Effects of organoclay Soxhlet extraction on mechanical properties, flammability properties and organoclay dispersion of polypropylene nanocomposites

The organic treatment on a layered silicate used in nanocomposite synthesis is the interface between the hydrophilic layered silicate (clay) and hydrophobic polymer in the case of polypropylene. However, the typical synthesis of an organoclay can result in excess organic treatment which can hinder mechanical and flammability benefits. This excess organic treatment may result in plasticization of the polymer matrix, possibly removing some of the mechanical and flammability property benefits provided by the nanocomposite. In this paper, the effects of using Soxhlet Extraction on the Organoclays after synthesis was investigated. Soxhlet extraction times on organoclays were found to have an effect on the mechanical and flammability properties of the resulting polypropylene nanocomposite. The removal of excess organic treatment by Soxhlet extraction resulted in improvements in flex modulus, improved clay dispersion, delayed time to ignition, and lowered heat release rate during burning.     

Effect of organoclay structure and mixing protocol on the toughening of amorphous polyamide/elastomer blends

An amorphous polyamide (a-PA) was blended with an ethylene-1-octene (EOR) elastomer with organoclays present to control the elastomer particle size. Four different organoclays, M₃(HT)₁, M₂(HT)₂, M₁H₁(HT)₂, and (HE)₂M₁T₁ and two different mixing protocols were used to investigate the effect of the organoclay structure and mixing protocol on the morphology and properties of the resulting blends. Wide angle X-ray scattering, transmission electron microscopy, and stress-strain behavior were used to evaluate the degree of exfoliation of the organoclays and the morphology of the elastomer particles for these blends. A detailed particle analysis was made to provide a quantitative assessment of elastomer particle size. The size and shape of the elastomer particles were dramatically affected by the amount of organoclay but the organoclay type and the mixing protocol led to slight differences. Broadly speaking, most of the MMT platelets are well exfoliated in the a-PA phase, but some locate at the interface and tend to envelop the EOR phase. The mechanical properties were not significantly affected by the organoclay type or the mixing protocol. While the organoclays reduced the EOR particles to size range where toughness might be expected, all blends proved to be brittle. A clear trade-off was observed between the Izod impact strength and tensile modulus for these blends containing organoclays.     

Polycarbonate nanocomposites. Part 1. Effect of organoclay structure on morphology and properties

Polycarbonate nanocomposites were prepared by melt processing from a series of organoclays based on sodium montmorillonite exchanged with various amine surfactants. To explore the effects of matrix molecular weight on dispersion, an organoclay was melt-mixed with a medium molecular weight polycarbonate (MMW-PC) and a high molecular weight polycarbonate (HMW-PC) using a twin screw extruder. The effects of surfactant chemical structure on the morphology and physical properties were explored for nanocomposites formed from HMW-PC. Wide angle X-ray scattering, transmission electron microscopy, and stress-strain behavior were employed to investigate the nanocomposite morphology and physical properties. The modulus enhancement is greater for nanocomposites formed from HMW-PC than MMW-PC. This trend is attributed to the higher shear stress generated during melt processing. A surfactant having both polyoxyethylene and octadecyl tails shows the most significant improvement in modulus with some of the clay platelets fully exfoliated. However, the nanocomposites formed from a range of other organoclays contained both intercalated tactoids and collapsed clay particles with few, if any, exfoliated platelets.     

Polyamide- and polycarbonate-based nanocomposites prepared from thermally stable imidazolium organoclay

This paper explores the possible advantages of the more thermally stable imidazolium-based organoclay over a more conventional ammonium-based organoclay for facilitating exfoliation and minimizing polymer matrix degradation in melt blended polyamide 6 (PA-6) and polycarbonate (PC) nanocomposites. The thermal stability of the two organoclays was evaluated by TGA analyses. The extent of clay exfoliation was judged by analysis of the morphology and tensile modulus of these nanocomposites formed using a DSM Microcompounder, while the extent of color formation and molecular weight change were used to evaluate polymer matrix degradation. For PA-6 and PC nanocomposites, the use of the imidazolium organoclay only produced slight differences in both exfoliation and molecular weight change, although the imidazolium organoclay is remarkably more thermally stable than the ammonium organoclay.     

Effect of organoclay structure on nylon 6 nanocomposite morphology and properties

A carefully selected series of organic amine salts were ion exchanged with sodium montmorillonite to form organoclays varying in amine structure or exchange level relative to the clay. Each organoclay was melt-mixed with a high molecular grade of nylon 6 (HMW) using a twin screw extruder; some organoclays were also mixed with a low molecular grade of nylon 6 (LMW). Wide angle X-ray scattering, transmission electron microscopy, and stress-strain behavior were used to evaluate the effect of amine structure on nanocomposite morphology and physical properties. Three surfactant structural issues were found to significantly affect nanocomposite morphology and properties in the case of the HMW nylon 6: decreasing the number of long alkyl tails from two to one tallows, use of methyl rather than hydroxy-ethyl groups, and use of an equivalent amount of surfactant with the montmorillonite, as opposed to adding excess, lead to greater extents of silicate platelet exfoliation, increased moduli, higher yield strengths, and lower elongation at break. LMW nanocomposites exhibited similar surfactant structure-nanocomposite behavior. Overall, nanocomposites based on HMW nylon 6 exhibited higher extents of platelet exfoliation and better mechanical properties than nanocomposites formed from the LMW polyamide, regardless of the organoclay used. This trend is attributed to the higher melt viscosity and consequently the higher shear stresses generated during melt processing.     

Rubber toughening of an amorphous polyamide by functionalized SEBS copolymers: morphology and Izod impact behavior

Rubber toughening of an amorphous polyamide (Zytel 330) using combinations of triblock copolymers of the type SEBS and a maleic anhydride functionalized version, SEBS-g-MA, was investigated and the results compared with those of nylon 6 and nylon 66. The effects of rubber content and the type of extruder on the morphology, Izod impact behavior and the ductile-brittle transition temperature were explored. The shape and sizes of the rubber particles in blends with this amorphous polyamide were found to be more similar to those in nylon 6 than in nylon 66 blends. The twin screw extruder produced smaller particles with a more narrow distribution of sizes than the single screw extruder. Higher rubber contents generally yielded tougher blends; there is a critical rubber particle size above which the ternary blends are brittle at 20 wt% total rubber. The ductile-to-brittle temperature was found to decrease with increased rubber content and decreased rubber particle size. In general, the trends for this amorphous polyamide are rather similar to those reported earlier for semi-crystalline nylon 6 and nylon 66.     

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     

Morphology and properties of thermoplastic polyurethane nanocomposites: Effect of organoclay structure

A series of alkyl ammonium/MMT organoclays were carefully selected to explore structure-property relationships for thermoplastic polyurethane (TPU) nanocomposites prepared by melt processing. Each organoclay was melt-blended with a medium-hardness, ester-based TPU, while a more limited number of organoclays was blended with a high-hardness, ether-based TPU. Wide-angle X-ray scattering, transmission electron microscopy, particle analysis, and stress-strain behavior were used to examine the effects of organoclay structure and TPU chemical structure on morphology and mechanical properties. Specifically, the following were observed: (a) one long alkyl tail on the ammonium ion rather than two, (b) hydroxy ethyl groups on the amine rather than methyl groups, and (c) a longer alkyl tail as opposed to a shorter one leads to higher clay dispersion and stiffness for medium-hardness TPU nanocomposites. Overall, the organoclay containing hydroxy ethyl functional groups produces the best dispersion of organoclay particles and the highest matrix reinforcement, while the one containing two alkyl tails produces the poorest. The two TPU's exhibit similar trends with regard to the effect of organoclay structure. The high-hardness TPU nanocomposites showed a slightly higher number of particles and clay dispersion. The organoclay structure trends are analogous to what has been observed for nylon 6-based nanocomposites; this suggests that polar polymers like polyamides, and apparently polyurethanes, have a relatively good affinity for the polar clay surface; and in the case of polyurethanes, the high affinity of the matrix for the hydroxy ethyl functional groups in the organoclay aids clay dispersion and exfoliation.     

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.     

Morphology and properties of nanocomposites formed from ethylene-vinyl acetate copolymers and organoclays

A series of ethylene-vinyl acetate copolymers, EVA, containing 0-40% VA and three organoclays, M₂(HT)₂, M₃(HT)₁ and (HE)₂M₁T_1, were melt processed to explore the relationship between the polarity of the polymer matrix and the organoclay structure on the extent of exfoliation and properties of the resulting nanocomposites. The degree of exfoliation of the nanocomposites was evaluated by TEM, WAXS, and mechanical testing. Quantitative particle analyses of TEM images were made to give various averages of the clay dimensions and aspect ratio. The results from different techniques were generally consistent with each other. These EVA copolymer nanocomposites show dramatically improved exfoliation of the organoclay as the VA content is increased. Nanocomposites based on the organoclay with two alkyl tails always gave better exfoliation than those based on the organoclays with a single tail at all VA levels; however, the relative advantage of the two tails versus one tail seems to diminish with increased VA level. The predictions of tensile modulus using a simple composite model based on Halpin-Tsai equations show rather good agreement with the experimental data.     

Synthesis and characterization of amorphous octakis-functionalized polyhedral oligomeric silsesquioxanes for polymer nanocomposites

We have synthesized the polyhedral oligomeric silsesquioxane (POSS) derivatives OS-POSS and OA-POSS through the hydrosilylation of styrene and 4-acetoxystyrene, respectively, with octakis(dimethylsiloxy)silsesquioxane (Q₈M₈^H). We then prepared OP-POSS through acetoxyl hydrazinolysis of OA-POSS with hydrazine monohydrate. The chemical structures of these POSS derivatives were characterized using FTIR and ¹H NMR spectroscopy and MALDI-TOF mass spectrometry. Unlike Q₈M₈^H, which is crystalline, these three hydrosilylated POSS derivatives are liquids at 25 °C. Through DSC and XRD analyses, we found that they exhibit polymer-like glass transitions and amorphous halos. These octakis-functionalized POSS derivatives can be regarded as amorphous glasses possessing low glass transition temperatures, the values of which depend on the intermolecular interactions of their outer organic groups. To investigate the dispersion of these POSS derivatives in polymer nanocomposites, we blended OS-POSS, OA-POSS, and OP-POSS with polystyrene, poly(4-acetoxystyrene), and poly(4-vinylpyridine), respectively, and investigated the effects of the resulting intermolecular aromatic hydrophobic, dipole-dipole, and hydrogen-bonding interactions, respectively. Dipole-dipole interactions provided the best dispersion of OA-POSS in poly(4-acetoxystyrene), in which the POSS-polymer intermolecular interactions were of similar strength to the POSS-POSS interactions.     

Morphology and properties of polypropylene nanocomposites based on a silanized organoclay

A silanized organoclay (s-M₂(HT)₂) was prepared by reaction of trimethoxyphenyl silane with an organoclay with a M₂(HT)₂ surfactant structure. Nanocomposites were formed from polypropylene (PP) and a blend of PP and maleic anhydride-grafted polypropylene (PP-g-MA) and the M₂(HT)₂ and s-M₂(HT)₂ organoclays by melt processing to explore the extent of exfoliation and the mechanical properties. Wide angle X-ray scattering (WAXS) and transmission electron microscopy (TEM) coupled with detailed particle analysis were used to determine the effect of the organoclay used and the PP-g-MA compatibilizer on exfoliation and mechanical, rheological, and thermal expansion properties. The PP/s-M₂(HT)₂ nanocomposites have higher particle densities than the PP/M₂(HT)₂ nanocomposites though the aspect ratio remains the same. Platelet dispersion is significantly improved by using PP-g-MA compatibilizer for both organoclays. The rheological properties and the relative modulus improve for the PP/s-M₂(HT)₂ nanocomposites but not to the same degree as either organoclay in a PP-g-MA compatibilized matrix. The thermal expansion properties, however, are not improved by using the s-M₂(HT)₂ organoclay. The s-M₂(HT)₂ organoclay is less prone to agglomeration during extrusion than the M₂(HT)₂ organoclay.     

Comparison of the toughening behavior of nylon 6 versus an amorphous polyamide using various maleated elastomers

The toughening effect of two types of elastomers based on ethylene/α-olefin copolymers, viz, an ethylene/propylene copolymer (EPR) with its maleated version, EPR-g-MA, and an ethylene/1-octene copolymer (EOR) with its maleated versions, EOR-g-MA-X% (X=0.35, 1.6, 2.5), for two classes of polyamides: semi-crystalline nylon 6 versus an amorphous polyamide (Zytel 330 from DuPont), designated as a-PA, was explored. The results are compared with those reported earlier based on a styrenic triblock copolymer having a hydrogenated midblock, SEBS, and its maleated version, SEBS-g-MA, elastomer system. Izod impact strength was examined as a function of rubber content, rubber particle size and temperature. All three factors influence the impact behavior considerably for the two polyamide matrices. The a-PA is found to require a somewhat lower content of rubber for toughening than nylon 6. Very similar optimum ranges of rubber particle sizes were observed for ternary blends of EOR-g-MA/EOR with each of the two polyamides while blends based on mixtures of EPR-g-MA/EPR and SEBS-g-MA/SEBS (where the total rubber content is 20% by weight) show only an upper limit for a-PA but an optimum range of particle sizes for nylon 6 for effective toughening. Higher EPR-g-MA contents lead to lower ductile-brittle transition temperatures (T_db) as expected; however, a-PA binary blends with EPR-g-MA have a much lower T_db than do nylon 6 blends when the content of the maleated elastomer is not high. A minimum in plots of ductile-brittle transition temperature versus particle size appears for ternary blends of each of the matrices with EOR-g-MA/EOR; blends based on SEBS-g-MA/SEBS, in most cases, show higher ductile-brittle transition temperatures, regardless of the matrix. However, blends with EPR-g-MA/EPR show comparable T_db with those based on EOR-g-MA/EOR for the amorphous polyamide but show the lowest ductile-brittle transition temperatures for nylon 6 within the range of particle sizes examined. For the blends with a bimodal size distribution, the global weight average rubber particle size is inappropriate for correlating the Izod impact strength and ductile-brittle transition temperature. In general, trends for this amorphous polyamide are rather similar to those of semi-crystalline nylon 6.     

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。     

Effect of hydrogen bonding on the rheology of polycarbonate/organoclay nanocomposites

The linear dynamic viscoelastic properties and non-linear transient rheology of polycarbonate (PC)/clay nanocomposites were investigated at temperatures ranging from 240 to 280 °C. For the study, nanocomposites of PC and natural montmorillonite (Cloisite Na⁺) or chemically modified clay (Cloisite 30B) were prepared by melt blending in a twin-screw extruder. Cloisite 30B is a natural montmorillonite modified with methyl, tallow, bis-2-hydroxyethyl, quaternary ammonium chloride (MT2EtOH). In both PC/Cloisite Na⁺ and PC/Cloisite 30B nanocomposites the concentration of clay was varied from 2.3 to 4.3 wt%. In situ Fourier transform infrared (FTIR) spectroscopy results show that at temperatures ranging from 30 to 280 °C the carbonyl groups in PC and the hydroxyl groups in MT2EtOH of Cloisite 30B in PC/Cloisite 30B nanocomposites formed hydrogen bonds, while no evidence of hydrogen bonding was observed in the PC/Cloisite Na⁺ nanocomposites. There are no discernible sharp reflections in the X-ray diffraction (XRD) patterns of PC/Cloisite 30B nanocomposites, after Cloisite 30B having the d₀₀₁ spacing of 1.85 nm was mixed with PC, whereas the d₀₀₁ spacing changes little (1.17 nm) before and after the mixing of Cloisite Na⁺ to PC. Transmission electron microcopy (TEM) images show that organoclay platelets are well dispersed in PC/Cloisite 30B nanocomposites, while the untreated clay platelets are poorly dispersed in PC/Cloisite Na⁺ nanocomposites. The observed differences in XRD patterns and TEM images between the two nanocomposite systems are explained by in situ FTIR spectroscopy. The results of rheological measurements (linear dynamic viscoelasticity, non-linear transient shear flow, and steady-state shear flow) support the conclusions drawn from the results of XRD, TEM, and FTIR spectroscopy.     

Effect of organoclay purity and degradation on nanocomposite performance, Part 2: Morphology and properties of nanocomposites

Part 1 of this series showed that the purification level and surfactant loadings of organoclays significantly affect their thermal stability; the higher rate of degradation of as-received commercial organoclay is primarily a result of excess surfactant that is intentionally or unintentionally part of the commercial organoclay. Polypropylene nanocomposites and nylon 6 nanocomposites were formed through melt processing to assess the practical consequences, in terms of nanocomposite formation and performance, of using a purified version of the organoclay with no excess surfactant and a lower rate of thermal degradation versus using the as-received organoclay. The properties and morphology of polymer-clay nanocomposites based on both as-received and purified organoclays were evaluated by TEM, WAXS, and mechanical testing. The results from the different techniques were generally consistent with each other suggesting that the differences in thermal stability of organoclays do not appear to have a significant effect on the morphology and properties of the nanocomposites formed from them.     

Structure,thermal stability,and mechanical properties of nanocomposites based on an amorphous polyamide

Polymer nanocomposites based on an amorphous polyamide (aPA) modified with three organoclays were obtained in the melt state. The observed T_g decreases indicated that some organic modifier of the OMMT (surfactant) migrated to the matrix during mixing. The decrease in the thermal stability of the aPA in nitrogen atmosphere on organoclay addition was attributed to the instability of the organoclays. The smaller decrease in the thermal stability of the nanocomposites in air atmosphere was attributed to a barrier effect. The largest dispersion (an average of only 1.2 layers per particle) occurred using the octadecylamine‐modified organoclay (I30) that has the maximum uncovered surface; this indicates the basic importance of this parameter on exfoliation. Despite the bulky nature of the aPA that hinders the matrix/inorganic surface interactions, this dispersion level is comparable to that of semicrystalline polyamides with similar polarity. This indicates that the relation between high polarity of the matrix and high dispersion level also works in bulky aPAs, as that of this study. The significant modulus increases (56% for the nanocomposite with 5% I30) are consistent with the measured high dispersion level. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Influence of organoclay and preparation technique on the morphology of polyamide6/polystyrene/organoclay nanocomposites

To have an improved insight about the compatibilization effect of organoclay on immiscible polymers, two different organoclays and preparation techniques were chosen to prepare polyamide6 (PA6)/polystyrene (PS)/organoclay ternary nanocomposites. The morphology analysis based on the results of X‐ray diffraction, transmission electron microscopy, and scanning electron microscopy demonstrated that the type of organoclay and preparation technique had a significant influence on the dispersion and distribution of organoclay in the polymer. It was concluded that blending PS/organoclay nanocomposite synthesized previously via in situ bulk polymerization, with PA6 can realize the full exfoliation of organoclay in the final ternarynanocomposite, while an intercalated structure was achieved by directly blending the three components. The distribution of organoclay could be controlled by tuning the surface property of clay, and hence the interfacial interaction between clay and the polymer matrix. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of processing conditions on morphology and mechanical properties of compatibilized polypropylene nanocomposites

This work focuses on the influence of processing conditions on the nanocomposites structure, i.e. intercalated or exfoliated, and on the enhancement of mechanical properties of polypropylene (PP) nanocomposites. These nanocomposites were prepared using the melt intercalation technique in a co-rotating intermeshing twin screw extruder. In order to optimise processing conditions, both screw speed and barrel temperature profile were changed. The role of the compatibilizer (maleic anhydride grafted polypropylene) was also studied. The results obtained show that the barrel temperature is a very important parameter: using lower processing temperature, the apparent melt viscosity and, consequently, the shear stress are higher and, therefore, the exfoliation of the clay is promoted. Even using optimised processing conditions, exfoliation of clay can be achieved only when an high compatibility between polymer and clay exists: the PP nanocomposites containing maleic anhydride show an exfoliated structure and a sensible enhancement of mechanical properties while PP nanocomposites without compatibilizer show a structure mainly intercalated and a lower improvement of mechanical properties.     

Effect of added ionomer on morphology and properties of PP/organoclay nanocomposites

Ethylene-methacrylic acid ionomer (Surlyn) with concentration up to 20 wt% based on total weight of polymer resin was added into polypropylene (PP)/organoclay hybrids. The microstructure, rheological properties, crystallization properties and mechanical properties of the obtained nanocomposites have been investigated. The addition of ionomer markedly enlarged interlayer spacing of the platelets and led to an improved degree of exfoliation. Moreover, clay silicates were found to selectively disperse either inside the ionomer phase or at the phase boundary. Compared to the binary immiscible blends, an improved interfacial adhesion was achieved for PP/Surlyn/OMMT hybrids. Unlike PP/Surlyn binary blends, the viscoelastic properties of the hybrids significantly increased with increasing Surlyn concentration, which could be attributed to the improved clay dispersion and the contribution of silicate layers at the interface between PP and Surlyn. A synergistic role between Surlyn and clay was also found to suppress the crystallization of PP matrix. In addition, PP/Surlyn/OMMT hybrids exhibited superior tensile strain compared to the corresponding PP/PP-g-MA/OMMT. Both tensile strength and elongation at break showed maximum at Surlyn concentration of 5 wt%. By comparing the experimental tensile yield strength with model prediction, it was suggested that the clay platelets localized at the interface could play a role of interfacial activation to some extent.