Dynamic mechanical properties of isotactic polypropylene/nitrile rubber blends: Effects of blend ratio,reactive compatibilization,and dynamic vulcanization

The effect of blend ratio and compatibilization on dynamic mechanical properties of PP/NBR blends was investigated at different temperatures. The storage modulus of the blend decreased with increase in rubber content and shows two T_g's indicating the incompatibility of the system. Various composite models have been used to predict the experimental viscoelastic data. The Takayanagi model fit well with the experimental values. The addition of phenolic modified polypropylene (Ph-PP) and maleic modified polypropylene (MA-PP) improved the storage modulus of the blend at lower temperatures. The enhancement in storage modulus was correlated with the change in domain size of dispersed NBR particles. The effect of dynamic vulcanization using sulfur, peroxide, and mixed system on viscoelastic behavior was also studied. Among these peroxide system shows the highest modulus. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 2309–2327, 1997     

Linear shear viscoelasticity of confined,end-attached polymers in a near-theta solvent

Diblock copolymers of polystyrene and polyvinylpyridine, end-attached to mica by the traditional method of selecting one block to be insoluble and the other block to be soluble in the solvent, were studied with surface-force experiments while immersed in trans-decalin, a near-theta solvent for the polystyrene block, with special attention given to the small-amplitude shear viscoelastic response. The relaxation time, defined as the inverse frequency at which the effective loss modulus equaled the effective storage modulus, was studied not only as a function of the film thickness but also as a function of the grafting density. The relaxation times started to slow in direct proportion to diminishing surface separation when the surface separation took the value D ≈ L_o/3 (where L_o is the thickness of the uncompressed end-attached layer). Attempts to make comparisons with available theories met with limited success. To test experimentally the origin of this shear viscoelastic slowdown, similar measurements were made with adsorbed polystyrene with a molecular weight similar to that of the polystyrene moiety of the diblock copolymer, and it was found that high magnitudes of the effective viscoelastic shear moduli appeared only when the compression was much larger. In a control experiment in which interpenetration between opposed end-attached chains was precluded, we also studied the case of adsorbed polystyrene–polyvinylpyridine on one side and a bare mica surface on the other side, and the effective viscoelastic shear forces were reduced by nearly 1 order of magnitude. By inference, in the opposed diblock copolymer systems, we attributed the slowdown of the relaxation times with decreasing film thickness to the interpenetration of end-attached chains. Additional comments are made regarding the ratio of shear forces to compressive forces, which is called the small-strain friction coefficient. This is believed to be the first quantification of the linear-response relaxation time of end-attached polymer layers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3487–3496, 2005     

Rheological behavior of polypropylene/octavinyl polyhedral oligomeric silsesquioxane composites

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     

Electric,dielectric, and dynamic mechanical behavior of carbon black/styrene‐butadiene‐styrene composites

The conductivity of styrene‐butadiene‐styrene block copolymers containing different amounts of extraconductive carbon black (CB) was investigated as a function of the mold temperature. The composites exhibited reduced percolation thresholds (between 1.0 and 2.0 vol % CB). The dynamic mechanical analysis characterization revealed that the glass‐rubber‐transition temperatures of both segments were not affected by the CB addition, although the damping of the polybutadiene phase displayed a progressive drop with an increase in the CB concentration. The normalized curves of tan δ/tan δ_max (where tan δ represents the value of the loss tangent at any measurement temperature and tan δ_max represents the loss tangent peak value at the corresponding temperature T_max) versus T/T_max (where T is the temperature and T_max is the maximum temperature), corresponding to both polystyrene and polybutadiene phases as well as the activation energy related to the glass‐rubber‐transition process, did not present any significant change with the addition of CB. The dielectric analysis revealed the presence of two relaxation peaks in the composite containing 1.5 vol % CB, the magnitude of which was strongly influenced by the frequency, being attributed to interfacial Maxwell‐Wagner‐Sillars relaxations caused by the presence of different interfaces in the composite. The mechanical properties were not affected by the presence of CB at concentrations of up to 2.5 vol %. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2983–2997, 2003     

Viscoelasticity of nanobubble‐inflated ultrathin polymer films: Justification by the coupling model

The nanobubble inflation method is the only experimental technique that can measure the viscoelastic creep compliance of unsupported ultrathin films of polymers over the glass–rubber transition zone as well as the dependence of the glass transition temperature (T_g) on film thickness. Sizeable reduction of T_g was observed in polystyrene (PS) and bisphenol A polycarbonate by the shift of the creep compliance to shorter times. The dependence of T_g on film thickness is consistent with the published data of free‐standing PS ultrathin films. However, accompanying the shift of the compliance to shorter times, a decrease in the rubbery plateau compliance is observed. The decrease becomes more dramatic in thinner films and at lower temperatures. This anomalous viscoelastic behavior was also observed in poly(vinyl acetate) and poly (n‐butyl methacrylate), but with large variation in the change of either the T_g or the plateau compliance. By now, well established in bulk polymers is the presence of three different viscoelastic mechanisms in the glass–rubber transition zone, namely, the Rouse modes, the sub‐Rouse modes, and the segmental α‐relaxation. Based on the thermorheological complexity of the three mechanisms, the viscoelastic anomaly observed in ultrathin polymer films and its dependence on chemical structure are explained in the framework of the Coupling Model. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Effect of domain morphology of butadiene—styrene block copolymers on viscoelastic properties and in tension shear

Dynamic viscoelastic properties of S—B—S block copolymers were measured in the tensile and shear deformation modes. Between the glass transitions of the polybutadiene and polystyrene domains the ratio of storage moduli E'/G' in tension and in shear for the same polymer varied from 3 to more than 30, depending on sample preparation. For films cast from good solvents this ratio was near 3; large ratios resulted from deposition from poor polybutadiene solvents or from compression molding. Above the polystyrene glass transition, E'/G' approached 3 for all samples. The effect is ascribed to various degrees of polystyrene domain connectivity. Electron micrographs confirm this interpretation. For morphologies of high polystyrene domain connectivity, the loss tangent in tension is heavily weighted by mechanical losses in the polystyrene phase; the loss tangent in shear is affected only moderately by differences in domain morphology.     

Influence of molecular architecture of S–S/B–S triblock copolymers on rheological properties

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 (G_t) 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     

A new method for in situ crosslinking of stationary phases on fused silica capillary columns

A new mixed crosslinking agent composed of dicumyl peroxide and tetra(methylvinyl)cyclotetrasiloxane was used to prepare fused silica capillary columns with in situ crosslinked stationary phases including PEG-20M, SE-54, and OV-1. These columns proved to have good thermostability and inertness. As examples of potential applications a mixture of isomers of nitrotoluene and dinitrotoluene, and pyrolyzates of polystyrene were separated by using these columns.     

Bulk and shear rheology of a symmetric three‐arm star polystyrene

The bulk and shear rheological properties of a symmetric three‐arm star polystyrene were measured using a self‐built pressurizable dilatometer and a commercial rheometer, respectively. The bulk properties investigated include the pressure–volume–temperature behavior, the pressure‐dependent glass transition temperature (T_g), and the viscoelastic bulk modulus and Poisson's ratio. Comparison with data for a linear polystyrene indicates that the star behaves similarly but with slightly higher T_gs at elevated pressures and slightly higher limiting bulk moduli in glass and rubbery states. The Poisson's ratio shows a minimum at short times similar to what is observed for the linear chain. The horizontal shift factors above T_g obtained from reducing the bulk and shear viscoelastic responses are found to have similar temperature dependence when plotted using T ? T_g scaling; in addition, the shift factors also exhibit a similar temperature dependence to linear polystyrene. The retardation spectra for the bulk and shear responses are compared and show that the long time molecular mechanisms available to the shear response are unavailable to the bulk. At short times, the two spectra have similar slopes, but the short‐time retardation spectrum for the shear response is significantly higher than that for the bulk, a finding that is, as yet, unexplained. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Influence of actinic wavelength on properties of light‐cured interpenetrating polymer networks

Interpenetrating polymer networks (IPNs) composed of different acrylate/epoxide ratios, were synthesized under UV and visible‐LED curing conditions. The formation of the IPNs was explored in terms of phase separation, polymerization mechanisms, final mechanical properties and surface morphology. For these purpose, we uniquely combined results of miscibility investigations, confocal Raman microscopy, dynamical mechanical analysis and atomic force microscopy. Transparent films were obtained for all compositions and both irradiation sources. The thermo‐mechanical properties of different IPNs were associated to the presence of acrylate‐ or epoxide‐rich phases, as well as, mixed interphases, resulting from the high interpenetration between both networks. Although the final conversions were similar under UV and visible‐LED irradiation, we have found evidence that the visible‐cured samples provide higher IPN homogeneity and lower T_g, for a higher epoxide content. To explain this trend, the mechanisms and sequence of the acrylate or epoxide networks formation, under UV or LED irradiation, is discussed. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1378‐1390     

Nanostructured latexes made by a sequential multistage emulsion polymerization

A series of linear and lightly crosslinked nanostructured latices was prepared by a sequential multistage semicontinuous emulsion polymerization process alternating styrene (S) and n‐butyl acrylate (BA) monomer feeds five times, that is ten stages, and vice versa, along with several control latices. Transmission electron micrographs of the RuO₄‐stained cross sections of nanostructured and copolymer latex particles and films showed that their particle morphologies were not very different from each other, but the nanostructured latex particles were transformed into a nanocomposite film containing both polystyrene (PS) and poly(n‐butyl acrylate) (PBA) nanodomains interconnected by their diffuse polymer mixtures (i.e. interlayers). The thermal mechanical behaviors of the nanostructured latex films showed broad but single T_gs slightly higher than those of their counterpart copolymer films. These single T_gs indicated that their major component phases were the diffuse interlayers and that they behaved like pseudopolymer alloys. The minimum film formation temperatures of nanostructured latices capped with PBA and PS, respectively, were 15 °C lower than and equal to those of their counterpart copolymer latices, but their T_gs were about 10 °C higher. Consequently, nanostructured latices enabled us to combine good film formation with high strengths for adhesives and coatings applications. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2826–2836, 2006     

A critical analysis of the effect of crosslinking on the linear viscoelastic behavior of styrene–butadiene rubber and other elastomers

The linear viscoelastic behavior in dynamic shear and tensile creep at temperatures from −30 to 70 °C is measured for an styrene–butadiene rubber (SBR) elastomer cured with dicumyl peroxide to crosslinking densities between 0 and 23.5 × 10⁻⁵ mol/cm³. The G′, G″, and tan δ isotherms are analyzed by time–temperature superposition (TTS), where the tan δ master curves are consistent with those of Mancke and Ferry. However, to achieve the TTS in the lightly crosslinked SBR systems, an anomalous vertical shift is required in the narrow temperature region from 10 to 30 °C. The vertical shift factor in this temperature region is not the standard from rubber elasticity. No anomalous behavior is detected in the equilibrium modulus, which is a linear function of temperature in accordance with the classical theory of rubber elasticity. In contrast to SBR, standard vertical shifts are required to effect TTS for uncrosslinked polybutadiene and an ethylene propylene diene monomer elastomer. © 2013 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Synthesis of peroxide‐curable butyl rubber via suzuki–miyaura coupling of halogenated butyl rubber with 4‐vinylphenylboronic acid

The Suzuki–Miyaura coupling reaction of brominated butyl rubber (BIIR) and/or chlorinated butyl rubber with a mixture of 4‐vinylphenylboronic acid and phenylboronic acid was carried out in THF under various conditions using a di‐μ‐chlorobis [5‐hydroxy‐2‐[1‐(hydroxyimino‐κN)ethyl]phenylκC] palladium(II) dimer, which is a type of cyclopalladated complex, as a catalyst. When BIIR and a small amount (Pd/Br ≈ 1/1000) of complex were used as the substrate and catalyst, respectively, a 4‐vinylphenyl and phenyl group could be introduced to butyl rubber in a high yield. Isomerization of the exo carbon–carbon double bond in BIIR was observed during the coupling reaction to give a cis and trans endo structure. The peroxide curing behavior of the resulting polymer at 170 °C indicated that the polymer could be cured by dicumyl peroxide, and the maximum torque of the resulting material, which reflects the crosslink density, was controllable by the composition of the boronic acids used. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Dynamic mechanical behavior of acrylonitrile butadiene rubber/poly(ethylene‐co‐vinyl acetate) blends

The dynamic mechanical behavior of uncrosslinked (thermoplastic) and crosslinked (thermosetting) acrylonitrile butadiene rubber/poly(ethylene‐co‐vinyl acetate) (NBR/EVA) blends was studied with reference to the effect of blend ratio, crosslinking systems, frequency, and temperature. Different crosslinked systems were prepared using peroxide (DCP), sulfur, and mixed crosslink systems. The glass‐transition behavior of the blends was affected by the blend ratio, the nature of crosslinking, and frequency. sThe damping properties of the blends increased with NBR content. The variations in tan δ_max were in accordance with morphology changes in the blends. From tan δ values of peroxide‐cured NBR, EVA, and blends the crosslinking effect of DCP was more predominant in NBR. The morphology of the uncrosslinked blends was examined using scanning electron and optical microscopes. Cocontinuous morphology was observed between 40 and 60 wt % of NBR. The particle size distribution curve of the blends was also drawn. The Arrhenius relationship was used to calculate the activation energy for the glass transition of the blends, and it decreased with an increase in the NBR content. Various theoretical models were used to predict the modulus of the blends. From wide‐angle X‐ray scattering studies, the degree of crystallinity of the blends decreased with an increasing NBR content. The thermal behavior of the uncrosslinked and crosslinked systems of NBR/EVA blends was analyzed using a differential scanning calorimeter. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1556–1570, 2002     

Multicomponent latex IPN materials: 2. Damping and mechanical behavior

The integrals of the linear loss shear modulus vs. temperature (loss area, LA) and linear tan δ vs. temperature (tan δ area, TA) were characterized for various core/shell latex particles with synthetic rubber, poly(butadiene-stat-styrene) [P (Bd/S), 90/10], and interpenetrating polymer networks (IPN) as the cores. The IPN cores were composed of P(Bd/S) (T_g ≃ − 70°C) and an acrylate based copolymer (T_g around 10°C) for potential impact and damping improvement in thermoplastics. Poly(styrene-stat-acrylonitrile) (SAN, 72/28) was the shell polymer for all these polymers. Under the same loading, for both toughening and damping controls, among the IPN core/shell, blend of separate core/shell, and multilayered core/shell polymers, the IPN core/shell polymers were the best dampers. However, the other core/shell polymers also showed higher LA values than P(Bd/S)/SAN core/shell polymer. A comparison of LA values via a group contribution analysis method was made, the effect of particle morphology and phase continuity on damping being studied. Inverted core/shell latex particles (glassy polymer SAN was synthesized first) showed much higher LA and TA values than normal core/shell ones (rubbery polymer was synthesized first). Models for maximum LA and TA behavior are proposed. The damping property was essentially controlled by the phase miscibility and morphology of the core/shell latex particles. The LA values for each peak in these multiphase materials provided some indication of the several fractional phase volumes. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1501–1514, 1997     

The effects of rigid polystyrene particles on the glass transition characteristics and mechanical wave attenuation of styrene‐butadiene rubber: Particle size and acoustic mismatch

Glass transition characteristics and mechanical wave attenuation of the neat and filled styrene‐butadiene rubber (SBR) containing 10 wt % of rigid monosize polystyrene particles of various diameters from several hundred microns down to several tens of nanometers were investigated by dynamic mechanical thermal analysis, impedance tube, and ultrasonic spectroscopy. The results showed the matrix damping capacity and the breadth of glass transition increase by reducing the size of rigid particles due to the matrix‐particles interfacial area increase as the major governing parameter. Matrix glass transition broadening toward higher temperatures was attributed to the increased dynamic heterogeneity induced by fillers, whereas the damping capacity increase was assigned to contribution of interfacial friction loss mechanism. The proposed postulation was confirmed based on the calculated temperature distribution of the relaxing matrix volume fraction. Sound wave attenuation by the matrix and PS particles filled systems led to a broad absorption peak for the former and appearance of a secondary absorption peak at lower frequencies for the latter. Intensity of this secondary peak was highest for the system containing PS nanoparticles. Finally, ultrasonic attenuation enhanced by the PS particle size to wavelength ratio increase according to α_sca ～ (d/λ)^0.38 scaling law and declined by replacing the dense particles with larger hollow PS particles. Comparison of the normalized attenuation of the PS particle filled SBR in various mechanical wave attenuation regimes implied low sensitivity to particle size in vibration, mild differentiation in the sound, and finally severe differentiation in the ultrasound regimes. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 82–88, 2010     

Morphology and mechanical and viscoelastic properties of natural rubber and styrene butadiene rubber latex blends

The morphology and mechanical and viscoelastic properties of a series of blends of natural rubber (NR) and styrene butadiene rubber (SBR) latex blends were studied in the uncrosslinked and crosslinked state. The morphology of the NR/SBR blends was analyzed using a scanning electron microscope. The morphology of the blends indicated a two phase structure in which SBR is dispersed as domains in the continuous NR matrix when its content is less than 50%. A cocontinuous morphology was obtained at a 50/50 NR/SBR ratio and phase inversion was seen beyond 50% SBR when NR formed the dispersed phase. The mechanical properties of the blends were studied with special reference to the effect of the blend ratio, surface active agents, vulcanizing system, and time for prevulcanization. As the NR content and time of prevulcanization increased, the mechanical properties such as the tensile strength, modulus, elongation at break, and hardness increased. This was due to the increased degree of crosslinking that leads to the strengthening of the 3‐dimensional network. In most cases the tear strength values increased as the prevulcanization time increased. The mechanical data were compared with theoretical predictions. The effects of the blend ratio and prevulcanization on the dynamic mechanical properties of the blends were investigated at different temperatures and frequencies. All the blends showed two distinct glass‐transition temperatures, indicating that the system is immiscible. It was also found that the glass‐transition temperatures of vulcanized blends are higher than those of unvulcanized blends. The time–temperature superposition and Cole–Cole analysis were made to understand the phase behavior of the blends. The tensile and tear fracture surfaces were examined by a scanning electron microscope to gain an insight into the failure mechanism. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2189–2211, 2000     

Pressure–volume–temperature behavior of two polycyanurate networks

The pressure–volume–temperature (PVT) behavior was studied for two polycyanurate networks having different crosslink densities using a pressurizable dilatometer. The samples were studied at temperatures ranging from 60 to 180 °C and at pressures up to 170 MPa to yield PVT data in both rubbery and glassy states. The Tait equation is found to well describe the isobaric temperature scan and isothermal pressure scan data. The thermal expansion coefficients, instantaneous bulk moduli, and thermal pressure coefficients are extracted from the data and their dependence on crosslink density is examined. The time‐dependent viscoelastic bulk modulus (K(t)) is also calculated in the vicinity of the α‐relaxation from previously published pressure relaxation experimental data, and the strength and shape of the dispersion are found to be independent of crosslink density. The limiting bulk moduli depend strongly on temperature with those of the more loosely crosslinked sample being lower at a given temperature and pressure, although at T_g(P), the limiting moduli of the more loosely crosslinked sample are slightly higher than those of the more highly crosslinked sample. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Anisotropic properties of poly(ethylene terephthalate) by Brillouin spectroscopy: Anisotropic properties of oriented bulk and nanostructured poly(ethylene terephthalate) determined by Brillouin spectroscopy and birefringence experiments

Using Brillouin spectroscopy (BS), the tensor of the elastic constants of oriented poly(ethylene terephthalate) was determined for a variety of morphologies obtained by different uniaxial drawing procedures. The extreme values of the moduli along the drawing direction at frequencies of a few gigahertz were C₃₃ = 40 GPa and C₄₄ = 1.8 GPa. As a result of the invariants of the single‐phase aggregate model, the oriented state is dominated by the Reuss average even at extreme draw ratios and subsequent to a deformation‐induced crystallization. This is documented in both the BS orientation parameter and the BS mode numbers in comparison with birefringence. Additional spectral lines observed at draw ratios larger than 6 are discussed in relation to the formation of nanostructured phases. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1201–1213, 2002     

Temperature and crosslinking effects on the swelling of poly(isoprene) in isopiestic conditions

Isopiestic measurements of solvent uptake have been made in the synthetic isoprene/benzene system for both crosslinked and uncrosslinked polymers in order to revisit the question of the swelling activity parameter S. Both the nonzero value of S at zero swelling and the appearance of a peak in S vs. degree of swelling have been observed in some solvent/rubber pairs and we here investigate both the crosslink and temperature dependencies of these phenomena. The data analysis is an extension of prior work from this laboratory using continuum thermodynamics concepts and avoiding molecular models in an attempt to establish the fundamental phenomenology of the process and the validity or lack of validity of the hypothesis that the mixing and elastic contributions to the free energy of networks are separable. We present results from measurements in benzene vapors at temperatures between 10 and 55°C for an uncrosslinked rubber and rubbers crosslinked with 1, 5, 10, and 15 parts per hundred dicumyl peroxide. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 817–826, 1997