Miscibility and mechanical properties of polymer blends

The tensile properties of 16 blends prepared from 12 different polymers were investigated in the whole composition range. The composition dependence of Young's modulus has shown less, while that of the yield and ultimate properties exhibited more significant variations with miscibility. The quantitative evaluation of the yield stress and tensile strength data resulted in a parameter, which could be related to the interfacial tension and miscibility.     

Transitions of tethered polymer chains: a simulation study with the bond fluctuation lattice model

A polymer chain tethered to a surface may be compact or extended, adsorbed or desorbed, depending on interactions with the surface and the surrounding solvent. This leads to a rich phase diagram with a variety of transitions. To investigate these transitions we have performed Monte Carlo simulations of a bond fluctuation model with Wang-Landau and umbrella sampling algorithms in a two-dimensional state space. The simulations' density-of-states results have been evaluated for interaction parameters spanning the range from good- to poor-solvent conditions and from repulsive to strongly attractive surfaces. In this work, we describe the simulation method and present results for the overall phase behavior and for some of the transitions. For adsorption in good solvent, we compare with Metropolis Monte Carlo data for the same model and find good agreement between the results. For the collapse transition, which occurs when the solvent quality changes from good to poor, we consider two situations corresponding to three-dimensional (hard surface) and two-dimensional (very attractive surface) chain conformations, respectively. For the hard surface, we compare tethered chains with free chains and find very similar behavior for both types of chains. For the very attractive surface, we find the two-dimensional chain collapse to be a two-step transition with the same sequence of transitions that is observed for three-dimensional chains: a coil-globule transition that changes the overall chain size is followed by a local rearrangement of chain segments.     

Miscibility and deformation behavior in some thermoplastic polymer blends containing poly(styrene-co-acrylonitrile)

Miscibility in blends of poly(styrene-co-acrylonitrile) (PSAN) with several other polymeric components has been investigated over a range of compositions by means of thermal analysis and transmission electron microscopy. Systems in vestigated were (i) PSAN/polycarbonate (PC), (ii) PSAN/styrene-maleic anhydride-methyl methacrylate terpolymer (S/MA/MM), (iii) PSAN/polynorbornene nitrile (PNN), and (iv) PSAN//S/MA/MM//PC. PSAN/PC was demonstrated to be partially miscible in all proportions over the PSAN copolymer composition range 23–70 wt % AN, while the miscibility or lack thereof of PSAN//S/MA/MM depended on the relative AN and MA contents of the PSAN and S/MA/MM, respectively. In contrast, PSAN/PNN was found to be immiscible in all proporations, while the system PSAN//S/MA/MM//PC was shown to be partially miscible. Deformation studies performed on rubber-modified versions of these blends defined deformation mode and microstructural deformation behavior. Dual extensometer tensile testing yielded relative contributions of crazing and of plastic flow, which correlated both with blend composition and with toughness. TEM observations of deformed specimens indicated a deformation process in the multiphase matrix blends consisting of craze initiation and propagation in the rubber-containing phase, craze arresting in the ductile second matrix phase, and coordinated extensive deformation of the matrix phases and of the rubber particles, where the ability to support the latter coordinated forms of deformation were observed to increase with increasing proportion of plastically deforming phase.     

Miscibility behavior of di(ethyl-2 hexyl) phthalate in binary and ternary chlorinated polymer blends

The miscibility behavior of ternary blends made by the addition of di(ethyl-2 hexyl) phthalate (DOP) to a mixture of chlorinated polymers was investigated by differential scanning calorimetry. Two chlorinated polymer mixtures were selected: polyvinyl chloride (PVC) with a chlorinated polyethylene containing 48 wt% Cl (CPE48), and PVC with a chlorinated PVC containing 67 wt% Cl (CPVC67). Each binary DOP/chlorinated polymer pair is miscible whereas PVC/CPE48 and PVC/CPVC67 blends are immiscible. DOP/CPE48/PVC and DOP/PVC/CPVC67 ternary blends containing, respectively, more than 55 and 20% DOP exhibit a single glass transition temperature (T_g). The spinodal between the one-T_g zone and the two-T_g zone is symmetrical in the two cases. At high DOP concentrations, a quantitative analysis of the results leads to the conclusion of the presence of a true ternary phase. At low DOP concentrations where two T_gs are observed, the DOP is distributed equally between the two chlorinated polymers forming, in the DOP/CPE48/PVC case for instance, two binary DOP/CPE48 and DOP/PVC phases. The broad immiscibility zone observed in the DOP/CPE48/PVC ternary blend as compared to the DOP/PVC/CPVC67 blend appears to be mainly caused by the high molecular weight of CPE48, as compared with PVC and CPVC67. © 1994 John Wiley & Sons. Inc.     

Selective laser sintering of polymer blends: Bulk properties and process behavior

Physically mixed powderous polymer blends consisting of at least two different thermoplastic materials with complementary properties could allow the successful fabrication of components with tailored and graded properties. In this work, powderous polymer blends of the partially miscible and chemically reactive blend system PBT/PC were produced from wet grinded powders at different weight ratios of 90/10, 80/20, 70/30 and 60/40, respectively. The PBT/PC is used as a model system for a blend with a semi-crystalline and amorphous component, while being relevant for industrial use, such as automotive applications. Before the implementation into the selective laser sintering process (SLS), the bulk properties of the powders were analyzed. The quadratic monolayer test specimens were generated with different energy densities by variating the laser power. The specimens' geometrical and microstructural properties were studied. The investigations showed that an improvement of geometric properties in terms of layer development can be achieved by increasing the PC content and that it is possible to generate polymer blends with matrix and dispersed phase from PBT/PC blends.     

Miscibility and crystallization behavior of PBT/epoxy blends

The miscibility and the isothermal crystallization kinetics for PBT/Epoxy blends have been studied by using differential scanning calorimetry, and several kinetic analyses have been used to describe the crystallization process. The Avrami exponents n were obtained for PBT/Epoxy blends. An addition of small amount of epoxy resin (3%) leads to an increase in the number of effective nuclei, thus resulting in an increase in crystallization rate and a stronger trend of instantaneous three‐dimensional growth. For isothermal crystallization, crystallization parameter analysis showed that epoxy particles could act as effective nucleating agents, accelerating the crystallization of PBT component in the PBT/Epoxy blends. The Lauritzen–Hoffman equation for DSC isothermal crystallization data revealed that PBT/Epoxy 97/3 had lower nucleation constant K_g than 100/0, 93/7, and 90/10 PBT/Epoxy blends. Analysis of the crystallization data of PBT/Epoxy blends showed that crystallization occurs in regime II. The fold surface free energy, σ_e = 101.7–58.0 × 10^?3 J/m², and work of chain folding, q = 5.79–3.30 kcal/mol, were determined. The equilibrium melting point depressions of PBT/Epoxy blends were observed and the Flory–Huggins interaction parameters were obtained. It indicated that these blends were thermodynamically miscible in the melt. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1320–1330, 2006     

Miscibility and phase separation in polymer blends studied by laser light scattering

In this paper major emphasis has been placed on the phase behavior of miscible polymer blends, especially on blends containing random copolymers. Blends containing random copolymers generally tend to phase separation at elevated temperatures (LCST behavior). Experimental determination of miscibility areas as a function of temperature and copolymer composition by laser light scattering provides the interaction parameters necessary for theoretical explanations and predictions of various phase separation phenomena. Just above the LCST polymer blends exhibit regular highly interconnected two-phase morphologies. The rate of decay of these structures is estimated. The phase separation kinetics can be pursued by laser light scattering and is discussed in terms of CAHN's linearized theory. It can be shown that the linear theory adequately describes the early stage of phase decomposition. The linear theory is also applicable to the reverse phenomenon, the phase dissolution below LCST. unlike the case of phase separation the diffusion-controlled regime is that in the late stage of phase dissolution.     

Local and chain dynamics in miscible polymer blends: A Monte Carlo simulation study

Local chain structure and local environment play an important role in the dynamics of polymer chains in miscible blends. In general, the friction coefficients that describe the segmental dynamics of the two components in a blend differ from each other and from those of the pure melts. In this work, we investigate polymer blend dynamics with Monte Carlo simulations of a generalized bond fluctuation model, where differences in the interaction energies between nonbonded nearest neighbors distinguish the two components of a blend. Simulations employing only local moves and respecting a no bond crossing condition were carried out for blends with a range of compositions, densities, and chain lengths. The blends investigated here have long time dynamics in the crossover region between Rouse and entangled behavior. In order to investigate the scaling of the self-diffusion coefficients, characteristic chain lengths N(c) are calculated from the packing length of the chains. These are combined with a local mobility mu determined from the acceptance rate and the effective bond length to yield characteristic self-diffusion coefficients D(c)=muN(c). We find that the data for both melts and blends collapse onto a common line in a graph of reduced diffusion coefficients DD(c) as a function of reduced chain length NN(c). The composition dependence of dynamic properties is investigated in detail for melts and blends with chains of length N=20 at three different densities. For these blends, we calculate friction coefficients from the local mobilities and consider their composition and pressure dependence. The friction coefficients determined in this way show many of the characteristics observed in experiments on miscible blends.     

Miscibility and crystallization behavior of solution-blended PEEK/PI blends

Miscibility and crystallization behavior of solution-blended poly(ether ether ketone)/polyimide (PEEK/PI) blends were investigated by using DSC, optical microscopy and SAXS methods. Two kinds of PIs, YS-30 and PEI-E, which consist of the same diamine but different dianhydrides, were used in this work. The experimental results show that blends of PEEK/YS-30 are miscible over the entire composition range, as all the blends of different compositions exhibit a single glass transition temperature. The crystallization of PEEK was hindered by YS-30 in PEEK/YS-30 blends, of which the dominant morphology is interlamellar. On the other hand, blends of PEEK/PEI-E are immiscible, and the effect of PEI-E on the crystallization behavior of PEEK is weak. The crystallinity of PEEK in the isothermally crystallized PEEK/YS-30 blend specimens decreases with the increase in PI content. But the crystallinity of PEEK in the annealed samples almost keeps unchanged and reaches its maximum value, which is more than 50%. The spherulitic texture of the blends depends on both the blend composition and the molecular structure of the PIs used. The more PI added, the more imperfect the crystalline structure of PEEK. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2267–2274, 1998     

Cooperative chain relaxation in miscible polymer blends

Orientation relaxation of dissimilar chains in the molten miscible blends, poly(methyl methacrylate)/poly(vinylidene fluoride) and poly(methyl methacrylate)/poly(vinylidene fluoride-co-trifluoroethylene), were investigated by measuring (1) the change of infrared dichroic ratio with time after the uniaxial stretching of film specimens, (2) the shear stress relaxation spectrum, and (3) birefringence relaxation in shear. The dissimilar polymers showed an identical time variation of the normalized Hermans orientation function. The blend showed a relaxation spectrum with a single characteristic relaxation time τ_c, depending on the blend composition. The birefringence relaxed monotonically, remaining positive. These results suggest that the dissimilar polymers do not relax independently but cooperatively. This behavior may be induced by a constraint due to the specific interactions between the dissimilar polymers, e.g., weak hydrogen bonding. For the cooperative chain relaxation, a third power relationship was found; τ_c/τ_e vprop; (M/M_e),³ where τ_e and M_e are the relaxation time and molecular weight of entanglement strand, respectively, and M is the number average molecular weight in the blend.     

Universal properties of a single polymer chain in slit: Scaling versus molecular dynamics simulations

We revisit the classical problem of a polymer confined in a slit in both of its static and dynamic aspects. We confirm a number of well known scaling predictions and analyze their range of validity by means of comprehensive molecular dynamics simulations using a coarse-grained bead-spring model of a flexible polymer chain. The normal and parallel components of the average end-to-end distance, mean radius of gyration and their distributions, the density profile, the force exerted on the slit walls, and the local bond orientation characteristics are obtained in slits of width D=4/10 (in units of the bead diameter) and for chain lengths N=50/300. We demonstrate that a wide range of static chain properties in normal direction can be described quantitatively by analytic model-independent expressions in perfect agreement with computer experiment. In particular, the observed profile of confinement-induced bond orientation is shown to closely match theory predictions. The anisotropy of confinement is found to be manifested most dramatically in the dynamic behavior of the polymer chain. We examine the relation between characteristic times for translational diffusion and lateral relaxation. It is demonstrated that the scaling predictions for lateral and normal relaxation times are in good agreement with our observations. A novel feature is the observed coupling of normal and lateral modes with two vastly different relaxation times. We show that the impact of grafting on lateral relaxation is equivalent to doubling the chain length.     

Small-angle neutron scattering study on the miscibility and concentration fluctuation of hydrogen-bonded polymer blends

Thermal concentration fluctuation in the blends of deuterated poly(ethylene oxide) (dPEO) and poly(vinyl acetate-co-vinyl alcohol) [P(VAc-VOH)] with various VOH contents f_OH were examined by small angle neutron scattering techniques at a fixed blend composition, dPEO/P(VAc-VOH) = 20/80 which is close to the critical composition. Blends at the highest f_OH (=0.35) showed a non-Lorentzian scattering profile: specifically the scattering intensities at the low q (angle) region were suppressed compared to those expected from the random phase approximation (RPA) theory. However, for the blends at lower f_OH (≤0.28), the profiles could be represented by the RPA. Using the RPA we determined effective values of the Flory-Huggins interaction parameter χ_eff as a function of f_OH (=0–0.28). The χ_eff showed the minimum around f_OH = 0.1–0.18 meaning the highest miscibility of the blend at these f_OH. On the basis of the random copolymer theory, we evaluated the three interaction parameters χ_Ac–EO, χ_EO–OH, and χ_Ac–OH separately from the χ_eff(f_OH) and found the order of magnitude; χ_Ac–EO < 0 < χ_EO–OH < χ_Ac–OH. The largest positive χ_Ac–OH showing intrachain interaction in the P(VAc-VOH) copolymer was concluded to be the origin of the enhanced miscibility at around f_OH = 0.1–0.18. On the basis of the Coleman and Painter's theory, the effects of hydrogen bonding on these three χ_A-B were discussed. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2556–2565, 2008     

Coil-globule transition of a single short polymer chain: an exact enumeration study

The authors present an exact enumeration study of short self-avoiding walks in two as well as in three dimensions that addresses the question, "what is the shortest walk for which the existence of all the three scaling regimes--coil, globule, and the theta--could be demonstrated." Even though they could easily demonstrate the coil and the globule phase from free energy considerations, they could demonstrate the existence of a theta temperature only by using a scaling form for the distribution of gyration radius. That even such short walks have a scaling behavior is an unexpected result of this work.     

Coil-globule transition: Self-assembly of a single polymer chain

The coil collapse problem is of interest not only because it represents the simplest model of protein folding, but also because of its fundamental importance as related to polymer nanostructures and fractionation. It is extremely difficult to observe the coil-to-globule transition experimentally because at finite concentrations in a poor solvent, the macromolecules tend to aggregate due to phase separation when the collapsed state is being achieved. In the mid-1980s, two-stage kinetics of a single-chain collapse was proposed theoretically.^1,2 The first successful experimental observation of a two-stage coil-to-globule transition was achieved by quenching a dilute solution of polystyrene (PS) in cyclohexane.³ By using a thinnest capillary tube cell with a wall thickness of 0.01 mm and a diameter of 5 mm for dynamic light scattering, two relaxation times, τ_crum for the crumpled globule state and τ_eq for the compact globule state, were determined⁴ for the first time. The relaxation times were much slower than expected. From the size of the crumpled globule and that of the compact globule and by assuming the intraglobular density to be uniform, the volume fraction of the PS chain in the crumpled globule state, ϕ_crum, and that in the compact globule state, ϕ_comp, can be estimated, with ϕ_crum = 0.02 and ϕ_comp ∼ 0.24-0.4 at 28°C for polystyrene in cyclohexane. The results imply that a single-chain globule contains a large amount of solvent. It should also be noted that ϕ_comp is temperature dependent, i.e., one would have to go to hypothetically low temperatures in order to squeeze out all the solvent (cyclohexane) in the compact PS globule. The single-chain coil collapse state could be achieved under equilibrium conditions by using a high molecular weight, M_w ∼ 1.08 × 10⁷ g/mol; M_w/M_n < 1.06) poly(N-isopropylacrylamide) (PNIPAM) in water,<⁵ even though the ten million molecular weight for PNIPAM was substantially lower than that for polystyrene (M_w ∼ 50 × 10⁶ g/mole).⁶ Under equilibrium conditions, it was feasible to determine both the hydrodynamic radius R_h and the radius of gyration R_g. The ratio of R_g/R_h changed from 1.45 to 0.77, clearly demonstrating the transition from the theta coil state to the compact globule state. At the maximum value of the scaled expansion factor α_s³ |τ| M_w^1/2, R_g/R_h = 1.33 where α_s = R_g/R_g (θ) and τ = |T-θ| / θ with θ being the theta temperature. In the compact globule, R_g/R_h was of the order of 0.7, implying that the PNIPAM compact globule in water still contained ∼80% water, of the same order of magnitude as the PS compact globule in cyclohexane at 7° below its theta temperature (35°C).     

Miscibility maps for polymer blends: Effects of temperature,pressure, and molecular weight

We study a Gibbs free energy model for describing the thermodynamics of compressible polymer blends in the case of nonpolar polymers. This model is a mean field model equivalent to the cell model of Prigogine et al. and close also to the model by Flory‐Orvoll and Vrij. The model is expressed as a function of the interaction energies between monomer pairs (a, b, and c), the degrees of polymerization (X_A and X_B), a close packing parameter ρ₀, the temperature, and the pressure. We derive an analytical expression regarding blend miscibility. All the already observed phase behaviors are recovered: the occurrence of two kinds of upper critical solution transition (UCST): case‐I and case‐II UCST for which the pressure has a destabilizing or stabilizing effect, respectively, and lower critical solution transition; cases where the pressure have a non‐monotonous effect on the UCST temperature; cases where the spinodal lines close up under high pressures; and the so‐called hour‐glass transition. The model allows for making explicit the effect of the different physical parameters on phase behavior. We calculate complete miscibility maps regarding the occurrence of the various possible kinds of transitions in the 2D space b/a and X_A, for different values of , applied pressure P, and chain length ratios. This approach may come as a complement to already existing, more quantitative and elaborated approaches. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 419–443     

Stepwise growth of a single polymer chain

By monitoring the modulation of an ionic current passing through a nanoreactor formed from a protein pore, the step-by-step growth of an individual polymer chain was monitored. The observation of polymer growth at the single-molecule level will be useful for studying the kinetics of chain growth or the movement of polymers under confinement. It might also be used to synthesize "molecular fishing lines" in situ, for applications in stochastic sensing.     

Adsorption of a single polymer chain on a surface: A molecular dynamics simulation study

We performed simulations of the physical adsorption of a single globular chain on a surface of hemispherical shape by means of molecular dynamics simulations. For the chain, we took advantage of a united atom model. Interactions within the chain were limited to stretching, bending, and torsional as well as nonbonded interactions between the nonadjacent atoms. The interaction between each chain element and the surface formation are reigned by a Lennard–Jones potential. In this article, we focused on differences in the behavior of the adsorbed globule to the free unadsorbed one particularly in two different zones of the immediate vicinity of the surface. There were strong indications for a localized acceleration of the dynamics as compared with the bulk that appears in an increase of trans–gauche switches. For explanation we came up with an adsorption scenario. Special attention was given to the shift of the percentage of trans and gauche conformations within the globule in dependence on the strength of the adsorption potential that might be related to crystallization or glass transition. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2333–2339, 2001     

Thermosetting polymer blends of unsaturated polyester resin and poly(ethylene oxide). I. Miscibility and thermal properties

The miscibility and thermal properties of polyethylene oxide(PEO)/oligoester resin (OER) blends and PEO/crosslinked polyester (PER) blends were studied by differential scanning calorimetry (DSC). The effect of quenching process on the crystallization behavior of PEO for these two systems were investigated and discussed in details. It has been found that a single, composition dependent glass transition temperature (T_g) was observed for all the blends, indicating that the two systems are miscible in the amorphous state at overall compositions. From the melting point depression of PEO, the interaction parameter χ₁₂ for PEO/OER blends and that for PEO/PER blends were found to be −1.29 and −2.01, respectively. The negative values of χ₁₂ confirmed that both PEO/OER blends and PEO/PER blends are miscible in the molten state. Quenching process has a greater hindrance on the crystallization of PEO/OER blends than on that of PEO/PER blends. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3161–3168, 1997     

The properties of a single polymer chain in solvent confined in a slit: A molecular dynamics simulation

A single polymer chain in solvent confined in a slit formed by two parallel plates is studied by using molecular dynamics simulation method. The square radii of gyration and diffusion behaviors of polymers are greatly affected by the distance between the two plates, but they do not follow the same way. The chain size decays drastically with increasing h (h is the distance between two plates), until a basin occurs, and a universal h/〈R _g〉₀ dependence for polymer chains with different degrees of polymerization can be obtained. While, for the chain’s diffusion coefficient, it decays monotonously and there is no such basin-like behavior. Furthermore, we studied the radial distribution function of confined polymer chains to explain the reason why there is a difference for the decay behaviors between dynamic properties and static properties. Besides, we also give the degree of confinement dependence of the static scaling exponent for a single polymer chain. Our work provides an efficient way to estimate the dynamics and static properties of confined polymer chains, and also helps us to understand the behavior of polymer chains under confinement.     

Molecular-dynamics simulations of the transport properties of a single polymer chain in two dimensions

Molecular-dynamics simulations are conducted to elucidate the critical factors affecting the transport properties of isolated polymer chains in strictly two dimensions. The relevance of surface inhomogeneity is critically examined. We unequivocally find that surface inhomogeneity is critical in obtaining transport behavior consistent with the recent measurements of surface diffusion for polymers adsorbed at the solid-liquid interface. For a systematic investigation of this point, heterogeneity was introduced by decorating the surface with impenetrable elements and we find that chain diffusivity crossed over from Rouse-type behavior to reptationlike with increasing surface coverage of obstacles. This transition in behavior occurred when the mean distance between obstacles is approximately equal to the end-to-end distance, Re, of the two-dimensional chain. Our results underscore the importance of surface disorder (not only literal obstacles but by reasonable extension also to other types of disorder) in determining the transport behavior of chains adsorbed to solids.