Structure formation of PVDF/PMMA blends studied

Conformational formation and crystallization dynamics of miscible PVDF/at-PMMA and PVDF/iso-PMMA polymer blends from the molten state were studied by the simultaneous DSC/FT-IR measurement. Formation of TGTG' conformation occurred before starting crystallization exothermic peak in the PMMA content (_PMMA) range from 0 to 0.4 for both blends. The formation rate of TGTG' conformation, crystal growth rate and surface free energy of PVDF crystal in blends depended linearly on _PMMA for PVDF/at-PMMA, however, those rates for PVDF/iso-PMMA slightly influenced by _PMMA. These results suggested that the former was miscible blend in molecular level, however, the latter was a miscible blend with large concentration fluctuation or a partially segregated system.     

Crystallization-induced composition inhomogeneities in PVDF/PMMA blends

Composition profiles develop around growing PVDF spherulites in a blend with PMMA. These profiles assume stationary courses after a certain crystallization time provided that the overall degree of crystallinity is not too high. The composition-dependent growth rate and the diffusion-controlled remove of the surplus PMMA from the spherulite surface are then in a stationary equilibrium. The internal structure of the spherulites will then be homogeneous, too. Upon isothermal crystallization of a PVDF/PMMA = 60/40 (wt %) blend at 160°C for at least 4 h, the spherulites internal degree of crystallinity x_c as related to the PVDF fraction obeys the inequality 55 wt % ≤ x_c ≤ 84 wt %. The overall PMMA content within the spherulites as averaged over its whole inside has been determined by IR microscopy. It amounts to about 15 wt %. In contrast, the PMMA content of the amorphous phase within the spherulites (averaged again over its whole inside) ranges between 28 and 52 wt %. This composition jumps at the spherulite surface to 52 wt %. From the slope of the composition profiles outside the spherulites that have a width of more than 50 μm, the effective chain diffusion coefficient in blends as averaged over both components can be calculated to amount to (250 ± 100) μm²h⁻¹. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2923–2930, 1998     

Nonisothermal crystallization and melting behavior of mPE/LLDPE/LDPE ternary blends

Nonisothermal crystallization kinetics of ternary blends of the metallocence polyethylene (mPE), low-density polyethylene (LDPE) and linear low-density polyethylene (LLDPE) were studied using DSC at various scanning rates. The Ozawa theory and a method developed by Mo were employed to describe the nonisothermal crystallization process of the two selected ternary blends. The results speak that Mo method is successful in describing the nonisothermal crystallization process of mPE/LLDPE/LDPE ternary blends, while Ozawa theory is not accurate to interpret the whole process of nonisothermal crystallization. Each ternary blend in this study shows different crystallization and melting behavior due to its different mPE content. The crystallinity of the ternary blends rises with increasing mPE content, and mPE improve the crystallization of the blends at low temperature. The crystallization activation energy of the five ternary blends that had been calculated from Vyazovkin method was increased with mPE content, indicating that the more mPE in the blends, the easier the nucleus or microcrystallites form at the primary stage of nonisothermal crystallization. LLDPE and mPE may form mixed crystals due to none separated-peaks were observed around the main melting or crystallization peak when the ternary blends were heating or cooling. The fixed small content of LDPE made little influence on the main crystallization behavior of the ternary blends and the crystallization behavior was mainly determined by the content of mPE and LLDPE.     

Phase behavior of polystyrene acrylonitril copolymer and polymethylmethacrylate blends under shear

Polymer blends undergo external stresses such as pressure and shear in course of processing cycles. The knowledge of their phase behavior at each step of these cycles is crucial for understanding their physical properties and eventually improves their performance in practical applications. The effects of shear on the phase diagram of binary polymer blends are considered. A theoretical formulism is used upon which the free energy is the sum of two terms. The first term is modeled with the Flory–Huggins free energy of mixing and describes the thermodynamic behavior of the system in the quiescent state. The second term represents the excess free energy stored during flow. In the presence of shear flow, the excess free energy is expressed in terms of the viscosity and the shear modulus. Both quantities depend on composition and shear rate. The curvature of the variation of viscosity versus composition has a tremendous impact upon the nature of phase separation. Phase diagrams are described by the spinodal curves and show for the case considered here miscibility enhancement with increasing shear rate. A good correlation is found with experimental data of the literature on blends of polystyrene acrylonitril copolymer and polymethylmethacrylate. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Phase behavior and a modified Kwei equation for ternary polymer blends containing stereoregular PMMA

Previously, poly(methyl methacrylate) (PMMA) was found to be almost immiscible with poly(vinyl acetate) (PVAc) regardless of tacticity of PMMA and casting solvent. Poly(vinyl phenol) (PVPh) was found successful previously in making immiscible atactic PMMA/PVAc miscible. In this investigation, tacticity effect of PMMA on a ternary composed of PMMA, PVAc and PVPh was studied. Isotactic PMMA ternary was shown to be miscible in all the studied compositions on the basis of single T_g observation. However, syndiotactic PMMA ternary demonstrated immiscibility at ca. 25% PVPh and miscibility was observed at higher PVPh concentrations. A modified Kwei equation based on the binary interaction parameters was proposed to describe the experimental T_g of the miscible ternary almost quantitatively.     

Melting behavior of poly(ether ether ketone) in its blends with poly(ether imide)

We detail the melting behavior of poly(ether ether ketone) (PEEK) and investigate its melting behavior in miscible blends with poly(ether imide) (PEI). The determination of the equilibrium melting point (T_m⁰) of PEEK is discussed by considering its inhomogeneous morphology. T_m⁰ is obtained by a long extrapolation of a Hoffman–Weeks plot to 384°C. Hindrance of PEEK crystal reorganization induced by PEI during heating is observed over the blend composition investigated (20–75 wt % PEEK). This behavior is correlated with the incorporation of PEI in the interlamellar zones of PEEK crystals. The interaction parameter χ of PEEK/PEI blends is estimated by the equilibrium melting point depression. This gives the interaction density B = ?1.2 cal/cm³, and x = ?0.40 at 400°C. © 1993 John Wiley & Sons, Inc.     

Miscibility enhancement and formation of interpenetrating spherulites in ternary blends of crystalline polymers

Miscible blends of three crystalline polymers, namely poly(butylene succinate) (PBS), poly(ethylene succinate) (PES), and poly(oxyethylene) (POE), exhibited interpenetrating spherulites, where a spherulite of one component grows inside the spherulites of other components. PBS and PES were immiscible above the melting points, T_m, of these substances, while ternary blends with POE showed miscibility, which depended on the molecular weight of POE. PBS and PES exhibited the same spherulitic growth process as in a miscible binary blend when they were crystallized from a homogeneous ternary melt. Spherulites of PBS, which is the highest‐T_m component, filled the whole volume first when a miscible ternary blend was quenched below T_m of POE, the lowest‐T_m component. Then, the blends showed either two types of crystallization processes. One was successive nucleation and growth of PES and POE spherulites, that is, PES nucleated and developed spherulites inside the PBS spherulites and then POE spherulites grew inside the interlocked spherulites of PBS and PES. The other was simultaneous growth and the formation of interpenetrating spherulites of PES and POE inside the PBS spherulites. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 706–711, 2010     

Prediction of miscibility regions in ternary blends of poly(styrene-stat-acrylonitrile), poly(acrylonitrile-stat-methyl methacrylate), and poly(styrene-stat-methyl methacrylate)

The miscibilities of ternary copolymer blends prepared from poly(styrene-stat-acrylonitrile), poly(styrene-stat-methyl methacrylate), and poly(methyl methacrylate-stat-acrylonitrile) were predicted by calculating the interaction parameter, χ_blend, for various blend combinations, from the corresponding binary segmental interaction parameters estimated from previous work. Binodal and spinodal curves were calculated using the Flory-Huggins theory and it was observed that the most accurate estimate of the boundary between miscible and immiscible blends was given by the spinodal. It has also been demonstrated that in some of the ternary blends with fixed copolymer compositions the miscibility of the blend can be altered by changing the ratio of the three components in the mixture. Conditions for miscibility in this ternary system, and possibly a general feature of all such systems, are (a) that at least two of the binary interaction parameters χ_ij are less than the critical value χ_crit, while the third should not be too much larger, that is, one of the copolymers may act as a compatibilizer for the other two copolymers, (b) that the difference Δχ = /χ₁₂ ? χ₁₃/ is small. © 1992 John Wiley & Sons, Inc.     

Phase behavior of polylactides in solvent–nonsolvent mixtures

Isothermal phase diagrams for the semicrystalline poly-L-lactide (PLLA) and the amorphous poly-DL-lactide (PDLLA) in combination with several solvent–nonsolvent combinations (dioxane/water, dioxane/methanol, chloroform/methanol, and NMP/water) have been determined. The locations of the liquid–liquid miscibility gap, the solid–liquid miscibility gap and the vitrification boundary in the isothermal phase diagrams at 25°C were identified. The liquid–liquid miscibility gap for the systems with PLLA was located in the same composition range as the corresponding systems with PDLLA. For the systems containing PLLA solid–liquid demixing was thermodynamically preferred over liquid–liquid demixing. Attempts were made to correlate the experimental findings with predictions on the basis of the Flory-Huggins theory for ternary solutions using interaction parameters derived from independent experiments. Qualitative agreement was found between the theoretical predictions and the experimentally obtained liquid–liquid miscibility gap. No good agreement was found for the solid–liquid miscibility gap. © 1996 John Wiley & Sons, Inc.     

Phase behavior of polymer/diluent/diluent mixtures and their application to control microporous membrane structure

Rechargeable battery separators containing controlled pores were fabricated via the thermally-induced phase separation (TIPS) process. Based on the idea that pores could be manipulated by controlling the liquid–liquid phase separation temperature in the TIPS process, phase boundaries of the polymer–diluent systems were controlled by using diluent mixtures. Phase behaviors of the polymer/diluent/diluent ternary blends consisting of polyethylene (PE) as polymer, and soybean oil (SBO) and dioctyl phthalate (DOP) as diluents were explored. PE/SBO and PE/DOP binary blends, and PE/SOB/DOP ternary blends exhibited typical upper critical solution temperature (UCST) type phase behaviors, and the phase separation temperatures of the PE/SBO blends were higher than those of the PE/DOP blends. When the mixing ratio of the polymer and diluent-mixture was fixed, the phase separation temperature of the PE/SBO/DOP blend initially increased with increasing SBO content in the diluent-mixture passing through a maximum centered at about 80 wt% SBO and decreased beyond this point. Furthermore, the phase separation temperature of the PE/diluent-mixture blend was always higher than that of the PE/SBO blend when the diluent-mixture contained more than or equal to 50 wt% SBO. To understand the observed phase behavior of the blends, thermodynamic analyses based on the lattice-fluid theory were performed. Larger pore membranes were fabricated from the blend when higher phase separation temperatures of the blend were exhibited.     

Phase behavior,morphology, and mechanical properties of polyethylene-copolymer blends

Binary blends of unbranched polyethylene (PE) and 5-10% model ethylene-butene random copolymers are used to determine the effects of composition heterogeneity on phase separation in the melt, semicrystalline morphology, plane strain fracture toughness J_C and tensile modulus and yield strength. Slowly cooled samples of melt-miscible blends are appreciably tougher (J_C = 5.2 kJ/m²) than unblended PE (J_C = 2.7 kJ/m²). A blend with the same average short chain branch concentration, but which is phase separated in the melt state, has J_C= 3.3 kJ/m²; dispersed domains of amorphous polymer have little effect on toughness. Enhanced toughness is associated with nonuniform morphology formed on slow cooling “one phase” melts composed of chains with different amounts of branching. The relative number of chemically different chains, as opposed to absolute branch concentrations, seems most important. Tensile properties are relatively unaffected by blending at these levels. Results from these model blends are used to consider the properties of compositionally heterogeneous ethylene copolymers. © 1994 John Wiley & Sons, Inc.     

Shear influence on the phase behavior of systems containing a homopolymer A and a block copolymer AB

Cloud point temperatures (T_cp) and crystallization temperatures (T_l/s) of the ternary system tetrahydronaphthalene/poly(ethylene oxide)/poly(dimethyl siloxane-b-ethylene oxide) have been measured at different constant shear rates using a rheo-optical device and an advanced rheometer. The cloud points temperatures (UCST-type phase diagram) are reduced by several degrees as the system flows; i.e. the shear can suppress the phase separation and enlarge the homogenous region. The crystallization kinetics of PEO in the ternary mixtures has been investigated isothermally and non-isothermally at quiescent state and under shear. The shear could strongly enhance the crystallization i.e. the (T_l/s) shifts to higher temperatures and the induction time, t₀ (the time needs for the onset of crystallization) substantially decreases with increasing shear rate during the non-isothermal and isothermal crystallization processes, respectively. The isothermal crystallization kinetics at quiescent state and at different shear rates was analyzed on the bases of Avrami approach. The Avrami exponent which provides qualitative information about the nature of the nucleation and growth process, was found to be shear rate and temperature dependent. The Avrami exponent increased from ∼3 at the quiescent state to as large as 9 at &&ggr;dot; = 100 s⁻¹.     

High density polyethylene/hydrogenated oligo(cyclopentadiene) blends: Phase structure,thermal and mechanical properties

The article discusses the influence of an oligomeric resin, hydrogenated oligo (cyclopentadiene) (HOCP), on the morphology and properties of its blends with high density polyethylene (HDPE). HDPE/HOCP blends after solidification contain three phases: the crystalline phase of HDPE and two amorphous phases, one rich in amorphous HDPE and the other in HOCP. DSC thermograms and the loss modulus behaviors show that the γ transition is influenced by HOCP molecules and, in addition to the α_c transition of HDPE, there is another transition that is attributed to the HOCP-rich phase. The hypothesis of the two amorphous phases is confirmed by the optical microscopy observations performed on isothermally crystallized blend films. © 1994 John Wiley & Sons, Inc.     

Effect of low contents of a polyaniline derivative on the crystallization and electrical properties of blends with PVDF

The effect of low levels of poly(o‐methoxyaniline) (POMA) on the crystallization, morphology, and electrical characteristics of blends with poly(vinylidene fluoride) (PVDF) were studied by infrared spectroscopy, AC electrical measurements, and optical microscopy. Undoped POMA has a strong effect in increasing the α‐phase and decreasing the β‐phase content of PVDF in blends crystallized from solution. For blends melt crystallized, doped POMA promotes much greater homogeneity than undoped POMA. Interestingly, doped POMA promotes the nucleation and growth of unringed PVDF spherulites, whereas undoped POMA hinders it. The doping state of the POMA was also extremely important in determining the electrical behavior of the blend. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1219–1224, 1999     

Phase behavior and miscibility limits in PC/hytrel blends

Polycarbonate of bisphenol-A (PC)/copolyetherester (Hy) blends have been obtained by melt mixing over the complete composition range. After testing the lack of interchange reactions and degradation under the conditions studied, the miscibility state was studied by DSC and DMTA. The blends appeared to be miscible in the melt state. A fairly complex phase behavior was obtained in the solid state with T_g-composition plots showing a single T_g at most of the compositions but very different after the first and second scans. This was attributed to the different crystalline content of the blends before the two scans. The presence of a Hy crystalline phase and a single PC/Hy amorphous phase in all the blends, with the exception of the 20/80 composition, was verified by DMTA. Several thermal treatments showed the presence of an immiscibility range and, thus, the presence of a UCST. A LCST, which in the case of the 50/50 and 40/60 blends would be at roughly 75°C, will also probably exist. © 1995 John Wiley & Sons, Inc.     

Phase behavior of crystalline blends of poly(tetrafluoroethylene) and of random fluorinated copolymers of tetrafluoroethylene

In the present article, we investigate by differential scanning calorimetry (DSC) the thermal behavior (melting, crystallization, and crystal–crystal transitions) far from equilibrium of blends constituted of two crystalline polymers. In particular, the following blends are examined: PTFE–PFMVE, PTFE–FEP, and FEP–PFMVE where PTFE is poly(tetrafluoroethylene), PFMVE is poly(tetrafluoroethylene‐co‐perfluoromethylvinylether), and FEP is poly(tetrafluoroethylene‐co‐hexafluoropropylene). The two last ones are random tetrafluoroethylene copolymers with small amounts of comonomer. Our results indicate that, under the experimental investigated conditions, the blends containing PTFE do not give cocrystallization on cooling from the melt, although under very rapid crystallization conditions, quenching, the presence of the copolymer would seem to slightly influence PTFE crystallization (lower peak temperatures are observed for the crystalline transitions and the melting with respect to those of the neat homopolymer). The behavior of the FEP–PFMVE blend is completely different; in fact, our results indicate the occurrence of cocrystallization, then miscibility in the crystalline phase, for almost all compositions and all investigated experimental conditions. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 679–689, 1999     

Role of monomer structure and compressibility on the properties of multicomponent polymer blends and solutions

Summary The lattice cluster theory of corrections to Flory-Huggins theory is applied to binary compressible blends (at a pressure of one atmosphere) that are formed by polymers having structured monomers. Calculations are performed in the high molecular weight limit for the dependence of the small angle neutron scattering effective interaction parameter _eff on composition ₁, monomer structure, microscopic interaction energies, and temperature. The limiting high molecular weight _eff (₁) curves have an overall general parabolic behavior with center, curvature, and magnitude that vary significantly with monomer structures and with interaction energies. The latter variation is stronger and occurs even at constant Flory-Huggins interaction parameter _FH ¹² where incompressible blend models cannot describe the strong dependence on the self-polymer-polymer-interactions obtained here. A quasi-athermal limit, in which _eff (₁) is nearly temperature independent, appears for high molecular weights only when _FH ¹² is vanishingly small. Phase diagrams are studied by evaluating the cloud points for coherent scattering from binary blends. Blends with negative _FH ¹² have only a LCST, but ones with positive _FH ¹² may have closed loop phase diagram or both LCST and UCST. However, one of the latter two critical points may be unobservable due to an intervening glass transition or because of thermal degradation.     

Crystallization,melting and structure of polypropylene/poly(vinylidene-fluoride) blends

Blends were prepared from isotactic polypropylene (iPP) along with its b-nucleated form and poly(vinylidene-fluoride) (PVDF). Melting, and crystallization characteristics as well as structure of the blends were studied by polarized light microscopy (PLM) and differential scanning calorimetry. According to PLM studies, the phase structure of these blends is heterogeneous in the molten state. The temperature range of crystallization of PVDF during cooling is higher than that of iPP. PVDF has a strong α-nucleating effect on iPP. The crystallization of iPP starts on the surface of dispersed PVDF droplets and an α-transcrystalline layer forms on the surface of the crystalline PVDF phase. The iPP matrix crystallizes predominantly in a-form in spite of the presence of a highly active b-nucleating agent. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thermodynamic analysis of the reaction-induced phase separation in model systems based on blends of a rubber in diepoxide / monoamine precursors

The reaction-induced phase separation in blends based on a carboxyl-terminated poly(butadiene-co-acrylonitrile) rubber (CTBN), dissolved in diglycidyl ether of bisphenol A (DGEBA) - benzylamine (BA) monomers, was studied. The polymerization kinetics was followed by size exclusion chromatography, for both the neat DGEBA-BA system and for blends containing 10 wt% CTBN. No effect of CTBN addition on the polymerization rate was observed within experimental error. The kinetics could be fitted with a model based on the presence of non-catalytic and OH-catalyzed reactions and assuming equal reactivity of primary and secondary amine hydrogens. Cloud-point conversions were determined at 60, 70 and 80 °C. The Flory-Huggins model provided a reasonable fitting of experimental data using an interaction parameter depending exclusively on temperature, and taking polydispersities of both linear polymers into account. Linear epoxy/amine systems may be used to test the reliability of thermodynamic theories in more complex situations (e.g., modifiers with a broad distribution of molar masses or mixtures of several modifiers).     

The competition between crystallization and demixing in polymer blends. IV. Detection of composition inhomogeneities around growing spherulites

In polymer blends of an amorphous and a semicrystalline component, the crystallization kinetics and the resulting morphology are heavily determined by the diffusion ability of the whole chains and by the dwelling site of the amorphous polymer. Depending on the relative rates of spherulite growth and chain diffusion, radial composition profiles around the growing spherulites and a gradual increase of the melt bulk composition can develop. The resulting change in composition, particularly at the crystallization front, causes a corresponding temporal variation of the spherulite growth rate. In the present article, two experimental techniques are introduced to prove the existence and to determine the course of these concentration profiles. They are based on the composition dependences of the spherulite growth rate and the number density of primary nuclei. Their efficiency is demonstrated by measurements on PVDF/PEA blends. The blend composition at the crystal growth front was found to change by absolute 25%, and the width of the profile can amount to up to 70 μm. © 1996 John Wiley & Sons, Inc.