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1.
Dynamic viscoelastic properties of blends of poly(methyl methacrylate) (PMMA) and poly(styrene‐co‐acrylonitrile) (SAN) with various AN contents were measured to evaluate the influence of SAN composition, consequently χ parameter, upon the melt rheology. PMMA/SAN blends were miscible and exhibited a terminal flow region characterized by Newtonian flow, when the acrylonitrile (AN) content of SAN ranges from 10 to 27 wt %. Whereas, PMMA/SAN blends were immiscible and exhibited a long time relaxation, when the AN content in SAN is less than several wt % or greater than 30 wt %. Correspondingly, melt rheology of the blends was characterized by the plots of storage modulus G′ against loss modulus G″. Log G′ versus log G″ plots exhibited a straight line of slope 2 for the miscible blends, but did not show a straight line for the immiscible blends because of their long time relaxation mechanism. The plateau modulus, determined as the storage modulus G′ in the plateau zone at the frequency where tan δ is at maximum, varied linearly with the AN content of SAN irrespective of blend miscibility. This result indicates that the additivity rule holds well for the entanglement molecular weights in miscible PMMA/SAN blends. However, the entanglement molecular weights in immiscible blends should have “apparent” values, because the above method to determine the plateau modulus is not applicable for the immiscible blends. Effect of χ parameter on the plateau modulus of the miscible blends could not be found. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

2.
The rheological behavior of blends of poly(styrene-co-acrylonitrile) (SAN) and poly(ε-caprolactone) (PCL) was investigated, using a cone-and-plate rheometer. For the study, blends of various compositions were prepared by melt blending using a twin-screw compounding machine. The rheological properties measured were shear stress (σ12), viscosity (η), and first normal stress difference (N1) as functions of shear rate (γ) in steady shearing flow, and dynamic storage modulus (G′) and loss modulus (G″) as functions of angular frequency (ω) in oscillatory shearing flow, at various temperatures. It has been found that logarithmic plots of N1 versus σ12, and logarithmic plots of G′ versus G″, become virtually independent of temperature but vary regularly with blend composition, and that the zero-shear viscosity of the blends, (ηo)blend, follows the relationship, 1/log(ηo)blend = wA/log η0A + wB/log η0B, where η0A and η0B are the zero-shear viscosities of components A and B, respectively, and wA and wB are the weight fractions of components A and B, respectively. The physical implications of the relationship found are discussed.  相似文献   

3.
The sensitivity to radiation of mixtures of poly(methyl methacrylate) (PMMA) and polystyrene-co-acrylonitile) (SAN) was studied over the entire range of composition. Polystyrene-co-acrylonitrile, like polystyrene, is highly resistant to ionizing radiation, having a small Gx value for crosslinking (0.077) and an even smaller Gs value for main chain scission (0.055). In contrast, PMMA degrades readily under irradiation (with Gs = 1.2). In γ-irradiated blends, the behavior of each polymer is largely influenced by the presence of the other component. Gel formation in SAN is impeded by PMMA, as a result of a decrease in Gx, and a concomitant increase in the ratio Gs/Gx. Flexural strength measurements, along with molecular weight determinations by gel permeation chromatography, demonstrated that SAN had a marked protective effect on PMMA by decreasing Gs (chain scission). This protective effect was not observed in earlier experiments with PMMA–PS blends, in spite of its chemical similarity to the system PMMA–SAN. The difference in behavior between PMMA–PS and PMMA–SAN may be explained on the basis of polymer compatibility. PMMA and SAN form a compatible pair, whereas PMMA and PS are incompatible; thus the short range protective effect of the phenyl groups in PS is inhibited.  相似文献   

4.
The effects of compatibilizer on the morphological, thermal, mechanical, and rheological properties of poly(methyl methacrylate) (PMMA)/poly(N‐methyl methacrylimide) (PMMI) (70/30) blends were investigated. The compatibilizer used in this study was styrene–acrylonitrile–glycidyl methacrylate (SAN‐GMA) copolymer. Morphological characterization of the PMMA/PMMI (70/30) blend with SAN‐GMA showed a decrease in PMMI droplet size with an increase in SAN‐GMA. The glass‐transition temperature of the PMMA‐rich phase became higher when SAN‐GMA was added up to 5 parts per hundred resin by weight (phr). The flexural and tensile strengths of the PMMA/PMMI (70/30) blend increased with the addition of SAN‐GMA up to 5 phr. The complex viscosity of the PMMA/PMMI (70/30) blends increased when SAN‐GMA was added up to 5 phr, which implies an increase in compatibility between the PMMA and PMMI components. From the weighted relaxation spectrum, which was obtained from the storage modulus and loss modulus, the interfacial tension of the PMMA/PMMI (70/30) blend was calculated using the Palierne emulsion model and the Choi‐Schowalter model. The results of the morphological, thermal, mechanical, and rheological studies and the values of the interfacial tension of the PMMA/PMMI (70/30) blends suggest that the optimum compatibilizer concentration of SAN‐GMA is 5 phr. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43856.  相似文献   

5.
Blends of bisphenol-A polycarbonate (PC) with poly- (styrene-co-acrylonitrile) (SAN) and poly (acrylonitrile-butadiene-styrene) (ABS) prepared by screw extrusion and solution-casting were investigated by differential scanning calorimetry and scanning electron microscopy. From the measured glass-transition temperatures (Tg) and specific heat increments (ΔCp) at the Tg, SAN appears to dissolve more in the PC-rich phase than does PC in the SAN-rich phase. Also, the decrease of Tg (PC) in PC/ABS blends is larger than in the PC/SAN blends. From the Tg behavior and the electron microscopy study, it is suggested that the compatibility increases more in the SAN-rich compositions than in the PC-rich compositions of the blends. In the study of extrudate swell of the PC/SAN blends and the PC/ABS blends, the maximum level of extrudate swell is reached at 0.5 weight fraction of PC for both blend systems. The Flory-Huggins polymer-polymer interaction parameter (χ12) between PC and SAN was calculated and found to be 0.034 ± 0.004. A similar value of χ for PC and SAN was found with the PC/ABS blends.  相似文献   

6.
A series of poly(methyl methacrylate) (PMMA) blends with rigid ladderlike polyphenylsilsesquioxane (PPSQ) were prepared at weight ratios of 100/0, 95/5, 90/10, 85/15, and 80/20 by solution casting and then hot‐pressing. Their rheological properties have been studied under both dynamic shear and uniaxial elongation conditions. Their rheological properties depend on the compositions. The storage modulus, G′, loss modulus, G″, and dynamic shear viscosity, η*, of the PMMA/PPSQ 95/5 blend were slightly lower than those of pure PMMA. However, the values of G′, G″, and η* for the other PMMA/PPSQ blends are higher than those of PMMA. The G′ values increase with an increase in PPSQ content from 5% through 15% PPSQ at low frequencies and then drop as the PPSQ content increases to 20%. Uniaxial elongational viscosity (ηE) data demonstrate that PMMA/PPSQ blends exhibit slightly weaker (5% PPSQ) and much weaker (10% PPSQ) strain‐hardening than PMMA. In contrast, the PMMA/PPSQ 85/15 blend shows strain‐softening. Neither strain‐hardening nor strain‐softening was observed in the 80/20 blend. The special rheological properties for the 95/5 blend is probably due to a decrease in PMMA entanglements brought by the specific PMMA–PPSQ interactions. Rheological properties of PMMA/PPSQ blends with higher PPSQ content (≥10%) are mainly affected by formation of hard PPSQ particles. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 352–359, 2007  相似文献   

7.
Steady and oscillatory shearing flow properties of compatible and incompatible polymer blend systems were measured, using a cone-and-plate rheometer. The compatible blend systems investigated are blends of two low-density polyethylenes (LDPE) having different values of molecular weight and blends of poly(methyl methacrylate) (PMMA) with poly(vinylidene fluoride) (PVDF). The incompatible blend system investigated is a blend of poly(methyl methacrylate) (PMMA) with polystyrene (PS). It was found that (1) plots of first normal stress difference (τ11 – τ22) vs. shear stress (τ12) and plots of storage modulus (G′) vs. loss modulus (G″) for the LDPE blends become independent of temperature and blend composition; (2) plots of τ11 – τ22 vs. τ12, and G′ vs. G″ for the PMMA/PVDF blends become independent of temperature but dependent upon blend composition. It was found further that, for the incompatible PMMA/PS blends, the dependence of τ11 – τ22 on blend composition, when plotted against τ12, is different from the dependence of G′ on blend composition, when plotted against G″. However, in both compatible and incompatible blend systems, plots of τ11 – τ22 vs. τ12 and plots of G′ versus G″ are independent of temperature. The seemingly complicated composition-dependent rheological behavior of the incompatible blend system is explained with the aid of photomicrographs describing the state of dispersion.  相似文献   

8.
Empirical correlations of flow properties of poly(vinyl chloride) were made using data reported by a number of investigators. Correlation was made by plotting the reduced variable viscosity η/η0 versus \documentclass{article}\pagestyle{empty}\begin{document}$ (\eta _0 \dot \gamma \bar M_w )/(_\rho RT) $\end{document} or \documentclass{article}\pagestyle{empty}\begin{document}$ (\eta _0 \dot \gamma \bar M_w ^{0.5} )/(_\rho RT) $\end{document} for unplasticized PVC and versus \documentclass{article}\pagestyle{empty}\begin{document}$ (\eta _0 \dot \gamma \bar M_w ^{0.5} )/(_\rho RTW_2 ^a ) $\end{document} with polymer concentration, W2, for PVC containing plasticizer.  相似文献   

9.
Polybutadiene‐g‐poly(styrene‐co‐acrylonitrile) (PB‐g‐SAN) impact modifiers with different polybutadiene (PB)/poly(styrene‐co‐acrylonitrile) (SAN) ratios ranging from 20.5/79.5 to 82.7/17.3 were synthesized by seeded emulsion polymerization. Acrylonitrile–butadiene–styrene (ABS) blends with a constant rubber concentration of 15 wt % were prepared by the blending of these PB‐g‐SAN copolymers and SAN resin. The influence of the PB/SAN ratio in the PB‐g‐SAN impact modifier on the mechanical behavior and phase morphology of ABS blends was investigated. The mechanical tests showed that the impact strength and yield strength of the ABS blends had their maximum values as the PB/SAN ratio in the PB‐g‐SAN copolymer increased. A dynamic mechanical analysis of the ABS blends showed that the glass‐transition temperature of the rubbery phase shifted to a lower temperature, the maximum loss peak height of the rubbery phase increased and then decreased, and the storage modulus of the ABS blends increased with an increase in the PB/SAN ratio in the PB‐g‐SAN impact modifier. The morphological results of the ABS blends showed that the dispersion of rubber particle in the matrix and its internal structure were influenced by the PB/SAN ratio in the PB‐g‐SAN impact modifiers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2165–2171, 2005  相似文献   

10.
An investigation of the effect of physical aging on excess enthalpy of compatible polymer blends was carried out. Poly(methyl methacrylate) (PMMA) and poly(styrene-co-acrylonitrile) (SAN) were chosen for this study. Blends of different ratios of PMMA and SAN were physically aged at different times and temperatures below their glass transition (Tg) and then subjected to enthalpy relaxation measurement in a differential scanning calorimeter (DSC). An improved procedure was developed and, employed to analyze the data. The error associated with the calculation of the normalized deviation in enthalpy, known as the “Φ” function, was below 4%. The relaxation was observed to proceed faster at higher aging temperature. It was also found that at higher aging temperatures of Tg – 20 and Tg– 35°C, enthalpy relaxation in SAN-rich blends proceeds faster than in PMMA rich blends, while at the low aging temperature of Tg– 50°C the rate of relaxation becomes independent of the composition.  相似文献   

11.
Blends of poly (vinyl chloride) (PVC) and acrylonitrile-butadiene styrene (ABS) terpolymer were prepared in different ratios by a melt blending technique. ABS containing three different levels of rubber content were used. A quantitative assessment of ABS in PVC/ABS blends has been shown by infrared studies. ABS content has been shown as the presence of the characteristic acrylonitrile peak. Differential scanning calorimetry (DSC) studies have been carried out to study the glass transition (Tg) behavior of the blends. Two Tg values corresponding to PVC and styrene-acrylonitrile (SAN) copolymer have been observed. Thermogravimetric analysis (TGA) reveals a significant improvement in thermal stability of these blends as compared to PVC. Mechanical properties show a significant increase in the impact strength which is related to rubber content of the ABS used. Morphological studies have been carried out by scanning electron microscopy which support the observation that an increase in rubber content results in greater ductility.  相似文献   

12.
ABS (acrylonitrile–butadiene–styrene) terpolymer is a two-phase thermoplastic with SAN (styrene–acrylonitrile) copolymer constituting the continuous phase (matrix). The flow properties of ABS with varying molecular parameters were studied using a capillary viscometer at the shear rate range encountered in its processing. The viscosity-average molecular weights (Mv) of matrix SAN with 26% acrylonitrile content are in the range of 90,000 to 150,000, and Mv of poly-butadiene-are in the range of 150,000 to 170,000. The weight-average molecular weight of the matrix SAN is the main controlling factor for the flow properties of ABS at low shear rate, while the molecular weight distribution of the matrix SAN becomes increasingly important with the increase of shear rate. The presence of SAN grafted polybutadiene increases the melt viscosity of ABS by 40–60% over comparable free SAN copolymer and also decreases the activation energy at constant shear stress to 24–25 kcal/mole from the 33–36 kcal/mole for free SAN. The die swell of ABS and SAN can be correlated with the dynamic shear modulus G′, and the melt fracture of ABS and SAN starts at G′ equal to 3.6 × 106 dynes/cm2.  相似文献   

13.
Criteria for rheological compatibility of polymer blends are suggested. The criteria suggested make use of plots of first normal stress difference (N1) against shear stress (σ12), and of storage modulus (G′) against loss modulus (G″). Compatible blend systems considered are (1) blends of two different grades of low-density polyethylene, (2) blends of poly(vinylidene fluoride) and poly(methyl methacrylate), (3) blends of poly(2,6-dimethyl-1,4-phenylene oxide) and polystyrene, and (4) blends of poly(styrene-co-acrylonitrile) and poly(styrene-co-maleic anhyride). And incompatible blend systems considered are (1) blends of nylon 6 and poly(ethylene-co-vinyl acetate) and (2) blends of nylon 6 and an ethylene-based multifunctional polymer. It has been found that plots of N1 vs. σ12 and G′ vs. G″ give (a) temperature-independent correlations for both compatible and incompatible blend systems; (b) composition-independent correlations for compatible blends; (c) composition-dependent correlations for incompatible blends.  相似文献   

14.
A series of poly(acrylonitrile‐butadiene‐styrene) (ABS) grafting modifiers were synthesized by emulsion grafting poly(acrylonitrile‐styrene) (SAN) copolymer onto polybutadiene (PB) latex rubber particles. The chain transfer reagent tert‐dodecyl mercaptan (TDDM) was used to regulate the grafting degree of ABS and the molecular weight of SAN copolymers. By blending these ABS modifiers with Chlorinated polyvinyl chloride (CPVC) resin, a series of CPVC/ABS blends were obtained. The morphology, compatibility, and the mechanical properties of CPVC/ABS blends were investigated. The scanning electron microscope (SEM) studies showed that the ABS domain all uniformly dispersed in CPVC matrix. Dynamic mechanical analyses (DMA) results showed that the compatibility between CPVC and SAN became enhanced with the TDDM content. From the mechanical properties study of the CPVC/ABS blends, it was revealed that the impact strength first increases and then decreases with the TDDM content, which means that the compatibility between CPVC and the SAN was not the only requirement for maximizing toughness. The decreasing of tensile strength and the elongations might attribute to the lower entanglement between chains of CPVC and SAN. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers  相似文献   

15.
The transport behavior of He, O2, N2, and CO2 in membranes of poly(vinyl chloride) (PVC)/acrylonitrile–butadiene–styrene (ABS) blends has been studied at 25°C. The blends were further characterized by dynamic mechanical measurements, differential thermal analysis (DTA), density measurements, and x-ray diffraction. The equilibrium sorption of CO2 and N2 was measured directly at atmospheric pressure using an electromicrobalance and compared with sorption values obtained as P/D ratios from permeation measurements. The rates of permeation (P) and diffusion (D) increase with increasing ABS content in the blends. The P and D values are not additive, and only slight indications of phase inversion in the blends are observed at 5–10 wt-% ABS in the blends. Experimental densities of the blends are higher than calculated densities assuming volume additivity. The data are interpreted to mean that the PVC/ABS blends form a two-phase system composed of a soft polybutadiene (rubber) phase and a rigid PVC/styrene–acrylonitrile copolymer (SAN) phase of mutually compatible components. DTA and dynamic mechanical measurements also show a two-phase system. Sorption values of CO2 and N2 by equilibrium sorption measurements increase with increasing ABS content in the blends without the large fluctuations which have been observed for the sorption values obtained from the time lag method. Comparison of the two types of sorption values (from direct measurements and from P/D ratios) show larger deviations for CO2 than for N2. This suggests that the time lag method is not valid for permeants with polar character in heterogeneous two-phase systems where chemical immobilizing effect on the permeant molecules occurs.  相似文献   

16.
Commercial, suspension-type PVC resin, poly (vinyl chloride), molecular weight Mw × 10?4 = 8.6 ± 0.9, polydispersity Mw/Mn = 2.26, was mixed with plasticizer di(2-ethyl hexyl)phthalate (DOP) and organo-tin stabilizer in four different proportions. The mixtures were milled and pressed into sheets for testing. The polymer content in these samples was 97, 80, 60, and 40 wt percent. The viscoelastic properties of the materials were investigated using a Weissenberg rheogoniometer in a cone-and-plate, steady-state shearing mode. The viscosities and primary normal stress difference coefficients were measured at shear rates of 10?2 ≤ \documentclass{article}\pagestyle{empty}\begin{document}$ \mathop \gamma \limits^. $\end{document} (sec?1) ≤ 102 and at temperatures from 151 to 246°C. The zero shear viscosities, plotted as log η0 vs 1/T (T is the absolute temperature) did not follow either a straight line dependence, reported for PVC melts at low shear rates at 170–190°C, nor was any discontinuity found near 195°C as by others; the data follows a continuous concave curve. The apparent activation energy of flow increases steeply with decreasing temperature. The data can be represented by a WLF type of equation, but the magnitudes of the parameters of this relation differ from expected values. A crossplot of log η0 (T = const.) vs log w (where w is the polymer content) also demonstrates a faster increase of η0 with w than expected from the straight line dependence. The primary normal stress difference coefficient was found to increase with w and decrease with T, paralleling the observed dependencies of η0.  相似文献   

17.
This study attempted to correlate morphological changes and physical properties for a high rubber content acrylonitrile–butadiene–styrene (ABS) and its diluted blends with a poly(styrene‐co‐acrylonitrile) (SAN) copolymer. The results showed a close relationship between rubber content and fracture toughness for the blends. The change of morphology in ABS/SAN blends explains in part some deviations in fracture behavior observed in ductile–brittle transition temperature shifts. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2606–2611, 2004  相似文献   

18.
An experimental study of shear viscosity η(\documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma $\end{document}), principal normal stress difference N1(\documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma $\end{document}), storage modulus G′(ω), dynamic viscosity η′(ω), and filament elongation to break LB is reported for solutions of several polyamides; namely, nylon 66 in sulfuric acid (H2SO4) and formic acid (HCOOH), poly(γ-benzyl-L -glutamate) (PγBLG) in m-cresol, Nomex in H2SO4 and dimethylacetamide (DMA)/5% LiCl, and Kevlar in H2SO4 at 25 and 60°C. The variation of properties with concentration, polymer backbone and chain configuration, and solvent type is emphasized. The nylon 66/H2SO4 solutions have higher viscosity, normal stresses, and storage modulus than the HCOOH solutions of equivalent concentrations. The Nomex/H2SO4 solutions have higher viscosity and higher normal stresses and storage modulus than the DMA/LiCl solutions at equivalent concentrations. The significance of polymer chain backbone rigidity in forming liquid crystalline phases in Kevlar and PγBLG solutions is discussed and its influence on flow properties in indicated. These systems allow polarized light to pass through crossed polarizers and show maxima in viscosity–concentration data. The 25°C Kelvar solutions are distinctive in that they exhibit apparent yield stress values. This gives distinctive shear flow and oscillatory data. Filament elongation-to-break data show Kelvar > Nomex > nylon 66 in H2SO4 solutions for the order of spinnability.  相似文献   

19.
The value of tmax in differential scanning calorimetry is correlated with the crystallization kinetics of poly(ethylene terephthalate) (PET). The Avrami exponent, n, obtained varies as a result of a change in slope of the curve at the point tn, a secondary crystallization transition. The plot of tn vs. tmax shows a linear relationship. The rate of crystallization depends upon both molecular weight and crystallization temperature. Under a nucleation controlling step, the plot of log tmax vs. \documentclass{article}\pagestyle{empty}\begin{document}$ t_{\max } vs.\frac{1}{{T^2 \Delta T}} $\end{document}gives a linear relationship. Theoretical concepts of the treatment are discussed.  相似文献   

20.
In this study, the structural and morphological properties of poly(methyl methacrylate)/poly(acrylonitrile‐g‐(ethylene‐co‐propylene‐co‐diene‐g‐styrene) (PMMA‐AES) blends were investigated with emphasis on the influence of the in situ polymerization conditions of methyl methacrylate. PMMA‐AES blends were obtained by in situ polymerization, varying the solvent (chloroform or toluene) and polymerization conditions: method A—no stirring and air atmosphere; method B—stirring and N2 atmosphere. The blends were characterized by infrared spectroscopy (FTIR), transmission electron microscopy (TEM), and dynamic mechanical analysis (DMA). The results showed that the PMMA‐AES blends are immiscible and present complex morphologies. This morphology shows an elastomeric dispersed phase in a glassy matrix, with inclusion of the matrix in the elastomer domains, suggesting core shell or salami morphology. The occlusion of the glassy phase within the elastomeric domains can be due to the formation of graft copolymer and/or phase inversion during polymerization. However, this morphology is affected by the polymerization conditions (stirring and air or N2 atmosphere) and by the solvent used. The selective extraction of the blends' components and infrared spectroscopy showed that crosslinked and/or grafting reactions occur on the elastomer chains during MMA polymerization. The glass transition of the elastomer phase is influenced by morphology, crosslinking, and grafting degree and, therefore, Tg depends on the polymerization conditions. On the other hand, the behavior of Tg of the glassy phase with blend composition suggests miscibility or partial miscibility for the SAN phase of AES and PMMA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

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