Isothermal crystallization kinetics and melting behavior of nylon/saponite and nylon/montmorillonite nanocomposites

DSC thermal analysis and X‐ray diffraction have been used to investigate the isothermal crystallization behavior and crystalline structure of nylon 6/clay nanocomposites. Nylon 6/clay has prepared by the intercalation of ε‐caprolactam and then exfoliating the layered silicates by subsequent polymerization. The DSC isothermal results reveal that introducing saponite into the nylon structure causes strongly heterogeneous nucleation induced change of the crystal growth process from a two‐dimensional crystal growth to a three dimensional spherulitic growth. But the crystal growth mechanism of nylon/montmorillonite nanocomposites is a mixed two‐dimensional and three‐dimensional spherulitic growth. The activation energy drastically decreases with the presence of 2.5 wt % clay in nylon/clay nanocomposites and then slightly increases with increasing clay content. The result indicates that the addition of clay into nylon induces the heterogeneous nucleation (a lower ΔE) at lower clay content and then reduces the transportation ability of polymer chains during crystallization processes at higher clay content (a higher ΔE). The correlation among crystallization kinetics, melting behavior, and crystalline structure of nylon/clay nanocomposites is also discussed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2196–2204, 2004     

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.     

Flame retardancy and char microstructure of nylon‐6/layered silicate nanocomposites

We investigated the effect of organically modified clay alone and in combination with zinc borate on the thermal/flammability behavior of nylon‐6 nanocomposites. Differential thermogravimetric analysis indicated that the peak decomposition temperature was not affected by the addition of clay, but the rate of weight loss decreased with increase in clay concentration. Nanocomposite films of approximately 0.5 mm thickness with 2.5 and 5 wt % clay burned for almost the same duration as neat nylon‐6 but with reduced dripping in horizontal flame test. The 10 wt % clay nanocomposite sample burned without any dripping and the flame spread rate was reduced by 25–30%. Zinc borate/clay containing nanocomposite developed into a very good intumescent system in cone calorimeter test, swelling about 10–13 mm height prior to ignition forming a cellular char structure. This was found to be an effective composition in reducing the heat release and mass loss rate of nylon‐6 by about 65% and at par with 10 wt % clay nanocomposite. Flame retardant behavior could be attributed to distinct char morphologies observed through scanning electron microscopy. Fourier transform infrared spectroscopy of the 10 wt % clay nanocomposite char showed the presence of amides, indicating possible residual polymer within the shielded char. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1540–1550, 2007     

Abrasion studies of nylon 6/montmorillonite nanocomposites using scanning electron microscopy,fourier transform infrared spectroscopy,and X‐ray photoelectron spectroscopy

In this article, abrasion performance of commercial nylon 6 and nylon 6/montmorillonite (MMT) nanocomposites was studied. The polymer nanocomposites showed poor abrasion resistance compared to the neat polymer. The wear loss increased linearly with clay concentration. Changes in surface morphology, composition, and structure were investigated by scanning electron microscopy (SEM), Fourier transform infrared (FTIR)‐attenuated total reflection spectroscopy, and X‐ray photoelectron spectroscopy (XPS). SEM images showed that all the abraded surfaces contained fractured particles. However, the abraded nanocomposite surfaces had much deeper grooves compared to the homopolymer. FTIR results showed an increase in the amount of α crystals and a decrease in the amount of γ crystals on all the surfaces after abrasion. This was attributed to the strain‐induced γ to α crystal transformation. The largest amount of α crystals was formed in the abraded surface of pure nylon 6, and the amount of α crystals formed decreased with increasing MMT content. XPS results showed an increase in the [Si]/[N] elemental ratio for all nanocomposites after abrasion, indicating an increase in the clay content of the surface. Abrasive wear mechanism is as follows: (1) tensile tearing is the dominant wear mechanism for all the samples; (2) the cutting mechanism becomes more important when MMT content increases; (3) the polymer matrix is easier to be removed than clay during the abrasion process; (4) in nylon 6/MMT systems, the poor abrasion resistance is attributed to defects at the clay‐polymer interface, resulting in greater wear of the polymer matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Morphology and properties of nylon 6 and high density polyethylene blends in presence of nanoclay and PE‐g‐MA

In this study, we report the synergistic effect of nanoclay and maleic anhydride grafted polyethylene (PE‐g‐MA) on the morphology and properties of (80/20 w/w) nylon 6/high density polyethylene (HDPE) blend. Polymer blend nanocomposites containing nanoclay with and without compatibilizer (PE‐g‐MA) were prepared by melt mixing, and their morphologies and structures were examined with scanning electron microscopy (SEM) and wide angle X‐ray diffractometer (WAXD) study. The size of phase‐separated domains decreased considerably with increasing content of nanoclay and PE‐g‐MA. WAXD study and transmission electron microscopy (TEM) revealed the presence of exfoliated clay platelets in nylon 6 matrix, as well as, at the interface of the (80/20 w/w) nylon 6/HDPE blend–clay nanocomposites. Addition of PE‐g‐MA in the blend–clay nanocomposites enhanced the exfoliation of clays in nylon 6 matrix and especially at the interface. Thus, exfoliated clay platelets in nylon 6 matrix effectively restricted the coalescence of dispersed HDPE domains while PE‐g‐MA improved the adhesion between the phases at the interface. The use of compatibilizer and nanoclay in polymer blends may lead to a high performance material which combines the advantages of compatibilized polymer blends and the merits of polymer nanocomposites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

聚合物纳米复合材料结晶行为研究综述

综述了国内外聚合物纳米复合材料结晶行为的最新研究进展。其聚合物基体主要包括有聚丙烯、尼龙、聚苯乙烯、聚对苯二甲酸乙二醇酯和聚乙烯等；填充的纳米粒子主要有：CaCO3、有机蒙脱土、黏土和SiO2等。同时，总结了研究聚合物纳米复合材料结晶行为的理论模型。对聚合物纳米复合材料结晶行为的研究进行了展望。     

聚合物纳米复合材料结品行为研究综述

综述了国内外聚合物纳米复合材料结晶行为的最新研究进展.其聚合物基体主要包括有聚丙烯、尼龙、聚苯乙烯、聚对苯二甲酸乙二醇酯和聚乙烯等;填充的纳米粒子主要有CaCO3、有机蒙脱土、黏土和SiO2等.同时,总结了研究聚合物纳米复合材料结晶行为的理论模型.对聚合物纳米复合材料结晶行为的研究进行了展望.     

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.     

Effect of uniaxial stretching on thermal,oxygen barrier,and mechanical properties of polyamide 6 and poly(m‐xylene adipamide) nanocomposite films

In this study, the effect of uniaxial stretching on the thermal, oxygen barrier and mechanical properties of aliphatic polyamide 6 (PA6) and aromatic Poly(m‐xylene adipamide) (MXD6) nylon films as well as their in‐situ polymerized nanocomposites with 4 wt% clay were studied. Cast films were prepared by extrusion process and rapidly cooled using an air knife. The precursor films were uniaxially stretched at 110°C with draw ratios varying from 1.5 to 5. DSC results showed that the cold crystallization temperature (T_cc) of the uniaxially stretched MXD6 and MXD6/clay films drastically shifted to the lower temperatures when draw ratio increased. The aromatic nylon films had lower oxygen permeability than those of the aliphatic films, due to more rigidity and chain packing. However, the oxygen permeability of the stretched films increased with draw ratio (DR) up to a critical value for each sample, while further stretching resulted in a reduction in the oxygen permeation. This phenomenon was related to the changes in free volume upon uniaxial stretching. The ability of different geometrical models to describe the experimental relative permeability data was investigated. The Bharadwaj model that took into account clay orientation was the most successful one to predict the oxygen barrier characteristics of the stretched nanocomposites at high draw ratios. The Young's modulus and tensile strength of the aliphatic and aromatic nylons increased with uniaxial deformation, while the flexibility and elongation at break of the former decreased with increasing DR. A larger increase in the Young's modulus of the uniaxially stretched nanocomposite films compared with the neat samples was observed and could be related to the improvement in the clay orientation as well as a better alignment of the crystalline phase due to incorporating the clay platelets in the polymer matrix. In contrast, the flexibility of the stretched MXD6 improved remarkably (ca., 25 times) compared with the precursor film (DR = 1) when the draw ratio increased to 1.5. This could be related to the effect of hot stretching on the enhancement of polymer chains relaxation and mobility at low draw ratios. POLYM. ENG. SCI., 55:1113–1127, 2015. © 2014 Society of Plastics Engineers     

Facile preparation of nylon 6 nanocomposites based on clay reinforcement and core‐shell latex toughening: Morphology,properties, and impact fracture behavior

This work is focused on a facile route to prepare a new type of nylon 6‐based nanocomposites with both high fracture toughness and high strength. A series of nylon 6‐matrix blends were prepared via melting extrusion by compounding with poly (methyl methacrylate‐co‐butadiene‐co‐styrene) (MBS) or poly(methyl methacrylate‐co‐methylphenyl siloxane‐co‐styrene) (MSIS) latices as impact modifier and diglycidyl ether of bisphenol‐A (DGEBA) as compatibilizer. Layered organic clay was also incorporated into above nylon 6 blends for the reinforcement of materials. Morphology study suggests that the MBS or MSIS latex particles could achieve a mono‐dispersion in nylon 6 matrix with the aid of DGEBA, which improves the compatibilization and an interfacial adhesion between the matrix and the shell of MBS or MSIS. High impact toughness was also obtained but with a corresponding reduction in tensile strength and stiffness. A moderate amount of organic clay as reinforcing agent could gain a desirable balance between the strength, stiffness and toughness of the materials, and tensile strength and stiffness could achieve an improvement. This suggests that the combination of organic clay and core‐shell latex particles is a useful strategy to optimize and enhance the properties of nylon 6. Morphology observation indicates that the layered organic clay was completely exfoliated within nylon 6 matrix. It is found that the core‐shell latex particles and the clay platelets were dispersed individually in nylon 6 matrix, and no clay platelets were present in MBS or MSIS latex particles. So the presence of the clay in nylon 6 matrix does not disturb the latex particles to promote high fracture toughness via particle cavitation and subsequent matrix shear yielding, and therefore, provides maximum reinforcement to the polymer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Processing and properties of polymeric nano‐composites

Polymeric nano‐composites are prepared by melt intercalation in this study. Nano‐clay is mixed with either a polymer or a polymer blend by twin‐screw extrusion. The clay‐spacing in the composites is measured by X‐ray diffraction (XRD). The morphology of the composites and its development during the extrusion process are observed by scanning electron microscopy (SEM). Melt viscosity and mechanical properties of the composites and the blends are also measured. It is found that the clay spacing in the composites is influenced greatly by the type of polymer used. The addition of the nano‐clay can greatly increase the viscosity of the polymer when there is a strong interaction between the polymer and the nano‐clay. It can also change the morphology and morphology development of nylon 6/PP blends. The mechanical test shows that the presence of 5–10 wt.% nano‐clay largely increases the elastic modulus of the composites and blends, while significantly decreases the impact strength. The water absorption of nylon 6 is decreased with the presence of nano‐clay. The effect of nano‐clay on polymers and polymer blends is also compared with Kaolin clay under the same experimental conditions.     

Fibrillation of thermotropic liquid crystalline polymer enhanced by nano-clay in nylon-6 matrix

The influence of well-dispersed nano-clay filler on the morphology of thermotropic liquid crystalline polymer (TLCP) in nylon-6 matrix was investigated by melt extrusion process. The good dispersion of clay in the hybrid blends was confirmed by X-ray diffraction, transmission electron microscopy and rheological measurement. Morphological observation showed that the clay platelets had dramatic influences on the dispersion and deformation of TLCP phase. The TLCP droplets got smaller at the clay content ≤3 wt%, and deformed into fibrils at the clay content up to 5 and 7 wt%. The morphology evolution of TLCP in the hybrid blends, especially at 7 wt% of clay loading, was consistent well with the prediction based on the micro-rheology parameters such as the viscosity ratio of the dispersed phase to the matrix (η_d/η_m) and the ratio of capillary number to the critical capillary number (Ca/Ca_crit). This enhanced fibrillation of TLCP droplets was attributed to the role of nano-clay particles as a compatibilizer to improve the interfacial adhesion and to suppress the interfacial slip between TLCP and nylon phases in the melt, so that the shear stress was effectively transferred to the dispersed TLCP phase.     

带有碳涂层的尼龙纤维增强混凝土的机敏性研究

采用PVD方法在尼龙表面沉积一层导电的碳薄膜，用带有碳层的尼龙纤维（0.4%-2.0%，按体积计增强混凝土，测试了该复合材料的应力-应变行为，结果表明：随着纤维的加入和含量的增加，混凝土的断裂从脆性断裂发展为准脆性断裂，进而发展为假延性断裂，产生假延性断裂的纤维最小体积分数为0.4%左右，在一次载菏和周期性载菏下，以电阻变化率为信号研究了该材料的机敏性，在弹性、非弹性和断裂区间有灵敏的响应；在弹性区间，信号稳定可塑，在非弹性区间，信号随材料中裂纹积累而不可逆增长；断裂时电阻值最大。     

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.     

Structure and thermal behaviour of nylon 6 nanocomposites

In this article, nylon 6/clay nanocomposites with 5 wt % clay (NCN5) were prepared by a twin screw extruder. The effects of annealing including solid‐state annealing (170 and 190°C) and melt‐state annealing (240°C) on the polymorphic behavior and thermal property of NCN5 and nylon 6 have been comparatively studied as a function of annealing time using modified differential scanning calorimetry (MDSC) and wide‐angle X‐ray diffraction. It was demonstrated that NCN5 and nylon 6 exhibit a similar polymorphic behavior when they were annealed at 190°C for different time durations. As the annealing temperature was elevated to 240°C, significant differences in thermal behavior and polymorphism between NCN5 and nylon 6 could be found. For example, the α crystal became the absolutely dominating crystalline phase for NCN5 sample independent on the annealing durations, whereas the formation of γ crystal is greatly enhanced in neat nylon 6 with increasing annealing time. Moreover, a small endothermic peak is observed around 180°C in both nylon 6 and NCN5 samples annealed at 170 and 190°C, which might be related to the melting of microcrystals formed in the amorphous regions during annealing. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3116–3122, 2006     

Static uniaxial compression of polyisoprene–montmorillonite nanocomposites monitored by 1H spin–lattice relaxation time constants

Previous work has focused on the use of microscopy to explore the mechanisms of deformation in polymer nanocomposites. That technique creates a qualitative representation that may not be statistically representative of the bulk properties. This paper illustrates the utility of solid‐state NMR, which inherently measures bulk behavior, to both identify and quantify mechanisms of deformation. Specifically, in this study, increases in the interfacial area of various modifications of Cloisite clay in 1,4‐cis polyisoprene nanocomposites were monitored during uniaxial compression. Interaction of the Fe⁺³ in the clay with the polymer decreases the polymer's ¹H spin–lattice relaxation time constant (T₁). In some of the nanocomposites, the increase in the interfacial area of the clay platelets was observed by a decrease in the polymer's T₁ with successive amounts of strain. The observation of these changes with static ¹H‐NMR is limited by the dispersion of the clay. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1806–1813, 2005     

Polymorphic behavior of nylon 6/saponite and nylon 6/montmorillonite nanocomposites

X‐ray diffraction methods and DSC thermal analysis have been used to investigate the structural change of nylon 6/clay nanocomposites. Nylon 6/clay has prepared by the intercalation of ε‐caprolactam and then exfoliaton of the layered saponite or montmorillonite by subsequent polymerization. Both X‐ray diffraction data and DSC results indicate the presence of polymorphism in nylon 6 and in nylon 6/clay nanocomposites. This polymorphic behavior is dependent on the cooling rate of nylon 6/clay nanocomposites from melt and the content of saponite or montmorillonite in nylon 6/clay nanocomposites. The quenching from the melt induces the crystallization into the γ crystalline form. The addition of clay increases the crystallization rate of the α crystalline form at lower saponite content and promotes the heterophase nucleation of γ crystalline form at higher saponite or montmorillonite content. The effect of thermal treatment on the crystalline structure of nylon 6/clay nanocomposites in the range between Tg and Tm is also discussed.     

Dioxane-Water Transport through Nylon 6 Membranes

Abstract

An experimental study was made of the permeation of water, paradioxane, and water-paradioxane mixtures through nylon 6 membranes. Laminated films were utilized to determine actual liquid permeate concentration profiles within the membrane structure. Knowledge of these profiles permitted the investigators to measure the concentration-dependent diffusivities and to characterize the mechanism of mass transfer. Since water plasticizes nylon, the behavior of the water-dioxane mixture could not be accurately predicted from pure component performance. Thus the transfer of water was enhanced and the dioxane depressed for equimolar feed mixtures. Moreover, it was demonstrated that a simple, acid surface-treatment of the separative membrane can greatly enhance the transfer of both components. Concentration profiles measured during the unsteady state leading to equilibrium suggested that the nylon polymer matrix was in the process of undergoing structural changes.     

Clay induced thermoplastic crystals in thermoset matrix: Thermal,Dynamic mechanical,and morphological analysis of clay/nylon‐6‐epoxy nanocomposites

A novel procedure to synthesize in situ clay/nylon‐6 composite suspension was explored via anionic solution polymerization. The suspension was efficiently blended with water‐based epoxy resin using mechanical stirrer at room temperature. Hence, a 3‐component coating system was obtained consisting of nano‐clay, nylon‐6 and epoxy resin. Large number of coatings and films were prepared with variation in clay and nylon‐6 loading. Concentration of clay was found to have profound effect on crystallinity of nylon‐6, thereby affecting the overall properties of clay/nylon/epoxy composite. All the films were characterized for thermal and dynamic mechanical behavior using differential scanning calorimeter (DSC) and dynamic mechanical analysis (DMA). Lower amount of clay was found to increase the crystallinity of nylon‐6 which in turn increased the plasticization of epoxy resin indicated by reduction in T_g. A multiphase morphology with distinct amorphous and crystalline zones was observed under scanning electron microscopy (SEM). A remarkable symmetrical morphology with branched dendritic crystal structure was observed for few of the clay/nylon/epoxy system. POLYM. COMPOS., 37:2206–2217, 2016. © 2015 Society of Plastics Engineers     

- VISCOELASTIC STRAIN-STRESS AND HEAT/MOISTURE TRANSFER -

ABSTRACT

The theoretical analysis was developed to predict the deformation characteristic of formed clay during a drying process in a ceramic production. The three dimensional strain-stress distribution as well as heat and moisture transfer in a slab shape of clay were simultaneously analyzed by a finite element method. Linear viscoelasticity was assumed for the strain-stress analysis to account the effect of creep. The calculated result agreed well with an experimental result performed for a slab clay heated by hot air flow during the preheating and constant drying rate periods. A large tensional stress, which may generate a crack, was observed initially around the surface area. It was also found that the time behavior of the volume change of the formed clay is significantly influenced on the drying conditions and/or the drying rate.