the composites was evaluated from TGA/DTG thermograms. The fiber–matrix morphology in the treated composites was confirmed by SEM analysis of the tensile fractured specimens. FTIR spectra of the treated and untreated composites were also studied, to ascertain the existence of type of interfacial bonds. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3306–3315, 2006     

Crystallization and thermal behavior of microcellular injection‐molded polyamide‐6 nanocomposites

This article presents the effects of nanoclay and supercritical nitrogen on the crystallization and thermal behavior of microcellular injection‐molded polyamide‐6 (PA6) nanocomposites with 5 and 7.5 wt% nanoclay. Differential scanning calorimetry (DSC), X‐ray diffractometry (XRD), and polarized optical microscopy (POM) were used to characterize the thermal behavior and crystalline structure. The isothermal and nonisothermal crystallization kinetics of neat resin and its corresponding nanocomposite samples were analyzed using the Avrami and Ozawa equations, respectively. The activation energies determined using the Arrhenius equation for isothermal crystallization and the Kissinger equation for nonisothermal crystallization were comparable. The specimen thickness had a significant influence on the nonisothermal crystallization especially at high scanning rates. Nanocomposites with an optimal amount of nanoclay possessed the highest crystallization rate and a higher level of nucleation activity. The nanoclay increased the magnitude of the activation energy but decreased the overall crystallinity. The dissolved SCF did not alter the crystalline structure significantly. In contrast with conventionally injection‐molded solid counterparts, microcellular neat resin parts and microcellular nanocomposite parts were found to have lower crystallinity in the core and higher crystallinity near the skin. POLYM. ENG. SCI., 46:904–918, 2006. © 2006 Society of Plastics Engineers     

Investigation of thermal degradation and flammability of polyamide‐6 and polyamide‐6 nanocomposites

In this paper, polyamide‐6 and polyamide‐6 nanocomposites were prepared by direct melt intercalation technique. The thermal degradation behavior of both polyamide‐6 and polyamide‐6 clay nanocomposites has been studied. The apparent activation energy of the nanocomposites is almost the same with that of pure polymer under nitrogen, but the apparent activation energy of the nanocomposites is greatly enhanced in air atmosphere. This increasing trend coincides with the thermal analysis and the cone calorimeter results, which may suggest that the polymer/clay nanocomposites have a higher thermal stability and lower flammability. The kinetic analysis also indicates that the pyrolytic degradation and the thermal oxidative degradation of PA6 and PA6/OMT nanocomposites are two kinds of different reaction models. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2297–2303, 2007     

Effect of long‐term natural aging on the thermal,mechanical, and viscoelastic behavior of biomedical grade of ultra high molecular weight polyethylene

In the total joint prostheses, Ultra High Molecular Weight Polyethylene (UHMWPE) may undergo an oxidative degradation in the long term. The overall properties of UHMWPE are expected to be altered due to the oxidative degradation. The goal of this study is to investigate the effects of natural aging up to 6 years in air on the thermal, mechanical, and viscoelastic properties of UHMWPE that was used in total joint replacement. The changes in UHMWPE properties due to aging are determined using Differential Scanning Calorimetry (DSC), uniaxial tensile tests, and Dynamic Mechanical Analysis (DMA). The DSC results show that the lamellar thickness and degree of crystallinity of UHMWPE specimens increase by 38% and 12% due to aging. A small shoulder region in the DSC thermograms is remarked for aged specimens, which is an indication of formation of new crystalline forms within their amorphous region. The tensile properties of aged and nonaged UHMWPE specimens show a significant decrease in the elastic modulus, yield, fracture stresses, and strain at break due to aging. The DM testing results indicate that the storage modulus and creep resistance of UHMWPE specimens decrease significantly due to aging. Also, it is remarked that the α relaxation peak for aged UHMWPE specimens occurs at lower temperature compared to nonaged ones. The significant reduction in the strength and creep resistance of UHMWPE specimens due to aging would affect the long‐term clinical performance of the total joint replacement and should be taken into consideration during artificial joint design. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Microstructure,crystallization and dynamic mechanical properties of polyamide/clay nanocomposites after melt‐state annealing

Polyamide 6/clay (PA/clay) nanocomposites produced by melt‐compounding were treated under various melt‐state annealing processes. The effect of melt‐state annealing on the microstructure, crystallization, and dynamic mechanical properties was characterized by transmission electron microscope (TEM), modulated differential scanning calorimetry (MDSC), X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and dynamic mechanical analysis (DMA). Clay layers were exfoliated in PA matrix. The crystalline transformation between α and γ‐crystalline phase was virtually dependent on the annealing process and clay loading. After melt‐state annealing between 230 and 250°C, clay induced the appearance of a new endothermic peak in PA/clay. PA/clay after melt‐state annealing exhibited a higher elastic modulus above T_g and a lower β relaxation below T_g as compared with the non‐annealed sample. FTIR analysis demonstrated that the melt‐state annealing caused strong hydrogen bonding interaction of amide groups with clay layers. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Role of processing history on the mechanical and electrical behavior of melt‐compounded polycarbonate‐multiwalled carbon nanotube nanocomposites

This work investigates the effects of primary compounding temperature and secondary melt processes on the mechanical response and electrical resistivity of polycarbonate filled with 3 wt % multiwalled carbon nanotubes (CNT). Nanocomposites were melt compounded in an industrial setting at a range of temperatures, and subsequently either injection molded or compression molded to produce specimens for the measurement of electrical resistivity, surface hardness, and uniaxial tensile properties. Secondary melt processing was found to be the dominant process in determining the final properties. The effects observed have been attributed to structural arrangements of the CNT network as suggested by morphological evidence of optical microscopy and resistivity measurements. Properties were found to be relatively insensitive to compounding temperature. The measured elastic moduli were consistent with existing micromechanical models. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42277.     

Relationship between mechanical properties and exfoliation degree of clay in polyurethane nanocomposites

Exfoliated and intercalated polyurethane (PU) nanocomposites were prepared by in situ polymerization of polyol/organoclay mixture, chain extender and diisocyanate. Wide‐angle X‐ray diffraction and transmission electron microscopy confirmed an exfoliated structure for clay C30B and an intercalated structure for C20A in polyol and PU. The realization of exfoliated state for clay C30B in polyol during the mixing stage can provide an effective approach for controlling the exfoliation degrees by adjusting the content of intercalated and exfoliated organoclay C20A and C30B before polymerization. The effect of exfoliation degree on the mechanical and viscoelastic properties of PU was investigated. The addition of organoclay improved the tensile strength, modulus and elongation, but the hysteresis loss ratio and relaxation rate increased, and the relaxation time distribution became broad. The effect of organoclay on PU properties varied with the hard segment content. By increasing the exfoliation degree, the tensile strength and modulus increased, whereas the elongation decreased. The exfoliated PU nanocomposite had a lower relaxation rate and hysteresis loss ratio than the intercalated PU. Copyright © 2005 Society of Chemical Industry     

Nonisothermal crystallization behavior of melt‐intercalated polyethylene‐clay nanocomposites

The influence of nanoclay particles on the nonisothermal crystallization behavior of intercalated polyethylene (PE) prepared by melt‐compounding was investigated. It is observed that the crystallization peak temperature (T_p) of PE/clay nanocomposites is slightly but consistently higher than the neat PE at various cooling rates. The half‐time (t_0.5) for crystallization decreased with increase in clay content, implying the nucleating role of nanoclay particles. The nonisothermal crystallization data are analyzed using the approach of Avrami (Polymer 1971, 12, 150), Ozawa (Polym Eng Sci 1997, 37, 443), and Mo and coworkers (J Res Natl Bur Stand 1956, 57, 217), and the validity of the different kinetic models to the nonisothermal crystallization process of PE/clay nanocomposites is discussed. The approach developed by Mo and coworkers successfully explains the nonisothermal crystallization behavior of PE and PE/clay nanocomposites. The activation energy for nonisothermal crystallization of neat PE and PE/clay nanocomposites is determined using the Kissinger (J Res Natl Bur Stand 1956, 57, 217) method. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3809–3818, 2006     

Thermal,morphological, and X‐ray study of polymer‐clay nanocomposites

Synthesis and characterization of polymer nanocomposites consisting of diglycidyl ether of bisphenol‐A with inorganic as well as organically modified nanosized clay fillers, for example, vermiculites and montmorillonite, obtained from trade, are studied. Confirmations of intercalation and exfoliation characteristics of these fillers into the cured epoxy resin matrix have been investigated by wide angle X‐ray diffraction studies. Scanning electron microscopy and atomic force microscopy techniques have been adopted to assess the nature of filler dispersion, size of the agglomerates, and the polymer‐filler adhesion. While significant improvement in the mechanical properties (i.e., tensile, flexural strength, and modulus) has been observed, the thermo‐oxidative stability of the composites measured by thermogravimetric analysis showed only marginal improvement. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Influence of clay type on exfoliation,cure and physical properties of in situ polymerised poly(methyl methacrylate) nanocomposites

BACKGROUND: The nature of the dispersion of clay platelets in a resin composite will play an important role in the process of enhancement of the physical properties of that material. This paper examines how different modifiers and the quantity of surface treatment for the Cloisite^® range of organically modified clays affect properties in in situ polymerised poly(methyl methacrylate). Another clay which is a mixture of rod‐ and platelet‐like minerals is also investigated to understand how the shape of the clay particles can affect the polymer properties. RESULTS: Five different clays, including Cloisite 30B and Cloisite 15A, were dispersed using ultrasound and the cure of the samples was monitored using the Strathclyde Rheometer. Rheology, transmission electron microscopy and X‐ray diffraction were used to determine that a good level of clay dispersion was achieved. The mixed mineral formed the most stable dispersion seen from settling tests. CONCLUSIONS: The cure accelerated in the presence of organoclay, although the affect was less pronounced at higher temperatures. The glass transition temperature was increased by 20 °C with only a few weight percent of clay and water uptake was not adversely affected. Copyright © 2008 Society of Chemical Industry     

Morphology,thermal and mechanical behavior of polypropylene nanocomposites toughened with poly(ethylene‐co‐octene)

Rubber‐toughened polypropylene (PP) nanocomposites containing organophilic layered silicates were prepared by means of melt extrusion at 230 °C using a co‐rotating twin‐screw extruder in order to examine the influence of the organoclay and the addition of PP grafted with maleic anhydride (PPgMAH) as a compatibilizer on the morphological, mechanical and thermal properties. The mechanical properties of rubber‐toughened polypropylene nanocomposites (RTPPNCs) were studied through tensile, flexural and impact tests. Scanning electron microscopy (SEM) was used for investigation of the phase morphology and rubber particles size. X‐ray diffraction (XRD) was employed to characterize the formation of nanocomposites. The thermal properties were investigated by using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The dynamic mechanical properties were examined by using dynamic mechanical analysis (DMA). From the tensile and flexural tests, the optimum loading of organoclay in RTPP was found to be 6 wt%. The optimum loading of PPgMAH, based on the tensile and flexural properties, was also 6 wt%. The increase in the organoclay and PPgMAH content resulted in a severe embrittlement, manifested by a drop in the impact strength and tensile elongation at break. XRD studies revealed that intercalated RTPPNCs had been successfully prepared where the macromolecular PP segments were intercalated into the interlayer space of the organoclay. In addition, the organoclay was dispersed more evenly in the RTPPNC as the PPgMAH content increased. TGA results revealed that the thermal stability of the RTPPNC improved significantly with the addition of a small amount of organoclay. Copyright © 2006 Society of Chemical Industry     

The effects of promoter and curing process on exfoliation behavior of epoxy/clay nanocomposites

The effects of a catalyst and coupling agent as well as a curing process on exfoliation behavior of CH₃(CH₂)₁₅NH₃+–montmorillonite clay in an anhydride‐cured epoxy–clay system have been investigated by XRD, DSC, and TEM. The results have shown that the organoclay is easily intercalated by the epoxy precursor during the mixing process, and the clay galleries continue to expand during the curing process, but the Na⁺–montmorillonite clay is not intercalated during either the mixing or the curing process. The results also suggest that in the cured system without any promoter although partial exfoliated clay layers have already formed, an amount of the intercalation structure still remains. Although addition of a promoter or coupling agent into the cured system significantly lowers the maximum reaction temperature, and during the curing process the layered organoclay can be gradually broken into nanoscale structures, in which no d₀₀₁ diffraction peaks are observed, the complete exfoliation is achieved at gel time or before. The possible mechanism for the complete exfoliation is discussed on the thermodynamic and kinetic point of view. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 808–815, 2000