Conducting poly(3,4-ethylenedioxythiophene)-montmorillonite exfoliated nanocomposites

Exfoliated nanocomposites formed by poly(3,4-ethylenedioxythiophene) and different concentrations of non-modified montmorillonite (bentonite), which range from 1% to 10% w/w, have been prepared by anodic electropolymerization in aqueous solution. Analyses of the electrochemical and electrical properties reveal that the electroactivity of the nanocomposites is higher than that of the individual homopolymer, while the electrical conductivity of the two systems is practically identical. On the other hand, the exfoliated distribution of the clay in the polymeric matrix and the morphology of the prepared materials have been characterized using transmission electron microscopy, X-ray diffraction and atomic force microscopy. The overall of the results represents a significant improvement with respect to other nanocomposites constituted by conducting polymers and clays, including those involving poly(3,4-ethylenedioxythiophene), and evidences the reliability of the preparation procedure employed in this work.     

Crystallization, morphology, and dynamic mechanical properties of poly(trimethylene terephthalate)/clay nanocomposites

The poly(trimethylene terephthalate) (PTT)/clay nanocomposite has been successfully prepared via melt intercalation using a co-rotating twin screw extruder. The nanocomposite was characterized by wide angle X-ray diffraction (WAXD), transmission electron microscope (TEM), differential scanning calorimetry (DSC), polarized light microscope (PLM) and dynamic mechanical analysis (DMA). The nanocomposite forms an exfoliated structure, which can be observed by WAXD and TEM. The effect of clay layers on the crystallization behaviors of PTT was studied through isothermal and non-isothermal crystallization methods. The results suggest that the introduction of nanosize clay layers accelerates the crystallization rate of PTT and the clay layers act as nucleation agents. The morphology of spherulites was investigated with PLM and the result is well in agreement with crystallization kinetics. DMA shows that glass transition temperature (T_g) and storage modulus (E^′) of the PTT matrix of the nanocomposite are higher than those of pure PTT.     

Poly(vinyl chloride)/clay nanocomposites: X-ray diffraction, thermal and rheological behaviour

The paper concentrates on poly(vinyl chloride) - PVC - from the point of view of structural characterisation of PVC/clay nanocomposites through X-ray diffraction, thermogravimetric analysis and dynamic rheometric analysis. PVC plasticizer was mixed with clay, natural and organophilic, and the suspension was then compounded with other components. Two factors were followed: effect of shearing alone, and in combination with temperature. The type of filler and the method of composite preparation affect the mechanical and thermal properties of the composite, through delamination and exfoliation levels. The results showed that the thermal degradation is shifted towards higher temperatures for organophilic clays, compared to chemically untreated natural clay.     

Poly(epsilon-caprolactone)/clay nanocomposites via “click” chemistry

Poly(epsilon-caprolactone)/clay nanocomposites were prepared by copper(I) catalyzed azide/alkyne cycloaddition (CuAAC) “click” reaction. In this method, ring-opening polymerization of epsilon-caprolactone using propargyl alcohol as the initiator has been performed to produce alkyne-functionalized PCL and the obtained polymers were subsequently attached to azide-modified clay layers by a CuAAC “click” reaction. The exfoliated polymer/clay nanocomposites were characterized by X-ray diffraction spectroscopy, thermogravimetric analysis and transmission electron microscopy.     

In situ polymerized poly(butylene succinate)/silica nanocomposites: Physical properties and biodegradation

A series of poly(butylene succinate)/silica (PBS/silica) nanocomposites were prepared by in situ polymerization. Solid-state ²⁹Si NMR and FTIR analysis indicated that silanol-bonded carbonyl groups are established within PBS/silica nanocomposite materials. Rheological effects inherent to the silica filler were evaluated by melt rheological analysis as a function of shear force in the molten state. Despite high shear force, PBS/silica nanocomposites maintained a relatively high melt viscosity, attributable to a network structure resulting from covalent bonding between silica and the polymer chain. Nanocomposite material containing 3.5 wt% silica exhibited greatly improved mechanical properties. The tensile strength at break and elongation were ca. 38.6 MPa and 515%, while those of the parent PBS were 26.3 MPa and 96%, respectively. PBS/silica nanocomposites showed composition dependency on biodegradation ascribable to reduced crystallinity and preferential microbial attack.     

Preparation and rheological characterization of poly(n-butyl methacrylate)/montmorillonite composites

Intercalated nanocomposites constituted of poly(butyl methacrylate) (PBMA) as the matrix and an organically modified montmorillonite as the nanosize filler were prepared and rheologically characterized in detail. The rheological behavior of the composites showed dependence on both temperature and clay content. For composites of low clay contents, the steady shear viscosity showed a Newtonian plateau in the low shear rate region at low temperatures and the plateau was replaced by a shear-thinning curve when the temperature was raised. For composites of higher clay contents, strong shear-thinning behavior were observed at all shear rates and all temperatures. The viscoelastic data of the composites showed unusual terminal behavior of a decreasing terminal slope at low frequencies with increasing temperature and clay loading. X-ray diffraction spectra showed that annealing process at higher temperatures shifted the Bragg reflection peaks to a lower angle and broadened the peaks, which provided the evidence for the existence of a temperature-induced solid-like structure that was responsible for the shear thinning and the unusual terminal viscoelastic behavior.     

Effect of a silicate filler on the crystal morphology of poly(trimethylene terephthalate)/clay nanocomposites

A series of intercalated poly(trimethylene terephthalate) (PTT)/clay nanocomposites were prepared in a twin‐screw extruder by the melt mixing of PTT with either quaternary or ternary ammonium salt‐modified clays. The morphology and structure, along with the crystallization and melting behavior, and the dynamic mechanical behavior of the composites were characterized by X‐ray diffraction, transmission electron microscopy, differential scanning calorimetry, and dynamic mechanical thermal analysis. The results showed that the PTT chains could undergo center‐mass transport from the polymer melt into the silicate galleries successfully during the blending and extrusion process. More coherent stacking of the silicate layers was reserved at higher clay concentrations and shorter blend times. Compared with conventionally compounded composites, the nanoscale‐dispersed organophilic clays were more effective as crystal nucleation agents. The influence of the nanosilicates on the crystallization and melting behavior of PTT became distinct when the concentration of clay was around 3 wt %. The changes in the crystallization behavior of the polymer/clay nanocomposites depended not only on the size of the silicates but also on the intrinsic crystallization characteristics of the polymers. The resulting nanocomposites showed an increase in the dynamic modulus of PTT and a decrease in the relaxation intensity (both in loss modulus and loss tangent magnitude). © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2275–2289, 2003     

Poly(vinyl chloride)-paste/clay nanocomposites: Investigation of thermal and morphological characteristics

The paper concentrates on poly(vinyl chloride) - PVC - from the point of nanocomposite characterisation through thermal degradation of samples, evolution of the changes caused by elevating temperature using TGA, FTIR and Congo Red methods combined with morphological characterisation by XRD and TEM analyses. A novel method of PVC-paste/nanocomposite preparation while processing was used. During preparation, PVC plasticizer was mixed with clay, both natural and organophilic, and the suspension was then compounded with the other components. Two factors were followed: effect of shearing alone, and in combination with temperature. As is presented, the type of nano-filler and its chemical modifier have obvious influence on final properties either thermal or morphological. Presented contribution follows previous part of investigation and brings further information from PVC-paste/nanocomposite field.     

Structure and mechanical properties of poly(l-lactide)/layered silicate nanocomposites

Poly(ε-caprolactone) (PCL) masterbatches with the intercalated and the exfoliated morphology were prepared by ring opening polymerization of ε-caprolactone in the presence of organomodified montmorillonite (MMT) Cloisite 30B. Poly(l-lactide) (PLLA) nanocomposites with Cloisite 30B or PCL masterbatches were prepared by melt blending. The effects of the silicate type, MMT content and the nanocomposite morphology on thermal and mechanical properties of PLLA nanocomposites were examined. The montmorillonite particles in PLLA/Cloisite 30B and PLLA/intercalated masterbatch nanocomposites were intercalated. In contrary to expectations, the exfoliated silicate layers of exfoliated masterbatch were not transferred into the PLLA matrix. Due to a low miscibility of PCL and PLLA, MMT remained in the phase-separated masterbatch domains. The stress-strain characteristics of PLLA nanocomposites, Young modulus E, yield stress σ_y and yield strain ε_y, decreased with increasing MMT concentration, which is associated with the increase in PCL content. The expected stiffening effect of MMT was low due to a low aspect ratio of its particles and was obscured by both plastifying effects of PCL and low PLLA crystallinity. Interestingly, in contrast to the neat PLLA, ductility was enhanced in all PLLA/Cloisite 30B materials and in PLLA/masterbatch nanocomposites with low MMT concentrations.     

Fire retardancy and biodegradability of poly(methyl methacrylate)/montmorillonite nanocomposite

The poly(methyl methacrylate) (PMMA)/montmorillonite (MMT) nanocomposite was prepared by emulsifier-free emulsion technique and its structure and properties were characterized with infra red, X-ray diffraction, transmission electron microscopy, thermogravimetric analysis, and cone calorimetry. The highly exfoliated MMT layers with dimension 1-2 nm in thickness were randomly dispersed in the polymer matrix containing MMT lower than 5% w/v, whereas the intercalated structure was predominant with MMT content higher than 5% w/v. Consequently, the fine dispersion of the MMT and the strong interactions between PMMA and MMT created significant improvement of the thermo-stability and fire retardancy of the nanocomposite. The combustion behavior has been evaluated using oxygen consumption cone calorimetry. In addition, a scheme was proposed to describe fire retardancy of PMMA and MMT as well as the correlation between the interaction and structure in polymer/clay systems. The biodegradability of the nanocomposite fire-retardant was tested for its better commercialization.     

Gamma irradiation of high density poly(ethylene)/ethylene‐vinyl acetate/clay nanocomposites: possible mechanism of the influence of clay on irradiated nanocomposites

A further study on mechanical properties and morphology evolution of high density poly (ethylene)/ethylene‐vinyl acetate/and organically‐modified montmorillonite (HDPE/EVA/OMT) nanocomposites exposed to gamma‐rays (0–200 kGy) has been achieved. The results showed that nanocomposites have superior irradiation‐resistant properties to HDPE/EVA blend in mechanical properties. A transmission electron microscope study verified that a face‐face ordered nanostructure had been induced by gamma‐rays. The aim of this paper is to provide a possible mechanism on how the OMT influences the general properties of irradiated nanocomposites, based on the results of thermal, flammability and mechanical behavior. Three facts are postulated to be responsible for the mechanism. The first is the segregation of nano‐dispersed clay layers not only reduces polymer oxidation but prevents crosslinking reactions. The second is the nanostructure evolution induced by gamma‐rays, which may impart nanocomposites improved elasticity. The last is due to the Hofmann degradation, whose degraded products have opposite roles, accelerating polymer oxidation or promoting crosslinking reactions. These facts interact as well as compete with others. The properties of the nanocomposites strongly depended on the prevalent effects developing with increasing irradiation doses. Copyright © 2005 John Wiley & Sons, Ltd.     

Study on rheological behaviour of poly(butylene terephthalate)/montmorillonite nanocomposites

Poly(butylene terephthalate)/montmorillonite composites (PBT/MMT) were prepared by melt intercalation and then investigated using X-ray diffractometer (XRD) and transmission electron microscope (TEM) as well as parallel plate rheometer. It was found that the composites had various phase morphologies with nanoscales and distinct behaviours of a percolation network structure under certain conditions. The linear viscoelastic region of the composites is much narrower than that for PBT matrix, the percolation threshold of the composites is near 3 wt.%, and the percolation network structure is not stable under a shear as well as in a quiescent annealing process. Moreover, PBT/MMT presents the nature of temperature independence of G′ versus G″ whether the internal percolated tactoids network formed or not. The magnitudes of the stress overshoots observed in the reverse flow experiments were strongly dependent on the rest time, which could be inferred that the ruptured network is reorganized under the quiescent annealing process. Furthermore, PBT/MMT shows a strain-scaling stress response to the startup of steady shear, indicating that the formation of the liquid crystalline-like phase structure in the nanocomposites may be the major drive force for the reorganization of the internal network.     

Synthesis and characterization of polymer/clay nanocomposites by intercalated chain transfer agent

In situ synthesis of poly(methyl methacrylate) (PMMA) and polystyrene (PS) nanocomposites by free radical polymerization using intercalated chain transfer agent (I-CTA) in the layers of montmorillonite (MMT) clay is reported. MMT clay was ion-exchanged with diethyl octyl ammonium ethylmercaptan bromide, which acts both as suitable intercalant and as chain transfer agent. These modified clays were then dispersed in methyl methacrylate (MMA) or styrene (St) monomers in different loading degrees to carry out the in situ free radical polymerization. The intercalation ability of the chain transfer agent and exfoliated nanocomposite structure were evidenced by both X-ray diffraction spectroscopy (XRD) and transmission electron microscopy (TEM). Thermal properties and morphologies of the resultant nanocomposites were also studied.     

Synthesis of polyurethane/clay intercalated nanocomposites

 A kind of polyurethane/organophilic montmorillonite (PU/OMT) nanocomposite based on polyether, OMT, phenylmethane diisocyante and diglycol was synthesized and characterized by X-ray diffraction (XRD) and high-resolution electron microscopy (HREM). A polyether/OMT hybrid was first prepared in a nanocomposite form as confirmed by XRD. It was shown that there is a multilayered structure consisting of alternating PU chains stacked with the layers of the silicate layers in the microstructure of the PU/OMT nanocomposite as confirmed by study of the XRD patterns and the HREM images. The contents of the hard segment of PU and OMT had an effect on the basal spacing of the PU/OMT nanocomposite. Received: 29 August 2000 Accepted: 16 February 2001     

Intercalated poly(vinylidene fluoride)/clay nanocomposites: Structure and properties

The preparation and characterization of melt‐intercalated poly(vinylidene fluoride) (PVDF)/clay nanocomposites are reported. Organophilic clay (clay treated with dimethyl dihydrogenated tallow quaternary ammonium chloride) was used for the nanocomposite preparation. The composites were characterized with X‐ray diffraction (XRD), differential scanning calorimetry (DSC), and dynamic mechanical analysis (DMA). XRD results indicated the intercalation of the polymer in the interlayer spacing. The incorporation of clay in PVDF resulted in the β form of PVDF. DSC nonisothermal curves showed an increase in the melting and crystallization temperatures along with a decrease in crystallinity. Isothermal crystallization studies show an enhanced rate of crystallization with the addition of clay. DMA indicated significant improvements in the storage modulus over a temperature range of ?100 to 150 °C. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 31–38, 2003     

Thermal stability, smoke emission and mechanical properties of poly(vinyl chloride)/hydrotalcite nanocomposites

Poly(vinyl chloride)/hydrotalcite (PVC/HT) nanocomposites were prepared through vinyl chloride suspension polymerization in the presence of HT nanoparticles surface modified with alkyl phosphate (AP). The thermal stability, smoke emission and mechanical properties of PVC/HT nanocomposites were investigated. It was found that AP molecules were effectively absorbed by HT particles with no intercalation into the interlayer of HT. The dispersion morphologies of PVC/HT nanocomposites were observed by transmission electron microscopy showing that the majority of HT particles were dispersed in the PVC matrix in the nanoscale. The Congo Red measurement and thermogravimetric analysis showed that the thermal stability time, and the temperatures at 10% weight loss and at the maximum weight loss rate of PVC resins increased as the weight fraction of HT in the composite resins increased. The well-dispersed nano-sized HT showed an obvious smoke suppression effect on PVC. The maximum smoke density decreased about 1/3 and 1/2 when 2.5 wt% and 5.3 wt% nano-sized HT were incorporated into PVC, respectively. Furthermore, PVC/HT nanocomposites exhibited greater tensile strength and impact strength than the pristine PVC.     

Preparation of poly(propylene)/clay layered nanocomposites by melt intercalation from pristine montmorillonite (MMT)

Poly(propylene)/clay nanocomposites were prepared by melt intercalation, using pristine montmorillonite (MMT), hexadecyl trimethyl ammonium bromide (C16), poly(propylene) (PP) and maleic acid (MA) modified PP (MAPP), The nanocomposites structure is demonstrated using X‐ray diffraction (XRD) and high resolution electronic microscopy (HREM). Our purpose is to provide a general concept for manufacturing polymer nanocomposites by melt intercalation starting from the pristine MMT. We found different kneaders (twin‐screw extruder or twin‐roll mill) have influence on the morphology of the PP/clay nanocomposites. Thermogravimetric analysis (TGA) shows that the thermal stability of PP/clay nanocomposites has been improved compared with that of pure PP. Copyright © 2003 John Wiley & Sons, Ltd.     

Preparation and characterization of poly(propylene carbonate)/montmorillonite nanocomposites by solution intercalation

Poly(propylene carbonate) (PPC) is a new biodegradable aliphatic polycarbonate. However, the poor thermal stability and low glass transition temperatures (T_g) have limited its applications. To improve the thermal properties of PPC, organophilic montmorillonite (OMMT) was mixed with PPC by a solution intercalation method to produce nanocomposites. An intercalated-and-flocculated structure of PPC/OMMT nanocomposites was confirmed by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The thermal and mechanical properties of PPC/OMMT nanocomposites were investigated by thermal gravimetric analysis (TGA), differential scanning calorimetric (DSC), and electronic tensile tester. Due to the nanometer-sized dispersion of layered silicate in polymer matrix, PPC/OMMT nanocomposites exhibit improved thermal and mechanical properties than pure PPC. When the OMMT content is 4 wt%, the PPC/OMMT nanocomposite shows the best thermal and mechanical properties. These results indicate that nanocomposition is an efficient and convenient method to improve the properties of PPC.     

The thermal degradation behaviour of polydimethylsiloxane/montmorillonite nanocomposites

A series of novel polydimethylsiloxane/montmorillonite (PDMS/MMT) nanocomposites was prepared. The thermal degradation behaviour of these nanocomposites was studied by means of Thermal Volatilization Analysis (TVA) and Thermogravimetric Analysis (TGA). The major degradation products were identified as cyclic oligomeric siloxanes from D₃ to D_7, and higher oligomeric siloxane residues. Other minor degradation products include methane, bis-pentamethylcyclotrisiloxane, propene, propanal, benzene and dimethylsilanone. The results demonstrate that the nanoclay significantly alters the degradation behaviour of the PDMS network, modifying the profile of the thermal degradation and reducing the overall rate of volatiles evolution. The results also indicate that the nanoclay promotes the formation of dimethylsilanone and benzene by inducing low levels of radical chain scission.     

Polymorphism behavior of poly(ethylene naphthalate)/clay nanocomposites

Thermally stable organically modified clays based on 1,3‐didecyl‐2‐methylimidazolium (IM2C10) and 1‐hexadecyl‐2,3‐dimethyl‐imidazolium (IMC16) were used to prepare poly(ethylene naphthalate) (PEN)/clay nanocomposites via a melt intercalation process. The clay dispersion in the resulting hybrids was studied by a combination of X‐ray diffraction, polarizing optical microscopy, and transmission electron microscopy. It was found that IMC16 provided better compatibility between the PEN matrix and the clay than IM2C10, as evidenced by some intercalation of polymer achieved in the PEN/IMC16‐MMT hybrid. The effects of clay on the crystal structure of PEN were investigated. It was found that both pristine MMT and imidazolium‐treated MMT enhanced the formation of the β‐crystal phase under melt crystallization at 200 °C. At 180 °C, however, the imidazolium‐treated MMT was found to favor the α‐crystal form instead. The difference in clay‐induced polymorphism behavior was attributed to conformational changes experienced by the clay modifiers as the crystallization temperature changes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1040–1049, 2006