Polyurethane/clay nanocomposites foams: processing, structure and properties

Polyurethane (PU)/montmorillonite (MMT) nanocomposites were synthesized with organically modified layered silicates (organoclays) by in situ polymerization and foams were prepared by a batch process. Clay dispersion of polyurethane nanocomposites was investigated by X-ray diffraction and transmission electron microscopy. The morphology and properties of PU nanocomposites and foams greatly depend on the functional groups of the organic modifiers, synthesis procedure, and molecular weight of polyols because of the chemical reactions and physical interactions involved. Silicate layers of organoclay can be exfoliated in the PU matrix by adding hydroxyl and organotin functional groups on the clay surface. The presence of clay results in an increase in cell density and a reduction of cell size compared to pure PU foam. In the polyurethane with high molecular weight polyol, a 6 °C increase in T_g, 650% increase in reduced compressive strength, and 780% increase in reduced modulus were observed with the addition of 5% organically treated clays. Opposite effects were observed in PU nanocomposite foams with highly crosslinked structure. The interference of the H-bond in the presence of clay is probably the reason.     

Surface properties of poly(dimethylsiloxane)-based inorganic/organic hybrid materials

Poly(dimethylsiloxane) (PDMS)-based hybrid materials were prepared by the sol-gel method on Si wafers, Al and polystyrene (PS) substrates. The reaction was monitored by attenuated total reflectance-infrared (ATR-IR) spectroscopy. The hybrid materials have always one surface made in contact with air and one with a substrate. These surfaces were investigated by using tapping mode atomic force microscopy (AFM), X-ray photo-electron spectroscopy (XPS), low-energy ion scattering (LEIS) and dynamic contact angle (DCA) analysis. The hybrid sample surfaces made in contact with air and substrates appeared to have different structures. The former have a silica-free PDMS top layer of ∼2 nm thick; while in the latter cases, SiO₂ are located at or just beneath the outermost atomic layer. In air and at room temperature, SiO₂ are likely beneath the outermost atomic layer. In contact with water, polar -OH groups at the surface of SiO₂ can easily stretch out to the outermost atomic layer. No correlation was found between the roughness of the surfaces and the amount of in situ formed SiO₂ present in the materials.     

Enzymatic synthesis of silicone fluorinated aliphatic polyesteramides

The enzymatic synthesis of silicone fluorinated aliphatic polyesteramides (SFAPEAs) is reported. These materials were synthesized by incorporating both the fluorinated aliphatic segments and the dimethylsiloxane segments into the same linear chain backbone. Immobilized lipase B from Candida antarctica (Novozym-435) was used to catalyze the reactions to prepare fluorosilicones containing both amide and ester linkages. Simultaneous reactions of an amidation between α,ω-aminopropyl terminated poly(dimethylsiloxane) (APDMS) and diethyl adipate (DEA) and a transesterification between diethyl adipate and four different fluorinated alkanediols (FADs), respectively were conducted. The condensation reactions were carried out in the bulk, in the temperature range 70-90 °C and under reduced pressure (50 mmHg vacuum gauge). The molar masses of the synthesized fluorosilicones were determined by GPC analysis. The effect of the chain length of the FADs on the molar mass build up of the respective polymers was investigated. The highest molar mass fluorosilicones were obtained with the 3,3,4,4,5,5,6,6-octafluoro 1,8-octanediol (OFOD) monomer, which has an additional methylene (-CH₂-) spacer between the fluorocarbon chain (-CF₂-)_n and the hydroxyl end groups (-OH) when compared to the other three FAD monomers namely - 2,2,3,3-tetrafluoro 1,4-butanediol (TFBD), 2,2,3,3,4,4-hexafluoro 1,5-pentanediol (HFPD) and 2,2,3,3,4,4,5,5-octafluoro 1,6-hexanediol (OFHD). The formation of amide and ester linkages during the polymerization was confirmed by FTIR and ¹H NMR spectroscopy. A series of copolymers were synthesized by varying the feed ratios of FAD to APDMS. Fluorinated polyesters (FPEs) and silicone polyamides (SPAs) were also enzymatically synthesized under similar reaction conditions. The DSC analysis revealed that the fluorosilicones were semi-crystalline, principally due to the presence of the FPE segments. The FPEs were found to be white solids at room temperature. However, the SFAPEA’s were found to be viscous materials due to the presence of highly flexible silicone segments in the backbone chain. The crystallinity was seen to disappear completely for the SFAPEA’s with greater than 15 mol% of silicone content. The TGA analysis revealed that thermal degradation/depolymerization characteristics of the fluorosilicones improved with increased silicone content. We envisage that these new fluorosilicones have potential for a variety of low surface energy applications.     

Poly(ethylene-oxide)/clay/silica nanocomposites: Morphology and thermomechanical properties

Poly(ethylene-oxide) PEO/clay/silica nanocomposites were prepared via solution intercalation by exploiting phase separation based on the bridging of particles by polymer chains. The intercalated morphology of nanocomposites was confirmed by XRD. Vibrational modes of the ether oxygen of PEO in the hybrids are shifted due to the coordination of the ether oxygen with the sodium cations of clay and the H-bonding interactions of the ether oxygen with the surface silanols of hydrophilic fumed silica. Based on SEM, the overall density of nanoparticle aggregates in the interspherulitic region was observed to be higher compared to that inside spherulites. PEO/clay/silica hybrids show significant property improvements compared to PEO/clay hybrids and pure PEO. The system containing 10 wt.% clay and 5 wt.% silica has substantially higher modulus and much lower crystallinity compared to the 15 wt.% clay system. The physics behind the reinforcement effect and the reduction of crystallinity as a function of fumed silica loading is discussed based on the morphological characterization of the hybrids. Lastly, PEO/clay/silica hybrids display good thermal stability and are much stiffer compared to pure PEO and PEO/clay nanocomposites.     

Stretching calorimetry studies of poly(ε-caprolactone)/organoclay nanocomposites

Poly(ε-caprolactone)/montmorillonite nanocomposites, prepared by bulk ring-opening polymerization of ε-caprolactone in the presence of tin(II) 2-ethylhexanoate as a catalyst and hydroxy groups of ammonium tethers of organoclay acting as chain-growth centers, were characterized by the stretching calorimetry technique.In the range of elastic (reversible) deformations, experimental Young's moduli and linear thermal expansivities of both the intercalated and exfoliated nanocomposites could be fitted to the predictions of Chow's model assuming the apparent aspect ratio of clay nanoparticles of the order of 10. In the range of anelastic deformations, the values of the internal energy increments ΔU/m for the intercalated nanocomposite lay somewhat below those for the corresponding neat polymer, while the ΔU/m vs. ε plots for the exfoliated nanocomposite and for the corresponding neat polymer were nearly identical both in shape and in absolute values over the entire range of strains, up to the breaking strains ε_b. These data suggested higher and lower probabilities of interfacial debonding in the range of anelastic deformations for intercalated and exfoliated samples, respectively.     

Morphology, thermal stability and rheology of poly(propylene carbonate)/organoclay nanocomposites with different pillaring agents

Unpillared montmorillonite PGV and five organoclays (Nanocor's Nanomer I.44P, I.24TL and I.34TCN and Southern Clay Product's C25A and C30B) were high shear melt-blended (2.5 wt%) into poly(propylene carbonate) (PPC). Solubility parameters of the clay pillaring agents versus that of PPC were used to predict clay/PPC miscibilities and these were compared to XRD and TEM nanoclay dispersion measurements. Clays I.34TCN and C30B, with the highest predicted pillaring agent/PPC miscibilites, had partially exfoliated morphologies. Clays I.24TL, C25A and I.44P, with pillaring agents predicted to be less PPC miscible, were less highly nanodispersed. Quaternary ammonium pillars with two 2-hydroxyethyl groups promoted the best nanodispersion in PPC. 12-Aminododecanoic acid (in I.24TL) promoted the intercalation. Dimethyl dialkyl quaternary ammoniums (in I.44P and C25A) were less effective. Organoclay dispersion improved the thermal stability. The PPC/I.24TL nanocomposite, with the most stable 12-aminododecanoic acid pillar, was the most thermally stable (PPC/I.34TCN and PPC/C30B were the second and third). The nanocomposites exhibited narrower linear viscoelastic zones than PPC and solid-like behaviors in these linear zones.     

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

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

Synthesis and properties of polymer brush consisting of poly(phenylacetylene) main chain and poly(dimethylsiloxane) side chains

A novel polymer brush consisting of poly(phenylacetylene) (PPA) main chain and poly(dimethylsiloxane) (PDMS) side chains was synthesized by the polymerization of phenylacetylene-terminated PDMS macromonomer (M-PDMS). The macromonomer was prepared by the esterfication of monohydroxy-ended PDMS (PDMS-OH, degree of polymerization (DP) = 42) with p-ethynylbenzoic acid. The polymerization of M-PDMS using [(nbd)RhCl]₂/Et₃N catalyst led to polymer brush, poly(M-PDMS), with M_n up to 349?000 (DP of main chain 104). Poly(M-PDMS) with narrow molecular weight distribution (M_n = 39?900, M_w/M_n = 1.11) was obtained with a vinyl-Rh catalyst, [Rh{C(Ph)CPh₂}(nbd){P(4-FC₆H₄)₃}]/(4-FC₆H₄)₃P. Poly(M-PDMS)s were brown to orange viscous liquids and soluble in organic solvents such as toluene and CHCl₃. The UV-vis absorptions of poly(M-PDMS) were observed in the range of 350-525 nm, which are attributable to the PPA main chain.     

Effects of epoxy treatment of organoclay on structure, thermo-mechanical and transport properties of poly(ethylene terephthalate-co-ethylene naphthalate)/organoclay nanocomposites

Poly(ethylene terephthalate-co-ethylene naphthalate) (PETN) nanocomposites containing two different organoclays, Cloisite 20A and 30B, were prepared by melt intercalation using an extruder. The organoclays was treated with epoxy monomer to further improve the polar interactions with PETN matrix. The morphological, thermal-mechanical, mechanical and gas barrier characteristics of the nanocomposites were evaluated using several characterization tools. It is found that the Cloisite 30B had better interactions with PETN and was more uniformly dispersed within PETN than Cloisite 20A. Epoxy treatment of Cloisite 30B organoclay resulted in improvements in d-spacing between silicate layers, thermo-mechanical and tensile properties, as well as thermal stability, processing and gas barrier characteristics of the PETN/30B nanocomposites. These results suggest that the epoxy acted as the compatibilizer as well as the chain extender, improving the chemical interactions between PETN and organoclay, while discouraging the macromolecular mobility of polymer chains in the vicinity clay particles. The implications and the mechanisms behind these observations are discussed.     

Effect of filler amount on thermoelastic properties of poly(dimethylsiloxane) networks

End-linked poly(dimethylsiloxane) (PDMS) networks were prepared in the presence of fumed silica particles with hydroxyl groups at their surfaces. The silica particles were introduced into the polymer solution prior to end-linking. Hydroxyl ended PDMS chains were end-linked via the tetra functional crosslinker, tetraethoxysilane. The filler content varied in the range 0-5 wt%. Atomic Force Microscopy was used to image and characterize the silica particles. Swelling, stress-strain and thermoelasticity experiments were performed. The temperature coefficient and the energetic part of the force in uniaxial extension are found to increase with increasing silica amount. This observation is ascribed to effects contributed possibly by the adsorption layer around the silica particles.     

Poly(lactic acid) nanocomposites: comparison of their properties with montmorillonite and synthetic mica (II)

Our study was to clarify the intercalation of polymer chains to organoclays and to improve the thermo-mechanical properties. Two organoclays were synthesized. One was a montmorillonite modified with hexadecylamine (C₁₆-MMT); the other was a fluorinated-mica modified with hexadecylamine (C₁₆-Mica). Dispersions of organoclays with poly(lactic acid) (PLA) were by using the solution intercalation method at different organoclay contents to produce nano-scale composites. The maximum ultimate tensile strength was observed for blends containing 4 wt% of either of the two organoclays and decreased with further increases in the organoclay content. The initial modulus increased with increasing organoclay content up to 4 wt% for C₁₆-MMT. When the C₁₆-MMT content was greater than this critical wt%, the modulus of the hybrids started to decrease. In contrast, the initial modulus of the hybrids using C₁₆-Mica increased continually with increasing clay content from 2 to 8 wt%. The tensile properties of the C₁₆-Mica hybrids were higher than those of the hybrids containing C₁₆-MMT. The optical translucency was not affected by the organoclay content up to 6 wt%; however, the films containing 8 wt% organoclays were slightly more cloudy.     

Poly(butylene sucinate-co-adipate)/montmorillonite nanocomposites: effect of organic modifier miscibility on structure, properties, and viscoelasticity

Poly(butylene succinate-co-adipate) (PBSA)/layered silicate nanocomposites were prepared by melt extrusion of PBSA and three different types of commercially available organically modified montmorillonite (OMMT). Using three types of OMMT modified with three different kinds of surfactants, the effect of organic modification on nanocomposites was investigated by focusing of three major aspects: morphological study, property measurements, and melt rheological behavior under both small and large deformation flows. X-ray diffraction (XRD) patterns revealed that increasing the level of interactions (miscibility) between the organic modifier and PBSA matrix increases the tendency of the silicate layers to delaminate and distributed nicely within the PBSA matrix. Transmission electron micrographic (TEM) observations showed that the ordering of silicate layers in PBSA matrix is well matched with the XRD patterns. Thermal analysis revealed that extent of crystallinity of PBSA matrix is directly related to the extent of exfoliation of silicate layers in the nanocomposites. Dynamic mechanical analysis and tensile property measurements showed concurrent improvement in mechanical properties when compared to the neat PBSA and the extent of improvement is directly related to the extent of delamination of silicate layers in the PBSA matrix. The same tendency was also observed in melt rheological measurements.     

Thermoplastic olefin/clay nanocomposites: Morphology and mechanical properties

Thermoplastic olefin (TPO)/clay nanocomposites were made with clay loadings of 0.6–6.7 wt %. The morphology of these TPO/clay nanocomposites was investigated with atomic force microscopy, transmission electron microscopy (TEM), and X‐ray diffraction. The ethylene–propylene rubber (EPR) particle morphology in the TPO underwent progressive particle breakup and decreased in particle size as the clay loading increased from 0.6 to 5.6 wt %. TEM micrographs showed that the clay platelets preferentially segregated to the rubber–particle interface. The breakup of the EPR particles was suspected to be due to the increasing melt viscosity observed as the clay loading increased or to the accompanying chemical modifiers of the clay, acting as interfacial agents and reducing the interfacial tension with a concomitant reduction in the particle size. The flexural modulus of the injection moldings increased monotonically as the clay loading increased. The unnotched (Izod) impact strength was substantially increased or maintained, whereas the notched (Izod) impact strength decreased modestly as the clay loading increased. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 928–936, 2004     

丁基橡胶/有机黏土纳米复合材料的结构和性能

采用溶液插层法制备了丁基橡胶／有机黏土纳米复合材料,并用透射电子显微镜和X射线衍射仪研究了该纳米复合材料的形态结构。结果表明,丁基橡胶／有机黏土纳米复合材料是插层型的纳米复合材料。与丁基橡胶相比,该纳米复合材料具有优异的力学性能和气体阻隔性能,并且这2种性能均随有机黏土用量的增加而增强。填料的形状会对该纳米复合材料的气体阻隔性能产生影响。     

Poly(ε-caprolactone)/clay nanocomposites prepared by melt intercalation: mechanical, thermal and rheological properties

(Nano)composites of poly(ε-caprolactone) (PCL) were prepared by melt blending the polymer with natural Na⁺ montmorillonite and montmorillonite modified by hydrogenated tallowalkyl (HTA)-based quaternary ammonium cations, such as dimethyl 2-ethylhexyl HTA ammonium and methyl bis(2-hydroxyethyl) HTA ammonium. Microcomposites or nanocomposites were prepared depending on whether neat or modified montmorillonites was used, as assessed by X-ray diffraction and transmission electron microscopy. Mechanical and thermal properties were studied as a function of the filler content by tensile testing, Izod impact testing, thermogravimetric analysis and differential scanning calorimetry. The rheological behaviour at 80 °C was also analysed in relation to the structure and content of the layered silicate. Effect of exfoliated silicates on the mechanical properties, thermal stability and flame resistance of PCL was considered. Stiffness and thermal stability improved with the filler loading until a content of 5 wt%. Further loading resulted in the levelling off and possibly in a decrease of these properties. A marked charring effect was observed upon exposure to a flame.     

Morphology and properties of PVC/clay nanocomposites via in situ emulsion polymerization

PVC/Na⁺–montmorillonite (MMT) nanocomposites were prepared via a simple technique of emulsion polymerization at several different MMT clay concentrations. X‐ray diffraction and transmission electron microscopy studies revealed the formation of a mixture of intercalated and exfoliated nanostructure. Tensile testing results showed that the tensile modulus of the nanocomposites increased with the addition of clay, while the tensile strength decreased little. The notched impact strength of the nanocomposites was also improved. For systems containing clay in the range of 2.1 to 3.5 wt %, the impact strength was almost two times as large as that of pure PVC. However, those mechanical properties began to decrease with the continuously increasing amount of clay. The fracture surface of pure PVC and the nanocomposites was observed by scanning electron microscope. Thermal properties of the nanocomposites were found to increase as a result of clay incorporation. The glass transition temperatures of the PVC/clay nanocomposites were nearly identical to that of pure PVC. The Vicat softening points exhibited a progressively increasing trend with the clay content added. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 277–286, 2004     

Synthesis and physicochemical characterization of a well-defined poly(butadiene 1,3)-block-poly(dimethylsiloxane) copolymer

For the first time, order-order and order-disorder transitions were detected and characterized in a model diblock copolymer of poly(butadiene-1,3) and poly(dimethylsiloxane) (PB-b-PDMS). This model PB-b-PDMS copolymer was synthesized by the sequential anionic polymerization (high vacuum techniques) of butadiene 1,3 (B) and hexamethylciclotrisiloxane (D₃), and subsequently characterized by nuclear magnetic resonance (¹H and ¹³C NMR), size exclusion chromatography (SEC), Fourier Transform infrared spectroscopy (FTIR), Small-Angle X-ray scattering (SAXS) and rheology. SAXS combined with rheological experiments shows that the order-order and order-disorder transitions are thermoreversible. This fact indicates that the copolymer has sufficient mobility at the timescale and at the temperatures of interest to reach their equilibrium morphologies.     

Foaming of PCL/clay nanocomposites with supercritical CO2 mixtures: The effect of nanocomposite fabrication route on the clay dispersion and the final porous structure

Supercritical fluids have been established as alternative foaming agents in various polymers as well as nanocomposite systems. Most recently, supercritical carbon dioxide (scCO₂) has also been used in some studies as a medium of clay dispersion in the polymer matrix providing a solvent-free fabrication route for nanocomposites. In this work, this latter route was followed for the development of porous poly(ɿ-caprolactone) (PCL)/clay nanocomposites after pressure quench. Similarly, PCL/clay nanocomposites were also prepared using the solvent casting and melt blending methods and were then processed with scCO₂ with the batch foaming technique (isothermal pressure quench) to produce their porous counterparts. Poor clay dispersion and non-uniform porous structures were observed when pure CO₂ was used as a dispersion medium for nanocomposite preparation and as a blowing agent, respectively. On the contrary, polymer intercalation and more uniform cell structures were produced when CO₂⿿ethanol mixtures were used as blowing agents.     

Synthesis and properties of polybenzoxazole-clay nanocomposites

A novel polybenzoxazole (PBO)/clay nanocomposite has been prepared from a PBO precursor, polyhydroxyamide (PHA) and an organoclay. The PBO precursor was made by the low temperature polycondensation reaction between isophthaloyl chloride (IC) and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane with an inherent viscosity of 0.5 dl/g. The organoclay was formed by a cation exchange reaction between a Na⁺-montorillonite (Na⁺-Mont) clay and an ammonium salt of dodecylamine. The PHA/clay was subsequently thermal cured to PBO/clay. Both X-ray diffraction and transmission electron microscope analyzes showed that the organoclay was dispersed in the PBO matrix in a nanometer scale. The in-plane coefficient of thermal expansion (CTE) of PBO/clay film decreased with increasing amounts of organoclay. The CTE of PBO/clay film containing 7 wt% clay was decreased by 21% compared to the pure PBO film. Both of the glass transition temperature (T_g) and the thermal decomposition temperature of PBO/clay increased with increasing amounts of organoclay. The thermal decomposition temperature and the T_g of PBO/clay containing 7 wt% clay increased to 12 and 16 °C, respectively.     

Transport properties of natural rubber latex layered clay nanocomposites

Natural rubber latex layered clay nanocomposites were prepared with low loadings of nanoclay using conventional compounding technique. A higher loading of clay resulted in processing difficulties due to viscosity build up. X‐ray analysis showed that nanocomposites in which layered silicate layers were either delaminated or ordered as in an intercalated structure was obtained. Partially exfoliated structure was observed from TEM photographs of nanocomposites with 3 phr nanoclay. The transport properties, sorption, diffusion, and permeation coefficients were measured using the solvent toluene at 303 K. A higher decrease for the diffusion coefficient for nanocomposites directs the presence of tortuous path for the diffusing molecules. Thermodynamic parameters show a better compatibility for the silicates with rubber resulted in the formation of an elastomeric network. Gas permeability results of the nanocomposites suggest a better barrier resistancefor oxygen molecules even in lower loading of nanoclay and different gas transport models (Nielsen, Bharadwaj, Cussler) were applied to describe the behavior of these nanocomposites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008