In situ fibrillation of polypropylene/polyamide 6 blends: Effect of organoclay addition

In situ fibrillation of PP/PA6 blends (85/15 wt %) is investigated in presence of two kinds of organically modified montmorillonite, differing by the polarity of their surfactant. The organoclay is primary dispersed either in the PP (for the low‐polarity Cloisite® 15A) or in the PA6 (for the high‐polarity Cloisite® 30B), according to its assumed affinity. In absence of organoclay, a fibrillar morphology is achieved after the melt‐blending and hot‐stretching step, as evidenced by SEM analysis. Upon clay addition, different morphological trends are evidenced. The C15A leads to a refinement of the fibrils whether the C30B induces a transition from fibrillar to nodular structure. These trends are ascribed to drastic changes in viscosity and elasticity ratios, due to the filler initial localization. Several techniques (DSC, STEM) point out a C15A migration from the PP to the PP/PA6 interface. Rheological measurements highlight the possibility of a double‐percolation phenomenon, linked to the fibrillar microstructure of the PP/PA6/C15A blend. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41680.     

Effect of processing procedures and conditions on structural,morphological, and rheological properties of polyethylene/polyamide/nanoclay blends

The article deals with the effect of processing procedures and conditions on structural, morphological, and rheological properties of ternary blends composed of polyethylene (PE), polyamide (PA)‐12, and organically modified montmorillonite nanoclay with selective affinity. Samples were prepared from PE/PA and PA/PE blends, either by simultaneous mixing or from a polymer/clay masterbatch, using two processing conditions. The results have shown the existence of a weight fraction threshold, above which no significant processing effect was observed. Below this weight fraction threshold, the results tend to underline the significant role of two parameters that depend on processing procedures and/or conditions: the contact time between PE and PA phases and the contact time between clay and PA. Clay structure, blend morphology, and rheological properties were all shown to depend on these two parameters, and also on the nature of the matrix (PE or PA), because of the selective affinity of clay toward polymer phases. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Effect of Clay Types on the Mechanical,Dynamic Mechanical and Morphological Properties of Polypropylene Nanocomposites

In the present investigation Polypropylene–Maleic anhydride grafted polypropylene–organically modified MMT (PP-MAPP-OMMT) nanocomposites were prepared by melt mixing in a twin screw extruder followed by injection molding. The effect of clay chemistry and compatibilizer on the properties of the nanocomposites has been studied. Sodium montmorillonite has been organically modified using quaternary and alkyl amine intercalants. A comparative account with commercial quaternary ammonium modified clays i.e Cloisite 20A, Cloisite 15A and Cloisite 30B has been presented. Storage modulus of PP matrix also increased in the nanocomposites, indicating an increase in the stiffness of the matrix polymer with the addition of organically modified nanoclays. The morphology of the nanocomposites has been examined using wide angle X-ray diffraction (WAXD) and transmission electron microscopy (TEM). Morphological findings revealed efficient dispersion of organically modified nanoclays within the PP matrix. MAPP compatibilized PP/Cloisite 15A nanocomposites displayed finely dispersed exfoliated nanomorphology as compared with other systems.     

Influence of polarity on the preferential intercalation behavior of clay in immiscible polypropylene/polystyrene blend

The immiscible polypropylene (PP)/polystyrene (PS) blend was prepared via melt compounding and the preferential intercalation behavior of clay was investigated by wide angle X‐ray diffraction (XRD) and transmission electron microscope (TEM). It was found that the clay platelets initially located in the PS phase in PP/PS/Clay composites and PS chains intercalated into the clay layers. However, all clay migrated from the PS phase to the modified PP phase after introducing polar maleic anhydride group (MAH) to PP chains. Interestingly, most of clay migrated from the modified PP phase to the modified PS phase again when PS matrix was modified with sulfonic group, and some enriched in the interphase region. The interaction energy density (B) of the blends was determined by combining the melting point variation with the ternary interaction model for heat of mixing. It was found that the value of B decreased with the introduction of polar group (MAH or sulfonic group), indicating that the polarization of PP and PS can enhance interaction between clay platelet and polymer component. Different interaction between clay platelet and polymer component leads to the preferential intercalation behavior. The higher polarity of the polymer generates higher interaction between clay and polymer component as well as results in stronger preferential intercalating ability. Moreover, the results of FTIR spectra after extraction of all samples gave additional explanation of the preferential intercalation behavior of clay in the immiscible PP/PS blends. On the basis of the results of the measurement mentioned above, a possible mechanism was proposed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

有机蒙脱土对PA6/PP合金体系的作用机制及其对材料性能的影响

研究了有机蒙脱土对PA6/PP合金体系的作用机制及其对材料性能的影响。结果表明,OMMT的添加可以提高体系的拉伸强度、弯曲强度和弯曲模量,但冲击强度会有某种程度的下降;OMMT主要分散在PA6连续相中,且当其添加量质量份数低于5%时,可以在PA6相中实现较充分的剥离;OMMT对PA6/PP合金体系有着显著的增容作用,这可能和片层对PP分散相凝聚时的阻隔,以及片层所起到的类似接枝物的增容作用有关;OMMT在PA6基体中被充分剥离后,将有利于使复合体系的拉伸强度、弯曲强度得到提高,但OMMT片层及和片层有关的类似接枝物的存在,将束缚并限制界面层附近PP相的屈服,而使材料冲击韧性下降。     

A combined experimental and theoretical approach to establish the relationship between shear force and clay platelet delamination in melt-processed polypropylene nanocomposites

In this article, a combined experimental and theoretical approach has been proposed to establish a relationship between the required shear force and the degree of delamination of clay tactoids during the melt-processing of polymer nanocomposites. Polypropylene (PP) was selected as a model polymer, and nanocomposites of PP with organically modified clay were prepared by a master batch dilution technique in a twin-screw extruder. The effect of PP throughput during the dilution of the master batch on the dispersion and orientation of clay platelets were studied in detail. Powder X-ray diffraction, small and wide angle X-ray scattering and high resolution transmission electron microscopy were used to study the structure and morphology of the obtained nanocomposites. The results showed that a lower feeding rate led to the orientation of clay platelets almost in the direction of extrusion. The adhesive force and the interaction energy between the clay platelets were theoretically calculated using the Hamaker approach. The analysis showed that the peeling mechanism is a practical explanation for the delamination of clay platelets during melt extrusion and that the dimensions of the clay platelet tactoids play an important role in the peeling due to the shear stress.     

Solid‐state mechanical properties of polypropylene/nylon 6/clay nanocomposites

The mechanical and thermomechanical properties as well as microstructures of polypropylene/nylon 6/clay nanocomposites prepared by varying the loading of PP‐MA compatibilizer and organoclay (OMMT) were investigated. The compatibilizer PP‐MA was used to improve the adhesion between the phases of polymers and the dispersion of OMMT in polymer matrix. Improvement of interfacial adhesion between the PP and PA6 phases occurred after the addition of PP‐MA as confirmed by SEM micrographs. Moreover, as shown by the DSC thermograms and XRD results, the degree of crystallinity of PA6 decreased in the presence of PP‐MA. The presence of OMMT increased the tensile modulus as a function of OMMT loading due to the good dispersion of OMMT in the matrix. The insertion of polymer chains between clay platelets was verified by both XRD and TEM techniques. The viscosity of the nanocomposites decreased as PP‐MA loading increased due to the change in sizes of PA6 dispersed phase, and the viscosity increased as OMMT loading increased due to the interaction between the clay platelets and polymer chains. The clay platelets were located at the interface between PP and PA6 as confirmed by both SEM and TEM. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Molecular interactions in intercalated organically modified clay and clay-polycaprolactam nanocomposites: Experiments and modeling

In this work we have evaluated molecular interactions in organically modified clay and polymer clay nanocomposite using a combination of experimental (photoacoustic FTIR, XRD) and computational (molecular dynamics (MD)) techniques. The FTIR data reveals hydrogen bond and ionic bond interaction between functional end groups of organic modifier and surface oxygen of interlayer clay sheet lying in the organically modified clay; and, the hydrogen bond formation between intercalated polymer and organic modifier and surface oxygen of clay sheet lying in the interlayer clay gallery in the polymer clay nanocomposite. In this work we report the nature of interactions between clay and polymer, clay and organic modifier in polymer-clay nanocomposites through experiments and molecular dynamics simulations.     

Surface modification of poly(propylene) by photoinitiators: Improvement of adhesion and wettability

Different benzophenone‐type photoinitiators were photografted onto poly(propylene) (PP). The polymer surfaces were analyzed by means of contact angle measurements, UV spectroscopy, and FTIR‐ATR. The modified samples showed a better wettability and higher surface energies, increasing from 26 mN/m for pure PP to 36 mN/m for the modified samples. The UV spectrum of the modified PP films showed two absorption bands that could be related to the grafted initiator. The effect of irradiation time and photoinitiator concentration was investigated. Different acrylates were grafted efficiently onto the modified polymer surfaces. FTIR‐ATR and contact angle measurements confirmed the presence of the grafted chains. The surface energy of the grafted surfaces of samples increased to 70 mN/m, depending on the type of acrylate used. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2341–2350, 2004     

Gold Nanolayers on Plasma-Treated Polypropylene

This work deals with characterization of polypropylene (PP) exposed to plasma discharge and gold layers deposited on the plasma modified PP. PP foils were exposed to Ar plasma and subsequently metallized with sputtered Au layer. Chemical structure of the plasma modified PP was studied using X-ray photoelectron spectroscopy (XPS) and Rutherford backscattering (RBS). Wettability of the plasma modified PP and its changes during sample aging were determined by goniometry. Surface morphology of PP and deposited Au layers was measured with atomic force microscopy (AFM). Continuity of Au layers was characterized by measuring their sheet resistance. With increasing exposure time in the plasma discharge the water contact angle decreases and the polymer surface becomes more hydrophilic. During the aging of the plasma treated samples the contact angle increases again. Plasma treatment leads to a decrease of the PP surface roughness and to generation of oxygen-containing polar groups on PP surface. During sample aging the concentration of the oxygen-containing groups decreases.     

Novel morphologies of poly(phenylene oxide) (PPO)/polyamide 6 (PA6) blend nanocomposites

Poly(phenylene oxide) (PPO)/polyamide 6 (PA6) (50/50 w/w) blend nanocomposites were prepared by melt mixing of PPO, PA6, and organically modified clay. The morphology of PPO/PA6 nanocomposite with various amounts of clay has been investigated using scanning electron microscope (SEM), transmission electron microscope (TEM), and wide-angle X-ray diffraction (WAXD). For the PPO/PA6 blend without clay, PPO is dispersed in the PA6 matrix with an average particle diameter of about 4.2 μm. The domain size of the dispersed PPO phase is significantly decreased to about 1.1 μm by adding a small amount of clay (2%). However, when the amount of organoclay is more than 5%, the matrix-domain structure is found to transform into the co-continuous morphology. The TEM observation shows that all the organoclay is dispersed only in the PA6 phase with a high degree of exfoliation and there is no any clay detectable in the PPO phase for the nanocomposites regardless of the amount of clay. It is considered that the dispersed clay platelets play an important role in the control of the PPO/PA6 blend morphology. Firstly, the selective localization of clay in PA6 phase changes the viscosity ratio of the PPO and PA6 phases. Therefore, clay has significant effects on the morphology of the polymer blend. Secondly, the high aspect ratio of the clay platelets prevents the coalescence of domains during melt mixing.     

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     

接枝聚丙烯增容改性PP/PA合金性能的研究

用PP接枝物增容PP/PA6共混体系,观察分析了共混合金的形态结构特点,测试了共混物的力学性能.结果表明：单独加入PP-g-MAH,力学性能均呈现先升后降的趋势,峰值时拉伸强度比未加接枝物时可提高20%,弯曲强度比未加接枝物时提高了54%,冲击强度比不添加接枝物时提高了3.6%.添加PP-g-MAH对不同比例PP/PA6共混物力学性能的影响不同,固定PP-g-MAH用量为4%,PA6质量分数为30%时共混物的综合力学性能达到最好.用PP-g-MAH和PP-g-GMA两种接枝物共同作为相容剂加入到PP/PA6共混物中比单独使用一种的效果要好,拉伸、弯曲和冲击强度都得到显著的提高.由共混物的SEM照片可以看到,PP-g-MAH使分散相的粒径变小,分布均匀,界面相互作用加强,所以是PP/PA6共混物的有效增容剂.     

Assessment of Nanoparticle Release from Polyamide 6- and Polypropylene-Silicon Composites and Cytotoxicity in Human Lung A549 Cells

The steady increase in application of nanoparticles in novel products over the past decade has triggered concerns about the impact of nanoparticles on human health. This study assessed the release of nanoparticles from polyamide 6 (PA6)- and polypropylene (PP)-silicon composites during drilling test and tested the toxicity of the released nanoparticles. The PA6 and PP polymers and their respective polymer–silicon composites, each containing 5 wt% of nano-fillers (silica nanoparticles, organically modified montmorrillonite) or larger fillers (glass fiber or foam glass crystal materials) were studied. It was shown that PA6-based materials generated up to ten times more nanoparticles than the PP-based materials. The polymer-silica nanocomposites generated the highest amount of nanoparticles, whilst the polymer-montmorrillonite composites and neat polymers generated the least. In human lung epithelial A549 cells, the toxicity for PA6-based nanoparticles appeared to be higher than PP-based nanoparticles. This study suggests that the assessment of nanoparticle release integrated with a nanoparticle toxicity study could reveal the potential risk of human exposure at certain stages of the product life cycle and the development of safe products.     

Thermal dehydroxylation of clay as alternative to organic modification: effects on properties of nanocomposites

Abstract

This study presents a novel approach towards clay modification via thermal dehydroxylation, for polymer nanocomposite application. The feasibility of modification of clay via thermal dehydroxylation and its influence on the polymer properties was investigated, with reference to the polyproplylene (PP) nanocomposites. In spite of ample available literatures on organophillic clay/polymer composites, use of organic compound for the clay modification has been found detrimental in various aspects. Therefore, in order to corroborate the advantage of the thermal dehydroxylation method over organophillic modification, a comparative aspect of the effect of the organically modified and thermally dehydroxylated clay on the polymer properties has been established. Wherein, remarkably greater mechanical, dynamic mechanical, thermal and microstructural properties were noticed in case of nanocomposites reinforced with thermally dehydroxylated clay. Modification of clay via thermal dehydroxylation method was found to be an effective approach for polymer nanocomposite application.     

Effect of POSS on morphology and mechanical properties of polyamide 12/montmorillonite nanocomposites

Sodium-montmorillonite (MMT) was modified with two types of AP-POSS and OA-POSS and dual-surfactants (POSS with a ditallow-based second surfactant: 04AP-POSS/08DTDMA and 04OA-POSS/08DTDMA), respectively, via ion-exchange reaction. The interlayer space, interlamellar structure, thermal and surface properties of these organo-montmorillonites were investigated by X-ray diffraction, thermogravimetric analysis, and contact angle measurement. The interlayer space of POSS modified clay was strongly dependent on the arrangement of POSS surfactants, but less on the POSS concentration. The POSS modified montmorillonites have partially exchanged silicate surfaces and good thermal stabilities due to steric hindering and thermal stability of the POSS molecules. Dual-surfactant modified montmorillonites showed higher exchange ratio and possessed better compatibility with PA12 due to the lower interfacial free energy. Polyamide 12-montmorillonite nanocomposites were prepared by conventional melt compounding with the four POSS based organo-montmorillonites. The best dispersion of modified montmorillonite was observed for 3 mass% 04AP-POSS/08DTDMA/MMT filled PA12 nanocomposites, which resulted in the best mechanical performance with an increase of 60% in tensile modulus and 10% in yield strength, respectively, compared to that of pure PA12. Compatibility between montmorillonites and polymer was not the only key factor affecting dispersion, thermal stability and interlayer space were also crucial for good dispersion of montmorillonites in polymer matrix.     

Effects of swelling agents on the crystallization behavior and mechanical properties of polyamide 6/clay nanocomposites

Montomorillonite was organically modified with three different swelling agents: n‐dodecylamine, 12‐aminolauric acid, and 1,12‐diaminodecane. These organoclays and polyamide 6 (PA6) were blended in a formic acid solution. X‐ray diffraction analysis showed that the clay still retained its layer structure in the PA6/clay nanocomposite. Consequently, these materials were intercalated nanocomposites. The effects of the swelling agent and organoclay content on the crystallization behavior of the PA6/clay nanocomposites were studied with differential scanning calorimetry. The results showed that the position and width of the exothermic peak of the PA6/clay nanocomposites were changed during the nonisothermal crystallization process. The clay behaved as a nucleating agent and enhanced the crystallization rate of PA6.The crystallinity of PA6 decreased with an increasing clay content. Different swelling agents also affected the crystallization behavior of PA6. The effects of the type and content of the swelling agent on the tensile and flexural properties of PA6/clay nanocomposites were also investigated. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1686–1693, 2003     

Adhesion characteristics of plasma-treated polypropylene to mild steel

The ability of polypropylene (PP) to adhere to mild steel depends to a large extent on the surface characteristics of both PP and steel. The adhesion of PP was improved by treatment in a cold plasma from oxidizing gases (O₂, H₂O, etc.). This surface functionalization was followed ex situ by means of contact angle measurements and XPS (X-ray photelectron spectroscopy) analysis. The polymer/steel assembly was fabricated by hot-pressing in vacuum, or after exposure to ambient air. Adhesion to steel, as determined by the lap-shear test, increased when the PP was treated with Ar-containing plasma gas and joined to steel after exposure to room atmosphere. Correlations between the polarity, the atomic (O/C, N/C) ratio, the dispersive component of the surface energy, and the degree of PP/steel adhesion are discussed.     

Characterization of latex-based isotactic polypropylene/clay nanocomposites

Polypropylene/clay nanocomposite (PCN) containing 1 wt% organo-modified clay was prepared by latex technology, previously successfully applied for preparation of carbon nanotubes (CNTs)/polymer composites. The level of dispersion of organoclay and the microstructure of the resulting PCNs were characterized by means of X-ray diffraction analysis, transmission electron microscopy (TEM), and scanning electron microscopy (SEM). The obtained results have demonstrated that the latex technique represents a promising method for preparation of PP/clay nanocomposites with good dispersion of exfoliated nanoclay particles. The influence of clay nanoparticles on nonisothermal crystallization of PCN was investigated by DSC. The crystallization onset temperature of the matrix rises for about 5 °C when crystallizing from the quiescent melt. Improved thermal stability of PP/nanoclay was observed as evaluated by TGA. The dynamic mechanical analysis reveals an increase in storage modulus of PP matrix in the nanocomposites for 30% over a temperature range, indicating an increase in the stiffness of the material with the addition of organically modified clay.     

超细CaCO3／PP复合纤维的制备和亲水行为研究

通过共混包粘一熔融纺丝法制备超细CaCO3／PP复合纤维,对复合纤维的亲水性能和力学性能进行了研究,通过接触角测量法研究超细CaCO3／PP复合纤维表面能参数的变化,并用FTIR和SEM对纤维结构和表面形态进行分析,结果表明,超细碳酸钙填充改性可使PP纤维接触角降低76．6％,表面能、粘附功、极化度和积极性分量显著提高。FTIR和SEM测试表明,复合纤维表面极性基团的形成和表面形态粗糙化对PP复合纤维亲水性能的改善有重要作用,且在超细CaCO3含量为6％（w）时,纤维性能最佳,断裂强度提高24．07％,模量提高38．40％,接触角下降57％。