Morphology evolutions of organically modified montmorillonite/polyamide 12 nanocomposites

Organically modified montmorillonites (OMMTs) by octadecylammonium chloride with two adsorption levels were dispersed in polyamide 12 (PA12) matrices with two molecular weights for different melt mixing times in order to investigate morphology evolutions and factors influencing fabrication of PA12 nanocomposites. Different adsorption levels of the modifier in the OMMTs provide different environments for diffusion of polymer chains and different attractions between MMT layers. Wide-angle X-ray diffraction (WAXD), transmission electron microscope (TEM) and gas permeability were used to characterize morphologies of the nanocomposites. Both OMMTs can be exfoliated in the PA12 matrix with higher molecular weight, but only OMMT with lower adsorption level can be exfoliated in the PA12 matrix with lower molecular weight. It was attributed to the differences in the levels of shear stress and molecular diffusion in the nanocomposites. The exfoliation of OMMT platelets results from a combination of molecular diffusion and shear. After intercalation of PA12 into interlayer of OMMT in the initial period of mixing, further dispersion of OMMTs in PA12 matrices is controlled by a slippage process of MMT layers during fabricating PA12 nanocomposites with exfoliated structure.     

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     

Effect of oligomeric‐modified montmorillonite on morphology and properties of polycarbonate/montmorillonite nanocomposites

Low‐molecular‐weight copolymers of styrene and vinylbenzyl ammonium salts (oligomeric surfactant) were used to modify montmorillonite (MMT). The oligomeric‐modified MMT showed good thermal stability, which made it suitable to be used for preparing polycarbonate(PC)/MMT nanocomposites at high temperature. A different series of PC/MMT nanocomposites had been prepared by melt processing using a twin screw extruder. The effect of oligomeric surfactant structure and clay loading on the morphology, mechanical property, thermal stability, and color appearance of the nanocomposites were explored. The results of X‐ray diffraction and transmission electron microscopy analyses indicated that the PC/MMT nanocomposites had partially exfoliated structures. The PC/MMT nanocomposites were found to retain light colored, which was important for optical application. Compared to neat PC, the nanocomposites showed better properties of thermal stability and heat insulation. The mechanical properties of the nanocomposites are significantly enhanced by incorporating clay into the PC matrix. The tensile strength of nanocomposites with 2 wt% clay content was up to 55 MPa, which was much higher than that of the neat PC (37 MPa). The maximum tensile modulus value was 19% higher than that of neat PC. POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

PA6/蒙脱土熔融插层复合材料结构与性能分析

通过熔融共混法插层复合制备了聚酰胺(PN)6／蒙脱土纳米复合材料，测试了力学性能并对不同蒙脱土含量的PA 6／蒙脱土纳米复合材料进行了对比。实验表明，通过熔融插层可使PN 6基体插层于蒙脱土中，所得到的复合材料的性能较PN 6有很大提高。蒙脱土特殊的层状结构使得利用熔融共混在机械力的作用下插层到纳米级复合材料成为可能。     

Barrier and mechanical properties of montmorillonite/polyesteramide nanocomposites

The barrier and mechanical properties of biodegradable melt‐mixed polyesteramide/octadecylamine‐treated montmorillonite clay (filler) have been studied. Extruded films containing 5 and 13 wt% filler were prepared by melt‐mixing. Samples compression molded after extrusion was also studied. Oxygen and water transmission rates were measured. X‐ray diffraction was used to assess the periodic distance of the clay layers and transmission electron microscopy was used to assess the composite morphology. An increase of the periodic distance from 23.7 Å for pure filler to 32–36 Å for the processed composites was observed. This suggested that the collapsed stacks of clay particle of the first order X‐ray reflection became intercalated upon extrusion. A decrease in the intensity with increasing rotation speed was observed, which suggested that higher shear rates promoted delamination, especially in composites with higher filler content. Transmission electron microscopy indicated that a sizable portion of the clay stacks were delaminated into smaller aggregates, containing generally one to three clay sheets. Density measurements indicated that shear‐induced voids were formed in the nanocomposite, and these were, according to transmission electron microscopy, almost exclusively located between the clay sheets. The presence of voids limited the improvement in barrier properties with increasing filler content. However, the very large improvement in stiffness and strength with filler content indicated that these properties were unaffected by these voids.     

Effects of compatibilizers and testing speeds on the mechanical properties of organophilic montmorillonite filled polyamide 6/polypropylene nanocomposites

In the present study, the fracture properties of different types of organophilic montmorillonite (OMMT) filled polyamide 6/polypropylene nanocomposites was investigated. Two types of compatibilizers, i.e., maleic anhydride grafted polypropylene (PP‐g‐MA) and maleic anhydride grafted styrene‐ethylene/butylene‐styrene (SEBS‐g‐MA) were used to compatibilize these systems. The tensile properties were studied through tensile test at two different testing speeds; 50 and 500 mm/min whereas the fracture properties were determined using single‐edge‐notch‐3 point‐bending (SEN‐3PB) specimens at three different testing speeds; 1, 100, and 500 mm/min. The presence of both PP‐g‐MA and SEBS‐g‐MA compatibilizers improved the tensile and fracture properties of nanocomposites due to the compatibilizing effect of both compatibilizers. SEBS‐g‐MA compatibilizer seemed to be more effective in improving the fracture toughness of nanocomposites than PP‐g‐MA especially at high testing speed. This was due to the elastomeric nature of SEBS‐g‐MA, which can provide a better toughening effect than the relatively harder PP‐g‐MA. POLYM. ENG. SCI., 50:1493–1504, 2010. © 2010 Society of Plastics Engineers     

Effect of epoxy resin on morphology and physical properties of PVC/organophilic montmorillonite nanocomposites

Poly(vinyl chloride)/organophilic montmorillonite (PVC/OMMT) nanocomposites were prepared by means of melt blending. A liquid epoxy resin was used to aid PVC chains in intercalating into silicate layers. The effects of the preparation methods and epoxy resin contents on the melt intercalation of PVC were investigated. The morphology development, mechanical properties and optical properties of the PVC/OMMT composites were tested as functions of epoxy resin content and OMMT content. Wide‐angle X‐ray diffraction, transmission electron microscopy and scanning electron microscopy were used to characterize the morphology of the resulting composites. After being pretreated by the epoxy resin, the OMMT layers were largely intercalated into the PVC matrix, and even exfoliated at high epoxy resin content. The addition of epoxy resin led to a decrease in optical clarity of the composites but improved the processing stability, as indicated by yellowness index and haze measurement. However, the optical clarity of the composites containing 4 phr of epoxy resin (PVC/E‐OMMT) was improved by increasing the OMMT content, as shown by light transmission. Both the tensile strength and notched Izod impact strength of the PVC/E‐OMMT composites reached their maximum values when the OMMT content was 0.5 phr and the epoxy resin content was 2 phr. With further increase of the OMMT content and the epoxy resin content, the tensile strength decreased but was still higher than that of original PVC. The method of addition of epoxy resin had little effect on the physical properties but mainly influenced the morphology of PVC/OMMT nanocomposites. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2184–2191, 2003     

Influence of glycerol on morphology and properties of polylactide/montmorillonite nanocomposites

The widespread use of polymers from renewable sources is currently unachievable, not only by economic constraints but by the limiting properties of this type of material. Several strategies have been developed to overcome this problem; one of the most extensively explored is the use of nanofillers to improve the biopolymer’s properties such as stiffness, impact strength and gas barrier, amongst others. However, several gaps in understanding the morphology formation of these systems still exist. This study evaluates the use of glycerol as an auxiliary additive during production of polylactide/montmorillonite nanocomposites. In this study, the presence of glycerol seems to influence the nanocomposites’ morphology, influencing the clay exfoliation in some cases, and the mechanical properties. On the other hand, the presence of glycerol seems to induce a greater molecular weight reduction during twin screw extrusion.     

Polyimide/POSS nanocomposites: interfacial interaction, thermal properties and mechanical properties

A series of functional polyhedral oligomer silsesquioxnae (POSS)/polyimide (PI) nanocomposites were prepared using a two-step approach, first, the octa(aminophenyl)silsesquioxane (OAPS)/NMP solution was mixed with polyamic acid (PAA) solution prepared by reacting 4,4′-diaminodiphenylmethane and 3,3′,4,4′-benzophenonetetracarboxylic dianhydride in NMP, and second, the polycondensation solution was treated by thermal imidization. The well-defined ‘hard particles’ (POSS) and the strong covalent bonds between the PI and the ‘hard particles’ lead to a significant improvement in the thermal mechanical properties of the resulting nanocomposites. The glass transition temperature dramatically increases while the coefficient of thermal expansion (CTE) decreases, owing to the significant increase of the cross-linking density in the PI-POSS nanocomposites. The thermal stability and mechanical property of the nanocomposites were also improved.     

Effects of clay on phase morphology and mechanical properties in polyamide 6/EPDM-g-MA/organoclay ternary nanocomposites

In this study, both organoclay and EPDM-g-MA rubber were used to simultaneously improve the toughness and stiffness of polyamide 6 (PA6). We first prepared PA6/EPDM-g-MA/organoclay ternary nanocomposites using melt blending. Then the composites were subjected to traditional injection molding and so-called dynamic packing injection molding. The dispersion of clay, phase morphology, crystallinity and orientation of PA6 as well the mechanical properties were characterized by WAXD, SEM, DSC, 2D-WAXS and mechanical testing, respectively. The effects of clay on phase morphology and mechanical properties of PA6/EPDM-g-MA blends could be summarized as follows: (1) weakening interphase adhesion between PA6 and EPDM-g-MA rubber particles, resulted in increasing of rubber particle size, as the clay and rubber contents are low; (2) preventing coalescence of rubber domains, arisen in decreasing of rubber particle size, as the clay and rubber contents are high; (3) the blocking effect on the overlap of stress volume around rubber particles caused broadening of the brittle-ductile transition region and decrease of toughness, and (4) the effective stress transfer leading a better reinforcement when the interparticle distance is smaller than the critical value.     

SEBS/蒙脱土纳米复合材料结构和性能研究

采用溶液混合方法制备了氢化苯乙烯/丁二烯三元嵌段共聚物(SEBS)/有机蒙脱土(OM-MT)纳米复合材料(NC)。对SEBS/OMMT NC的插层结构和物理力学、动态力学、耐热等性能进行了研究。结果表明,与SEBS复合,OMMT层间距明显增大,制备出具有插层型结构的NC。加入OMMT可明显提高SEBS的拉伸断裂强度、300%定伸强度和断裂伸长率,但永久变形也增大。DMA研究表明,SEBS/OMMT NC的储能模量和损耗模量比纯SEBS显著提高,PEB链段的tanδ降低,而PS链段增加。SEBS/OMMT NC比SEBS的热稳定性明显提高。     

Barrier and mechanical properties of injection molded montmorillonite/polyesteramide nanocomposites

Properties of injection‐molded biodegradable polyesteramide composites containing 5 and 13 wt% octadecylammonium‐treated montmorillonite clay have been studied. Oxygen transmission rates and mechanical properties were measured. X‐ray diffraction was used to assess the degree of intercalation of the clay layer stacks, and transmission electron microscopy (TEM) was used to assess the morphology and degree of layer delamination. A substantial reduction in oxygen permeability was observed when clay was added to the composites. The oxygen permeability of the 13 wt% clay sample was only 20% of that of the pure polymer. The in‐plane stiffness and in‐plane strength of the sheets were greatly improved without any embrittlement. These beneficial effects were probably due to the high degree of clay layer exfoliation and orientation observed by TEM. Heat shrinkage, toughness analysis, and cutting operations suggested that the polymer chains and the clay layers were oriented parallel to the plane of the sheet. TEM and X‐ray showed that stacked layers were still present but that these were significantly intercalated. The clay‐layer periodic spacing increased from 25 Å to approximately 35 Å during processing. POLYM. ENG. SCI. 45:135–141, 2005. © 2004 Society of Plastics Engineers     

Nanostructure and dynamic mechanical properties of silane-functionalized montmorillonite/epoxy nanocomposites

In this work sodium montmorillonite (Na-MMT) was functionalized with N-(2-aminoethyl)-3-aminopropyl-trimethoxysilane and the corresponding silylated clay was used to modify epoxy matrix cured with triethylenetetramine. The grafting/intercalation of the aminosilane inside the clay galleries were followed by infrared spectroscopy, X-ray diffraction, thermogravimetric analysis and ²⁹Si cross-polarization magic-angle-spinning nuclear magnetic-resonance (CP/MAS NMR) spectroscopy. Epoxy-based nanocomposites were prepared with different amounts of silylated clay or commercial organoclay, Cloisite 30B, whose intercalating agent consists of a methyl, tallow, bis-2-hydroxyethyl quaternary ammonium salt. The degree of intercalation/exfoliation was estimated by X-ray diffraction experiments and confirmed by small angle X-ray scattering. Nanocomposites prepared with silylated clay displayed no peak in both XRD and SAXS curves whereas those prepared with Cloisite 30B exhibited a clear interference peak corresponding to an interlayer spacing d₀₀₁ of 4.1 nm. The former also presented a better dispersion, with a high proportion of tactoids smaller than 2 nm, as estimated by SAXS. From the results of dynamic mechanical analysis it was observed that most of the nanocomposites display higher storage modulus mainly at temperatures above the glass transition temperature. The glass transition temperature is similar or higher than the neat epoxy network for nanocomposites containing 1 wt.% of silylated clay or higher.     

Effect of dynamic cross-linking on phase morphology and dynamic mechanical properties of polyamide 12/ethylene vinyl acetate copolymer blends

Dynamic cross-linking of polyamide 12 (PA12) and ethylene vinyl acetate copolymer (EVA) blends in the mixing chamber of a torque rheometer was investigated. EVA was selectively cross-linked within the PA12 phase through free radical reactions using dicumyl peroxide. The torque level and temperature in the torque rheometer chamber were monitored to follow the evolution of the EVA cross-linking during the dynamic cross-linking process. The degree of cross-linking of EVA in the PA12/EVA materials was estimated based on the gel content (insoluble EVA fraction). The PA12/EVA phase morphology was investigated by scanning electron microscopy. The solid viscoelastic properties were investigated by dynamic mechanical thermal analysis (DMTA). The morphology, interfacial tension and viscoelastic results showed the immiscible nature of this system. The morphology of the blends was observed and the results revealed a two-phase system. The PA12/EVA 70/30 showed disperse-phase morphology, however a co-continuous phase was observed in blend ratios of 50/50 and 60/40. The dynamic cross-linking process resulted in a more stable EVA phase morphology with disperse and interconnected structures in the thermoplastic PA12 domains.     

Rheological,mechanical, optical,and transport properties of blown films of polyamide 6/residual monomer/montmorillonite nanocomposites

Exfoliated nanocomposites of polyamide 6 (PA6) with residual monomer and an organically treated montmorillonite (3 and 5 wt %) were produced by twin‐screw extrusion. The composites had their steady state, dynamic, and transient rheological properties measured by parallel‐plates rheometry; their exfoliation level was characterized by wide angle X‐rays diffraction (WAXD) and transmission electron microscopy (TEM). The characterization showed as follows: (i) the nanoclay's lamellas were well dispersed and distributed thru the PA6, (ii) the postpolymerization of the residual monomer produced more branched chains than linear ones in the pure PA6, (iii) the nanoclay's lamellas acted as entanglement points in the nanocomposites, and (iv) the molecular weight of the PA6 in the nanocomposites decreased. Blown films of the nanocomposites were produced by single screw extrusion; the die pressure during the film blowing of the nanocomposites strongly decreased. The tensile mechanical properties of the blown films were also measured. Along the machine direction (MD), the best mechanical properties were obtained with the 5 wt % nanocomposite, whereas along the transverse direction (TD), the 3 wt % nanocomposite had the best behavior. The glass transition temperature (T_g) of the blown films was measured by dynamic mechanical thermal analyses (DMTA). The 5 wt % nanocomposite had the highest T_g of all the films. The optical properties were measured by spectrophotometry; the nanoclay decreased the films' haze, but the level of transmittance was not affected. The water vapor and oxygen permeability rates of the nanocomposites films were found to be lower than in the pure PA6 blown film as a result of a tortuosity effect. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Crystallization behavior of polypropylene/polyamide 6/montmorillonite nanocomposites

Polymer blended materials such as polyamide 6 (PA6)/polypropylene (PP) blends have received considerable attention in recent years. To improve the compatibility of PA6 and PP, compatibilizers like maleic anhydride‐g‐polypropylene (MPP) are often added. In addition, organically modified montmorillonite (MMT) is also used to improve the properties of various materials. In this work, the crystallization behavior of PP/PA6/MMT nanocomposites with MPP compatibilizer was investigated systematically. The annealing process effectively improved the crystallization of α‐PP. The crystallization temperature (T_c) of PA6 was increased by ca 2–3 °C on introducing MPP or MMT alone to the PP/PA6 system, whereas T_c of PP underwent no obvious change. However, when MPP and MMT were added simultaneously, T_c of PP and PA6 increased by 6.6 and 4.2 °C, respectively, and a new crystallization peak corresponding to PP‐g‐PA6 copolymer phase was observed at 162.5 °C. The combined effect of MPP and MMT led to better compatibility of PP with PA6. Moreover, the results of a non‐isothermal crystallization kinetics experiment revealed that the simultaneous introduction of MPP and MMT markedly shortened the crystallization time. Copyright © 2010 Society of Chemical Industry     

Thermal stability and flammability of polyamide 66/montmorillonite nanocomposites

Exfoliated nanocomposites based on polyamide 66 (PA66) and montmorillonite (MMT) were prepared and their thermal stability and combustion behaviour were investigated by using thermal gravity analysis and cone calorimeter. The nanocomposites exhibit higher thermal stability and good flame retardancy. The catalytic decomposition effect of MMT and the barrier effect of layer silicates are presented directly in isothermal oxidation experiment. The initial heat release rate plots show that the addition of MMT can accelerate the ignition of PA66 matrix. A ceramic-like char forms in the surface of the nanocomposites during burning. It is characterized by attenuated total reflection infrared spectra and scanning electron microscopy.     

Rheological behavior and mechanical properties of PVC/MAP‐POSS nanocomposites

The polyhedral oligomeric silsesquioxanes which contains methylacryloylpropyl groups (MAP‐POSS) was synthesized. The MAP‐POSS/PVC nanocomposites were prepared. The influences of composition, shear rate' shear stress on melting rheological behavior of MAP‐POSS/PVC nanocomposites were discussed. The dynamic mechanical properties, mechanical properties, and morphology were determined by DMA, material tester and SEM, respectively. The result shows that the plastic times decreases and melt viscosity increases with increasing MAP‐POSS content. The n has a maximal value at 5 wt% MAP‐POSS content, but have best impact strength at 3%. MAP‐POSS can use as process aid and impact aid of PVC at appropriate contents. POLYM. COMPOS., 31:1822–1827, 2010. © 2010 Society of Plastics Engineers.     

Compatibilizing effect of maleated polypropylene on the mechanical properties and morphology of injection molded polyamide 6/polypropylene/organoclay nanocomposites

Polyamide 6/polypropylene (PA6/PP=70/30 parts) blends containing 4 phr (parts per hundred resin) of organophilic modified montmorillonite (organoclay) were prepared using twin screw extruder followed by injection molding. Maleated polypropylene (MAH-g-PP) was used to compatibilize the blend system. The mechanical properties of PA6/PP nanocomposites were studied through tensile and flexural tests. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to assess the fracture surface morphology and the dispersion of the organoclay, respectively. X-ray diffraction (XRD) was used to characterize the formation of nanocomposites. The thermal properties were characterized by using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The dynamic mechanical properties of PA6/PP nanocomposites were analyzed by using dynamic mechanical thermal analyzer (DMTA). The strength and stiffness of PA6/PP nanocomposites were improved significantly in the presence of MAH-g-PP. This has been attributed to the synergistic effect of organoclay and MAH-g-PP. The MAH-g-PP compatibilized PA6/PP nanocomposites showed a homogeneous morphology supporting the compatibility improvement between PA6, PP and organoclay. TEM and XRD results revealed the formation of nanocomposites as the organoclay was intercalated and exfoliated. A possible chemical interaction between PA6, PP, organophilic modified montmorillonite and MAH-g-PP was proposed based on the experimental work.     

Effect of organoclay structure on morphology and properties of nanocomposites based on an amorphous polyamide

An amorphous polyamide (a-PA) and three organoclays, M₃(HT)₁, M₂(HT)₂ and (HE)₂M₁T₁, were melt processed to explore the effect of the organoclay structure on the extent of exfoliation and properties of these nanocomposites. Wide angle X-ray scattering, transmission electron microscopy, and stress-strain behavior were used to determine the degree of exfoliation of the nanocomposites. For quantitative assessment of the structure of the nanocomposites, a detailed particle analysis was made to provide various averages of the clay dimensions and aspect ratio. The results evaluated from different methods were generally consistent with each other. Nanocomposites based on the organoclays with one alkyl tail and hydroxyl ethyl groups gave well-exfoliated structures and high matrix reinforcement while nanocomposites from two-tailed organoclay contain a considerable concentration of intercalated stacks. Nanocomposites from the organoclays with one alkyl tail showed slightly better exfoliation and matrix reinforcement than those from the organoclays with hydroxyl ethyl groups. The organoclay structure trends for a-PA are analogous to what has been observed for nylon 6; this suggests that a-PA, like nylon 6, has good affinity for the pristine silicate surface of the clay leading to better exfoliation and enhanced mechanical properties with one-tailed organoclay than multiple-tailed organoclay. Furthermore, heat distortion temperatures were predicted from the dynamic mechanical properties of nanocomposites.