Structure and morphology of solution blended poly(vinylidene fluoride)/montmorillonite nanocomposites

Nanocomposites based on poly(vinylidene fluoride) were prepared with montmorillonite by solution blending. The samples were characterized by small angle X‐ray scattering, wide angle X‐ray diffraction, Fourier transform infrared spectroscopy, and differential scanning calorimetry. Different crystallization conditions, that is, evaporation of the solvent and coprecipitation with two different antisolvents, H₂O or supercritical CO₂ (scCO₂), were tested and their influence on the resulting structure and morphology of the samples were studied. Coprecipitation with scCO₂ induced an ordinate crystalline framework and an intercalated morphology of clay, with a consequent large improvement in modulus. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Unique nucleation of multi-walled carbon nanotube and poly(ethylene 2,6-naphthalate) nanocomposites during non-isothermal crystallization

Multi-walled carbon nanotube (MWCNT) and poly(ethylene 2,6-naphthalate) (PEN) nanocomposites are prepared by a melt blending process. There are significant dependence of non-isothermal crystallization behavior and kinetics of PEN/MWCNT nanocomposites on the MWCNT content and cooling rate. The incorporation of MWCNT accelerates the mechanism of nucleation and crystal growth of PEN, and this effect is more pronounced at lower MWCNT content. Combined Avrami and Ozawa analysis is found to be effective in describing the non-isothermal crystallization of the PEN/MWCNT nanocomposites. The MWCNT in the PEN/MWCNT nanocomposites exhibits much higher nucleation activity than any nano-scaled reinforcement. When a vary small quantity of MWCNT was added, the activation energy for crystallization is lower, then gradually increased, and becomes higher than that of pure PEN above 1.0 wt% MWCNT content. The incorporation of MWCNT improves the storage modulus and loss modulus of PEN/MWCNT nanocomposites.     

Viscoelasticity and thermal stability of poly(arylene ether nitrile) nanocomposites with various functionalized carbon nanotubes

Poly(arylene ether nitrile) (PEN) nanocomposites containing various functionalized multi‐walled carbon nanotubes (MWCNTs) were prepared through a solution‐casting method. The as‐prepared PEN nanocomposites were investigated using parallel‐plate rheometry and thermogravimetric analysis, aimed at examining the effect of surface functionalization on the dispersion of MWCNTs from the viscoelastic and thermal properties. The linear viscoelasticy results indicated that 4‐aminophenoxyphthalonitrile‐grafted MWCNTs presented better dispersion in the PEN matrix than purified and carboxylic MWCNTs because the corresponding composite showed the lowest rheological percolation threshold, which was further confirmed from scanning electron microscopy, dissolution experiments and solution rheological experiments. The thermogravimetric analysis results revealed that the presence of 4‐aminophenoxyphthalonitrile‐grafted and carboxylic MWCNTs retarded the depolymerization compared with purified MWCNTs, showing a marked increase in the temperature corresponding to a loss of 5 wt% (increased by 14–22 °C) and maximum rate of decomposition (increased by 4–8 °C). Both the state of dispersion and the surface functionalization of MWCNTs are very important to the thermal stability of the PEN matrix. Copyright © 2011 Society of Chemical Industry     

Deformation behavior of banded spherulite during drawing investigated by simultaneous microbeam SAXS-WAXS and POM measurement

The local deformation behavior inside a poly(ε caprolacton) (PCL)/polyvinylbutyral (PVB) banded spherulite during drawing was observed by in-situ microbeam small-angle X-ray scattering (SAXS) - wide-angle X-ray scattering (WAXS) - polarized optical microscopy (POM) simultaneous measurements. From experimental results, we found that the local deformation of a PCL/PVB banded spherulite can be divided into four stages. In stage I, disordering of the crystalline structure occurs. In stage II, the disordering of the crystalline structure ceases and disordering of the stacking and coarse slippage of the lamellae occur. In stage III, after the breakdown of the twisted lamella structure, the reconstruction of a long period structure occurs. In stage IV, further lamella slippage occurs. Our results show no evidence of fine slippage at a local region during the drastic decrease in the long period. This strongly indicates that the melting and recrystallization mechanism occurs during the lamella reconstruction of PCL/PVB.     

Preparation and characterization of poly(vinylidene fluoride) nanocomposites containing multiwalled carbon nanotubes

Poly(vinylidene fluoride) (PVDF) nanocomposites with different loadings of multiwalled carbon nanotubes (MWNT) were prepared by melt‐compounding technique. A homogeneous dispersion of MWNT throughout PVDF matrix was observed on the cryo‐fractured surfaces by scanning electron microscopy. Thermogravimetric analysis results indicated that the thermal stability of neat PVDF was improved with the incorporation of MWNT. Dynamic mechanical analysis showed a significant improvement in the storage modulus over a temperature range from ?125 to 75°C with the addition of MWNT. The melt‐rheological studies illustrated that incorporating MWNT into PVDF matrix resulted in higher complex viscosities (|η*|), storage modulus (G′), loss modulus (G″), and lower loss factor (tan δ) than those of neat PVDF. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Melting and crystallization behaviour of elastoplastic semicrystalline copolymers: poly(ether ester)

The melting and crystallization behaviour of an elastoplastic semi-crystalline poly(etherester) has been studied by differential scanning calorimetry. The shape of the melting endotherm is strongly dependent on heating rate and annealing time and results from the sum of simultaneous melting and crystallization phenomena. Samples prepared by different techniques, i.e. by solvent evaporation or by melt extrusion, behave very differently owing to specific crystal morphologies. By applying the Hoffman-Weeks plot, the equilibrium melting temperature has been extrapolated. The Avrami treatment allows the calculation of the index n and of the rate constant K from the isothermal kinetic data.     

Processing and assessment of poly(butylene terephthalate) nanocomposites reinforced with oxidized single wall carbon nanotubes

Thermoplastic composites with carbon nanotubes (CNT) have a great potential as structural material because of their superior mechanical properties and ease of processing. The objective of this report is to evaluate the effect of oxidized single walled carbon nanotubes (oSWCNT) on the properties of poly(butylene terephthalate) (PBT) thermoplastic polymers, as a function of their weight content. The nanocomposites are obtained by introducing the oSWCNT into the reaction mixture whilst the synthesis of PBT. The polymers without and with carbon nanotubes were synthesised using an in situ polycondensation reaction process. Weight percentages ranging from 0.01 to 0.2 wt% of single walled nanotubes were dispersed in 1,4-butanediol (BD) by ultrasonication and ultrahigh speed stirring. After polycondensation the nanocomposites were extruded followed by injection moulding. The samples were characterised by thermal analysis, electron microscopy, dynamic-mechanical analysis, and tensile testing.The addition of only a small amount of oSWCNT was enough to improve the thermo-mechanical properties of the nanocomposites. The Young's modulus, tensile strength, and strain to failure increased with increasing amount from 0.01 to 0.1 wt% of CNT in the PBT matrix. However, when the content of CNT was increased from 0.1 to 0.2 wt%, the strength and the strain of the nanocomposites decreased slightly.     

Role of mixing parameters in the preparation of poly(ethylene vinyl acetate) nanocomposites by melt blending

Polymer/layered‐silicate nanocomposites have gathered momentum as cost‐effective and versatile materials since the middle of the 20th century. Many publications discuss the chemistry of organomodification and properties of nanocomposites, but relatively few deal with the significance of processing conditions. This article takes into account three mixing parameters and discusses the contribution of each toward nanocomposite formation. Organomodified natural sodium‐type bentonite clay was used in this study. The nanocomposites formed were characterized by X‐ray diffraction and mechanical property tests. Response surface regression was used to optimize the tensile modulus. The analysis shows that nanocomposite formation is promoted by a diffusion mechanism and that the interactions of parameters are as important as individual parameters. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2652–2658, 2006     

Electrical, mechanical, and glass transition behavior of polycarbonate-based nanocomposites with different multi-walled carbon nanotubes

Five commercially available multi-walled carbon nanotubes (MWNTs), with different characteristics, were melt mixed with polycarbonate (PC) in a twin-screw micro compounder to obtain nanocomposites containing 0.25-3.0 wt.% MWNT. The electrical properties of the composites were assessed using bulk electrical conductivity measurements, the mechanical properties of the composites were evaluated using tensile tests and dynamic mechanical analysis (DMA), and the thermal properties of the composites were investigated using differential scanning calorimetry (DSC). Electrical percolation thresholds (p_cs) were observed between 0.28 wt.% and 0.60 wt.%, which are comparable with other well-dispersed melt mixed materials. Based on measurements of diameter and length distributions of unprocessed tubes it was found that nanotubes with high aspect ratios exhibited lower p_cs, although one sample did show higher p_c than expected (based on aspect ratio) which was attributed to poorer dispersion achieved during mixing. The stress-strain behavior of the composites is only slightly altered with CNT addition; however, the strain at break is decreased even at low loadings. DMA tests suggest the formation of a combined polymer-CNT continuous network evidenced by measurable storage moduli at temperatures above the glass transition temperature (T_g), consistent with a mild reinforcement effect. The composites showed lower glass transition temperatures than that of pure PC. Lowering of the height of the tanδ peak from DMA and reductions in the heat capacity change at the glass transition from DSC indicate that MWNTs reduced the amount of polymer material that participates in the glass transition of the composites, consistent with immobilization of polymer at the nanotube interface.     

Copolyester nanocomposites based on carbon nanotubes: reinforcement effect of carbon nanotubes on viscoelastic and dielectric properties of nanocomposites

Nanocomposites based on an amorphous copolyester, poly(ethylene glycol‐co‐cyclohexane‐1,4‐dimethanol terephthalate) and carbon nanotubes were fabricated using a simple melt processing technique. The reinforcement effect of carbon nanotubes in the copolyester was investigated experimentally using different approaches based on dynamic mechanical analysis, rheology and dielectric analysis. The nanocomposites show a mechanical reinforcement effect with significant increase in the stiffness especially in the rubbery regime with increasing nanotube content. An increase in T_g and a decrease in damping are seen, which are derived from the presence of a percolating superstructure of the filler. Rheological experiments show an increase in storage modulus up to four orders of magnitude. Viscolelastic characterization shows that the percolation threshold is at 3 wt% of nanotubes. Dielectric relaxation spectroscopy confirms the presence of this percolating structure. We conclude that the responses of both rheological and electrical properties are different, although both are related to the formation of a percolating network superstructure of the filler. Copyright © 2007 Society of Chemical Industry     

Morphology and micromechanical behaviour of ethylene cycloolefin copolymers (COC)

Cyclic olefin copolymers (COC) of ethylene and different types of cyclic monomers were investigated in detail. In particular, the influence of the type and the content of cyclic monomers on the micromechanical deformation behaviour was studied using electron microscopy. Several deformation modes as fibrillated crazes, homogeneous deformation zones, shear-bands, and occasionally a combination of some of these deformation structures were observed in these materials. The different deformation modes are correlated with the mechanical properties. A tendency to an increase in brittleness with increasing cyclic monomer content was observed. COC with larger side chains in the cyclic monomer show a more ductile behaviour with the corresponding deformation structures than COC with norbornene.     

Effect of carbon nanotubes functionalization on properties of their nanocomposites with polycarbonate/poly(acrylonitrile-butadiene-styrene) matrix

In this work, a comparative study evaluating the influence of different functionalization of carbon nanotubes on the properties of nanocomposites with polymeric matrix was performed. A 50/50 wt% polycarbonate (PC)/poly(acrylonitrile-butadiene-styrene) (ABS) blend was used as polymeric matrix of the nanocomposites. The comparison was made between nanocomposites reinforced with covalently functionalized multiwall carbon nanotubes (MWCNTf) and MWCNTf/nanoclay hybrid functionalization. The effect on the mechanical and morphological properties of the nanocomposites was evaluated through tensile and Izod impact tests and scanning electron microscopy and transmission electron microscopy (TEM) analyses. The thermal characterization of PC/ABS blends and nanocomposites was performed by differential scanning calorimetry (DSC). Results showed that both methods of functionalization of MWCNTs increased the stiffness and impact resistance of the nanocomposites. TEM micrographs indicated the preferred location of the reinforcements in the SAN phase of ABS. Results from DSC indicated an increase in the thermal resistance of the nanocomposites.     

Study of the orientation and the degree of exfoliation of nanoparticles in poly(ethylene‐vinyl acetate) nanocomposites

Nanocomposites formed from organically modified montmorillonite and poly(ethylene‐co‐vinyl acetate) were studied by X‐ray diffraction techniques. Wide‐ and small‐angle X‐ray scattering intensities (SAXS and WAXS) were recorded by transmission mode on test bars cut from compression‐molded plaques tilted by different angles with respect to the plane of the plaque. The height of the Bragg peaks characteristic of intercalated particles reduced to the baseline at tilt angles greater than 30°. Guinier analysis of the SAXS characteristic of particle scattering showed a radius of gyration of 0.69 nm and the scattering intensity was slightly dependent on the tilt angle. Recording of WAXS in the usual (i.e., in reflective) mode enhanced the effect of the structural features of the surface area and showed much higher degree of intercalation and particle size of the scattering particles than that in transmission mode. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3026–3031, 2003     

Effect of clay modifier and matrix molar mass on the structure and properties of poly(ethylene oxide)/Cloisite nanocomposites via melt-compounding

The present study is concerned with the preparation and characterisation of PEO/clay nanocomposites via melt-extrusion. Two different matrix molar masses of PEO were investigated as well as various types of the Cloisite clay range. PEO/Cloisite Na⁺ nanocomposites give rise to intercalated structures displaying only a moderate improvement of the mechanical properties at higher clay concentrations, regardless of the matrix molar mass. The chemical nature of the organic modifier was proven to be detrimental for the final nanocomposite structure and resulting mechanical properties. PEO nanocomposites based on the Cloisite 30B clay, incorporating a polar modifier, give rise to exfoliated structures. They display a strongly increased storage modulus, regardless of the matrix molar mass. The structural organisation of the nanocomposites based on Cloisite 20A, containing an apolar modifier, is very dependent on the matrix molar mass. An exfoliated structure can only be achieved upon melt mixing with a high molar mass PEO. In general, the mechanical properties of the nanocomposites based on the high molar mass PEO matrix are slightly superior. The thermal properties are also distinctly influenced by the addition of clay, although the actual structural organisation of the nanocomposite is proven to be less important. The melt temperature, as well as the crystallinity, decreases upon the addition of clay, especially for the low molar mass PEO matrix. The decomposition temperature shows a slight increase upon the addition of clay, especially for the Cloisite 30B nanocomposites.     

Thermal behaviour of nanocomposites based on linear-low-density poly(ethylene) and carbon nanotubes prepared by high energy ball milling

The thermal behaviour of nanocomposites of linear-low-density-poly(ethylene) (LLDPE) and carbon nanotubes (CNT), prepared by the method of High Energy Ball Milling (HEBM) has been in-depth investigated. The CNT affect the nucleation of LLDPE, in that they act as nucleating agents for LLDPE. Moreover, as it is shown by self-nucleation experiments, in the presence of CNT a direct transition from domain I to domain III, with lack of domain II takes place. Isothermal experiments show that the crystallization rate of the nanocomposites is much higher than that of neat LLDPE. It is worthy noting that such effect is very high even for low contents of CNT in the sample (i.e. 1% by weight), then additions of CNT do not have any further effect. Lastly, the dynamic-mechanical properties of LLDPE are slightly modified in the nanocomposites.     

Glass transition behaviour of poly(ether ether ketone)/poly(aryl ether sulphone) blends: dynamic mechanical and dielectric relaxation studies

Blends of poly(ether ether ketone) (PEEK) and poly(aryl ether sulphone) (PES) have been prepared in the whole composition range. The molecular dynamics and α-relaxation behaviour of these materials have been studied using dynamic mechanical and dielectric relaxation spectroscopy. From dynamic mechanical relaxation studies, two α-relaxation peaks corresponding to the segmental relaxation process of pure components in the blend was observed. Also, it was found that the temperature at which α-process of the homopolymers occurs, shows a slight change with blend composition, corresponding to a PEEK-rich and PES-rich phase. The relaxation intensities of the homopolymers in the blend compared to that in pure state were approximately proportional to their respective content in the blend. From the phase composition of the respective phases obtained using Fox equation, it has been inferred that PEEK dissolves more in PES than vice-versa. The α-relaxation of PES could not be detected from dielectric relaxation spectroscopy because of the possible influence of dc conduction and electrode polarization losses. Otherwise, the α-relaxation behaviour of PEEK-rich phase observed from dielectric relaxation studies agree with those inferred from dynamic mechanical relaxation studies. Furthermore, activation energies for molecular motions (E_a) at the α-relaxation have also been determined using an Arrhenius form of equation and it has been found that E_a for both PEEK-rich and PES-rich phase show variation with composition. Similarly, the relaxation times associated with the mobility of relaxing species in both PEEK and PES are influenced in the blends. It is likely that these observations are related to some interactions and a partial segmental mixing between the blend components, which result in changes in the local molecular environment on blending.     

Electrical conductivity and transparency of polymer hybrid nanocomposites based on poly(trimethylene terephthalate) containing single walled carbon nanotubes and expanded graphite

Single‐walled carbon nanotubes (SWCNT)/expanded graphite (EG)/poly(trimethylene terephthalate) (PTT) hybrid nanocomposites were prepared via in situ polymerization. Raman spectroscopy and scanning electron microscopy (SEM) were employed to determine both, purity and morphology of the nanofillers and the dispersion of nanotubes and nanosheets. The electrical and optical properties of thin polymer films based on both “single” nanocomposites and hybrid nanocomposites were studied. For PTT/SWCNT nanocomposites, results confirmed that films optical transmittance decreases as the concentration of SWCNT increases, attaining almost no optical transmittance for 0.3 wt % of nanofiller. Conversely, the electrical conductivity of nanocomposites was found to increase by increasing the nanofiller amount and the σ_dc values indicate that percolation occurs at a very low SWCNT content (around 0.05 wt %). In the case of PTT/SWCNT + EG nanocomposites, when the content of SWCNT is 0.05%, the hybrid system presents lower conductivity than that corresponding to the “single” nanocomposite. The incorporation of additional EG to the PTT/SWCNT nanocomposite has a small effect on the electrical conductivity but inhibits the transparency of the system. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44370.     

Polymer nanocomposites containing carbon nanotubes and miscible polymer blends based on poly[ethylene‐co‐(acrylic acid)]

Four binary polymer blends containing poly [ethylene‐co‐(acrylic acid)] (PEAA) as one component, and poly(4‐vinyl phenol‐co‐2‐hydroxy ethyl methacrylate) (P4VPh‐co‐2HEMA) or poly(2‐ethyl‐2‐oxazoline) (PEOx) or poly(vinyl acetate‐co‐vinyl alcohol) (PVAc‐co‐VA) or poly (vinylpyrrolidone‐co‐vinyl acetate) (PVP‐co‐VAc) as the other component were prepared and used as a matrix of a series of composite materials. These binary mixtures were either partially or completely miscible within the composition range studied and were characterized by differential scanning calorimetry (DSC) and Fourier transformed infrared spectroscopy (FTIR). Carbon nanotubes (CNTs) were prepared by a thermal treatment of polyester synthesized through the chemical reaction between ethylene glycol and citric acid over an alumina boat. High resolution transmission electron microscopy (HRTEM) was used to characterize the synthesized CNTs. Films of composite materials containing CNTs were obtained after evaporation of the solvent used to prepare solutions of the four types of binary polymer blends. Young's moduli of the composites were obtained by thermomechanical analysis at room temperature. Only one glass transition temperature was detected for several compositions on both binary blends and the composite material matrices. Evidence of hydrogen bond formation was recorded for both miscible blends and composite materials. The degree of crystallinity and Young's moduli of the CNT‐polymer composites increased compared to the single polymer blends. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Preparation of multiwall carbon nanotubes/poly(p‐phenylene benzobisoxazole) nanocomposites and analysis of their physical properties

Raw multiwall carbon nanotubes (MWNTs) were first treated with strongly oxidated acid to form MWNTs–COOH and driven to a high dispersion quality in the dispersing medium via ultrasonic method. Then the MWNTs/poly (p‐phenylene benzobisoxazole)(MWNTs–COOH/PBO) nanocomposites were prepared by an in situ polymerization technique. In this process, the morphological structure of MWNTs and MWNTs–COOH were investigated by XPS, FTIR, and TEM. The experimental results showed that the carboxyl group was introduced into the surface of nanotubes and the length of nanotubes was shortened. The images of SEM and AFM illustrated that the MWNTs–COOH was homogeneously dispersed in PBO matrix, and the DTA analysis indicated that the molecular weight of MWNTs–COOH/PBO was almost equal to that of PBO. Furthermore, the thermogravimetry results proved that the thermal property of MWNTs–COOH/PBO was more stable than that of PBO. Also, the knot strength and the tensile strength of MWNTs–COOH/PBO were 30% higher than that of PBO. In addition, the reaction route of the MWNTs–COOH and PBO oligomer was given according to the ATR–FTIR spectra of PBO polymer and MWNTs–COOH/PBO. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2500–2508, 2006     

Multiwalled carbon nanotube nucleated crystallization behavior of biodegradable poly(butylene succinate) nanocomposites

Poly(butylene succinate) (PBS) nanocomposites with multiwalled carbon nanotubes (MWNTs) prepared by melt compounding were studied for the effect of MWNT dispersion on the modulus and crystallization kinetics. The nucleating effect of the addition of 0.1 wt % MWNT to PBS was clearly demonstrated. Differential scanning calorimetry nonisothermal crystallization studies showed a clear decrease in the half‐time of crystallization with increasing MWNT content in PBS/MWNT nanocomposites. It was observed with the Ozawa method that the Ozawa parameter values for the nanocomposites were lower than those for neat PBS, and this indicated that the crystal morphology was different. The storage modulus of the nanocomposites increased about 23% with the addition of only 0.1% MWNT in comparison with neat PBS, whereas the glass‐transition temperature was unaltered. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009