Sub-micron dispersed-phase particle size in polymer blends: overcoming the Taylor limit via solid-state shear pulverization

A comparison was made of the fineness of dispersion in immiscible polymer blends achieved by a continuous mechanical alloying technique, solid-state shear pulverization, relative to that achieved by melt mixing. Two polymer blend systems were investigated. A polystyrene (PS)/polyethylene (PE) wax blend was studied because, based on a classic analysis by G.I. Taylor, melt mixing was expected to yield a number-average dispersed-phase domain size, D_n, well above 1 μm. A PS/high density polyethylene (HDPE) blend was also studied because it was known to produce a sub-micron number-average dispersed-phase particle size when mixed by twin-screw extrusion. In the case of the PS/PE wax blend at compositions ranging from 1 to 15 wt% polyethylene wax, pulverization resulted in nearly identical D_n values (typical value of 0.7 μm) independent of minor-phase content; these D_n values were an order of magnitude smaller than the anticipated Taylor limit for melt-mixed blends. In contrast, PS/PE wax blends made by batch, intensive melt mixing yielded D_n values between ∼3 μm at both 1 and 5 wt% minor-phase content and 17.5 μm at 15 wt% minor-phase content. The increase in D_n with increasing dispersed-phase content in the melt-mixed blend is a consequence of coalescence present during melt processing; such effects are disallowed in the pulverization process occurring in the solid state. Scanning electron microscopy of a 95/5 wt% PS/HDPE blend provided D_n values of 500 and 270 nm in the twin-screw extruded and pulverized samples, respectively. Fractionated crystallization studies further corroborated the ability of pulverization to result in a finer, nanoscopic dispersion of the minor phase as compared to extrusion.     

Space charge behaviors of low-density polyethylene blended with polypropylene copolymer

In this study, the space charge behaviors of the blend polymers of low-density polyethylene (LDPE) and polypropylene copolymer were investigated by the pulsed electro-acoustic method (PEA) with the electrode system of aluminium/specimen/semiconductive layer. The blend specimen composed by 90 wt% LDPE and 10 wt% polypropylene copolymer (B10) showed a larger amount of space charge than pure LDPE (PE) under a DC field of 50 MV m⁻¹ at both 30 and 60 °C. Positive carriers moved more slowly in B10 than in PE under a positive DC voltage applied to the semiconductive electrode at 30 °C. DC currents were also measured under the same experimental condition as the space charge measurement. The DC current of B10 was lower than that of PE at 30 °C, but higher at 60 °C. The experimental results were explained by the introduction of traps by blending.     

Reactive compatibilizer precursors for LDPE/PA6 blends. II: maleic anhydride grafted polyethylenes

Several home made and commercially available polyethylene (PE) samples grafted with maleic anhydride (MA) (PE-g-MA) were used as compatibilizer precursors (CPs) for the reactive blending of low density PE (LDPE) with polyamide-6 (PA). Scope of the work was to compare the effectiveness of these CPs with that of a number of ethylene-acrylic acid copolymers (EAA), which had been employed in a previous study for the reactive compatibilization of the same blends, and to get a deeper insight into the coupling reactions producing the PA-g-CP copolymers that are thought to act as the true compatibilizers in these systems. To this end, binary CP/LDPE and CP/PA and ternary LDPE/PA/CP blends were prepared with a Brabender mixer and were characterized by DSC, SEM and solvent fractionation. The results show that the PE-g-MA copolymers react more rapidly with PA than the EAA copolymers and that their CP effectiveness depends critically on the microstructure and the molar mass of their PE backbones. In particular, the CPs produced by functionalization of LDPE were shown to be miscible with this blend component and to be scarcely available at the interface where reaction with PA is expected to occur. Conversely, the CPs prepared from the HDPE grades were immiscible with LDPE and showed better CP performance. Whereas the effectiveness of the EAA copolymers studied earlier had been shown to increase with an increase in the concentration of the carboxyl groups, the concentration of the succinic anhydride groups of the PE-g-MA CPs studied in this work was found to play a minor role, at least in the investigated range (0.3-3.0 wt% MA).     

Enhancement in interfacial reactive compatibilization by chain mobility

This study investigates the role of polymer chain mobility, through the addition of a plasticizer, N-butylbenzene sulfonamide (BBSA), on the overall blending dynamics and interfacial copolymer chain formation in the reactive blending of brominated poly(isobutylene-co-p-methylstyrene) (BIMSM) and polyamide (PA). Compared to a non-reactive poly(isobutylene-co-p-methylstyrene) (IMSM)/PA blend, the reactive BIMSM/PA blend demonstrates a rapid, order of magnitude increase in viscosity, and attains a plateau viscosity at higher temperatures. The addition of a BBSA plasticizer (5–10 wt%) surprisingly increases the viscosity even further, suggesting an enhancement in interfacial reaction due to increased chain mobility. It is also found to increase the level of grafting from about 46 to 57% and has a significant influence on the morphology of the blend system. It is shown that the reactive grafting has an onset at lower temperatures for the blend system with 10 and 43% plasticizer. The morphologies of the blends with 5–10% plasticizer have a more uniform distribution (d_v/d_n) with a reduced d_v for the dispersed BIMSM particles. At 43 wt% plasticizer the blends show an increased phase size resulting from the significantly enhanced phase coalescence. These results indicate that enhanced chain mobility through plasticizer usage can impact interfacial compatibilization and phase coalescence and that a threshold level of 5–10 wt% plasticizer provides an optimum level of chain mobility for this reactive blending system.     

Reactively compatibilised polyamide6/ethylene-co-vinyl acetate blends: mechanical properties and morphology

Mechanical properties and morphological studies of compatibilised blends of PA6/EVA-g-MA and PA6/EVA/EVA-g-MA were studied as functions of maleic anhydride content (MA) and dispersed phase (EVA-g-MA) concentrations, respectively at blending composition of 20 wt% dispersed phase (EVA-g-MA or combination of EVA and EVA-g-MA). The maleic anhydride (MA) was varied from 1 to 6 wt% in the PA6/EVA-g-MA blend, whereas MA concentration was fixed at 2 wt% in the ternary compositions with varying level of EVA-g-MA. ATR-IR spectroscopy revealed the formation of in situ copolymer during reactive compatibilisation of PA6 and EVA-g-MA. It was found that notched Izod impact strength of PA6/EVA-g-MA blends increased significantly with MA content in EVA-g-MA. The brittle to tough transition temperature of reactively compatibilised blends was found to be at 23 °C. The impact fractured surface topology reveals extensive deformation in presence of EVA-g-MA whereas; uncompatibilised PA6/EVA blend shows dislodging of EVA domains from the matrix. Tensile strength of the PA6/EVA-g-MA blends increased significantly as compared to PA6/EVA blends. Analysis of the tensile data using predictive theories showed an enhanced interaction of the dispersed phase and the matrix. It is observed from the phase morphological analysis that the average domain size of the PA6/EVA-g-MA blends is found to decrease gradually with increase in MA content of EVA-g-MA. A similar decrease is also found to observe in PA6/EVA/EVA-g-MA blends with increase in EVA-g-MA content, which suggest the coalescence process is slower in presence of EVA-g-MA. An attempt has been made to correlate between impact strength and morphological parameters with regard to the compatibilised system over the uncompatibilised system.     

Polyethylene multiwalled carbon nanotube composites

Polyethylene (PE) multiwalled carbon nanotubes (MWCNTs) with weight fractions ranging from 0.1 to 10 wt% were prepared by melt blending using a mini-twin screw extruder. The morphology and degree of dispersion of the MWCNTs in the PE matrix at different length scales was investigated using scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM) and wide-angle X-ray diffraction (WAXD). Both individual and agglomerations of MWCNTs were evident. An up-shift of 17 cm⁻¹ for the G band and the evolution of a shoulder to this peak were obtained in the Raman spectra of the nanocomposites, probably due to compressive forces exerted on the MWCNTs by PE chains and indicating intercalation of PE into the MWCNT bundles. The electrical conductivity and linear viscoelastic behaviour of these nanocomposites were investigated. A percolation threshold of about 7.5 wt% was obtained and the electrical conductivity of PE was increased significantly, by 16 orders of magnitude, from 10⁻²⁰ to 10⁻⁴ S/cm. The storage modulus (G′) versus frequency curves approached a plateau above the percolation threshold with the formation of an interconnected nanotube structure, indicative of ‘pseudo-solid-like’ behaviour. The ultimate tensile strength and elongation at break of the nanocomposites decreased with addition of MWCNTs. The diminution of mechanical properties of the nanocomposites, though concomitant with a significant increase in electrical conductivity, implies the mechanism for mechanical reinforcement for PE/MWCNT composites is filler-matrix interfacial interactions and not filler percolation. The temperature of crystallisation (T_c) and fraction of PE that was crystalline (F_c) were modified by incorporating MWCNTs. The thermal decomposition temperature of PE was enhanced by 20 K on addition of 10 wt% MWCNT.     

Co-continuous nanostructured nanocomposites by reactive blending of carbon nanotube masterbatches

Masterbatches of reactive polymers containing carbon nanotubes are used to prepare nanocomposites by reactive blending. By mixing masterbatches of low molecular-weight amino-terminated polyamide-6 (PA6) containing ～10 wt% or ～17 wt% of multi-walled carbon nanotubes (MWNT) with maleic anhydride functionalized polyethylene (PE*) at temperatures above melting of PA6 it is possible to obtain fine and homogeneous dispersions of carbon nanotubes. In the PA6 concentration range explored, from 19 wt% to 37 wt%, nanostructured co-continuous blend morphologies are achieved. Selective extractions show that a high amount of graft copolymer PE*-g-PA6 is synthesized during mixing. The swelling experiments in selective solvents demonstrate co-continuous blend morphologies. Electron microscopy confirms good quality of MWNT dispersion and shows structures on mesoscopic scales. Fine dispersion of carbon nanotubes and the matrix co-continuity concur to yield a unique combination of properties such as solvent resistance, electrical conductivity, mechanical strengthening and ductility.     

Ionic conductivity in polyethylene-b-poly(ethylene oxide)/lithium perchlorate solid polymer electrolytes

The ionic conductivity and phase arrangement of solid polymeric electrolytes based on the block copolymer polyethylene-b-poly(ethylene oxide) (PE-b-PEO) and LiClO₄ have been investigated. One set of electrolytes was prepared from copolymers with 75% of PEO units and another set was based on a blend of copolymer with 50% PEO units and homopolymers. The differential scanning calorimetry (DSC) results, for electrolytes based on the copolymer with 75% of PEO units, were dominated by the PEO phase. The PEO block crystallinity dropped and the glass transition increased with salt addition due to the coordination of the cation by PEO oxygen. The conductivity for copolymers 75% PEO-based electrolyte with 15 wt% of salt was higher than 10⁻⁵ S/cm at room temperature and reached to 10⁻³ S/cm at 100 °C on a heating measurement. The blend of PE-b-PEO (50% PEO)/PEO/PE showed a complex thermal behavior with decoupled melting of the blocks and the homopolymers. Upon salt addition the endotherms associated with PEO domains disappeared and the PE crystals remained untouched. The conductivity results were limited at 100 °C to values close to 10⁻⁴ S/cm and at room temperature values close to 3 × 10⁻⁶ S/cm were obtained for the 15 wt% salt electrolyte. Raman study showed that the ionic association of the highly concentrated blend electrolytes at room temperature is not significant. Therefore, the lower values of conductivity in the case of the blend with 50% PEO can be assigned to the higher content of PE domains leading to a morphology with lower connectivity for ionic conduction both in the crystalline and melted state of the PE domains.     

Rheology, phase morphology, mechanical, impact and thermal properties of polypropylene/metallocene catalysed ethylene 1-octene copolymer blends

Blends of a polypropylene (PP) and a metallocene catalysed ethylene-octene copolymer (EOC) were prepared using a single screw extruder fitted with a barrier screw design. The EOC used had 25 wt% 1-octene content and the weight fraction of EOC in the blends covered the range 1-30 wt.% Viscosity values for the blends determined experimentally from dual capillary rheological studies were similar to those calculated theoretically using the log additivity principle described by Ferry. This result together with scanning electron microscopy (SEM) observations and evidence from tan δ curves from dynamic mechanical thermal analysis showed PP and EOC to be partially miscible for blends having 10 wt% EOC or less. The tensile modulus, break strength and flexural modulus of the blends decreased with respect to virgin PP as the weight fraction of EOC was increased to 30 wt.% The diminution in mechanical properties was concomitant with an initial increase in elongation at break from 40% for neat PP to 140% for the blend with 15 wt% EOC before decreasing to 65% when 30 wt% EOC was blended. The optimum impact modification of the PP used in this study, in the temperature range −40 to 23 °C, was achieved by blending with between 20 and 30 wt% EOC.     

Viscoelastic effects on the phase separation in thermoplastics modified cyanate ester resin

A high temperature thermosetting bisphenol-A dicyanate, BADCy was blended with a thermoplastic poly(ether imide) (PEI). The phase separation behavior of the blend was investigated by scanning electron microscopy (SEM) and time resolved light scattering (TRLS). It was found by SEM that the blend with 20 and 25 wt% PEI had a phase inversion structure. The results of TRLS displayed clearly that the phase separation took place according to a spinodal decomposition (SD) mechanism and the evolution of both scattering vector q_m and the maximum scattering intensity I_m followed Maxwell-type relaxation equation. The temperature-dependent relaxation time τ for the blends can be described by the Williams-Landel-Ferry equation. It demonstrated experimentally that the phase separation behaviors in PEI/BADCy blends were affected by viscoelastic effect.     

A facile route for preparing stable co-continuous morphology of LLDPE/PA6 blends with low PA6 content

A facile method is employed to prepare a series of LLDPE/PA6 blends with co-continuous morphology with low PA6 content via reactive extrusion. In these blends, co-continuous morphology is obtained by introducing graft copolymers with both high and low molecular weight trunk chains to the interface simultaneously. Maleic anhydride functionalized polybutadine (PB-g-MAH, and MAH content = 10 wt%) is first melt grafted onto the LLDPE backbones with dicumyl peroxide (DCP) as an initiator. Part of PB-g-MAH is grafted onto LLDPE to form LLDPE-g-PB-g-MAH copolymer. During reactive extrusion, in-situ formed Copolymer II (polybutadiene-graft-polyamide, PB-g-PA6) with a low molecular weight trunk chain (PB) is obtained from the reaction between the maleic anhydride group of free or non-grafted PB-g-MAH and the amino group on PA6 molecules; while Copolymer I (LLDPE-g-PB-g-PA6) is obtained via the reaction between the maleic anhydride group of the grafted PB-g-MAH (i.e., LLDPE-g-PB-g-MAH) and the amino group of PA6. Copolymer I with a high molecular weight trunk chain, LLDPE, should strengthen the interface and favor stress transfer, enabling the deformation of PA6; and Copolymer II (PB-g-PA6) with a low molecular weight trunk chain, PB, facilitates the formation of a flat interface between LLDPE and PA6, thus promoting an elongated PA6 phase. Therefore, co-continuous morphology of LLDPE/PA6 blend is successfully prepared with only 25 wt% PA6 by controlling suitable amounts of Copolymers I and II in the blend.     

Experimental measurement and numerical simulation of viscosity reduction effects in HMMPE containing a small amount of exfoliated organoclay-modified TLCP composite

A small amount (1 wt%) of organoclay-modified thermotropic liquid crystalline polymer (TLCP) acting as a viscosity reduction agent in high molecular mass polyethylene (HMMPE) was characterized and compared with purified TLCP (1 wt%) in HMMPE at 190 °C and 230 °C, respectively, where the TLCP displayed nematic and nematic-isotropic biphase structures. In the TLCP/PE blend at 190 °C and 230 °C, dramatic reductions in viscosity were observed with significant improvement in extrudate surface smoothness and an enlarged processing window. For the organoclay-modified TLCP in PE, the viscosity reduction ability of TLCP was further enhanced with viscosity dropped by up to >98.5% and >97.4% at 190 °C and 230 °C and processing window enlarged to >700 s⁻¹ and >900 s⁻¹ respectively in comparison to that of PE. Moreover, yielding stress, initial transition shear rate and transition region decreased to lower magnitudes than those of the TLCP/PE blend. A phenomenological model was applied to elucidate the mechanism of organoclay, TLCP and PE conformation before and after yielding in the confined capillary environment. A binary flow pattern model was applied to successfully predict the rheological behavior of the blends at 190 °C.     

Effects of AN-contents and shear flow on the miscibility of PC/SAN blends

The miscibility of polycarbonate (PC) with styrene-co-acrylonitrile random copolymer (SAN) has been systematically investigated as functions of acrylonitrile content and shear flow. Various AN-contents ranged from 11 to 74 wt% and different simple shear flow values up to 90 s⁻¹ have been used to explore the effect of both material and proceeding parameters on the miscibility of PC and SAN blends. The finest phase dispersion of the SAN particles was observed at AN=25 wt% for PC/SAN=70/30 blends under the same processing condition using scanning electron microscope (SEM). The obtained morphologies indicated that PC and SAN could form a partial miscibility blend and the maximum miscibility occurred at AN=25 wt%. This observation was supported by considering the shifts in the glass processes of the two rich phases of the blend using the dynamical mechanical analysis (DMA) measurements. The optimum interaction of the two components at AN=25 wt% calculated from ellipsometric technique was found to be the only responsible parameter for the high miscibility of the blend. The viscoelastic properties of the pure polymer components were found to play a minor role in the obtained morphologies. The effect of simple shear flow on the morphology of PC/SAN-25=70/30 blend has been also investigated using a special shear apparatus of parallel plate geometry. It has been found that the dispersed phase of SAN was elongated and broken-up in the direction of flow with weaker contrast at high shear rates. The shear rate was found to enhance the miscibility of SAN (dispersed phase) in the PC matrix to a great extent as seen in the weak contrast of the two phases observed by transmission electron microscope (TEM).     

A chemically amplified positive-working photosensitive polyimide based on a blend of poly(amic acid ethoxymethyl ester) and poly(amic acid)

We prepared a novel chemically amplified photosensitive polyimide based on a blend of poly(amic acid ethoxymethyl ester) (PAAE) and poly(amic acid); this blend produces polyimide (PI) films with improved mechanical properties after imidization with photoacid generator (PAG). PAAE and poly(amic acid) were end-capped with 5-norbornene-2,3-dicarboxylic dianhydride and 2,3-dimethyl maleic anhydride, respectively, to lower their molecular weights without compromising the properties of the resulting PI films. As a result of the blending of these PI precursors, the mechanical properties of the PI films were found to be less affected by the strong acid generated from the PAG than PI films fabricated by imidization of PAAE alone. The relatively high solubility of the blended PI precursor film in basic aqueous solutions was found to be effectively controlled by the use of a high-temperature post-exposure bake process to partially imidize the end-capped PAA. It was found that a 10-μm-thick film of the PSPI precursor system containing 13 wt% PAGs exhibits a sensitivity (D⁰) of 700 mJ/cm² when developed with 2.38 wt% aqueous tetramethyl ammonium hydroxide solution at room temperature. A fine positive pattern was fabricated in a 12 μm thick film with 1000 mJ/cm² of i-line exposure. The resultant PI film was also found to exhibit excellent mechanical and thermal properties, which are critical to its practical use as a stress buffer layer in semiconductor packaging.     

Broadband dielectric spectroscopy of nanostructured maleated polypropylene/polycarbonate blends prepared by in situ polymerization and compatibilization

The miscibility and molecular dynamics of nanostructured maleated polypropylene (mPP)/polycarbonate (PC) blends prepared by in situ polymerization of macrocyclic carbonates with polypropylene modified with 0.5 wt% of maleic anhydride-reactive groups were investigated over a wide range of frequencies (10⁻²-0.5 × 10⁷ Hz) at different constant temperatures using broadband dielectric spectroscopy and scanning transmission electron microscope (STEM). The molecular dynamics of the glass relaxation process of the blend (α-relaxation process) appeared at a lower temperature range compared with that of the pure PC. This shift in the molecular relaxation process is attributed to the partial miscibility of the two polymer components in the blends as previously confirmed by the morphology via STEM. Nanoscale morphologies with average domain diameters as small as 50 nm were obtained for the different blend compositions studied. The STEM photographs show that the graft mPP-g-PC prefers to locate at the interfaces as previously reported. The relaxation spectrum of pure PC and mPP/PC blends was resolved into α- and β-relaxation processes using the Havriliak-Negami equation and ionic conductivity. The dielectric relaxation parameters, such as relaxation peak broadness, maximum frequency, f_max, and dielectric strength, Δ? (for the α- and β-relaxation processes), were found to be blend composition dependent. The kinetics of the α-relaxation processes of the blends were well described by Vogel-Fulcher-Tammann (VFT) equation. The local process of PC was resolved into two relaxation processes β₁ and β₂, associated with the carbonyl groups' motion and the combined motions of carbonyl and phenylene groups, respectively. Only β₂ shifted to lower frequency in the blend while β₁ was relatively not affected by blending. The electric modulus of the blends was used to get a sufficient resolution of the different relaxation processes in the samples, i.e., α-, β-relaxation processes, ionic conductivity, and interfacial polarization. In addition, the blending method used was found to increase the d.c. conductivity without affecting the charge carrier transport mechanism, making it possible to develop novel polymer blends with tunable dielectric properties and morphology from existing polymers.     

Effect of molding temperature on crystalline and phase morphologies of HDPE composites containing PP nano-fibers

A high-density polyethylene (HDPE)/isotactic polypropylene (PP) (75/25) blend containing 25 wt% of PP was fibrillated by roller drawing at 138 °C. The fibrillated blend was processed again at temperatures ranging from 155 to 200 °C by compression molding or extrusion. The effects of molding temperature on the morphology and mechanical properties of the blend were investigated. Wide angle X-ray scattering (WAXS) and transmission electron microscopy (TEM) were used to study the morphology of the samples. The roller-drawn blend exhibited a fibrous structure with the chain direction aligned parallel to the drawing direction. After molding at 155 °C, the HDPE formed parallel-stacked lamellae retaining the parallel orientation after the melting of the PE crystals. As the molding temperature increased the parallel orientation gradually vanished and some of the parallel-stacked lamellae changed into twisted lamellae. The PP phase existed as fibrils in the PE matrix and the crystals stayed with their molecular chain aligned parallel to the fibrillation direction even when the molding temperature was far above the melting temperature of PP. Nevertheless, the orientation of the crystals did not change as the molding temperature increased from 155 to 165 °C. The internal structure of the PP fibrils changed from a needle structure to a parallel-stacked one. The PP fibrils induced the crystallization of the PE melt, leading to the formation of a trans-crystalline layer at their surface. As the molding temperature increased, more PE lamellae protruded into the PP fibrils and the interface between the PP fibrils and the PE matrix became diffuse.     

Anisotropy and instability of the co-continuous phase morphology in uncompatibilized and reactively compatibilized polypropylene/polystyrene blends

The present work describes the anisotropy and instability observed upon the formation of co-continuous phase morphologies in model polystyrene/polypropylene melt-extruded blends. Uncompatibilized and reactively compatibilized blends using amino-terminated polystyrene, PS-NH₂, and maleic anhydride grafted polypropylene, PP-MAh, reactive precursors were investigated. Differences in phase morphology are discussed based on the viscoelastic properties of the components used, the blend composition and, the type and content of the compatibilizer precursor employed. As expected, for the same polystyrene grade at a concentration in the blend below 20 wt%, a polypropylene matrix having a higher viscosity enables the formation of a more co-continuous phase morphology than a less viscous one, as quantified by solvent extraction. The co-continuous phase morphology developed was found to exhibit a highly elongated structure upon melt flow through the die of the extruder. Isotropic co-continuity, observed inside the barrel of extruder, was transformed into anisotropic phase co-continuity in the form of interconnected infinite strands of the minor phase highly oriented in the extrusion direction.When the blends were thermally annealed, a 50/50 PS/PP co-continuous blend exhibits a substantial phase coarsening from micro- to millimeter scale without alteration of the phase co-continuity. The reactive compatibilization of the polypropylene and the polystyrene phases using 5 wt% PP-graft-PS, reactively in situ generated was able to significantly retard the phase evolution process.     

Microstructure and dielectric properties control of Ba4(Nd0.7Sm0.3)9.33Ti18O54 microwave ceramics

Microwave ceramics of Ba₄(Nd_0.7Sm_0.3)_9.33Ti₁₈O₅₄ with 0–3 wt% Ag additions were synthesized by a citrate sol–gel method. The BaO–B₂O₃–SiO₂ glass was also added into the sol–gel derived BNST ceramic powders as sintering aids. The undoped, Ag- and BaBS-doped samples can be sintered at 1250 °C, 1150 °C and 1000 °C, respectively. The microstructure and dielectric properties were then controlled by doping Ag or BaBS glass. Near isoaxial grains with about 250 nm and typical columnar grains were obtained for the silver-doped and BaBS-doped samples, respectively. For the <1 wt% silver-doped samples, the dielectric constant and Q × f retained unaltered but τ_f decreased from 9 ppm/°C to 1.4 ppm/°C. With increasing silver content from 1 wt% to 3 wt%, the dielectric constant and τ_f significantly increased but Q × f decreased. For the BaBS-doped samples, both dielectric constant and Q × f decreased but τ_f increased with increasing BaBS content.     

Synthesis and characterization of multi-walled carbon nanotubes reinforced polyamide 6 via in situ polymerization

Polyamide 6 (PA6)/carbon nanotubes (PA6/CNTs) composites have been prepared by in situ polymerization of ε-caprolactam in the presence of pristine and carboxylated multi-walled carbon nanotubes (MWNT and MWNTCOOH). Viscosity measurements show that adding 0.5 wt% of carbon nanotubes (CNTs) does not affect the molecular weight of PA6. Compared with pure PA6, the yield strength of PA6/CNTs composites loaded with 0.5 wt% CNTs is almost unchanged, and the tensile strength is increased slightly. Dynamic mechanical analysis (DMA) demonstrates that both the storage modulus (E′) and glass transition temperature (T_g) of the PA6/CNTs composites increase, particularly for PA6/MWNTCOOH, indicating there is some chemical bonding between PA6 and MWNTCOOH. Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and ultra small-angle X-ray scattering (USAXS) show that MWNT and MWNTCOOH are well dispersed in PA6 matrix. Comparison of the USAXS data with a stiff-rod model and wormlike rod model reveals that the CNTs are quite flexible, regardless the degree of chemical modification. Due to the flexibility of CNTs, mechanical properties of the PA6/CNTs composites are marginally enhanced.     

Secondary effects of antioxidant on PS/PVME blends

Interactions between the antioxidant Santonox (4,4′-thiobis(6-tert-butyl-m-cresol)) and the LCST polymer blend of polystyrene (PS) and polyvinylmethylether (PVME) were examined. The presence of the antioxidant caused inhomogeneities in blend films cast from toluene solutions at antioxidant compositions greater than 0.25 wt% of the PVME. Also, the cloud-point of the blend decreased linearly with antioxidant content with a slope of 21 °C/wt%. As expected, the ability of the antioxidant to prevent degradation of the PVME within the blend was found to increase with increasing Santonox composition. Based on these results, an antioxidant composition of no more than 0.10 wt% is recommended in the studies of PS/PVME blends.