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1.
Stable aqueous dispersion of polyaniline (PAn) stabilized by a hydrophilic polymer poly(vinyl pyrrolidone) (PVP) exhibits interesting rheological properties different from its components. Shear thinning observed for both PVP and PAn–PVP colloid (PP) indicates partially entangled nature of the later. Linear viscoelastic response of PVP solution exhibit strong frequency dependence of elastic (G′) and viscous (G″) modulus over the whole frequency range (0.1–100 ras/s) where G′ never exceeds G″ indicating the applicability of the Rouse‐Zimm model to this system. On the other hand, there is a crossover of G′ and G″ in the rheological profile of PP dispersion so that a single relaxation time model can be applicable. Therefore, PVP presents an entangled polymeric system and supposed to have a spectrum of relaxation times, whereas PP resembles to a physically crosslinked system with a single relaxation time. Increasing the extent of hydrogen bonding within the system (by raising the fraction of PAn or by leaving the solution undisturbed for long) relaxation time also becomes longer. The large difference in values of steady and complex shear viscosity (η and η*) within LVE regime reflects that original Cox‐Merz rule is obviously inapplicable to these systems. But at larger strain amplitude, η and η* are satisfactorily coincident that indicates a broader applicability of the modified Cox‐Merz rule. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2443–2455, 2008  相似文献   

2.
Dynamic rheological measurements were carried out on blends of poly(ether ether ketone) (PEEK)/poly(aryl ether sulfone) (PES) in the melt state in the oscillatory shear mode. The data were analyzed for the fundamental rheological behavior to yield insight into the microstructure of PEEK/PES blends. A variation of complex viscosity with composition exhibited positive–negative deviations from the log‐additivity rule and was typical for a continuous‐discrete type of morphology with weak interaction among droplets. The point of transition showed that phase inversion takes place at composition with a 0.6 weight fraction of PEEK, which agreed with the actual morphology of these blends observed by scanning electron microscopy. Activation energy for flow, for blend compositions followed additive behavior, which indicated that PEEK/PES blends may have had some compatibility in the melt. Variation of the elastic modulus (G′) with composition showed a trend similar to that observed for complex viscosity. A three‐zone model used for understanding the dynamic moduli behavior of polymers demonstrated that PEEK follows plateau‐zone behavior, whereas PES exhibits only terminal‐zone behavior in the frequency range studied. The blends of these two polymers showed an intermediate behavior, and the crossover frequency shifted to the low‐frequency region as the PEEK content in PES increased. This revealed the shift of terminal‐zone behavior to low frequency with an increased PEEK percentage in the blend. Variation of relaxation time with composition suggested that slow relaxation of PEEK retards the relaxation process of PES as the PEEK concentration in the blend is increased because of the partial miscibility of the blend, which affects the constraint release process of pure components in the blend. A temperature‐independent correlation observed in the log–log plots of G′ versus loss modulus (G″) for different blend systems fulfilled the necessary condition for their rheological simplicity. Further, the composition‐dependent correlations of PEEK/PES blends observed in a log–log plot of G′ versus G″ showed that the blends are either partially miscible or immiscible and form a discrete‐continuous phase morphology. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1548–1563, 2004  相似文献   

3.
Dispersions of a bisphenol A‐based epoxy resin with an organophilic montmorillonite (Nanofil 919) were studied by X‐ray diffraction and oscillatory shear rheometry. X‐ray studies reveal that the clay is intercalated by the epoxy and forms stable dispersions. The viscoelastic behavior of the nanodispersions was measured as a function of the Nanofil concentration and temperature. An increase in both G′ and G″ moduli was detected as the concentration increases. Furthermore, a transition from a liquid‐like behavior, at low temperatures, to a solid‐like behavior, at higher temperatures, was observed for all the samples. This transition is accounted for the formation of a percolated structure of interconnected tactoids through hydrophobic interactions. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1837–1844, 2008  相似文献   

4.
A method was adopted to fix a series of polymers of PE‐b‐PEO with different PEO/PE segments on the chains of LLDPE. Maleic anhydride (MA) reacting with hydroxyl group of PE‐b‐PEO (mPE‐b‐PEO) was used as the intermediate. The structures of intermediates and graft copolymers were approved by 1H NMR and FTIR. XPS analysis revealed a great amount of oxygen on the surface of grafted copolymers although the end group of PEO was fixed on the LLDPE chains through MA. Thermal properties of the graft copolymers as determined by differential scanning calorimetry (DSC) showed that PE segments in the grafted monomers could promote the heterogeneous nucleation of the polymer, increase Tc, and crystal growth rate. While the amorphous PEO segments which attached to the crystalline PE segments in LLDPE, impaired their ability to fit the crystal lattice, and depressed the crystallization of LLDPE backbones. In this study, it was also verified through the dynamic rheological data that increasing Mn of grafted monomers significantly increased the complex viscosity and enhanced the shear‐thinning behavior. Long‐branched chains formed by grafted monomers enhanced the complex moduli (G′ and G″) value and retarded relaxation rate. However, there were little influence on the rheological properties when increasing the amounts of PEO segments (or decreasing PE segments) of grafted monomers with similar molecular weight. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 506–515, 2008  相似文献   

5.
The effect of temperature on dynamic viscoelastic measurements of miscible poly (vinyl chloride) (PVC)/ethylene‐vinyl acetate–carbon monoxide terpolymer (EVA‐CO) and immiscible PVC/high‐density polyethylene (HDPE) and PVC/chlorinated polyethylene (CPE) molten blends is discussed. PVC plasticized with di(2 ethyl hexyl) phthalate (PVC/DOP) and CaCO3 filled HDPE (HDPE/CaCO3) are also considered for comparison purposes. Thermorheological complexity is analyzed using two time–temperature superposition methods: double logarithmic plots of storage modulus, G′, vs. loss modulus, G″, and loss tangent, tan δ, vs. complex modulus, G*, plots. Both methods reveal that miscible PVC/EVA‐CO and PVC/DOP systems are thermorheologically complex, which is explained by the capacity of PVC to form microdomains or crystallites during mixing and following cooling of the blends. For immiscible PVC/HDPE and PVC/CPE blends the results of log G′ vs. log G″ show temperature independence. However, when tan δ vs. log G* plots are used, the immiscible blends are shown to be thermorheologically complex, indicating that the morphology observed by microscopy and constitued by a PVC phase dispersed in a HDPE or CPE matrix, is reflected by this rheological technique. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 469–477, 2000  相似文献   

6.
A rheological technique is proposed for determining the thermally induced order–disorder transition of block copolymers. In the present investigation, a cone-and-plate rheometer was used to measure dynamic storage and loss moduli, G′(ω) and G″(ω), as a function of angular frequency ω of a commercial grade polystyrene-block-polyisoprene-block-polystyrene (SIS) tri-block copolymer (KRATON D-1107, Shell Development Company) in the temperature range from 140 to 240°C. For comparison purposes, dynamic viscoelastic properties of a commercial grade low-density polyethylene (LDPE) were also determined in the temperature range from 160 to 238°C. We have found that log G′ versus log G″ plots for the LDPE show no temperature dependence, whereas log G′ versus log G″ plots for the SIS block copolymer do show systematic temperature dependence in the temperature range 140–230°C. This observation leads us to conclude that the order–disorder transition of the SIS block copolymer takes place gradually as the temperature is raised from 140 to 230°C. This conclusion is in good agreement with that drawn from the study of Roe (Ref. 33), who employed the same block copolymer using small-angle x-ray scattering. It is not possible to reach such a conclusion using log G′(ω) versus log ω, log G″(ω) versus log ω, or log η′(ω) versus log ω plots in which η′ is the dynamic viscosity. We have demonstrated further that the use of frequency-temperature superposition is inappropriate for investigating the rheological behavior of block copolymer in the temperature range over which a thermally induced transition from an ordered structure to a disordered homogeneous phase occurs. We therefore suggest that when using information on dynamic viscoelastic properties, log G′ versus log G″ plots be used for determining the thermally induced order–disorder transition of block copolymers.  相似文献   

7.
The effect of phase‐separated morphology on the rheological properties of polystyrene/poly(vinyl methyl ether) (PS/PVME) blend was investigated by optical microscopy (OM), light scattering (LS) method, and rheology. The blend had a lower critical solution temperature (LCST) of 112°C obtained by turbidity experiment using LS at a heating rate of 1°C/h. Three different blend compositions (critical 30/70 PS/PVME by weight) and two off‐critical (50/50 and 10/90)) were prepared. The rheological properties of each composition were monitored with phase‐separation time after a temperature jump from a homogeneous state to the preset phase‐separation temperature. For the 30/70 and 50/50 blends, it was found that with phase‐separation time, the storage and loss moduli (G′ and G″) increased at shorter times due to the formation of co‐continuous structures resulting from spinodal decomposition. Under small oscillatory shearing, shear moduli gradually decreased with time at longer phase‐separation times due to the alignment of co‐continuous structures toward the flow direction, as verified by scanning electron microscopy. However, for the 10/90 PS/PVME blend, the rheological properties did not change with phase‐separation times. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 889–906, 1999  相似文献   

8.
This article presents a method that provides the molecular weight distribution (MWD) of polymeric material from rheological data. The technique has been developed to deal with linear polymers with a log‐normal molecular weight distribution. The rheological data must include the shear storage modulus, G′(ω), and the shear loss modulus, G″ (ω), ranging from the terminal zone to the rubberlike zone. It was not necessary to achieve the relaxation spectrums via the extremely unstable problem of inverting integral equations. The method has been tested with different polymers (polydimethylsiloxane, polyisoprene, random copolymer of ethylene and propylene, and polystyrene) and the calculated MWDs were in good agreement with experimental data. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1539–1546, 2000  相似文献   

9.
A study on the correlation between electrical percolation and viscoelastic percolation for carbon black (CB) and carbon fiber (CF) filled high‐density polyethylene (HDPE) conductive composites was carried out through an examination of the filler concentration (?) dependence of the volume resistivity (ρ) and dynamic viscoelastic functions. For CB/HDPE composites, when ? was higher than the modulus percolation threshold (?G ~ 15 vol %), the dynamic storage modulus (G′) reached a plateau at low frequencies. The relationship between ρ and the normalized dynamic storage modulus (Gc/Gp, where Gc and Gp are the dynamic storage moduli of the composites and the polymer matrix, respectively) was studied. When ? approached a critical value (?r), a characteristic change in Gc/Gp appeared. The critical value (Gc/Gp)c was 9.80, and the corresponding ?r value was 10 vol %. There also existed a ? dependence of the dynamic loss tangent (tan δ) and a peak in a plot of tan δ versus the frequency when ? approached a loss‐angle percolation (?δ = 9 vol %). With parameter K substituted for A, a modified Kerner–Nielson equation was obtained and used to analyze the formation of the network structure. The viscoelastic percolation for CB/HDPE composites could be verified on the basis of the modified equation, whereas no similar percolation was found for CF/HDPE composites. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1199–1205, 2004  相似文献   

10.
The reactive blending composites of isotactic polypropylene (PP)/octavinyl polyhedral oligomeric silsesquioxane (POSS) were prepared in the presence of dicumyl peroxide. Comparison of the rheological behavior of physical and reactive blending composites was made by oscillatory rheological measurements. It was found that the viscosity of physical blending composites drops at lower POSS content (0.5–1 wt %) and thereafter increases with increasing POSS content; that of reactive blending composites increases with increasing POSS content and displays a solid‐like rheological behavior at low frequency region when POSS content is higher than 1 wt %. The deviation of reactive blending composites from the scaling log G′–log G″ of linear polymer in Han plot, upturning at high viscosity in Cole–Cole plot, and from van Gurp–Palmen plot are related to the gelation behavior reactively. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 526–533, 2008  相似文献   

11.
The influence of middle and outer block composition of symmetric triblock copolymers consisting of a polystyrene–polybutadiene (S/B) random middle block and two polystyrene (PS) outer blocks on morphology and rheological behavior has been investigated. Master curves are obtained by shifting the experimental data measured at different temperatures using time‐temperature superposition principle, the validity of which was confirmed in the linear viscoelastic regime. The rheological properties are observed to be strongly influenced by the relative composition of the S‐SB‐S triblock copolymers. Increasing the S/B ratio from 1:1 to 1:2 in the middle block has lead to a change in morphology from wormlike to lamellar, which is also accompanied with broad and sharp tan δ peaks in the dynamic mechanical measurements, respectively. The storage and loss modulus have been observed to increase with the increase in PS contents in the outer blocks and PB content in the middle block. The triblock copolymer with wormlike structure showed terminal linear viscoelastic behavior, whereas the ones with lamellar morphology showed nonterminal flow behavior in the similar low‐frequency regime. The relaxation modulus (Gt) has been observed to increase four times when the S/B ratio is increased from 1:1 to 1:2, whereas it increases threefold when the PS‐content in the outer block was increased by just 8 wt %. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2776–2788, 2006  相似文献   

12.
We propose in this article a study of the viscoelastic behavior of reticulated PU systems that are synthesized from a triisocyanate and a polyetherdiol of molar mass 1000 or 2000 g · mol−1. We initially sought to confirm the expected results concerning the phenomenon of gelation, and in particular, that the power law G′ ∼ G″ ∼ ωΔ is verified. The appearance of a maximum of tan δ on the rheological curves led us to consider a second state of transition, namely vitrification. This could constitute an invaluable source of information on the complex morphology of the final material due to the microheterophased character of PU. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 544–551, 2000  相似文献   

13.
Studies on the relationship between resistivity and dynamic rheological properties of carbon black‐filled high‐density polyethylene (CB/HDPE) composites were carried out. Change of resistivity ρ is associated with the dynamic modulus before the positive temperature coefficient/negative temperature coefficient (PTC/NTC) transition temperature. When the temperature approaches the melting point of HDPE, ρ increases rapidly with a decreasing modulus, corresponding to PTC transition. The resistivity‐dynamic viscoelasticity relationship in the PTC region can be divided into two parts in which the changes of ρ with storage modulus G′ and loss modulus G″ can be described by the scaling laws given by the critical storage modulus and loss modulus Gc and Gc; adjustable parameters ρ′1c, ρ′2c, ρ″1c and ρ″2c; and nonlinear exponents n and m, respectively. The accordance between the experimental data and the scaling functions of the dimensionless quantities (G′/Gc ? 1) and (G″/Gc ? 1) in the PTC transition region suggests that the ρ jump may be the result of a modulus‐induced percolation. Gc and Gc increase, but the four scaling resistivitis, ρ′1c, ρ′2c, ρ″1c, and ρ″2c, decrease with increasing CB concentration, implying that the microstructure change of the composites is the determinant factor for the PTC behavior and the resistivity‐dynamic modulus relationship. However, ρ′2c and ρ″2c exhibit no scaling dependence. It is suggested that a threshold concentration exists for the modulus of the composites on the basis of examining the plot of both Gc and Gc against CB concentration. The scaling laws G′ ~ Φx and G″ ~ Φy hold for the concentration dependence of the critical modulus when Φ > Φc and the estimated values of x and y are 1.10 ± 0.10 and 0.89 ± 0.29, respectively. The resistivity‐dynamic modulus can shift to form a master curve. The horizontal factors aG and aG and the vertical factors a′ and a″ are relevant to the concentration dependence of the dynamic modulus or PTC behavior. It is believed that the former would be involved in changing the mechanical microstructure formed by the complicated interaction of CB particle and polymer segments, and the latter would be involved in the overall changes of conducting a network during the PTC transition region. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 983–992, 2003  相似文献   

14.
The effect of the novel N‐crotyl‐N,N‐dimethyl‐4‐methylanilinium hexafluroantimonate (CMH) initiator on cure kinetics and rheological properties of diglycidylether of bisphenol A (DGEBA) epoxy cationic system was investigated. From DSC measurements of the DGEBA/CMH system, it was found that this system exhibited excellent thermal latent characteristics at a given temperature and revealed complex cure behavior as indicated by multiple exotherms. The conversion and conversion rate of the DGEBA/CMH system increased with increasing the concentration of initiator, attributed to the high activity of CMH. Viscoelastic properties during gel formation of DGEBA initiated by CMH were investigated by rheological techniques under isothermal conditions. The gel time obtained from the modulus crossover point t(G′) = G″ was affected by a high curing temperature and the concentration of CMH, resulting in a high degree of network formation in cationic polymerization. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2397–2406, 2001  相似文献   

15.
The mobility of free macromolecular chains is of importance to the growth of crystallites in a crystallizing sustainable polylactide (PLA), which was scarcely explored by rheology. In this study, the time‐resolved rheological properties for PLA during isothermal crystallization were investigated first, showing that the storage and loss modulus experience 2–3 decades of increase. The Avrami analysis reveals that the crystallization kinetics in rheological measurement protocol follows the homogeneous nucleation and three‐dimensional growth mechanism. The linear viscoelastic properties in the vicinity of physical gelation point were then studied at the inverse quenching temperature of 165 °C. The results show that physical gelation occurs when the critical absolute crystallinity reaches 13% as determined by the rheological method. Relaxation time spectra reveal that the interfacial relaxation is greatly retarded but the presence of growing spherulites possesses little constraint on the mobility of free chains in matrix especially before physical gelation point. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1235–1244  相似文献   

16.
We have studied the dewetting process of thin polystyrene films on nonwettable substrates in the viscoelastic regime slightly above the glass transition temperature. The evolution of the shape of the dewetting rim for varying film thickness, molecular weights and dewetting temperatures allowed us to determine the relaxation rates of residual stresses, which originated from nonequilibrated polymer chain conformations formed during film preparation by spin‐coating. For long chain polymers, we found rates notably faster than the longest bulk relaxation processes, highly independent of molecular weight and temperature. Our study demonstrates that dewetting is a powerful tool for sensitive characterization of nonequilibrium properties of thin polymer films. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 515–523  相似文献   

17.
Monoquaternary cationic polymerizable surfactants of type N‐acryloyl‐N′‐methyl‐N′‐alkyl piperazinium bromide based on piperazine heterocycle was synthesized by reacting N‐acryloyl‐N′methyl piperazine with the corresponding n‐alkyl bromide (decyl, dodecyl, tetradecyl, and hexadecyl) in anhydrous acetone at room temperature. The resulting surfactants were deliquescent to display any sharp melting points. The surface activity was studied by surface tension measurements. Due to the complex head group geometry of these surfactants, the critical micelle concentration value was high in comparison to the analogous alkyltrimethyl ammonium bromides of similar alkyl chain length. The surfactants were polymerized by micellar (in water) and isotropic (in benzene) conditions and the resulting polymers were characterized by solubility and viscosity studies. The polymers prepared in water showed higher viscosity than the ones prepared in benzene as a result of micellar aggregation in water. The reduced viscosity of the polymers in polar solvents such as methanol and dimethyl formamide (DMF) showed polyelectrolyte‐like behavior, whereas nonelectrolyte behavior was observed in chloroform. pH‐responsive hydrogels were prepared by polymerizing the surfactants in the bicontinuous phase of a microemulsion. The resulting polymers did not exhibit any definite micro/nanostructure due to cross‐polymerization of the hydrophilic oil in the bicontinuous network structure. The gels were highly responsive to changes in pH of the medium and showed high‐swelling degree in acidic media owing to the protonation of the tertiary nitrogen of the piperazine ring. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2059–2072, 2009  相似文献   

18.
The stretched exponential relaxation modulus of regular and polymer modified asphalts is studied. It is shown that this relaxation function can generate the dynamic functions of these materials very well on any finite interval of the reduced frequencies (master curves). By continuation one can, in principle, cover the whole region of master curves of G′ and G″. The dispersive defect diffusion mechanism, which leads to the stretched exponential law, points to the stronger three-dimensional structure of modified asphalt at low temperatures. The method of calculating G′ and G″ from the stretched exponential relaxation modulus is proposed and tested on one regular and one modified asphalt. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1225–1232, 1997  相似文献   

19.
The effect of ion‐dipole interaction between lithium cations and oxygen atoms in poly(methyl methacrylate) (PMMA), which leads to the great enhancement of glass transition temperature (Tg), on the linear viscoelastic properties is studied using binary blends of PMMA and lithium trifluoromethanesulfonate (LiCF3SO3). The strong interaction at low temperature leads to the high modulus in the glassy region even near Tg. The interaction becomes weak as increasing the temperature. Consequently, the rheological terminal region is clearly detected without a marked enhancement of steady‐state compliance, although the zero‐shear viscosity increases by the LiCF3SO3 addition. The result indicates that the crosslinking due to the ion‐dipole interaction has a lifetime that decides the longest relaxation time. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2388–2394  相似文献   

20.
The effect of hydrocarbon oil incorporation on the rheological and phase behaviors of poly(styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene) (SEBS) has been investigated. SEBS‐A1 (neat SEBS) shows a presence of very long relaxation time mode even at the highest temperature carried out here. On the other hand, G′ of SEBS‐A3 (oil concentration = 50 wt %) drastically decreases with increase of temperature at a critical temperature, which can be assigned to be order–disorder transition (ODT). The critical temperature was determined by two rheological criteria. Incorporation of hydrocarbon oil affects the ODT temperature. The rheological response is very sensitive to a few temperature increases around the ODT temperature. Above the critical temperature, G′ finally yields the terminal flow in the low frequency range. The morphological observation at various temperatures was determined using atomic force microscopy (AFM) equipped with environmental controller. This enabled in situ observation of structural change of SEBS induced by temperature and phase transition. We found that the layered texture, mostly aligned along the surface can be seen for SEBS‐A1 ranging from room temperature to 230 °C, though the image contrast reduced by an increase of temperature. SEBS‐A3 showed sphere domains at room temperature and also remains the structure at a critical temperature. The phase separated structure disappeared almost completely above ODT temperature, which was confirmed by the rheologial criteria. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 955–965, 2009  相似文献   

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