Effect of sodium montmorillonite source on nylon 6/clay nanocomposites

The effect of sodium montmorillonite source on the morphology and properties of nylon 6 nanocomposites was examined using equivalent experimental conditions. Sodium montmorillonite samples acquired from two well-known mines, Yamagata, Japan, and Wyoming, USA, were ion exchanged with the same alkyl ammonium chloride compound. The resulting organoclays were extruded with a high molecular weight grade of nylon 6 under the same processing conditions. Quantitative analysis of TEM photomicrographs of the two nanocomposites reveal a slightly larger average particle length and a slightly higher degree of platelet exfoliation for the Yamagata based nanocomposite than the Wyoming version, thus, translating into a higher particle aspect ratio. The stress-strain behavior of the nanocomposites appears to reflect the nanocomposite morphology, in that higher stiffness and strengths are attainable with the increased particle aspect ratio. Moreover, the trends in stiffness behavior between the two types of nanocomposites may be explained by conventional composite theory.     

Crystallization behavior of nylon 6 nanocomposites

The crystallization behavior of nylon 6 nanocomposites formed by melt processing was investigated. Nanocomposites were produced by extruding mixtures of organically modified montmorillonite and molten nylon 6 using a twin screw extruder. Isothermal and non-isothermal crystallization studies involving differential scanning calorimetry (DSC) were conducted on samples to understand how organoclay concentration and degree of clay platelet exfoliation influence the kinetics of polyamide crystallization. Very low levels of clay result in dramatic increases in crystallization kinetics relative to extruded pure polyamide. However, increasing the concentration of clay beyond these levels retards the rate of crystallization. For the pure nylon 6, the rate of crystallization decreases with increasing the molecular weight as expected; however, the largest enhancement in crystallization rate was observed for nanocomposites based on high molecular weight polyamides; this is believed to stem from a higher degree of platelet exfoliation in these nanocomposites. Wide angle X-ray diffraction (WAXD) and DSC were further used to characterize the polymer crystalline morphology of injection molded nanocomposites. The outer or skin layer of molded specimens was found to contain only γ-crystals; whereas, the central or core region contains both the α and γ-forms. The presence of clay enhanced the γ-structure in the skin; however, the clay has little effect on crystal structure in the core. Interestingly, higher levels of crystallinity were observed in the skin than in the core for the nanocomposites, while the opposite was true for the pure polyamides. In general, increasing the polymer matrix molecular weight resulted in a lower degree of crystallinity in molded samples as might be expected.     

Phase transition in nylon 6/clay nanocomposites on annealing

The γ→α crystalline phase transition in nylon 6/clay nanocomposite prior to melting was investigated by X-ray diffraction. The phase transition in the nanocomposite took place at 160 °C, 40 °C higher than that of nylon 6 at 120 °C. The transition extent in the nanocomposite was lower than that in nylon 6. This could be caused by the strongly confined spaces between layers, and the favorable environment for the formation of the γ phase in the existence of clay. Besides, the less grown crystallites of the α phase transformed from the γ phase in the nanocomposite began to melt at much lower temperature than its normal melting temperature.     

Nylon 6 nanocomposites prepared by a melt mixing masterbatch process

A melt mixing masterbatch process for preparing nylon 6 nanocomposites that provides good exfoliation and low melt viscosities has been investigated. It is known that high molecular weight (HMW) grades of nylon 6 lead to higher levels of exfoliation of organoclays than do low molecular weight (LMW) grades of nylon 6. However, LMW grades of nylon 6 have lower melt viscosities, which are favorable for certain commercial applications like injection molding. To resolve this, a two-step process to prepare nanocomposites based on nylon 6 is explored here. In the first step, a masterbatch of organoclay in HMW nylon 6 is prepared by melt processing to give exfoliation. In the second step, the masterbatch is diluted with LMW nylon 6 to the desired montmorillonite (MMT) content to reduce melt viscosity. Wide angle X-ray scattering, transmission electron microscopy, and stress-strain analysis were used to evaluate the effect of the clay content in the masterbatch on the morphology and physical properties of the final nanocomposite. The melt viscosity was characterized by Brabender Torque Rheometry. The physical properties of the nanocomposites prepared by the masterbatch approach lie between those of the corresponding composites prepared directly from HMW nylon 6 and LMW nylon 6. A clear trade-off was observed between the modulus and melt processability. Masterbatches that have lower MMT content offer a significant decrease in melt viscosity and a small reduction in modulus compared to nanocomposites prepared directly from HMW nylon 6. Higher MMT concentrations in the masterbatch lead to a less favorable trade-off.     

Rheological and mechanical comparative study of in situ polymerized and melt-blended nylon 6 nanocomposites

The rheological and mechanical properties of commercial neat nylon 6 and nylon 6 nanocomposites containing organically-modified montmorillonite (organoclays) produced by either in situ polymerization or melt-blending were investigated. The dynamic and steady shear, capillary and extensional viscosity of the neat nylon 6 and nylon 6 nanocomposite melts were studied, as well as the tensile properties of the solid material. X-ray diffraction (XRD) and transmission electron microscopy (TEM) indicated that the organoclays were largely very well exfoliated, although the lateral size scale of the platelets was different for each material. The in situ polymerized nanocomposite exhibited higher melt viscosity and higher tensile ductility than the melt-blended nanocomposite which was related to improved dispersion and polymer-silicate interactions for this material. Scanning electron microscopy confirmed that the nanocomposite failure surfaces showed more evidence of brittle behavior than the failure surfaces of neat nylon 6, and also that agglomerates of organoclay could be seen easily in the fracture surface of the melt-blended nanocomposite, but not to the same degree as in the in situ polymerized nanocomposite. This is in addition to very fine, individually-dispersed silicate laminates that form in each case.     

Nanoindentation and morphological studies on nylon 66 nanocomposites. I. Effect of clay loading

Nanoindentation technique has been used to investigate the mechanical properties of exfoliated nylon 66 (PA66)/clay nanocomposites in present study. The hardness, elastic modulus and creep behavior of the nanocomposites have been evaluated as a function of clay concentration. It indicates that incorporation of clay nanofiller enhances the hardness and elastic modulus of the matrix. The elastic modulus data calculated from indentation load-displacement experiments are comparable with those obtained from dynamic mechanical analysis and the tensile tests. However, the creep behavior of the nanocomposites shows an unexpected increasing trend as the clay loading increases (up to 5 wt%). The lowered creep resistance with increasing clay content is mainly due to the decrease of crystal size and degree of crystallinity as a result of clay addition into PA66 matrix, as evidenced by optical microscopy and X-ray diffraction. At lower clay concentration (here ≤5 wt%), morphological changes due to addition of clay plays the dominant role in creep behavior compared with the reinforcement effect from nanoclay.     

Preparation and characterization of nylon 11/organoclay nanocomposites

Nylon 11/organoclay nanocomposites have been successfully prepared by melt-compounding. X-ray diffraction and transmission electron microscopy indicate the formation of the exfoliated nanocomposites at low clay concentrations (less than 4 wt%) and a mixture of exfoliated and intercalated nanocomposites at higher clay contents. Thermogravimetric and dynamic mechanical analyses as well as tensile tests show that the degree of dispersion of nanoclay within polymer matrix plays a vital role in property improvement. The thermal stability and mechanical properties of the exfoliated nylon 11/clay nanocomposites (containing lower clay concentrations) are superior to those of the intercalated ones (with higher clay contents), due to the finer dispersion of organoclay among the matrix.     

Transport properties of electrically conducting nylon 6/foliated graphite nanocomposites

In this work, we analyze the conductivity data of the nylon 6/FG nanocomposites using the normalized percolation equations and the general effective equation. From the interpretations of the derived results, we demonstrate that the microstructure of the nanocomposites can be readily deduced. Taking several factors into account, it turns out that the tunneling mechanism should be responsible for the observed non-universality of the critical exponents. Experimental evidences show that the existence of the tunneling conduction should be attributed to the particular structure of the prepared materials.     

Polymer/layered clay nanocomposites: 2 polyurethane nanocomposites

A kind of novel polyurethane/Na⁺-montmorillonite nanocomposites has been synthesised using modified 4,4′-di-phenymethylate diisocyanate (M-MDI), modified polyether polyol (MPP) and Na⁺-montmorillonite (layered clay). Here, MPP was used as a swelling agent to treat the layered clay. Experimental results indicated that with increasing the amount of layered clay, the strength and strain-at-break increased. The storage modulus below the glass transition temperature of the soft segments in the polyurethane was increased by more than 350%. With increased loading of layered clay, the thermal conductivity decreased slightly rather than increased. This finding will provide valuable information for polyurethane industry.     

Properties of polyamide 6/clay nanocomposites processed by low cost bentonite and different organic modifiers

Nanocomposites based on polyamide 6 have been directly prepared by melt compounding, using modified low cost bentonites by three selected quaternary ammonium cations, in particular quaternized octadecylamine (ODA), dimethyl benzyl hydrogenated tallow quaternary ammonium (B2MTH) and dimethyl hydrogenated ditallow quaternary ammonium (2M2TH). Thermal stability of organic modifiers and organoclays has been studied by TGA and results allow evaluating the degree of modifier incorporation into clay galleries. The influence of the organic modifier on the morphology and properties of the obtained nanocomposites has been studied by X-ray diffraction and TEM analysis. Depending on the degree of bentonite modification, different mechanisms were reported to explain the improved mechanical properties of the resulting nanocomposites.     

Nanoindentation and morphological studies on nylon 66/organoclay nanocomposites. II. Effect of strain rate

Strain rate effects on surface deformation behavior of exfoliated nylon 66 (PA66)/organoclay nanocomposites have been explored by nanoindentation in present study. Sharp indenter (Berkovich) has been used to indent on the surfaces of polymer/clay nanocomposite with different strain rates. Significant strain-rate hardening has been found consistently existing in both neat PA66 and its nanocomposite systems from surface to subsurface (a few micron deep into the bulk). However, strain rate shows almost no effect on the elastic moduli of the neat system and the nanocomposites. The elastic modulus and hardness increase with the indentation depth due to inhomogeneous distributions of the crystalline morphology as well as clay concentration for the case of the nanocomposites along the indentation direction. The mechanical properties observed are correlated with the inhomogeneous microstructures of the studied systems. The plastic index of PA66 and the nanocomposites have been evaluated as a function of strain rate.     

Structural studies of electrospun nylon 6 fibers from solution and melt

Nylon 6 (N6) fibers have been fabricated via two different electrospinning schemes, from solution of N6 and formic acid at room temperature as well as from N6 melt at elevated temperature. The crystal structures of electrospun N6 fibers from solution and melt, and the annealing effect on the structures were studied by using various techniques. Combined analysis of the differential scanning calorimetry (DSC) at various heating rates, temperature-dependent X-ray diffraction (XRD), and Fourier-transform infrared (FTIR) spectroscopy indicates that N6 fibers from melt predominantly exhibit the meta-stable γ-crystalline forms and low molecular orientation, while solution electrospun fibers from slowly evaporating solvent show both α- and γ-form crystals and higher degree of molecular orientation. At high annealing temperature, the meta-stable γ-crystals in melt electrospun fibers easily transform into thermodynamically stable α-form crystals, while crystals in solution electrospun fibers exhibit higher thermal stability. Nonisothermal modeling and in-situ measurements of jet temperature indicate that rapid quenching due to enhanced heat transfer by electrohydrodynamically driven air flow near the jet is responsible for the less stable γ-crystals and lower degree of molecular orientation in melt electrospun fibers.     

Fibre reinforced nanocomposites: Mechanical properties of PA6/clay and glass fibre/PA6/clay nanocomposites

In this paper, the effect of two different reinforcements: clay at the nanoscale and glass fibres at the micro-scale, on the mechanical properties of PA/clay and GF/PA/clay are studied. The Halpin-Tsai model is used to predict the modulus of PA/Clay and GF/PA/Clay, both of which are influenced by two factors: reinforcement shape and volume fraction. The relationships between the modulus and reinforcement shape and volume fraction are discussed. Tensile modulus, measured in tensile tests is used to fit the Halpin-Tsai models. The results demonstrate a synergy between the reinforcements at the two different scales.     

尼龙6/粘土纳米复合材料的性能

对尼龙6/粘土纳米复合材料(PA6CN)的力学性能、结晶性能、流变性能、热稳定性、阻隔性能、阻燃性能、各向异性和可纺性进行了综述。加入粘土后,基体尼龙6的晶型变为γ型,改善了尼龙6的力学性能,提高了热变形温度,降低了吸水率,改善了气体阻隔性和材料的阻燃性,拓宽了复合材料的应用范围。     

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     

Molecular origins of toughening mechanism in uniaxially stretched nylon 6 films with clay nanoparticles

Introduction of nanoplatelets into the nylon matrix preorients the polymer chains in the film plane during melt casting leading to uniplanar (001) texture in nylon 6 crystalline as well as clay phase. This behavior enhances the uniformity of films during cold deformation well above the glass transition temperature by suppressing the localized necking behavior. The clay platelets reduce the polymer interchain hydrogen bonding and entanglements leading to decrease of long range “connectivity”. As a result, a delay in strain hardening during deformation occurs allowing much larger deformations to be attained without fracture. This in turn leads to increase in toughness.     

Organoclay degradation in melt processed polyethylene nanocomposites

Melt processed nanocomposites were formed from low-density polyethylene, LDPE, and organoclays over a wide range of processing temperatures. These composites show limited exfoliation, and hence, their X-ray analysis reveals a distinct peak corresponding to the interplatelet distances in the unexfoliated clay galleries. The degradation of the quaternary ammonium surfactant of the organoclay in these systems was characterized by examining the change in the position of these peaks as a function of the melt processing temperature. Upon degradation, the mass of the surfactant within the clay galleries decreases, which causes the platelets to collapse and shifts the WAXS peak to lower d-spacings. The results of the WAXS analysis suggest that a significant portion of the surfactant is lost from the organoclays when the melt processing temperature is increased from 180 to 200 °C or higher. The extent of surfactant degradation in these composites was determined to be independent of the organoclay content. Organoclay degradation appears to limit the extent of exfoliation or dispersion in LDPE as revealed by stress-strain analyses of nanocomposites processed at different temperatures. The amount of surfactant lost during thermogravimetric analysis of various organoclays indicates that surfactants with multiple alkyl tails have greater thermal stability than those with a single alkyl tail. A comparison of the mass of surfactant lost during melt processing of nanocomposites and during thermogravimetric analysis of organoclays (in the absence of polymer) indicated that at a given time, a larger surfactant loss from the clay galleries occurs during extrusion than during the TGA experiment. This is attributed to the greater ease with which the degradation products (predominantly α-olefins) are solubilized in polyethylene for the composites as opposed to evaporated from the organoclay during TGA.     

Comparison of nanocomposites based on nylon 6 and nylon 66

Nylon 6 and nylon 6,6 organoclay nanocomposites were prepared by melt processing using a twin screw extruder. The effects of polyamide type and processing temperature on the mechanical properties and the morphology of the nanocomposites were examined. Mechanical properties, transmission electron microscopy (TEM), wide-angle X-ray diffraction (WAXD), percentage crystallinity and isothermal thermo-gravimetric analysis (TGA) data are reported. A particle analysis was performed to quantitatively characterize the morphology; these results are later employed in modeling the modulus of these materials using composite theory. No significant difference was observed in the mechanical properties and morphology of PA-6 nanocomposites processed at two different temperatures. PA-6 nanocomposites had superior mechanical properties than those made from PA-66. The tensile strength of PA-66 nanocomposites deviated from linearity at high levels of MMT. WAXD and TEM results show that the PA-6 nanocomposites are better exfoliated than the PA-66 nanocomposites, which exhibit a mixture of intercalated and exfoliated structures. Mechanical properties were consistent with the morphology. DSC reveals a higher percentage of crystallinity in the PA-66 samples. Isothermal TGA shows only a 5% difference in the degradation of the organic modifier on the organoclay processed at 240 °C versus 270 °C. Particle analysis shows a higher average particle length and thickness, and a lower average particle density and aspect ratio in nanocomposites based on PA-66 versus PA-6. The Halpin-Tsai and Mori-Tanaka composite theories predict satisfactorily the behavior of the PA-6 nanocomposites, while the PA-66 nanocomposites were predicted acceptably up to a certain volume fraction where the non-linear behavior takes effect. All the results indicate that there is a lower degree of exfoliation in the nanocomposites produced with a PA-66 matrix apparently stemming from the chemical differences between PA-6 and PA-66.     

The effect of clay on the thermal degradation of polyamide 6 in polyamide 6/clay nanocomposites

The degradation pathway of polyamide 6/clay nanocomposites was studied as a function of clay content. Well-dispersed polymer-clay nanocomposites can be easily obtained by simple melt blending between organically-modified clays and polyamide 6. Polyamide 6-clay nanocomposites exhibit a large reduction in the peak heat release rate, 60%, measured by cone calorimetry. There are no significant differences in the evolved products during thermal degradation of polyamide 6 and polyamide 6/clay nanocomposites in terms of composition and functionality. The main degradation pathway of polyamide 6 is aminolysis and/or acidolysis, primarily through an intra-chain reaction, producing ε-carprolactam, which is the monomer of polyamide 6. As the clay loading is increased, the relative quantity of ε-carprolactam in the evolved products decreases and the viscosity of the soluble solid residues increases. It is thought that inter-chain reactions become significant in the presence of clay because the degrading polymer chains are trapped in the gallery space of the clay during thermal degradation.