Melt rheological properties of polypropylene–polyamide6 blends compatibilized with maleic anhydride‐grafted polypropylene

The melt rheological properties of binary uncompatibilized polypropylene–polyamide6 (PP–PA6) blends and ternary blends compatibilized with maleic anhydride‐grafted PP (PP–PP‐g‐MAH–PA6) were studied using a capillary rheometer. The experimental shear viscosities of blends were compared with those calculated from Utracki's relation. The deviation value δ between these two series of data was obtained. In binary PP–PA6 blends, when the compatibility between PP and PA6 was poor, the deformation recovery of dispersed PA6 particles played the dominant role during the capillary flow, the experimental values were smaller than those calculated, and δ was negative. The higher the dispersed phase content, the more deformed the droplets were and the lower the apparent shear viscosity. Also, the absolute value of δ increased with the dispersed phase composition. In ternary PP–PP‐g‐MAH–PA6 systems, when the compatibility between PP and PA6 was enhanced by PP‐g‐MAH, the elongation and break‐up of the dispersed particles played the dominant role, and the experimental values were higher than calculated. It was observed that the higher the dispersion of the PA6 phase, the higher the δ values of the ternary blends and the larger the positive deviation. Unlike uncompatibilized blends, under high shear stress with higher dispersed phase content, the PP‐g‐PA6 copolymer in compatibilized blends was pulled out from the interface and formed independent micelles in the matrix, which resulted in reduced total apparent shear viscosity. The δ value decreased with increasing shear stress. Copyright © 2006 Society of Chemical Industry     

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

Nanocomposites containing a thermoplastic blend and organophilic layered clay (organoclay) were produced by melt compounding. The blend composition was kept constant [polyamide 6 (PA6) 70 wt % + polypropylene (PP) 30 wt %], whereas the organoclay content was varied between 0 and 10 wt %. The mechanical properties of the nanocomposites were determined on injection‐molded specimens in both tensile and flexural loading. Highest strength values were observed at an organoclay content of 4 wt % for the blends. The flexural strength was superior to the tensile one, which was traced to the effect of the molding‐induced skin‐core structure. Increasing organoclay amount resulted in severe material embrittlement reflected in a drop of both strength and strain values. The morphology of the nanocomposites was studied by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy‐dispersion X‐ray analysis (EDX), and X‐ray diffraction (XRD). It was established that the organoclay is well dispersed (exfoliated) and preferentially embedded in the PA6 phase. Further, the exfoliation degree of the organoclay decreased with increasing organoclay content. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 175–189, 2004     

Exfoliation targeted toughness enhancement in polypropylene‐blend‐ montmorillonite nanocomposites

BACKGROUND: Both exfoliated and toughened polypropylene‐blend‐montmorillonite (PP/MMT) nanocomposites were prepared by melt extrusion in a twin‐screw extruder. Special attention was paid to the enhancement of clay exfoliation and toughness properties of PP by the introduction of a rubber in the form of compatibilizer toughener: ethylene propylene diene‐based rubber grafted with maleic anhydride (EPDM‐g‐MA). RESULTS: The resultant nanocomposites were characterized using X‐ray diffraction, atomic force microscopy, scanning electron microscopy, thermogravimetric analysis, dynamic mechanical analysis and Izod impact testing methods. It was found that the desired exfoliated nanocomposite structure could be achieved for all compatibilizer to organoclay ratios as well as clay loadings. Moreover, a mechanism involving a decreased size of rubber domains surrounded with nanolayers as well as exfoliation of the nanolayers in the PP matrix was found to be responsible for a dramatic increase in impact resistance of the nanocomposites. CONCLUSION: Improved thermal and dynamic mechanical properties of the resultant nanocomposites promise to open the way for highly toughened super PPs via nanocomposite assemblies even with very low degrees of loading. Copyright © 2008 Society of Chemical Industry     

Rubber toughening of polyamide 6/organoclay nanocomposites obtained by melt blending

Rubber toughening of polyamide 6 (PA6)/layered‐silicate nanocomposites was investigated. Different systems were prepared via melt blending according to different formulations. Wide‐angle X‐ray diffraction and transmission electron microscopy analyses showed that the nanocomposites had an appreciable degree of exfoliation. A linear elastic fracture mechanics approach was applied to characterize the material fracture behavior in dry conditions, whereas, because of the considerable ductility exhibited by the samples in the wet state, an elastic–plastic approach based on the essential work of fracture methodology was employed. In the absence of rubber, the presence of silicate layers makes the material fracture resistance decrease relative to neat polymer, depending on the degree of humidity. The results showed that the toughening action of rubber strongly depends on the degree of humidity of the material, at least for the rubber contents considered in this study (lower than 10 wt %). In particular, in slightly wet conditions, it was found that the addition of small amounts of rubber increased the fracture resistance of PA6/layered‐silicate nanocomposites without appreciably impairing the material stiffness. Thus, the results indicated that, for the given humidity conditions, a good balance between stiffness and toughness was obtainable by employing a suitable ratio of rubber to layered‐silicate content. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3406–3416, 2006     

Water absorption and hygrothermal aging study on organomontmorillonite reinforced polyamide 6/polypropylene nanocomposites

The water absorption and hygrothermal aging behavior of organomontmorillonite (OMMT) reinforced polyamide 6/polypropylene (PA6/PP ratio = 70/30), with and without maleated PP (MAH‐g‐PP), was studied at three different temperatures (30, 60, and 90°C). The water absorption and hygrothermal aging response of the composites was studied and analyzed by tensile tests and morphology assessment (scanning electron microscopy and transmission electron microscopy), indicating the effect of the immersion temperature, OMMT, and MAH‐g‐PP compatibilizer. The mathematical treatment used in analyzing the data was the single free phase model of diffusion, which assumed Fickian diffusion and utilized Fick's second law of diffusion. The kinetics of water absorption of the PA6/PP nanocomposites conformed to Fickian law behavior, whereby the initial moisture absorption follows a linear relationship between the percentage gain at any time t and t^1/2 (the square root of time), followed by saturation. It was found that the equilibrium moisture content and the diffusion coefficient are dependent on the OMMT loading, MAH‐g‐PP concentration, and immersion temperatures. Both the tensile modulus and strength of the PA6/PP nanocomposites deteriorated after being exposed to hygrothermal aging. MAH‐g‐PP acted as a good compatibilizer for PA6/PP/OMMT nanocomposites, which was attributed to its higher retention ability in modulus and strength (in the wet and redried states), lower equilibrium moisture content, and reduced water diffusivity of the nanocomposites. Morphological sketches for both uncompatibilized and MAH‐g‐PP compatibilized PA6/PP/OMMT nanocomposites, toward water uptake are proposed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 780–790, 2005     

Effects of organoclay modification on microstructure and properties of polypropylene–organoclay nanocomposites

We prepared polypropylene nanocomposites based on a modified organoclay with isobutyl trimethoxysilane to investigate the effects of such modifications of organoclay on the microstructure and properties of the nanocomposite. The organoclay was preliminarily intercalated with distearyldimethylammonium bromide via an ion exchange before being grafted with silane. The morphology of the polypropylene–organoclay nanocomposites was characterized by wide‐angle X‐ray diffraction analyses and transmission electron microscopy. The modification of the edges of clay platelets with organic silane resulted in a more uniform dispersion of nonagglomerated tactoids, which consisted of several intercalated clay platelets. However, the unmodified organoclay led to a mixed morphology with both agglomerated and nonagglomerated tactoids. The grafting of the clay edges with organic silane also affected the linear viscoelastic properties of the nanocomposites in the melt state, which was shown to be sensitive to the interaction between the edges of clay platelets as well as to the interaction of the polymer with the platelet edges. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1752–1759, 2006     

Preparation and mechanical properties of polypropylene–clay hybrids based on modified polypropylene and organophilic clay

Polypropylene–clay hybrids (PPCHs) were prepared by melt blending maleic anhydride modified PP and organophilic clay. In these PPCHs the silicate layers of the clay were exfoliated and dispersed to the monolayers. The hybridization of the clay in PP was achieved with modified PP with a small amount of maleic anhydride groups. The tensile modulus of the PPCH with 5 wt % clay was 1.9 times higher than that of the matrix resin at 25°C. The dynamic storage moduli (E′) of the PPCHs were also higher than those of the modified PP. The E′ was 2.5 times higher than that of the matrix resin at 60°C. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1918–1922, 2000     

Melting characteristic and β‐crystal content of β‐nucleated polypropylene/polyamide 6 alloys prepared using different compounding methods

BACKGROUND: The distribution of nucleating agents in different phases is still an open question in general, and how to control conditions to prepare alloys rich in β‐crystals of polypropylene (PP) is hardly reported. The main goal of this study was to find out the factors influencing the β‐crystal content in β‐nucleated PP/polyamide 6 (PA6) alloys and determine the best preparation conditions to obtain β‐nucleated PP/PA6 alloys rich in β‐crystals. RESULTS: The compounding methods had little influence on the crystallization temperature of both PP and PA6. However, the melting characteristic and β‐crystal content in β‐nucleated PP/PA6 alloys not only depended upon the compounding methods, but also on the temperature at which the nucleating agent was added. A higher β‐crystal content can be obtained by adding the nucleating agent at a temperature below 190 °C, which is also dependent on the mixing time. CONCLUSION: It is proved by etching the alloys with sulfuric acid that the nucleating agent mainly disperses in the PA6 phase and/or the interface between PP and PA6 when blended at high temperature. Copyright © 2009 Society of Chemical Industry     

Preparation and properties of polyamide 6/polypropylene–vermiculite nanocomposite/polyamide 6 alloys

Polypropylene–vermiculite nanocomposites can be achieved by simple melt mixing of maleic anhydride‐modified vermiculite with polypropylene. Maleic anhydride acts either as a compatibilizer for the polymeric matrix or as a swelling agent for the silicate. Compatibilized blends are injection molded directly from polyamide 6 and polypropylene–vermiculite nanocomposites. Scanning electron microscopy observation reveals that a two‐phase structure consisting of polypropylene–vermiculite nanocomposite and polyamide 6 is formed in the blends. The absence of vermiculite reflections in the X‐ray powder diffraction patterns indicates that the polypropylene–vermiculite phase exhibits nanocomposite characteristics. Tensile test shows that the tensile modulus of the polymer alloy tends to increase with increasing polypropylene–vermiculite nanocomposite content. The tensile strength of composite containing 8 wt % vermiculite is higher than that of pure polyamide 6. Finally, the thermal properties of the nanocomposites are determined by dynamic mechanical analysis, differential scanning calorimetry, and thermogravimetric measurements. The effects of maleic anhydride addition on the formation of polypropylene–vermiculite nanocomposite reinforcement and on the mechanical properties of composites are discussed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2330–2337, 2002     

Morphology,thermal, and mechanical properties of polyamide 66/clay nanocomposites with epoxy‐modified organoclay

A new kind of organophilic clay, cotreated by methyl tallow bis‐2‐hydroxyethyl quaternary ammonium and epoxy resin into sodium montmorillonite (to form a strong interaction with polyamide 66 matrix), was prepared and used in preparing PA66/clay nanocomposites (PA66CN) via melt‐compounding method. Three different types of organic clays, CL30B–E00, CL30B–E12, and CL30B–E23, were used to study the effect of epoxy resin in PA66CN. The morphological, mechanical, and thermal properties have been studied using X‐ray diffraction, transmission electron microscopy (TEM), mechanical, and thermal analysis, respectively. TEM analysis of the nanocomposites shows that most of the silicate layers were exfoliated to individual layers and to some thin stacks containing a few layers. PA66CX–E00 and PA66CX–E12 had nearly exfoliated structures in agreement with the SAXS results, while PA66CX–E23 shows a coexistence of intercalated and exfoliated structures. The storage modulus of PA66 nanocomposites was higher than that of the neat PA66 in the whole range of tested temperature. On the other hand, the magnitude of the loss tangent peak in α‐ or β‐transition region decreased gradually with the increase in the clay loading. Multiple melting behavior in PA66 was also observed. Thermal stability more or less decreased with an increasing inorganic content. Young's modulus and tensile strength were enhanced by introducing organoclay. Among the three types of nanocomposites prepared, PA66CX–E12 showed the highest improvement in properties, while PA66CX–E23 showed properties inferior to that of PA66CX–E00 without epoxy resin. In conclusion, an optimum amount of epoxy resin is required to form the strong interaction with the amide group of PA66. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1711–1722, 2006     

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     

Recycled PET‐organoclay nanocomposites with enhanced processing properties and thermal stability

Preparation of thermally stable recycled PET‐organoclay nanocomposites with improved processing and mechanical properties is a challenging task from the environmental as well as industrial and commercial point of view. In this work, both modification of sodium‐type montmorillonite with 1,2‐dimethyl‐3‐octadecyl‐1H‐imidazol‐3‐ium chloride and additional treatment with [3‐(glycidyloxy)propyl]trimethoxysilane was performed. Thermal stability of the organoclays and nanocomposites prepared by melt compounding was tested by thermogravimetric analysis, differential scanning calorimetry, and melt rheology. In comparison with the organoclays modified with quaternary ammonium compounds, the prepared clays showed substantial suppression of matrix degradation during melt mixing. The increase in interlayer distance of silicate platelets and homogeneity of dispersions in the recycled and virgin PET matrices have been evaluated by transmission electron microscopy and wide‐angle X‐ray scattering. The higher degree of delamination in the nanocomposites filled with imidazole organoclays was in a good agreement with improved rheological characteristics and led to significant enhancement in mechanical properties and thermal stability. A difference in structure (besides the level of delamination and homogeneity of silicate platelets) of recycled versus virgin PET nanocomposites was detected by X‐ray diffraction patterns. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Influence of blending sequence on micro‐ and macrostructure of PA6/mEPDM/EPDMgMA blends reinforced with organoclay

The structure of the PA6/mEPDM/EPDMgMA/organoclay ternary hybrids was characterized and related to its properties. The nanoblends were prepared through four different blending sequences based on one‐ or two‐step processes: (1) The PA6/organoclay nanocomposite was prepared and then mixed with the mEPDM+ EPDMgMA compound; (2) the mEPDM+EPDMgMA+ organoclay compound was first prepared and then mixed with PA6; (3) the PA6, mEPDM, EPDMgMA, and organoclays were blended in one step; and (4) the PA6/mEPDM/EPDMgMA blend was prepared and then mixed with the organoclay. The microscopic study of the nanoblends showed a relationship between the blending sequence and the dispersion of the organoclay and the rubber. Nevertheless, the mechanical characterization showed slight differences bet ween the blending sequence because of the presence of the organoclay in the matrix, rubber, or interface. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Processability of polysulfone improved by adding polyamide 6 and polysulfone‐polyamide 6 block copolymer

Although polysulfone (PSU) is a potential thermoplastic engineering plastic with high heat resistance, good dimensional stability and excellent mechanical properties, its poor processability has greatly restricted its application in electrical, aerospace, and medical fields. In this work, polyamide 6 (PA6) and PSU‐PA6 block copolymer (PSU‐b‐PA6) were used to improve the processibility and formability of PSU depending on their excellent fluidity and good compatibility between two components. Furthermore, the fluidity, thermal and mechanical properties of the blends were carefully investigated. It was found that, melt flow index of PSU could be increased above 10 times, and strength and toughness could be enhanced by 4–10% with the introduction of 10 wt % PA6 and PSU‐b‐PA6 without compromising the heat resistance of PSU obviously. The processing conditions of PSU could be improved while maintaining a decent comprehensive performance. Thus, the method has great potential for extending the applications of PSU. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41139.     

尼龙6/聚丙烯共混改性研究

用固相力化学方法制备的聚丙烯接枝马来酸酐作增容剂 ,制备了尼龙 6/聚丙烯共混合金 ,研究了尼龙 6/聚丙烯的比例和增容剂用量对共混合金力学性能的影响 ,通过Molau实验和FT IR分析对增容机理作了初步探讨。     

Preparation and characterisation of polyamide–polyimide organoclay nanocomposites

BACKGROUND: Ternary nanocomposites containing an organomodified layered silicate polyimide additive within a polyamide matrix have been investigated to gain greater insight into structure–property relationships and potential high‐temperature automotive applications. RESULTS: Polyamide nanocomposite blends, containing 3 wt% of organoclay, were prepared and compared with organoclay‐reinforced polyamide and neat polyamide. Nanoclay addition significantly increased heat distortion temperature, as well as both the tensile and flexural moduli and strength. The addition of polyimide demonstrated further increases in heat distortion temperature, glass transition temperature and the flexural and tensile moduli by about 17, 21 and 40%, respectively. The tensile and flexural strengths were either unaffected or decreased modestly, although the strain‐to‐failure decreased substantially. Morphological studies using transmission electron microscopy (TEM) and X‐ray diffraction showed that the nanoclay was dispersed within the ternary blends forming highly intercalated nanocomposites, regardless of the presence and level of polyimide. However, TEM revealed clay agglomeration at the polyamide–polyimide interface which degraded the mechanical properties. CONCLUSIONS: A range of improvements in mechanical properties have been achieved through the addition of a polyimide additive to a polyamide nanocomposite. The decrease in ductility, arising from the poor polyamide–polyimide interface and nanoclay clustering, clearly requires improving for this deficiency to be overcome. Copyright © 2008 Society of Chemical Industry     

Melt rheological properties of polypropylene–maleated polypropylene blends. I. Steady flow by capillary

Melt rheological properties of blends of polypropylene (PP) and PP grafted with maleic anhydride (PP‐g‐MA) are studied using a capillary rheometer. A pseudoplastic flow behavior is observed. The pseudoplasticity of the melt reduces with an increase of PP‐g‐MA content and/or temperature. The PP‐g‐MA component in the blend acts as decreasing melt viscosity, especially in the lower shear rate region, while the addition of PP‐g‐MA to PP does not cause obvious increase of die swell ratio. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1641–1648, 1999     

Effect of transfer film on tribological behavior of polyamide 66‐based binary and ternary nanocomposites

BACKGROUND: In a polymer–metal sliding system, the formation and performance of the transfer film have important effects on the tribological behavior of the polymer. In order to reveal the wear mechanism of polyamide 66 (PA 66) and its composites consisting of styrene–(ethylene/butylene)–styrene triblock rubber grafted with maleic anhydride (SEBS‐g‐MA) particles and organoclay nano‐layers, the tribological behavior and transfer films of polyamide 66 and its composites were investigated under dry sliding. RESULTS: The incorporation of SEBS‐g‐MA rubber particles reduces the wear mass loss of PA 66, while the addition of organoclay nano‐layers increases the wear mass loss. The transfer films formed by neat PA 66 and PA 66/organoclay binary nanocomposite include a dark portion and bright portion. In the dark portion, the transfer film is thicker; in the bright portion, the steel ring surface is exposed. The transfer film formed by PA 66/SEBS‐g‐MA/organoclay ternary nanocomposite is thinner and more uniform than the transfer films formed by the other materials. CONCLUSION: When SEBS‐g‐MA rubber particles and organoclay nano‐layers are added simultaneously to PA 66, the wear resistance of PA 66 can be improved markedly. The main reason is that PA 66/SEBS‐g‐MA/organoclay ternary nanocomposite can form a thin and uniform transfer film on the steel ring surface. Copyright © 2008 Society of Chemical Industry     

Oxygen permeation through films of compatibilized polypropylene/polyamide 6 blends

Polypropylene/polyamide 6 blends were prepared by melt mixing, without or with the addition of a suitable commercial product, a polypropylene grafted with 1% maleic anhydride, used as an interfacial modifier. The oxygen permeation through their films was studied as a function of temperature and the effect of the presence of the compatibilizer on the barrier properties of the material was examined. In addition, the diffusion coefficients were measured. The relationships between transport parameters and blend morphology were investigated by microscopic observations, together with chemical etchings, and a simple model was applied for interpreting the experimental permeation data. Differential scanning calorimetry was used in the determination of the degree of crystallinity of the blends. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1941–1949, 1999     

Processing and properties of modified polyamide 66-organoclay nanocomposites

Binary polyamide 66 nanocomposites containing 2 wt % organoclay, polyamide 66 blend containing 5 wt % impact modifier, and ternary polyamide 66 nanocomposites containing 2 wt % organoclay and 5 wt % impact modifier were prepared by melt compounding method. The effects of E-GMA and the types of the organoclays on the interaction between the organoclay and the polymer, dispersion of the organoclay, morphology, mechanical, flow, and thermal properties of the nanocomposites were investigated. Partial exfoliation and improved mechanical properties are observed for Cloisite® 15A and Cloisite® 25A nanocomposites. On the other hand, the organoclay was intercalated or in the form of tactoids in Cloisite® 30B nanocomposites. Components of the nanocomposites containing Cloisite® 15A and Cloisite® 25A were compounded in different addition orders. Mixing sequence of the components affected both the dispersion of the organoclay and the mechanical properties drastically. SEM analyses revealed that homogeneous dispersion of the organoclay results in a decrease in the domain sizes and promotes the improvements in the toughness of the materials. Melt viscosity was also found to have a profound effect on the dispersion of the organoclay according to MFI and XRD results. Crystallinity of the nanocomposites did not change significantly. It is only the type of the constituents and their addition order what dramatically influence the nanocomposite properties. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008