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1.
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   

2.
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   

3.
The miscibility was investigated in blends of poly(methyl methacrylate) (PMMA) and styrene‐acrylonitrile (SAN) copolymers with different acrylonitrile (AN) contents. The 50/50 wt % blends of PMMA with the SAN copolymers containing 5, 35, and 50 wt % of AN were immiscible, while the blend with copolymer containing 25 wt % of AN was miscible. The morphologies of PMMA/SAN blends were characterized by virtue of scanning electron microscopy and transmission electron microscopy. It was found that the miscibility of PMMA/SAN blends were in consistence with the morphologies observed. Moreover, the different morphologies in blends of PMMA and SAN were also observed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

4.
Organically‐modified montmorillonite clay nanocomposites of poly(styrene‐co‐acrylonitrile) (SAN), poly(methyl methacrylate) (PMMA) and SAN/PMMA miscible blend are investigated. Structure characteristics at the nanoscale and microscale and thermal and tensile properties are studied as a function of polymer blend composition and filler loading fraction. Blend miscibility and Tg are unaffected by up to 10% by wt. organoclay. Thermal degradation stability increases with SAN content and exhibits an optimum value of clay loading. Stiffness shows significant improvement. Tensile strength and elongation‐at‐break suffer as a result of nanocomposite formation. Modulus shows a maximum enhancement of 57% (5 ± 0.06 GPa at 10 wt% filler, 20/80 SAN/PMMA) and varies linearly with clay fraction for all compositions of matrix phase. Predictions of Halpin–Tsai composite model are in excellent agreement with the experimental behavior over full range of polymer blend composition. Fundamental aspects of a polymer blend–clay nanocomposite are clarified, such as lack of additional synergy between clay platelets and matrix, and tensile ductility reduction, compared with polymer–clay system. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers  相似文献   

5.
Nanocomposites of blends of polymethylmethacrylate (PMMA) and poly(styrene‐co‐acrylonitrile) (SAN) with multi‐walled carbon nanotubes (MWCNTs) were prepared by melt mixing in a twin‐screw extruder. The dispersion state of MWCNTs in the matrix polymers was investigated using transmission electron microscopy. Interestingly enough, in most of the nanocomposites, the MWCNTs were observed to be mainly located at SAN domains, regardless of the SAN compositions in the PMMA/SAN blend and of the processing method. One possible reason for this morphology may be the π–π interactions between MWCNTs and the phenyl ring of SAN. The shift in G‐band peak observed in the Raman spectroscopy may be the indirect evidence proving these interactions. The percolation threshold for electrical conductivity of PMMA/SAN/MWCNT nanocomposites was observed to be around 1.5 wt %. Nanocomposites with PMMA‐rich composition showed higher electrical conductivity than SAN‐rich nanocomposites at a fixed MWCNT loading. The dielectric constant measurement also showed composition‐dependent behavior. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

6.
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   

7.
Summary The melting point depression of poly(-caprolactone)/poly(styrene-co-acrylonitrile) (PCL/SAN) blends with changes in acrylonitrile content of SAN and in blend ratio was investigated by differential scanning calorimetry. For the melting points at a constant blend ratio occur a minimum in dependence on the copolymer composition for blends containing about 20 wt% acrylonitrile in SAN. From melting point depression data a negative, binary interaction parameter was obtained for PCL/SAN blends containing a SAN with 19.2 wt% AN. By optical microscopy it can be shown that the shape of the spherulites changes with copolymer composition of SAN and blend ratio.  相似文献   

8.
A poly(vinyl chloride) (PVC)/poly(methyl methacrylate) (PMMA) (80/20 w/w) polymer blend was studied by mechanical spectroscopy. Two relaxations can be distinguished: in the glassy state, a very large secondary relaxation in the range of 100 K to 325 K which results from the combination of secondary relaxations of PVC and PMMA; and only one main relaxation at 364 K associated to the glass rubber transition. The relaxation spectrum in the range of the β relaxation has been described by a relaxation time distribution function based upon a Gaussian function and a series-parallel model. The α relaxation was studied by means of a theoretical approach for the nonelastic deformation of polymers. We found that the miscibility of this blend appears to be a function of the observation scale: the PVC/PMMA blend is heterogeneous at the scale of molecular movements involved for the β relaxation process but homogeneous at the scale of the chain segments responsible for the α relaxation dynamics. © 1996 John Wiley & Sons, Inc.  相似文献   

9.
A study was made on the stress relaxation behavior at 25°C of poly(methyl methacrylate) in uniaxial tension as a function of physical aging at both room temperature and 60°C. Test specimens were compression molded at 165°C, then quenched to room temperature and allowed to age for up to 30 days prior to testing. Stress relaxation curves measured after different aging times could be superposed to a single master curve for each aging temperature. Superposition was achieved by applying vertical and horizontal shifts. Hence, the shape of the response curves was not changed by aging. This is in accordance with observations made by Struik for tensile creep curves. Volume changes as a function of physical aging were also determined. Simple exponential relationships were observed between volume and both horizontal and vertical shifts. The horizontal shift implies a shift in the effective time scale caused by a change in free volume. The vertical shifts could be correlated with changes in Young's modulus caused by a change in density. For the range of aging studied, the response time scale varied over nearly two decades of log-time. For the same conditions modules varied by 30 percent.  相似文献   

10.
C. G. Robertson  G. L. Wilkes   《Polymer》2000,41(26):155-9204
The influence of blend composition on physical aging behavior was assessed for miscible blends of atactic polystyrene (a-PS) and poly(2,6-dimethyl-1,4-phenylene oxide) (PPO). At aging temperatures of 15 and 30°C below the midpoint glass transition temperature (Tg), the a-PS/PPO blends exhibited volume relaxation rates that were retarded compared to additivity based upon the aging rates for pure a-PS and PPO. This negative deviation diminished with increased undercooling, and eventually the volume relaxation rates displayed a nearly linear trend with respect to composition at the greatest undercooling of 60°C that was employed. The compositional nature of unaged glassy density and secondary relaxation intensity, both influenced by the presence of specific attractive interactions in the blend system, were likely causes for the variation of volume relaxation rate with composition and undercooling. For aging at 30°C below Tg, the dependence of enthalpy relaxation rate on composition was similar to that observed for volume relaxation. Mechanical aging rates determined from time–aging time superposition of creep compliance data showed significantly less than additive behavior for the blends aged at Tg−30°C, but unlike the volume relaxation results, this trend persisted at the 60°C undercooling.  相似文献   

11.
The morphology and coarsening behaviour of polycarbonate (PC) blend with styrene-co-acrylonitrile (SAN) random copolymer of 25 wt% AN have been investigated as a function of shear history using transmission electron microscope (TEM) and time resolved light scattering techniques. Simple shear apparatus of two parallel plates geometry was used to generate different shear rate values depending on the different distances from the centre of the sample disk. The morphology of PC/SAN-25=70/30 blend showed that the dispersed phase of SAN was elongated and broken-up in the direction of flow with weaker contrast at high shear rate values. The shear rate was found to suppress the concentration fluctuations and enhance the miscibility of SAN (dispersed phase) in the PC matrix to a great extent. The average of the dispersed particle diameter was evaluated as a function of different shear memories at 240 °C for different time intervals based on the Debye-Bueche theory. The obtained data were found to be shear memory dependent i.e. the average particle diameter decreases with increasing shear memory. This result indicated that the coarsening process is greatly suppressed by shear memory and the shear could produce a permanent morphological change (irreversible change) over the time scale of the measurement. This behaviour was attributed to the very high melt viscosities of the blend components, which in turn led to a very long relaxation time and consequently a high difficulty to erase the effect of shear at the experimental temperature. Furthermore, the coarsening process for all the measured samples followed the general power law, , regardless of the shear memory of the blend. This behaviour implied that the shear could only retard the rate of domain growth without any effect on the coarsening mechanism.  相似文献   

12.
The compatibility of polymer blends of poly(?-caprolactone) (PCL) and poly(styrene-co-acrylonitrile) (SAN) containing various acrylonitrile (AN) contents was studied to evaluate the influences of copolymer composition and PCL concentration upon blend compatibility. Blend compatibility was characterized by the occurence of a single glass transition intermediate between the transitions of the respective pure components. The glass transitions were determined by differential scanning calorimetry (DSC) and dynamic mechanical measurement (Rheovibron). It was found that SAN and PCL form compatible blends when the AN content of SAN ranges from 8% to 28% by weight. These blends are compatible in all proportions except for SAN 28 (AN wt % = 28) and PCL blends containing 70 or 85 wt % PCL. Blends of PCL and SAN were found to be incompatible when the AN content in SAN is greater than 30 wt % or less than 6 wt %. Lower critical solution temperature (LCST) behavior, which can be attributed to phase separation, was found to occur when these blends were heated to elevated temperatures. The cloud point, or phase separation, was found to vary with AN content in SAN and the concentration of SAN in the blend.  相似文献   

13.
Microlayers of polycarbonate (PC) with poly(methylmethacrylate) (PMMA) or poly(styrene‐co‐acrylonitrile) (SAN) were processed with varying layer thicknesses. Adhesion between PC and PMMA was found to be an order of magnitude higher than between PC and SAN, as determined with the T‐peel method. To probe the effect of the adhesion difference on yielding and deformation of PC/PMMA and PC/SAN microlayers, the macroscopic stress–strain behavior was examined as a function of layer thickness and strain rate, and the results were interpreted in terms of the microdeformation behavior. During yielding, crazes in thick SAN layers opened up into cracks; however, PC layers drew easily because local delamination relieved constraint at the PC/SAN interface. Adhesion of PC/PMMA was too strong for delamination at the interface when PMMA crazes opened up into cracks at low strain rates. Instead, PMMA cracks tore into neighboring PC layers and initiated fracture. At higher strain rates, good adhesion produced yielding of thick PMMA layers, a phenomenon not observed with thick SAN layers. The change in microdeformation mechanism of PMMA with increasing strain rate produced a transition in the yield stress of PC/PMMA microlayers. Microlayers of both PC/SAN and PC/PMMA with thinner layers (individual layers 0.3–0.6 μm thick) exhibited improved ballistic performance compared to microlayers with thicker layers (individual layers 10–20 μm thick), which was due to cooperative yielding of both components. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1545–1557, 2000  相似文献   

14.
The rheological behavior of blends of poly(methyl methacrylate) (PMMA) and poly(acrylonitrile-stat-styrene)-graft-polybutadiene (ABS) was investigated using a cone-and-plate rheometer. The rheological properties measured were shear stress (σ12), viscosity (η), and first normal stress difference (N1) as functions of shear rate (\documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma$ \end{document}) in steady shearing flow, and storage modulus (G′) and loss modulus (G″) as functions of frequency (ω) in oscillatory shearing flow. It has been found that the rheological behavior of blends of ABS and PMMA was very similar to that of blends of poly(styrene-stat-acrylonitrile) (SAN) and PMMA, in that N1 in logarithmic plots of N1 versus σ12, and G′ in logarithmic plots of G′ versus G″, vary regularly with blend composition. This has led us to conclude that the rubber particles that are grafted on an SAN resinous matrix in ABS resin plays only a minor role in influencing the compatibility of ABS/PMMA blends, and that the SAN chains attached to the surface of rubber particles, and the SAN matrix phase, play a major role in compatibilizing ABS resin with PMMA.  相似文献   

15.
In polymer blends, the composition and microcrystalline structure of the blend near surfaces can be markedly different from the bulk properties. In this study, the enzymatic degradation of poly(ε‐caprolactone) (PCL) and its blends with poly(styrene‐co‐acrylonitrile) (SAN) was conducted in a phosphate buffer solution containing Pseudomonas lipase, and the degradation behavior was correlated with the surface properties and crystalline microstructure of the blends. The enzymatic degradation preferentially took place at the amorphous part of PCL film. The melt‐quenched PCL film with low crystallinity and small lamellar thickness showed a higher degradation rate compared with isothermally crystallized (at 36, 40, and 44°C) PCL films. Also, there was a vast difference in the enzymatic degradation behavior of pure PCL and PCL/SAN blends. The pure PCL showed 100% weight loss in a very short time (i.e., 72 h), whereas the PCL/SAN blend containing just 1% SAN showed ~50% weight loss and the degradation ceased, and the blend containing 40% SAN showed almost no weight loss. These results suggest that as degradation proceeds, the nondegradable SAN content increases at the surface of PCL/SAN films and prevents the lipase from attacking the biodegradable PCL chains. This phenomenon was observed even for a very high PCL content in the blend samples. In the blend with low PCL content, the inaccessibility of the amorphous interphase with high SAN content prevented the attack of lipase on the lamellae of PCL. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 868–879, 2002  相似文献   

16.
Compatible polymer blends can be used to test critically the viability of the damped Debye lattice (DDL) model of relaxation in the primary (glass-to-rubber) transition region. Since these blends form because of specific intermolecular interaction, the force constants that characterize intermolecular elastic interactions can be controlled to some extent by varying blend composition. The model predicts an unusual sharpening of the stress relaxation master curve of a marginally two-dimensional DDL upon dilution with a plasticizer. We have prepared an appropriate two-dimensional DDL by adding modest amounts of partially brominated poly(2,6-dimethyl 1,4-phenylene oxide) to polystyrene to form compatible blends. As predicted by the model, sharpening of the stress relaxation behavior upon dilution was observed for all blend compositions and for all diluents used. However, at higher brominated poly(phenylene oxide) concentrations, the anticipated diluent concentration dependence was not always observed and the sharpening of the stress relaxation behavior was less than expected. In similar experiments carried out on diluted homopolymers, the relative values of the solubility parameters of the polymers and the diluents strongly influenced the effectiveness of the diluent in changing the stress relaxation behavior. In this blend system, the particular chemical nature of the diluent was found to be much less important; in fact, the three diluents used all evoked approximately the same behavior despite their having solubility parameters that differed significantly.  相似文献   

17.
The effects of silica nanoparticles on the phase separation of poly (methyl methacrylate)/poly (styrene-co-acrylonitrile) (PMMA/SAN) blends are studied by the rheological method. The binodal temperatures of near-critical compositions were obtained by the gel-like behavior during spinodal decomposition, which is a character of polymer blends with co-continuous morphology. The shifted Cole–Cole plot method was introduced to determine the binodal temperatures of off-critical compositions based on the appearance of shoulder-like transition in the terminal regime of blends with droplet morphology. Such method is found also applicable in nanoparticle filled polymer blends. Moreover, a new method to determine the spinodal temperature from Fredrickson-Larson mean field theory was suggested, where the concentration fluctuation's contribution to the storage modulus is used instead of the whole dynamic moduli. This method was also successfully extended to nanoparticle filled polymer blend. The influences of the concentration and the average diameter of silica particles on the phase separation temperature were studied. It was found that the small amount of the silica nanoparticles in PMMA/SAN blends will significantly change the phase diagram, which is related to the selective location of silica in PMMA. The comparisons with thermodynamic theory of particle-filled polymer blends are also discussed.  相似文献   

18.
The molecular dynamics and miscibility of highly interacting binary polymer blends of poly(methyl methacrylate) (PMMA) and poly[styrene‐co‐(maleic anhydride)] random copolymer with 8 wt% maleic anhydride content (SMA) were investigated as a function of composition over a wide range of frequency (10?2–106 Hz) at different constant temperatures (30–160 °C). Only one common glass relaxation process (α‐process) was detected for all measured blends, and its dynamics and broadness were found to be composition dependent. The existence of only one common α‐relaxation process located at a temperature range between those of the pure polymer components indicated the miscibility of the two polymer components over the entire range of composition. The miscibility was also confirmed by measuring the glass transition temperatures of the blends, Tg, using differential scanning calorimetry. The composition dependence of Tg of the blends showed a positive deviation from the linear mixing rule and well described by the Gordon–Taylor–Kwei equation. The relaxation spectrum of the blends was resolved into α‐ and β‐relaxation processes using the Havriliake–Negami (HN) equation and ionic conductivity. The dielectric relaxation parameters obtained from HN analysis, such as broadness of relaxation processes, maximum frequency, fmax, and dielectric strength, Δ? (for the α‐ and β‐relaxation processes), were found to be blend composition dependent. The kinetics of the α‐relaxation process of the blends were well described by the Meander model, while an Arrhenius‐type equation was used to evaluate the molecular dynamics of the β‐relaxation process. Blending of PMMA and SMA was found to have a considerable effect on the kinetics and broadness of the β‐relaxation process of PMMA, indicating that the strong interaction and miscibility between the two polymer components could effectively change the local environment of each component in the blend. © 2013 Society of Chemical Industry  相似文献   

19.
Effect of the blend ratios on the morphology and melt rheology of poly(lactic acid) (PLA)/poly(butylene succinate adipate) (PBSA) blends were investigated using scanning electron microscope, strain-controlled rheometer, and capillary rheometer techniques. The morphological analysis shows that the average radius of the dispersed droplets of PBSA particles increases with change in the blend composition, and a co-continuous structure was generated when PBSA content reached 40%. For the linear viscoelasticity, the increase in the storage modulus at low-frequency region was more distinct in PLA/PBSA blends than in their pure components. A second plateau is clearly observed when the PBSA content was 20% or higher. Weight relaxation spectra showed that there was a longer relaxation time for blend system. These relaxation times were considered to be the shape relaxation periods of the droplets, which increase with change in the blend composition. The interfacial tensions of the PLA/PBSA blends at different compositions were between 5.3 and 6.1?mN/m, calculated from the weighted relaxation spectra and slightly higher than those obtained from Palierne model. These values are relatively high, indicating the poor miscibility of the two polymers. Both pure PLA and PBSA follow the Cox?CMerz rule, in good manner. Though, the rule does not satisfy with the PLA/PBSA blends. In addition, PLA/PBSA blends show more non-Newtonian tendencies than their pure components.  相似文献   

20.
The simultaneous measurements of stress and birefringence during hot-stretching, and after the cessation of stretching, were performed using a miscible blend of poly(methyl methacrylate) (PMMA) and 10 wt% of 4-cyano-4′-pentylbiphenyl (which is commonly known as 5CB). The birefringence of the blend exhibited anomalous behavior during stretching, that is, it initially decreased, then rapidly increased to a positive value. A concave curve with a minimum birefringence was prominent at low temperatures, during which PMMA determined birefringence. After passing the yield point, which corresponded to the minimum birefringence, the birefringence increased in proportion to the applied stress. That is to say, the stress-optical coefficient remained constant. In this region, the 5CB molecules oriented themselves with the PMMA chains, that is, there was nematic interaction. After stretching ceased, the stress initially decreased rapidly; during this period, the stress-optical coefficient was determined mainly by the deformation of PMMA, that is, glassy component. Subsequently, the orientation relaxation of 5CB, which occurred with the orientation relaxation of PMMA chains in the stage with a long time region, determined the birefringence. These results demonstrated that nematic interaction does not occur when inelastic deformation is governed.  相似文献   

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