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.     

Synthesis and characterization of in situ polymerized segmented thermoplastic elastomeric polyurethane/layered silicate clay nanocomposites

Nanocomposites based on thermoplastic elastomeric polyurethane (TPU) and layered silicate clay were prepared by in situ synthesis. The properties of nanocomposites of TPU with unmodified clay were compared with that of organically modified clay. The nanocomposites of the TPU and organomodified clay showed better dispersion and exhibited superior properties. Exfoliation of the clay layers was observed at low organoclay contents, whereas an intercalated morphology was observed at higher clay contents. As one of major purposes of this study, the effect of the silicate layers in the nanocomposites on the order–disorder transition temperature (T_ODT) of the TPU was evaluated from the intensity change of the hydrogen‐bonded and free carbonyl stretching peaks and from the peak position change of the N? H bending peak. The presence of the organoclay increased T_ODT by approximately 10°C, which indicated improved stability in the phase‐separated domain structure. The layered silicate clay caused a tremendous improvement in the stiffness of the TPU; meanwhile, a reduction in the ultimate elongation was observed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3048–3055, 2006     

Effect of organoclay on the morphology,mechanical, thermal,and rheological properties of organophilic montmorillonite nanoclay based thermoplastic polyurethane nanocomposites prepared by melt blending

Polymer nanocomposites based on the thermoplastic polyurethane (TPU) and organically modified montmorillonite (OMMT) was prepared by melt intercalation technique using a laboratory internal batch mixer followed by compression molding. Varying amount of organically modified nanoclays (1, 3, 5, 7, and 9 wt%) was added to the TPU matrix to examine the influence of organoclay on nanophase morphology and structure–property relationships. The interaction between TPU matrix and nanofiller was studied by infrared spectroscopy. The morphology of nanocomposites was studied by X‐ray diffraction, transmission electron microscopy, and atomic force microscopy that shows melt mixing by a batch mixer is an effective method for dispersing OMMT throughout the TPU matrix. Thermogravimetric analysis revealed that incorporation of organoclay enhances the thermal stability of the nanocomposites significantly. Differential scanning calorimetry was employed to measure the melting point and glass transition temperature (T_g) of soft segments. The reinforcing effect of the organoclay was determined by dynamic mechanical analysis and physico–mechanical testing. The effects of nanoclay concentration and processing parameters on the dynamic viscoelastic properties of the nanocomposites were studied by a rubber process analyzer using frequency sweep. A significant increase in the viscosity and storage modulus of the nanocomposites was found with the increasing clay content. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

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 characterization of nanoclay‐filled polyurethane/polypropylene blends

Ester‐based thermoplastic polyurethane (TPU) nanocomposites were prepared by melt blending at 190°C, using 3 wt% Cloisite 10A (organically modified montmorillonite clay) as the nanoscale reinforcement [TPU(C10A)]. The nanocomposites were subsequently melt‐blended with polypropylene (PP) using maleic anhydride–grafted polypropylene (MA‐g‐PP) as a compatibilizer [in the ratio of 70/30‐TPU/PP, 70/25/5‐TPU/PP/MA‐g‐PP, 70/25/5‐TPU (C10A)/PP/MA‐g‐PP]. Besides giving substantial increase in modulus, tensile strength, and other properties, organoclay reinforcement functions as a surface modifier for TPU hard segment resulting in improved dispersion. The morphology and other characteristics of the nanocomposite blends were investigated in terms of X‐ray diffraction, fourier transform infrared spectroscopy, differential scanning calorimetry, dynamic mechanical analysis, tensile properties, scanning electron microscopy, and atomic force microscopy. The results indicate that the ester‐TPU(C10A)/PP/MA‐g‐PP exhibited better dispersion than other blend systems; abrasion resistance and water absorption resistance were also better for this system. POLYM. ENG. SCI., 50:1878–1886, 2010. © 2010 Society of Plastics Engineers     

Preparation and characterization of thermoplastic polyurethane/organoclay nanocomposites by melt intercalation technique: Effect of nanoclay on morphology,mechanical, thermal,and rheological properties

Nanocomposites based on thermoplastic polyurethane (TPU) and organically modified montmorillonite (OMMT) were prepared by melt blending. Organically modified nanoclay was added to the TPU matrix in order to study the influence of the organoclay on nanophase morphology and materials properties. The interaction between TPU matrix and nanofiller was studied by infrared spectroscopy. Morphological characterization of the nanocomposites was carried out using X‐ray diffraction, transmission electron microscopy, and scanning electron microscopy techniques. The results showed that melt mixing is an effective process for dispersing OMMT throughout the TPU matrix. Nanocomposites exhibit higher mechanical and thermal properties than pristine TPU. All these properties showed an increasing trend with the increase in OMMT content. Thermogravimetric analysis revealed that incorporation of organoclay enhances the thermal stability of nanocomposites significantly. Differential scanning calorimetry was used to measure the melting point and the glass transition temperature (T_g) of soft segments, which was found to shift toward higher temperature with the inclusion of organoclays. From dynamic mechanical thermal analysis, it is seen that addition of OMMT strongly influenced the storage and loss modulus of the TPU matrix. Dynamic viscoelastic properties of the nanocomposites were explored using rubber process analyzer. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Dynamic mechanical properties of nanoclay filled TPU/PP blends with compatibiliser

Abstract

Blends of thermoplastic polyurethane (TPU) and polypropylene (PP) are highly incompatible because of large differences in polarities and high interfacial tensions. On one hand, PP is added to TPU to improve TPU's thermal stability, chemical properties, mechanical properties (modulus, strength and hardness) and processing performance and to reduce TPU's cost. On the other hand, TPU is blended with PP to improve PP's properties (e.g. abrasion, flexibility, tear strength, shock absorbing capabilities, impact strength, adhesion and paintability/printability). Earlier works in polyurethane/organoclay nanocomposites, PP/organoclay nanocomposites and TPU/PP blends were studied. In our experimental work, both ester and ether based TPU nanocomposites were prepared by melt blending using 3?wt-% Cloisite 10A (organically modified montmorillonite clay) as the nanoscale reinforcement and blended with PP with/without PP-graft-maleic anhydride as the compatibiliser. Blends of nanoclay filled TPU/PP were evaluated for dynamic mechanical properties such as storage modulus E′, loss modulus E″ and dissipation factor tanδ.     

Rheological properties and crystal morphology of poly(ethylene oxide)/clay nanocomposites

Poly(ethylene oxide) (PEO)/organoclay nanocomposites were prepared by a solution intercalation method. The crystallization behavior of the nanocomposites was investigated by a cross‐polarized optical microscopy (CPOM) fitted with a hot‐stage facility. A decrease in size and regularity were observed as a result of incorporation of clay into the PEO matrix. The dynamic viscoelastic behavior of PEO/organoclay nanocomposites was assessed using a strain‐controlled parallel plate rheometer. The effects of clay concentration on the rheological properties of the nanocomposites were extensively studied. A significant increase in the viscosity and storage modulus of the nanocomposites was found with increasing clay content. The reinforcing effect of the organoclay was determined by using a dynamic mechanical analyzer (DMA) and compared with the theoretically calculated values. POLYM. COMPOS., © 2011 Society of Plastics Engineers.     

Effect of modifiers on morphology and thermal properties of novel thermoplastic polyurethane‐peptized laponite nanocomposite

Laponite RDS (Laponite containing pyrophosphate based peptizer) was modified with cetyl trimethyl ammonium bromide (cLS) and dodecylamine hydrochloride (dLS), respectively. Thermoplastic polyurethane (TPU)‐modified Laponite RDS nanocomposites were prepared by solution mixing technique. Morphologies of these two modified clay‐nanocomposites are found to be markedly different. cLS based TPU nanocomposites exhibit partly exfoliated, intercalated, and aggregated structure at lower clay content but a network type of structure is observed at higher clay content. However, dLS based TPU nanocomposites demonstrate spherical cluster type of structure at all clay contents. Nearly two fold increase in storage modulus is observed in both glassy and rubbery state with merely 1% cLS content which gradually decreases with an increase in the clay content. However, in case of dLS filled nanocomposite, gradual increase in storage modulus is observed with an increase in the clay content. Thermogravimetric analysis (TGA) studies indicate that the temperature corresponding to 5 wt % degradation of TPU is enhanced by 19.1 and 12.5°C with the addition of merely 1% cLS and dLS, respectively. However, the activation energy of degradation of neat TPU, as determined by isothermal TGA analysis, is found to be higher than that of the nanocomposites containing 1% of cLS and dLS, respectively. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and Properties of Ethylene Vinyl Acetate (EVA)/Organoclay/Compatibilizer Nanocomposites: Effects of Organoclay Loading and Methyl Ethyl Ketone

Ethylene vinyl acetate (EVA)/organoclay/compatibilizer nanocomposites were produced using a melt compounding technique in an internal mixer, Haake Rheometer, at 120°C and 50 rpm rotor speed. Effects of organoclay loading (from 2 to 10 phr—parts per hundred of resin and methyl ethyl ketone (MEK), used as a compatibilizer, on the processing properties, tensile properties, morphology, thermal degradation, and water absorption behavior of EVA/organoclay nanocomposites were studied. Results indicate that the presence of organoclay increase the processing torque, tensile properties, thermal degradation, and resistance to water absorption. The optimum organoclay loading was achieved at 2 phr. This was caused by the dispersion state of individual silicate layers (intercalation/exfoliation) in EVA matrix. The intercalation/exfoliation structure affects the properties of EVA/organoclay nanocomposites as evidenced from the morphology studies such as x-ray diffraction (XRD) and transmission electron microscopy (TEM) evaluation. The addition of MEK has the ability to improve the tensile properties, thermal degradation, and slightly reduces the resistance of water permeation of EVA/organoclay nanocomposites. The enhanced properties were seen as a result of the better matrix and filler interaction. The EVA/organoclay/MEK nanocomposites shows better intercalation/exfoliation of individual silicate layers in the EVA matrix as indicated by TEM. Moreover, the XRD evaluation shows that intercalation/exfoliation of the organoclay was formed in the EVA matrix.     

Preparation and properties of polyethylene-octene elastomer (POE)/organoclay nanocomposites

Polyethylene-octene elastomer/organoclay nanocomposites were prepared by a melt blending process. It was found that the addition of a small amount of glycidyl methacrylate and a peroxide during the melt mixing induced facile intercalation of the polymer chains into the organoclay and dispersion of the clay particles on the nanometer scale, which was confirmed by X-ray diffraction and transmission electron microscopy. Enhanced mechanical properties of the nanocomposites were observed from tensile, dynamic mechanical, and tear testing. Oscillatory shear-controlled rheology in the molten state of the nanocomposites revealed a pseudo solid-like behavior as well as an enhanced shear thinning behavior.     

Effect of clay surface modification and organoclay purity on microstructure and thermal properties of poly(l-lactic acid)/vermiculite nanocomposites

Vermiculite (VMT) was successfully modified by cationic exchange of hexadecyltrimethyl ammonium ions, covalent grafting of glycidoxypropyl trimethoxy silane, and combining grafting and intercalation. The complete removal of excess surfactant from VMT resulted in a change in the interlayer structure and higher thermal stability of the organoclay mineral. The organosilane grafted on the clay mineral edges improved the thermal stability of the organoclay mineral. The organoclay minerals were melt compounded with poly(l-lactic acid) (PLLA), and the effect of the nanofiller concentration, type of modification and organoclay mineral purity on the nanostructure and thermal properties of nanocomposites was investigated. The removal of excess surfactant and organosilane functionalization enhanced the dispersion level of the organoclay mineral. PLLA degradation that occurred during nanocomposite processing depended on the clay mineral concentration, the extent of clean surface and the clay mineral dispersion state. The removal of excess surfactant and organosilane functionalization improved the thermal stability of nanocomposites.     

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.     

Morphology and thermal properties of poly(L‐lactic acid)/organoclay nanocomposites

A modified clay was used to prepare poly(L ‐lactic acid)/clay nanocomposite dispersions. X‐ray diffraction and transmission electron microscopy experiments revealed that poly(L ‐lactic acid) was able to intercalate the clay galleries. IR spectra of the poly(L ‐lactic acid)/clay nanocomposites showed the presence of interactions between the exfoliated clay platelets and the poly(L ‐lactic acid). Thermogravimetric analysis and differential scanning calorimetry were performed to study the thermal behavior of the prepared composites. The properties of the poly(L ‐lactic acid)/clay nanocomposites were also examined as functions of the organoclay content. The exfoliated organoclay layers acted as nucleating agents, and as the organoclay content increased, the crystallization temperature increased. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Improvement of toughness in polypropylene nanocomposite with the addition of organoclay/silicone copolymer masterbatch

Polypropylene nanocomposites were prepared with organic‐modified montmorillonite, by blending the polymer and the organoclay (direct addition), or by blending the polymer with an organoclay/silicone copolymer masterbatch. The effect of the organoclay/silicone copolymer masterbatch on the morphology and properties of polypropylene was compared with that nanocomposite obtained with the direct organoclay addition. The results showed that the morphology of both polypropylene nanocomposites is constituted by clay tactoids together with some few individual platelets and clay aggregates. Smaller tactoids were observed for the nanocomposite prepared with the masterbatch, in which the silicone copolymer remained intercalated in the clay or adjacent to tactoids. The introduction of the organoclay in the polymer matrix resulted only in an increase in the Young's modulus (28%), while yielding stress, elongation at break and Izod impact strength remained practically unchanged. On the other hand, the incorporation of organoclay by using the masterbatch resulted in a marked improvement (111%) in the elongation at break and in Izod impact strength (85%). The improvement in the elongation at break came with the reduction of the modulus and the yielding stress, by 25 and 15%, respectively. POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

Effect of compatibilizer and organoclay content on structure,thermal, and mechanical properties of poly(butylene succinate)/(Ethylene acrylic acid)/Organoclay nanocomposites

Poly(butylene succinate) (PBS)/(ethylene acrylic acid) (EAA)/organoclay nanocomposites were prepared by using the melt intercalation technique. EAA was used as compatibilizer and organoclay was used as inorganic filler. X‐ray diffraction and transmission electron microscopy results indicated the addition of compatibilizer led to a large increase in basal spacing of nanocomposites and better overall dispersion of organoclay in the PBS matrix. However, the basal spacing was found to be invariant as the organoclay content increased. The differential scanning calorimetry analyses revealed that the incorporation of the organoclay and EAA and the variation of organoclay content altered the melting behavior and crystallization properties of PBS. Storage and loss modulus of virgin matrix increased with the incorporation of organoclay and EAA, and a maximum for the nanocomposite with 9 wt% organoclay. Moreover, the glass transition temperatures also increased for the various organoclay‐containing samples. Mechanical properties showed an increase with the incorporation of organoclay and EAA. The 5 wt% organoclay‐filled PBS gave the highest tensile strength and notched Izod impact strength among all the composites. Further increments in organoclay loading reduced the tensile strength and notched impact strength of nanocomposites, which was thought to be the result of agglomeration. However, increments in clay loading enhanced the flexural strength and flexural modulus of nanocomposites, with a maximum at 9 wt% organoclay. J. VINYL ADDIT. TECHNOL., 23:219–227, 2017. © 2015 Society of Plastics Engineers     

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.     

Shear rheology and melt compounding of compatibilized‐polypropylene nanocomposites: Effect of compatibilizer molecular weight

Direct melt compounding was used to prepare nanocomposites of organophilic montmorillonite (o‐mmt) clay dispersed in maleated polypropylenes (PPgMA) as well as nanocomposites of organoclay and polypropylene (PP) modified with various grades of PPgMA compatibilizers. The thermal effect on the rheology and melt compounding was first investigated with a plasticorder. The shear viscosities and the melt flow indices (MFI) of the PPgMA compatibilizers were sensitive to the blending temperature, which had to be varied with the compatibilizer grade to achieve desirable level of torque for extensive exfoliation of organoclay in the plasticorder. However, for low molecular weight oligomer, the clay dispersion was poor because of low shear viscosity and thermal instability. Next, the PPgMA‐modified PP/organoclay nanocomposites were prepared on a corotating twin‐screw extruder. The nanoscale dimensions of the dispersed clay platelets led to significantly increased linear viscoelastic properties, which were qualitatively correlated with the state of exfoliation in the nanocomposites. The relative viscosity (relative to the silicate‐free matrix) curves revealed a systematic trend with the extent of clay exfoliation. Furthermore, the degree of clay dispersion was found to increase with the loading of compatibilizers; however, high loading of compatibilizer compromised the final moduli of the nanocomposites. POLYM. ENG. SCI. 46:289–302, 2006. © 2006 Society of Plastics Engineers     

Synthesis of imidazolium salts and their application in epoxy montmorillonite nanocomposites

Considerable research has been conducted in improving the performance characteristics of nanocomposites, however, relatively few attempts have been made to address the thermal stability of nanocomposites. An attempt is being made to improve the thermal properties of nanocomposites by synthesizing imidazolium salts from 2-methyl imidazole and ion exchanging the salts with clay minerals. This study focuses on the role of the chemistry of imidazolium salt(s) used in functionalizing clay and processing conditions in the formulation of epoxy nanocomposites. The nanodispersion of clay in an epoxy matrix is evaluated qualitatively by X-ray diffraction (XRD), transmission electronic microscopy (TEM), and laser scanning confocal microscopy (LSCM). We demonstrate the use of LCSM for quantitative image analysis and to study the dispersion of clay layers, tagged with a fluorescent dye in the epoxy matrix. XRD and TEM results reveal that the hand mixed nanocomposite has tactoid morphology, while ultrasonicated organoclay (without hydroxyl group) epoxy nanocomposite exhibits a mixed morphology, and an ultrasonicated organoclay (with hydroxyl group) epoxy nanocomposite had well dispersed clay distribution in the epoxy matrix. Results from the three complimentary techniques enable the characterization of the clay platelets over several length scales ranging from the micrometer to the nanometer scale.     

Chemorheology and properties of epoxy/layered silicate nanocomposites

The effect of the organoclay nanoparticles on the rheology and development of the morphology and properties for epoxy/organoclay nanocomposites has been studied. The interlayer spacing increases with the temperature of cure resulting in intercalated morphologies with varying degrees of interlayer expansion, depending on the cure temperature used. Rheological studies of the curing process indicate that intergallery diffusion before curing is essential for exfoliation, before the morphology is frozen in by gelation and vitrification. The maximum increase in modulus was observed for the 2 wt% clay loading. Viscoelastic behavior and mechanical properties of the cured samples were correlated with the morphological and rheological study.