Effect of hydrodynamics on dynamics of phase separation in polystyrene/poly(vinyl methyl ether) blend

Polystyrene/poly(vinyl methyl ether) (PS/PVME) phase diagram was assessed by rheological tools and by on-line microscopy observations both under quiescent and shear flow conditions. Shear flow was found to induce both mixing and demixing of the mixture depending on the amplitude of the imposed shear rate. Viscoelastic properties of PS/PVME blends were also measured under steady shear flow near the phase separation temperature. At lower shear rate, flow enhances concentration fluctuation and induces phase segregation. At high shear rate, flow suppresses fluctuations and the polymer mixture keeps its miscible state. Several rheological signatures of phase transition were found. In steady shear flow, a secondary plateau in viscosity was observed when the temperature was close to T_s whereas, at the start-up shear flow, transient shear stress showed a second overshoot after a few minutes of shearing.     

Phase separation in polymer blend thin films studied by differential AC chip calorimetry

AC chip calorimetry is used to study the phase separation behavior of 100 nm thin poly(vinyl methyl ether)/poly(styrene) (PVME/PS) blend films. Using the on-chip heaters, very short (10 ms-10 s) temperature jumps into the temperature window of phase separation are applied, simulating laser heating induced patterning. These temperature pulses produce a measurable shift in the glass transition temperature, evidencing phase separation. The effect of pulse length and height on phase separation can be studied. The thus phase separated PVME/PS thin films remix rapidly, in contrast with measurements in bulk. AC chip calorimetry seems to be a more sensitive technique than atomic force microscopy to detect the early stages of phase separation in polymer blend thin films.     

Mechanical properties of HDPE/(PEC/PS)/SEBS blends

Various amounts of a styrene-butadiene-based triblock copolymer (SEBS) was used to compatibilize immiscible blends of high density polyethylene (HDPE) and an amorphous glassy phase consisting of either pure polystyrene (PS) or a miscible blend of PS and a polyether copolymer (PEC). PEC is structurally similar to poly(2,6-dimethyl-1,4-phenylene oxide) (PPO). Mechanical properties were determined for blends fabricated by injection and compression molding. The inherently brittle two-phase HDPE/(PEC/PS) blends show significant increases in ductility and impact strength resulting from addition of SEBS. These improvements coincide with a slight loss in modulus and yield strength. If the amount of HDPE and SEBS is held constant, impact strength and ductility increase with the amount of PEC in the glassy phase. These trends evidently result from the added ductility of glassy phases containing PEC and perhaps from better interfacial adhesion in blends after adding SEBS. The latter stems from the thermodynamic miscibility between PEC and PS endblocks of SEBS which provide an enthalpic driving force for compatibilization. Differences between the properties of compression and injection-molded blends can be attributed to the degree of crystallinity and orientation induced during molding.     

Composition fluctuations before dewetting in polystyrene/poly(vinyl methyl ether) blend thin films

We report structural development in blend thin films of deuterated polystyrene (dPS) and poly(vinyl methyl ether) (PVME) below 200 nm in two phase region during the incubation period before dewetting using neutron reflectivity (NR) and atomic force microscopy (AFM). As was predicted by the former optical microscope (OM) and small-angle light scattering (LS) measurements on blend thin films of protonated PS and PVME [Ogawa H, Kanaya T, Nishida K, Matsuba G. Polymer 2008;40:254–62.], the NR results clearly showed that the tri-layer structure consisting of the surface PVME layer, the middle blend layer and the bottom PVME layer was formed in the one phase region. After the temperature jump into the two phase region, it was found that the phase separation of the middle blend layer proceeded in the depth direction during the incubation period before dewetting, suggesting that the dewetting was induced by the composition fluctuations during the incubation period.     

Construction of the state diagram of polymer blend thin films using differential AC chip calorimetry

The phase separation behavior of polymer blend thin films of 100-150 nm was studied using differential AC Chip calorimetry. By taking advantage of the low sensor and sample mass inherent to chip calorimetry, a new methodology based on temperature jumps was developed. This methodology allowed the construction of the state diagram of polymer blend thin films as evidenced for two model systems (PVME/PS and PVME/Phenoxy) displaying a lower critical solution temperature behavior.The state diagram in thin films was compared to the one obtained in bulk using Modulated Temperature DSC. In comparison with bulk, a lower phase separation temperature and a broadening of the homogeneous glass transition temperatures is observed for both model systems. This might be an indication of a surface induced ‘destabilization’ by composition gradients which are not present in bulk.     

Ternary miscibility in blends of three polymers with balanced binary interactions

This study demonstrates and discusses ternary miscibility in a three‐polymer blend system based on balanced binary interactions. A truly miscible ternary blend comprising poly(ε‐caprolactone) (PCL), poly(benzyl methacrylate) (PBzMA), and poly(vinyl methyl ether) (PVME), was discovered and reported. Miscibility with phase homogeneity (excluding the PCL crystalline domain) in a wide composition range has been demonstrated using criteria of thermal transition behavior, cloud point, and microscopy characterization. At ambient temperature, the three‐polymer ternary system is completely miscible within the entire composition range (i.e., no immiscibility loop). However, at slightly elevated temperatures above the ambient. phase separation readily occurred in this originally miscible ternary blend. A quite low “lower critical solution temperature” (LCST) near 75°C was found for the ternary blend, which is much lower than any of those for the binary pairs. Balanced interactions with no offsetting Δχ among the three binary pairs were a key factor leading to a ternary miscible system.     

The effect of incorporation of POSS units on polymer blend compatibility

In this work, the compatibility of poly(methyl methacrylate) (PMMA) and polystyrene (PS) polymers with their polyhedral oligomeric silsesquioxane (POSS) copolymers combined by solution blending is investigated, to determine the effect of incorporation of the POSS unit on polymer compatibility. The morphology of these tethered POSS copolymer/polymer blends was studied by electron microscopy, thermal analysis, and density. Although the basic PS/PMMA blend was clearly immiscible, it was also found that the incorporation of POSS into the PS chain led to incompatibility when the POSScoPS copolymer was blended with PS homopolymer. However, conversely, in the case where the POSS moiety was included as part of a copolymer with PMMA, the copolymer was miscible with the PMMA homopolymer. The presence of isobutyl units on the corners of POSS cage is clearly sufficient to encourage miscibility with PMMA. Interestingly, blends of the two different POSS copolymers led to an immiscible structure, despite having the common POSS units, the interactions between the POSS moieties clearly not being sufficient to drive compatibility. The POSS copolymers have also been used as interfacial agents in immiscible PS and PMMA blend, and it has been found that the appearance of the interface bonding is improved, although the phase morphology is only slightly changed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Correlating miscibility of PVC/PMMA blend with polymer chain orientation

Blends of poly (vinyl chloride) (PVC) and poly (methyl methacrylate) (PMMA) with varying concentrations of the polymers were prepared in a film form by standard solution casting method, using methyl ethyl ketone (MEK) as a common solvent. The miscibility of the blend was studied by dynamic mechanical analysis. The chain orientation behaviors of PVC and PMMA in the stretched blend films were studied by infrared dichroism method. Up to 60 wt % PVC concentration in the blend, PVC showed negative values for orientation function whereas PMMA showed independent positive values for its orientation function. On further increasing PVC concentration in the blend, the orientation function of PVC flipped to positive values, and both PVC and PMMA showed same magnitude and trend in orientation behavior. The chain orientation behavior of individual polymers in the immiscible compositions of the blend was observed to be independent, while there was a high degree of cooperation for chain orientation in the miscible composition. Change in the miscibility of the blend was simultaneously accompanied by conformational changes in PVC. The change in orientation behavior is interpreted in terms of curling of polymer chains in the immiscible phase. The polymer chain curling hypothesis used here is applicable independent of the type of polymers in the blend. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 624–630, 2006     

Excimer fluorescence study on the miscibility of poly(vinyl methyl ether) and styrene-butadiene-styrene triblock copolymer

The excimer fluorescence of a triblock copolymer, styrene-butadiene-styrene (SBS) containing 48 wt% polystyrene was used to investigate its miscibility with poly(vinyl methyl ether) (PVME). The excimer-to-monomer emission intensity ratio I_M/I_E can be used as a sensitive probe to determine the miscibility level in SBS/PVME blends: I_M/I_E is a function of PVME concentration, and reaches a maximum when the blend contains 60% PVME. The cloud point curve determined by light scattering shows a pseudo upper critical solution temperature diagram, which can be attributed to the effect of PB segments in SBS. The thermally induced phase separation of SBS/PVME blends can be observed by measuring I_M/I_E, and the phase dissolution process was followed by measuring I_M/I_E at different times.     

Rheo-Optical behavior of binary polymer blends: The effect of simple shear flow on phase behavior

The phase behavior of polymer blends under simple shear flow has been studied using a custom-designed rheo-optical system consisting of a two-dimensional small-angle light scattering (SALS) device incorporated into a conventional rheometer. Two-dimensional SALS images were gathered for model polymer blend systems with different quiescent phase behavior: polystyrene/polyisobutylene (PS/PIB) that exhibits upper critical solution temperature phase behavior and polystyrene/poly(vinyl methyl ether) (PS/PVME) that shows lower critical solution temperature phase behavior. For the PS/PIB blend, shear-induced phase mixing occurred at a critical shear rate. Below that critical shear rate, the dispersed phase was highly elongated parallel to the flow direction. For PS/PVME blends, a streak scattering pattern was observed even though the sample became optically clear after shearing. We observed, apparently for the first time, the development of a bright-streak pattern from a transient dark-streak pattern for a polymer blend system under shear. Rheo-microscopy studies revealed an intriguing wave pattern that developed coincident with the observation of a streak pattern by SALS. The relationship between the two phenomena has not yet been established.     

Elongational viscosity for miscible and immiscible polymer blends. I. PMMA and AS with similar elongational viscosity

The effects of miscibility and blend ratio on uniaxial elongational viscosity of polymer blends were studied by preparing miscible and immiscible samples at the same composition by using poly(methyl methacrylate) (PMMA) and poly(acrylonitrile-co-styrene) (AS). Miscible polymer blend samples for the elongational viscosity measurement were prepared by using three steps: solvent blends, cast film, and hot press. A phase diagram of blend samples was made by visual observation of cloudiness. Immiscible blend samples were prepared by maintaining the prepared miscible samples at 200°C, which is higher than cloud points using a LCST (lower critical solution temperature) phase diagram. The phase structure of immiscible blends was observed by an optical microscope. The elongational viscosity of all samples was measured at 145°C, which is lower than the cloud-point temperature at all blend ratios. The elongational viscosity of PMMA and AS was similar to each other. The strain-hardening property of miscible blends in the elongational viscosity was only slightly influenced by the blend ratio, and this was also the case with immiscible blends. The strain-hardening property was only slightly influenced, whether it was miscible or immiscible at each blend ratio. Polydispersity in molecular weight for blend samples was not changed by GPC (gel permeation chromatography) analysis. Almost no change in the polydispersity of the molecular weight for blends and the similarity of elongational viscosity between PMMA and AS resulted in little influence of the blend ratio and miscibility on the strain-hardening property. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 757–766, 1999     

Synthesis and morphological studies of polyisoprene-block-polystyrene-block-poly(vinyl methyl ether) triblock terpolymer

The triblock terpolymer (PI-b-PS-b-PVME) consisting of polyisoprene (PI), polystyrene (PS) and poly(vinyl methyl ether) (PVME) was synthesized by coupling reaction between living PI-b-PS anion and end-chlorinated PVME prepared via living cationic polymerization. This polymer is an amphiphilic block polymer and unique in a sense that it exhibits complex phase behavior because PS and PVME have a lower critical solution temperature (LCST)-type phase diagram while PI and PS (or PVME) have an UCST-type phase diagram. This unique architecture would result in a step-wise microphase separation to form a three-phase microdomain structure. It was observed by transmission electron microscopy with ultrathin sections that the toluene-cast film of PI-b-PS-b-PVME has a two-phase lamellar structure consisting of PI microdomains and mixed PS/PVME microdomains. Applying a drop of water onto the ultrathin sections induced further microphase separation between PS and PVME within the lamellar microdomains resulting in the three-phase structure. Water is a selective solvent for PVME and might have lowered the order-disorder temperature between PS and PVME. This step-wise microphase separation may be a new technique to control microphase-separated structures in triblock terpolymers.     

Effect of shear memory on the coarsening behaviour of polystyrene and poly(vinyl methyl ether) blend

The effect of shear memory on the coarsening behaviour of polystyrene/poly(vinyl methyl ether) (PS/PVME) blend which shows a typical lower critical solution temperature (LCST)-type phase diagram has been thoroughly investigated for the near critical composition (PS/PVME=30/70) using a time-resolved light scattering technique. The measurements were carried out at 135 °C (20 °C above the quiescent cloud point) at two different directions, parallel and normal to the direction of flow. Different shear memories were generated in the melt using a simple shear apparatus of parallel plate geometry. The coarsening process was influenced to a great extent by the shear history of the blend over the time scale of the measurement. The average domain size of the dispersed particles obtained from the analysis of the light scattering data on the basis of Deby Bueche theory was found to be shear memory dependent. The coarsening process was elevated and suppressed at low and high shear memory, respectively. This behaviour was attributed to the shift of the cloud point observed under same values of shear rates. In addition, the coarsening behaviour of this blend was found to be flow direction independent due to the very high viscosity ratio of the blend, which led to in turn rather circular domains of PS in PVME matrix without any elongation or orientation in the direction of flow. Furthermore, the coarsening process for all the measured samples was followed the general power low, regardless the shear history and the flow direction of the blends. This result indicated that; the shear could only retard or elevate the rate of domain growth without any effect on the coarsening mechanism.     

Effects of miscibility and viscoelasticity on shear creep resistance of natural‐rubber‐based pressure‐sensitive adhesives

Natural rubber (NR) was blended in various ratios with 29 kinds of tackifier resins. Miscibilities of all the blend systems were illustrated as phase diagrams. From these blend systems, we selected 8 systems having typical phase diagrams (completely miscible, immiscible, lower critical solution temperature [LCST] types) and carried out measurements of shear creep resistance (holding power). Holding time was recorded as required time for the pressure‐sensitive adhesive (PSA) tape under shear load to completely slip away from the adherend. Holding time of miscible PSA systems tended to decrease as the tackifier content increased. This is attributable to a decrease in plateau modulus of the PSA with increasing tackifier content. There was rather large difference in holding time by tackifier among the miscible PSA systems; the reason for this is also considered to be a difference in plateau modulus. Holding time of an immiscible PSA system scarcely changed by tackifier content. But in another immiscible system, holding time tended to increase with increasing tackifier content. In fact, in the case of immiscible PSAs, the effect of tackifier content on holding time was different from tackifier to tackifier. This may be caused by difference in extent of phase separation. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1535–1545, 2000     

Effect of thermal history on the molecular orientation in polystyrene/poly(vinyl methyl ether) blends

The effect of thermal history on the orientation and relaxation behavior of blends of polystyrene with poly(vinyl methyl ether) (PS/PVME) has been studied using polarization modulation infrared linear dichroism (PM-IRLD) and differential scanning calorimetry (DSC). DSC shows that miscible PS/PVME blends containing 70% of PS can be physically aged at temperatures above their mean glass transition temperature (T_g). PM-IRLD measurements reveal that both components become more oriented upon stretching at 51 °C (8 °C above T_g) if the sample is aged at the deformation temperature prior to stretching. Room-temperature aging can also lead to an increased orientation if the heating time at 51 °C is kept short. Moreover, PS and PVME develop a larger orientation in phase-separated blends than in miscible ones, and their relaxation is hindered. The results have been interpreted considering the morphology of the samples, including the presence of concentration fluctuations in miscible blends, and the effect of the local environment on the rigidity of the chains.     

Refractive index crossover and the phase diagram of an iPP/PEOc blend

The phase diagram of an isotactic polypropylene/poly(ethylene-octene) copolymer (iPP/PEOc) blend system was investigated using phase contrast optical microscopy, laser light scattering and differential scanning calorimetry (DSC). The sample goes through immiscible (opaque) region to transparent region (seemingly miscible) and back to immiscible (opaque) again as temperature increases through 300 °C region. But it turns out that this is not a real one phase region. It is caused by a temperature dependent inversion of refractive indices between the two component polymers, which can be easily misinterpreted as a miscible region between an upper critical solution temperature (UCST) state and a lower critical solution temperature (LCST) state. With a proper interpretation and analysis of this refractive index inversion, the UCST phase diagram of this iPP/PEOc blend system has been obtained.     

Effects of miscibility on probe tack of natural-rubber-based pressure-sensitive adhesives

Natural rubber (NR) was blended in various ratios with 29 kinds of tackifier resins, which were prepared from rosin, terpenes, and petroleum. Miscibilities of all the blend systems were illustrated as phase diagrams in our previous articles. From these blend systems, we selected 7 systems having typical phase diagrams [completely miscible, completely immiscible, and lower critical solution temperature (LCST) types] and carried out measurements of probe tack. Probe tack values were measured at various rates of separation and temperatures to obtain master curves. In the case of miscible pressure sensitive adhesives (PSAs) at the condition of measurement, the peak position in the master curve of probe tack shifted to the lower velocity (higher temperature) as the tackifier content increased. On the contrary, immiscible PSAs had much smaller probe tack values than miscible ones and did not give manifest shift of peaks. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 771–776, 1998     

Comparison of morphologies and mechanical properties of crosslinked epoxies modified by polystyrene and poly(methyl methacrylate)) or by the corresponding block copolymer polystyrene-b-poly(methyl methacrylate)

Polystyrene (PS, M_n=28,400, PI=1.07), poly(methyl methacrylate) (PMMA, M_n=88,600, PI=1.03), and PS (50,000)-b-PMMA (54,000) (PI=1.04), were used as modifiers of an epoxy formulation based on diglycidyl ether of bisphenol A (DGEBA) and m-xylylene diamine (MXDA). Both PS and PMMA were initially miscible in the stoichiometric mixture of DGEBA and MXDA at 80 °C, but were phase separated in the course of polymerization. Solutions containing 5 wt% of each one of both linear polymers exhibited a double phase separation. A PS-rich phase was segregated at a conversion close to 0.02 and a PMMA rich phase was phase separated at a conversion close to 0.2. Final morphologies, observed by scanning electron microscopy (SEM), consisted on a separate dispersion of PS and PMMA domains. A completely different morphology was observed when employing 10 wt% of PS-b-PMMA as modifier. PS blocks with M_n=50,000 were not soluble in the initial formulation. However, they were dispersed as micelles stabilized by the miscible PMMA blocks, leading to a transparent solution up to the conversion where PMMA blocks began to phase separate. A coalescence of the micellar structure into a continuous thermoplastic phase percolating the epoxy matrix was observed. The elastic modulus and yield stress of the cured blend modified by both PS and PMMA were 2.64 GPa and 97.2 MPa, respectively. For the blend modified by an equivalent amount of block copolymer these values were reduced to 2.14 GPa and 90.0 MPa. Therefore, using a block copolymer instead of the mixture of individual homopolymers and selecting an appropriate epoxy-amine formulation to provoke phase separation of the miscible block well before gelation, enables to transform a micellar structure into a bicontinuous thermoplastic/thermoset structure that exhibits the desired decrease in yield stress necessary for toughening purposes.     

Physical aging in the mechanical properties of miscible polymer blends

Changes in mechanical properties during isothermal physical aging were investigated for three miscible blends: polystyrene (PS)/poly(2,6-dimethyl 1,4-phenylene oxide) (PPO), PS/poly(vinylmethylether) (PVME), and poly(methylmethacrylate) (PMMA)/poly(ethyleneoxide) (PEO). The kinetics of stress relaxation was investigated for the blend, dilute in one component, and compared with that of the neat major component at equal temperature distances, Tg-T, from the midpoint glass transition temperature. It is demonstrated that for all three blends, the mean stress relaxation time (τ) does not scale with Tg-T. For PS/PPO and PS/PVME blends, the stress relaxation rates are faster compared to neat PS; for PMMA/PEO, they are slower than for neat PMMA. Two effects appear to be important in contributing to this discrepancy. First, addition of the second component produces a change in the packing density of the blend: less dense for PS/PPO and PS/PVME; more dense for PMMA/PEO. Comparison of average free volume hole sizes and fractional free volumes measured via orthopositronium annihilation lifetime measurements for all three blends versus the pure constituents are qualitatively consistent with this interpretation. Second, because of the presence of concentration fluctuations in the blend, it is expected that the initial stress decay is dominated by regions enriched in the more mobile component. From observations of the change in width of the stress relaxation time distribution, this effect appears to be particularly significant in the PS/PVME blend. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 483–496, 1997     

Effect of selective localization of cellulose nanowhiskers on viscoelastic phase separation

Viscoelastic phase separation (VPS) is a fundamental physical phenomenon that creates percolated network structure in dynamically asymmetric mixtures. The object of this study was to investigate the effect of rod shape nanoparticles with different surface chemistries on VPS in the polystyrene/poly(vinyl methyl ether), PS/PVME, blend. For this purpose, hydrophilic (CNWs) and hydrophobic (M‐CNWs) cellulose nanowhiskers (CNWs) were prepared to be used as nanorods. Rheological measurments were employed to investigate the effect of nanowhiskers on phase separation temperature, kinetics of phase separation, and dynamic asymmetry. The evolution of morphology during the phase separation at a fixed quench depth was assessed using polarized optical microscopy. The nanowhiskers were effective in decreasing the correlation length, which slowed down the phase separation. CNWs self‐assembled into the PVME‐rich phase during the phase separation, which led to a decrease in the dynamic asymmetry and beyond a critical volume fraction of CNWs, the VPS mechanism changed to spinodal decomposition (SD). However, in the presence of M‐CNW, the localization of M‐CNWs into the PS‐rich phase enhanced the dynamic asymmetry and at 2 vol% M‐CNWs, the induced PS‐rich network by VPS was arrested. The linear and non‐linear viscoelastic behavior of the samples were studied as well. POLYM. ENG. SCI., 58:928–942, 2018. © 2017 Society of Plastics Engineers