Rheology and thermal stability of polylactide/clay nanocomposites

Polylactide/clay nanocomposites (PLACNs) were prepared by melt intercalation. The intercalated structure of PLACNs was investigated using XRD and TEM. Both the linear and nonlinear rheological properties of PLACNs were measured by parallel plate rheometer. The results reveal that percolation threshold of the PLACNs is about 4 wt%, and the network structure is very sensitive to both the quiescent and the large amplitude oscillatory shear (LAOS) deformation. The stress overshoots in the reverse flow experiments were strongly dependent on the rest time and shear rate but shows a strain-scaling response to the startup of steady shear flow, indicating that the formation of the long-range structure in PLACNs may be the major driving force for the reorganization of the clay network. The thermal behavior of PLACNs was also characterized. However, the results show that with the addition of clay, the thermal stability of PLACNs decreases in contrast to that of pure PLA.     

Polyimide/montmorillonite nanocomposites with photolithographic properties

Polyimide/montmorillonite nanocomposites with photolithographic properties (PSPI/MMT) were prepared by in situ polymerization using an intrinsic photosensitive polyimide (PSPI) based on 4,4^′-diamino-3,3^′-dimethyldiphenylmethane (MMDA) and benzophenone-3,3^′,4,4^′-tetracarboxylic dianhydride (BTDA). XRD, TEM were used to obtain the information on morphological structure of PSPI/MMT nanocomposites. The exfoliated structure was obtained in the MMT content range studied. Satisfactory photolithographic patterns were obtained when the MMT content was below 2 wt.%. Universal tester, TGA, DSC were applied to characterize the mechanical and thermal properties of the nanocomposites. The introduction of MMT led to increase in tensile strength to the PSPI matrix while the elongation at break was not obviously effected. The introduction of MMT also resulted in improved thermal stability, marked decrease in coefficient of thermal expansion, decrease in solvent uptake, slight increase in glass transition temperature and increase in modulus.     

Polylactide compositions. The influence of ageing on the structure, thermal and viscoelastic properties of PLA/calcium sulfate composites

High-performance composites prepared by melt-blending polylactide (PLA, l/d isomer ratio of 96/4) with various amounts of β-anhydrite II (AII), the dehydrated form of calcium sulfate hemihydrate obtained by a specific thermal treatment at 500 °C, have been aged to study the evolution of their physical and mechanical properties with time. The effect of 1-year ageing under ambient conditions (below T_g of PLA) for selected composites, i.e., filled with 20 and 40 wt% AII, was determined and compared to unfilled PLA with the same processing and ageing history. Samples with an initial amorphous PLA matrix, obtained by fast quenching from the melt, were characterized before and during ageing. The changes in physical parameters have been studied using dynamic mechanical thermal analysis (DMTA), differential scanning calorimetry (DSC), X-ray diffraction (XRD) and density measurements. Surprisingly, for all the samples, an increase of the storage modulus (E′) was recorded, as a result of ageing. This improvement was ascribed to the reorganization of the PLA structure induced by ageing. The structural reorganization was also reflected by a slight increase of PLA density and changes in thermal behaviour. The X-ray investigations showed unchanged crystallographic structure of AII both during blending with molten PLA and in the composite systems after ageing. The surprising stability of the thermo-mechanical properties of PLA and PLA/AII composites is in agreement with the results of size exclusion chromatography analysis (SEC) which did not show significant changes of PLA molecular weights brought out by ageing.     

The thermal and dielectric properties of high performance cyanate ester resins/microcapsules composites

Novel high performance bisphenol A dicyanate ester (BADCy) resins/poly(urea-formaldehyde) microcapsules filled with epoxy resins (MCEs) composites have been prepared. The effects of different contents of MCEs on the thermal and dielectric properties of cured BADCy were investigated using dynamic mechanical analyzer (DMA), thermalgravimetric analyzer (TGA) and broadband dielectric analyzer. The dielectric properties of BADCy/MCEs treated in hot water and hot air were also discussed. The morphologies of BADCy/MCEs composites were characterized by scanning electron microscopy (SEM). Results indicate that the appropriate content of MCEs can improve or maintain the thermal stability, the low dielectric constant and dielectric loss of cured BADCy mainly owing to higher conversion of cyanate ester (-OCN) groups. After aged in hot water and hot air, respectively, BADCy/MCEs composites with small content of MCEs can retain the low dielectric constant and dielectric loss.     

The effect of halloysite nanotubes and N,N'- ethylenebis (stearamide) on the properties of polylactide nanocomposites with amorphous matrix

Amorphous polylactide/halloysite nanotube (PLA/HNT) nanocomposites were prepared and examined. Neat HNT and HNT treated with N,N'- ethylenebis(stearamide) (EBS) were used as nanofillers. The role of HNT and/or EBS content on the cold crystallization of amorphous PLA matrix, HNT dispersion, as well as on the dynamic mechanical and optical properties of the materials was determined.The PLA/HNT-based nanocomposites contained well-distributed nanotubes and occasionally micron-sized aggregates, especially at high loading. HNT, EBS treated HNT and EBS influenced the cold crystallization of PLA, therefore the formation of the disorder α′ and the order α crystallographic forms of PLA.The nanocomposites exhibited increased stiffness and decreased transparency compared to the neat PLA. Due to the reinforcing effect and additional specific features of HNT, the addition of the nanofiller allows tuning of the properties of the nanocomposites with amorphous PLA matrix.     

Structural characterization and thermal properties of polyamide 6.6/Mg, Al/adipate-LDH nanocomposites obtained by solid state polymerization

A new nanocomposite was obtained by dispersing an adipate-modified layered double hydroxide (Ad-LDH) with adipic acid and hexamethylene diamine. These samples were polymerized in the solid phase under a nitrogen flow for 200 min at 190 °C. The structural and compositional details of the nanocomposite were determined by powder X-ray diffraction (PXRD), fourier transform infrared (FTIR) spectroscopy, focused ion beam (FIB), thermogravimetric analysis (TGA) and differential thermal analysis (DTA). The PXRD patterns and FIB images show a partially intercalated and partially exfoliated dispersion of layered crystalline materials in the polyamide 6.6 matrix. The best dispersion level is achieved in polyamide 6.6/LDH nanocomposites with low LDH loading. Some residual tactoids and particle agglomerates are also evident at high concentration. The best thermal stability of the nanocomposites is shown by the sample with 0.1% LDH content, for which it is higher than that of pure polyamide.     

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.     

A simple and green route to transparent boron nitride/PVA nanocomposites with significantly improved mechanical and thermal properties

A simple and green method is developed to prepare hexagonal boron nitride(h-BN)/poly(vinyl alcohol) (PVA) nanocomposites by using water as a common solvent of h-BN nanosheets and PVA.The obtained h-BN/PVA nanocomposites are highly transparent,and have significantly improved mechanical and thermal properties.They may outperform nano-clay and nano-alumina/PVA nanocomposites as flexible optoelectronic devices,optical windows and heat-releasing materials operated in oxidative or corrosive environment.     

Poly(cetyl trimethylammonium 4-styrenesulfonate)-wrapped carbon nanotubes filled in polylactide nanocomposites: Fabrication and properties

Poly(cetyl trimethylammonium 4-styrenesulfonate) (PSS-CTA) was synthesized by the ionic exchange reaction of poly(sodium 4-styrenesulfonate) (PSS-Na) with cetyl trimethylammonium bromide (CTAB). It was then used as a surface modifier for carbon nanotubes (CNTs) to improve dispersion in and interfacial adhesion with a polylactide (PLA) matrix to fabricate high performance PLA/CNT nanocomposites via a solution precipitation method. The morphology, electrical conductivity, crystallization and mechanical properties of the PLA nanocomposites were investigated in detail. The results indicate that CNTs wrapped (coated) with a suitable amount of PSS-CTA dispersed in the PLA matrix homogeneously. The electrical conductivity of PLA was enhanced by up to 10 orders of magnitude with the incorporation of 1.0 wt% PSS-CTA-modified CNTs (mCNTs). The crystallization rate of PLA was improved due to the nucleation effect of mCNTs towards the crystallization of PLA, but the crystallization mechanisms and crystal structure of PLA remained unchanged with the incorporation of mCNTs. Both the tensile strength and toughness of PLA were improved by the incorporation of mCNTs, and the fracture behaviour of PLA changed from brittle e to ductile during tensile testing.     

Tube-like natural halloysite/fluoroelastomer nanocomposites with simultaneous enhanced mechanical, dynamic mechanical and thermal properties

A novel kind of fluoroelastomer nanocomposites based on tube-like halloysite clay mineral were successfully prepared using a bis-phenol curing system, which resulted in prominent improvements in mechanical and dynamic mechanical properties and in the elevation as high as 30 K of the thermal decomposition temperature. Wide-angle X-ray scattering and transmission electron microscopy techniques were employed to assess the morphology developed in the nanocomposites, while stress strain diagrams were used to evaluate the mechanical properties. These nanocomposites were further characterized by moving die rheometer, dynamic mechanical properties and thermo-gravimetric analysis. Structure-properties relationship and the improvement of the mechanical, dynamic mechanical and thermal properties of fluoroelastomers are reported in the present study. Increasing amount of the filler reduced the curing efficiency of the bis-phenol curing system, which was evident from the rheometric and physical properties of the resulting composites. A sort of filler–filler interaction was perceived during the strain sweep analysis of the composites. The polymer–filler interaction was reflected in the improved mechanical and thermal properties which were the consequence of proper dispersion of the nanotubes in the polymer matrix; whereas the intercalation of macromolecular chains into the nanotubes was not reflected in the X-ray diffraction analysis.     

Enhancing dielectric and mechanical behaviors of hybrid polymer nanocomposites based on polystyrene,polyaniline and carbon nanotubes coated with polyaniline

The dielectric and mechanical properties of hybrid polymer nanocomposites of polystyrene/polyaniline/carbon nanotubes coated with polyaniline(PCNTs) have been investigated using impedance analyzer and extensometer. The blends of PS/PANI formed the heterogeneous phase separated morphology in which PCNTs are dispersed uniformly. The incorporation of a small amount of PCNTs into the blend of PS/PANI has remarkably increased the dielectric properties. Similarly, the AC conductivity of PS/PANI is also increased five orders of magnitude from 1.6 × 10~(-10) to 2.0 × 10~(-5) S·cm~(-1) in the hybrid nanocomposites. Such behavior of hybrid nanocomposites is owing to the interfacial polarization occurring due to the presence of multicomponent domains with varying conductivity character of the phases from insulative PS to poor conductor PANI to highly conductive CNTs. Meanwhile, the tensile modulus and tensile strength are also enhanced significantly up to 55% and 160%, respectively, without much loss of ductility for three phase hybrid nanocomposites as compared to the neat PS. Thereby, the hybrid nanocomposites of PS/PANI/_P CNTs become stiffer, stronger and tougher as compared to the neat systems.     

Toughening of ethylene-propylene random copolymer/clay nanocomposites: Comparison of different compatibilizers

Ethylene/propylene-random-copolymer(PPR)/clay nanocomposites were prepared by two-stage melt blending. Four types of compatibilizers,including an ethylene-octene copolymer grafted maleic anhydride(POE-g-MA) and three maleic-anhydride-grafted polypropylenes(PP-g-MA) with different melt flow indexes(MFI),were used to improve the dispersion of organic clay in matrix.On the other hand,the effects of organic montmorillonite(OMMT) content on the nanocomposite structure in terms of clay dispersion in PPR matrix,thermal behavior and tensile properties were also studied. The X-ray diffraction(XRD) and transmission electron microscopy(TEM) results show that the organic clay layers are mainly intercalated and partially exfoliated in the nanocomposites.Moreover,a PP-g-MA compatibilizer(compatibilizer B) having high MFI can greatly increase the interlayer spacing of the clay as compared with other compatibilizers.With the introduction of compatibilizer D(POE-g-MA),most of the clays are dispersed into the POE phase,and the shape of the dispersed OMMT appears elliptic,which differs from the strip of PP-g-MA.Compared with virgin PPR,the Young’s modulus of the nanocomposite evidently increases when a compatibilizer C(PP-g-MA) with medium MFI is used.For the nanocomposites with compatibilizer B and C,their crystallinities(X_c) increase as compared with that of the virgin PPR. Furthermore,the increase of OMMT loadings presents little effect on the melt temperature(T_m) of the PPR/OMMT nanocomposites,and slight effect on their crystallization temperature(T_c).Only compatibilizer B can lead to a marked increases in crystallinity and T_c of the nanocomposite when the OMMT content is 2 wt%.     

Physical, thermal, dielectric and chemical properties of a hyperbranched polyether and its linear analog

The hyperbranched and the linear polyethers were prepared by one-pot nucleophilic displacement polymerization technique using cyanuric chloride and aromatic diol as reported earlier. The physical, thermal, dielectric and chemical properties of the hyperbranched polyether and its linear analog have been studied. The amorphous character of both the polyethers was observed in XRD study. The solubility studies showed that the hyperbranched polyether has relatively higher solubility in different solvents compared to its linear analog. The thermal properties of both polymers have been studied by thermogravimetric (TG) and differential scanning calorimetric (DSC) analyses. The chemical resistance tests indicated that both polyethers are very good chemical resistances except in dilute aqueous alkali solution. The dielectric properties such as dielectric constant and loss factor for both polyethers have also been studied with respect to changes of frequency (50-500 kHz) and temperature (303-343 K).     

Study of flammability and thermal properties of high-impact polystyrene nanocomposites

To increase thermal stability and flammability of high-impact polystyrene (HIPS) nanocomposites with silica nanoparticles and two types of polyphosphate flame retardants were prepared by extrusion. Nanocomposites were characterized by thermogravimetric analysis, differential scanning calorimetry, X-ray diffraction, scanning electron microscopy, limiting oxygen index (LOI) analysis and the evaluation of mechanical properties. It was found that organic polyphosphate in combination with silica increased thermal stability and fire retardancy by 50% in LOI test. Morphology characterization revealed existence of crystalline order which affected mechanical properties; tensile strength was approximately the same as virgin HIPS while elasticity was sharply decreased. Ammonium polyphosphate did not affect mechanical properties as much as the organic material but was not equally efficient in flame retardancy which was just marginally increased.     

Studies of ABS-graft-maleic anhydride/clay nanocomposites: Morphologies, thermal stability and flammability properties

ABS-g-MAH (maleic anhydride) with different grafting degree, ABS/OMT (organo montmorillonite) and ABS-g-MAH/OMT nanocomposites were prepared via melt blending. The grafting reaction, phase morphology, clay dispersion, thermal properties, dynamic mechanical properties and flammability properties were investigated. FTIR spectra results indicate that maleic anhydride was successfully grafted onto butadiene chains of the ABS backbone in the molten state using dicumyl peroxide as the initiator and styrene as the comonomer and the relative grafting degree increased with increasing loading of MAH. TEM images show the size of the dispersed rubber domains of ABS-g-MAH increased and the dispersion is more uniform than that of neat ABS resin. XRD and TEM results show that intercalated/exfoliated structure formed in ABS-g-MAH/OMT nanocomposites and the rubber phase intercalated into clay layers distributed in both SAN phase and rubber phase. TGA results reveal the intercalated/exfoliated structure of ABS-g-MAH/OMT nanocomposites has better barrier properties and thermal stability than intercalated ones of ABS/OMT nanocomposites. The T_g of ABS-g-MAH/OMT nanocomposites was also higher than that of neat ABS/OMT nanocomposites. The results of cone measurements show that ABS-g-MAH/OMT nanocomposites exhibit significantly reduced flammability when compared to ABS/OMT nanocomposites even at the same clay content. The chars of ABS-g-MAH/OMT nanocomposites were tighter, denser, more integrated and fewer surface microcracks than ABS/OMT residues.     

Effect of montmorillonite treatment on the thermal stability of poly(vinyl chloride) nanocomposites

The aim of this research was to study the effect of different intercalants on the thermal degradation/dehydrochlorination of poly(vinyl chloride) (PVC). PVC nanocomposites were prepared containing 2 phr of montmorillonite clay. The montmorillonite was treated with different organic intercalants and analysed by thermogravimetric analysis and X-ray diffraction. All intercalants were found to intercalate the clay. The nanocomposites were prepared on a two-roll mill and pressed into 0.7 mm thick plates. The degradation was analysed by yellowness index, Congo red test and UV–visible spectroscopy. All cationic intercalants were found to accelerate the dehydrochlorination of PVC whereas the non-ionic did not affect thermal degradation. On the other hand, some non-ionic intercalants showed poor dispersion.     

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.     

Poly(methyl methacrylate)/silica/titania ternary nanocomposites with greatly improved thermal and ultraviolet-shielding properties

Poly(methyl methacrylate) (PMMA)/silica/titania ternary nanocomposites with covalent bonding interaction between polymer and inorganic phases have been prepared using a novel non-hydrolytic sol-gel method. Transmission electron microscope (TEM) image of silica/titania binary inorganic component indicates a core-shell-like structure. Scanning electron microscope (SEM) images suggest that the well dispersed silica/titania particles in the hybrid are on the nanometer-scale. The transparencies of nanocomposites are maintained in visible region while the absorption band in ultraviolet (UV) region is red shifted with increasing inorganic content. The thermogravimetric analysis (TGA) results show that the thermal stability of PMMA copolymer increases dramatically with the addition of silica/titania moieties both in nitrogen and in air.     

Internal structure and linear viscoelastic properties of EVA/asphalt nanocomposites

The effect of the addition of two different organoclays as a third component in polymer-modified asphalts has been investigated. Ternary mixtures were prepared by adding clay and poly(ethylene-co-vinyl acetate) to the asphalt, either separately, or in the form of a premixed master batch. The performed characterizations allowed the determination of how the two methods of mixing influence the interactions between asphalt and polymer and therefore the final rheological properties. In particular, it was shown that the clay had a compatibilizing effect on asphalt and polymer and that a high compatibility between clay and polymer led to a better dispersion of the polymer in the asphalt, thus influencing the final rheological properties of the studied systems.     

Polylactide/exfoliated graphite nanocomposites with enhanced thermal stability,mechanical modulus,and electrical conductivity

We have prepared a series of polylactide/exfoliated graphite (PLA/EG) nanocomposites by melt‐compounding and investigated their morphology, structures, thermal stability, mechanical, and electrical properties. For PLA/EG nanocomposites, EG was prepared by the acid treatment and following rapid thermal expansion of micron‐sized crystalline natural graphite (NG), and it was characterized to be composed of disordered graphite nanoplatelets. It was revealed that graphite nanoplatelets of PLA/EG nanocomposites were dispersed homogeneously in the PLA matrix without forming the crystalline aggregates, unlike PLA/NG composites. Thermal degradation temperatures of PLA/EG nanocomposites increased substantially with the increment of EG content up to ～3 wt %, whereas those of PLA/NG composites remained constant regardless of the NG content. For instance, thermal degradation temperature of PLA/EG nanocomposite with only 0.5 wt % EG was improved by ～10 K over PLA homopolymer. Young's moduli of PLA/EG nanocomposites increased noticeably with the increment of EG content up to ～3 wt %, compared with PLA/NG composites. The percolation threshold for electrical conduction of PLA/EG nanocomposites was found to be at 3–5 wt % EG, which is far lower graphite content than that (10–15 wt % NG) of PLA/NG composites. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 850–858, 2010