Miscibility and morphology of poly(vinylidene fluoride)/poly[(vinylidene fluoride)‐ran‐trifluorethylene] blends

This study presents an investigation of the effect of the different crystalline phases of each blend component on miscibility when blending poly(vinylidene fluoride) (PVDF) and its copolymer poly[(vinylidene fluoride)‐ran‐trifluorethylene] [P(VDF–TrFE)] containing 72 mol % of VDF. It was found that, when both components crystallized in their ferroelectric phase, the PVDF showed a strong effect on the crystallinity and phase‐transition temperature of the copolymer, indicating partial miscibility in the crystalline state. On the other hand, immiscibility was observed when both components, after melting, were crystallized in their paraelectric phase. In this case, however, a decrease in crystallization temperatures suggested a strong interaction between monomers in the liquid state. Blend morphologies indicated that, in spite of the lack of miscibility in the crystalline state, there is at least miscibility between PVDF and P(VDF–TrFE) in the liquid state, and that a very intimate mixture of the two phases on the lamellar level can be maintained upon crystallization. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1362–1369, 2002     

Spatio-temporal growth of broken spiral and concentric ringed spherulites in blends of poly(vinylidene fluoride) and ethylene-vinylacetate copolymers

Melting and crystallization behavior in mixtures of poly(vinylidene fluoride) (PVDF) and several ethylene-vinyl acetate copolymers (EVAc) with various ethylene contents have been investigated by means of differential scanning calorimetry, atomic force microscope, and optical microscopy. PVDF/EVAc-80 exhibits the melting point depression of PVDF crystals, suggestive of a miscible character of the pair. Crystallization behavior and morphology development in blends of PVDF/EVAc-80 have been investigated with an emphasis on the spherulitic growth demonstrating the spiral and concentric ringed (or target) patterns. Of particular interest is the break-up of the spiral or concentric ringed patterns at very shallow supercoolings, which may be attributed to instabilities driven by the exclusion of amorphous PVDF and EVAc chains into the emerging inter- and intra-spiral (or target) lamellar regions.     

Surface segregation and miscibility in blends of poly(ethyl acrylate) with poly(vinylidene fluoride-co-hexafluoroacetone)

In blends of poly(ethyl acrylate) (PEA) and poly(vinylidene fluoride-co-hexafluoroacetone) [P(VDF-HFA)], surface segregation of the P(VDF-HFA) component was confirmed by X-ray photoelectron spectroscopy. The PEA/P(VDF-HFA) blends exhibited lower critical solution temperature phase behaviour, with a critical temperature of 150°C. Since the surface tension value of P(VDF-HFA) is lower than that of PEA, this may influence surface segregation behaviour in PEA/P(VDF-HFA) blends. Surface segregation results of the PEA/P(VDF-HFA) blends are compared with those from a previous study on immiscible acrylate copolymer/fluoro copolymer blends.     

Surface segregation and miscibility in blends of poly(vinylidene fluoride-co-hexafluoro-acetone) with poly(butyl acrylate)

The surface segregation in poly(butyl acrylate) (PBA)/poly(vinylidene fluoride-co-hexafluoro-acetone) [P(VDF-HFA)] blends was confirmed by X-ray photoelectron spectroscopy (XPS), and is thought to be caused because the surface tension of P(VDF-HFA) is smaller than that of PBA. The PBA/P(VDF-HFA) blends were miscible at room temperature and exhibited a lower critical solution temperature (LCST) phase behavior. Thus, it was considered that the surface segregation of the P(VDF-HFA) component in PBA/P(VDF-HFA) blends was caused by the difference in surface tension between the components. Depth profiles [In(<Ø₁ (d) -Ø^b ₁) vs. depth (d), where Ø₁ (d) and Ø^b ₁ are the volume fractions at depth d from the surface and into the bulk, respectively] for PBA/P(VDF-HFA) blends were constructed by the mean-field treatment. The ln(Ø₁(d) - Ø^b ₁) vs. d plots for the PBA/P(VDF-HFA) blends could be approximated by a straight line.     

Miscibility of C60‐containing poly(methyl methacrylate)/poly(vinylidene fluoride) blends

The miscibility of C₆₀‐containing poly(methyl methacrylate) (PMMA‐C₆₀) with poly(vinylidene fluoride) (PVDF) was studied. Two PMMA‐C₆₀ samples containing 2.6 and 7.4 wt % C₆₀ were found to be miscible with PVDF based on single glass transition temperature criterion and melting point depression of PVDF. However, the interaction parameters of the two blend systems are less negative than that of the PMMA/PVDF blend system, showing that the incorporation of C₆₀ reduces the ability of carbonyl groups of PMMA to interact with PVDF. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1393–1396, 2000     

Viscoelastic and pressure–volume–temperature properties of poly(vinylidene fluoride) and poly(vinylidene fluoride)–hexafluoropropylene copolymers

The relationship between the pressure, volume, and temperature (PVT) of poly(vinylidene fluoride) homopolymers (PVDF) and poly(vinylidene fluoride)–hexafluoropropylene (PVDF–HFP) copolymers was determined in the pressure range of 200–1200 bar and in the temperature range of 40°C–230°C. The specific volume was measured for two homopolymers having a molecular weight (M_w) of 160,000–400,000 Da and three copolymers containing between 3 and 11 wt % HFP with a molecular weight range of 320,000–480,000 Da. Differential scanning calorimetry (DSC) was used to simulate the cooling process of the PVT experiments and to determine the crystallization temperature at atmospheric pressure. The obtained results were compared to the transitions observed during the PVT measurements, which were found to be pressure dependent. The results showed that the specific volume of PVDF varies between 0.57 and 0.69 cm³/g at atmospheric pressure, while at high pressure (1200 bar) it varies between 0.55 and 0.64 cm³/g. For the copolymers, the addition of HFP lowered its melting point, while the specific volume did not show a significant change. The TAIT state equation describing the dependence of specific volume on the zero‐pressure volume (V₀,T), pressure, and temperature has been used to predict the specific volume of PVDF and PVDF–HFP copolymers. The experimental data was fitted with the state equation by varying the parameters in the equation. The use of the universal constant, C (0.0894), and as a variable did not affect the predictions significantly. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 230–241, 2001     

Biodegradable poly(L‐lactic acid)/poly(butylene succinate‐co‐adipate) blends: Miscibility,morphology, and thermal behavior

Blends of two biodegradable and semicrystalline polymers, poly(L ‐lactic acid) (PLLA) and poly(butylene succinate‐co‐adipate) (PBSA), were prepared by solvent casting in different compositions. The miscibility, morphology, and thermal behavior of the blends were investigated using differential scanning calorimetry and optical microscopy. PLLA was found to be immiscible with PBSA as evidenced by two independent glass transitions and biphasic melt. Nonisothermal crystallization measurements showed that fractionated crystallization behavior occurred when PBSA was dispersed as droplets, evidenced by multiple crystallization peaks at different supercooling levels. Crystallization and morphology of the blends were also investigated through two‐step isothermal crystallization. For blends where PLLA was the major component, different content of PBSA did not make a significant difference in the crystallization mechanism and rate of PLLA. For blends where PBSA was the major component, the crystallization rate of PBSA decreased with increasing PLLA content, while the crystallization mechanism did not change. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Counterion dependent crystallization kinetics in blends of a perfluorosulfonate ionomer with poly(vinylidene fluoride)

Blends of poly(vinylidene fluoride) (PVDF) with a perfluorosulfonate ionomer, Nafion^®, have been prepared and examined in terms of the crystallization kinetics of the PVDF component. In blends of PVDF with Na⁺-form Nafion^®, the rates of bulk crystallization, as observed by DSC, and the spherulitic growth rates of the PVDF component, as observed using optical microscopy, were found to be very similar to that of pure PVDF. This behavior was attributed to the course phase separation of Na⁺-form Nafion^® from PVDF and melt incompatibility of the physically cross-linked ionomer with the crystallizable component. In this segregated state, the PVDF component of the blend is allowed to crystallize in pure phases that are isolated under the influence of Nafion^®. In contrast, when the ionomer was exchanged with more weakly interacting quaternary alkylammonium counterions, a decrease in both the rate of bulk crystallization and spherulitic growth was observed. Furthermore, the crystallization kinetics of PVDF in these blends was found to be dependent on the counterion size; as the size of counterions associated with the Nafion^® component increased, the rate of crystallization decreased. This behavior was attributed to a weakening of the electrostatic interactions in the ionomer phase and thus an increase in the extent of phase mixing with the larger ions.     

The effect of ionic interaction on the miscibility and crystallization behaviors of poly(ethylene glycol)/poly(L‐lactic acid) blends

The effect of end groups (2NH₂) of poly(ethylene glycol) (PEG) on the miscibility and crystallization behaviors of binary crystalline blends of PEG/poly(L ‐lactic acid) (PLLA) were investigated. The results of conductivity meter and dielectric analyzer (DEA) implied the existence of ions, which could be explained by the amine groups of PEG gaining the protons from the carboxylic acid groups of PLLA. The miscibility of PEG(2NH₂)/PLLA blends was the best because of the ionic interaction as compared with PEG(2OH, 1OH‐1CH₃, and 2CH₃)/PLLA blends. Since the ionic interaction formed only at the chain ends of PEG(2NH₂) and PLLA, unlike hydrogen bonds forming at various sites along the chains in the other PEG/PLLA blend systems, the folding of PLLA blended with PEG(2NH₂) was affected in a different manner. Thus the fold surface free energy played an important role on the crystallization rate of PLLA for the PEG(2NH₂)/PLLA blend system. PLLA had the least fold surface free energy and the fast crystallization rate in the PEG(2NH₂)/PLLA blend system, among all the PEG/PLLA systems studied. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Crystalline transformations in spherulites of poly(vinylidene fluoride)

Parts of poly(vinylidene fluoride) spherulites of the α-phase undergo a transformation to the higher-melting γ-form when crystallized at high temperatures. As a rule, this transformation originates at the periphery of α-spherulites where their lamellae are in contact with, and oppositely directed to, lamellae of γ-spherulites; the latter are formed only at high temperatures. The transformation on then retreats towards the nuclei of α-spherulites at a slow (～10^?4μm s^?1), linear rate, which increases with temperature. At very high temperatures, this transformation is also initiated at some α-nuclei; a few of the α-spherulites also exhibit areas of the high-melting phase irregularly dispersed within their interiors. In samples crystallized below ～154°C, the transformation is of very limited extent, even after prolonged annealing at higher temperatures.     

Investigation on the miscibility of the blends of poly(methyl methacrylate) and poly(styrene‐co‐acrylonitrile)

The miscibility was investigated in blends of poly(methyl methacrylate) (PMMA) and styrene‐acrylonitrile (SAN) copolymers with different acrylonitrile (AN) contents. The 50/50 wt % blends of PMMA with the SAN copolymers containing 5, 35, and 50 wt % of AN were immiscible, while the blend with copolymer containing 25 wt % of AN was miscible. The morphologies of PMMA/SAN blends were characterized by virtue of scanning electron microscopy and transmission electron microscopy. It was found that the miscibility of PMMA/SAN blends were in consistence with the morphologies observed. Moreover, the different morphologies in blends of PMMA and SAN were also observed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Compatibilization of immiscible nylon 6/poly(vinylidene fluoride) blends using graphene oxides

A new strategy to compatibilize immiscible blends is proposed, using graphene oxide (GO) nanosheets taking advantage of their unique amphiphilic structures. When 0.5 or 1 wt% GOs were incorporated in immiscible nylon 6/poly(vinylidene fluoride) (PVDF) (90/10 wt%) blends, the dimension of PVDF dispersed particles was markedly reduced and became more uniform, revealing a well‐defined compatibilization effect of GOs on the immiscible blends. Correspondingly, the ductility of the compatibilized blends increased several times compared with uncompatibilized immiscible blends. In order to explore the underlying compatibilization mechanism, Fourier transform infrared and Raman spectra were applied to suggest that the edge polar groups of GOs can form hydrogen bonds with nylon 6 while the basal plane of GOs can interact with electron‐withdrawing fluorine on PVDF chains leading to the so‐called charge‐transfer C–F bonding. In this case, GOs exhibit favorable interactions with both nylon 6 and PVDF phase, therefore stabilizing the interface during GO migrations from PVDF/GO masterbatch to nylon 6 phase, which can minimize the interfacial tension and finally lead to compatibilization effects. Obviously, this work may open a broad prospect for GOs to be widely applied as a new compatibilizer in industrial fields. © 2012 Society of Chemical Industry     

Effect of bisphenol A on the miscibility,phase morphology,and specific interaction in immiscible biodegradable poly(ε‐caprolactone)/poly(L‐lactide) blends

We have investigated the enhancement in miscibility, upon addition of bisphenol A (BPA) of immiscible binary biodegradable blends of poly(ε‐caprolactone) (PCL) and poly(L ‐lactide) (PLLA). That BPA is miscible with both PCL and PLLA was proven by the single value of T_g observed by differential scanning calorimetry (DSC) analyses over the entire range of compositions. At various compositions and temperatures, Fourier transform infrared spectroscopy confirmed that intermolecular hydrogen bonding existed between the hydroxyl group of BPA and the carbonyl groups of PCL and PLLA. The addition of BPA enhances the miscibility of the immiscible PCL/PLLA binary blend and transforms it into a miscible blend at room temperature when a sufficient quantity of the BPA is present. In addition, optical microscopy (OM) measurements of the phase morphologies of ternary BPA/PCL/PLLA blends at different temperatures indicated an upper critical solution temperature (UCST) phase diagram, since the ΔK effect became smaller at higher temperature (200°C) than at room temperature. An analysis of infrared spectra recorded at different temperatures correlated well with the OM analyses. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1146–1161, 2006     

Compatibility of poly(vinylidene fluoride) (PVDF)/polyamide 12 (PA12) blends

Poly(vinylidene fluoride) (PVDF)/polyamide 12 (PA12) blends showed new peaks in XRD profile with increasing PA12 and the crystallinity of PA12 significantly decreased with the addition of PVDF. PVDF showed three relaxation regions at about −40, 40, and 100°C, respectively, and glass transition temperature (T_g ) of PA12 increased in blends (10.8→30.14°C) and α‐relaxation of PVDF decreased from 100.26 to 86.46°C. Complex viscosities (η*) vs. composition curve showed a great positive deviation in PVDF‐rich and a small negative deviation in PA12‐rich blends. The N—H and C=O stretching band of PA12 shifted slightly toward higher wavelength, and from curve‐fitted data the area of hydrogen‐bonded C=O stretching bands of PA12 decreased with the addition of PVDF, especially in the 30/70 blend, implying the existence of interactions between the β‐hydrogen atom of PVDF and amide carbonyl group of PA12 in the blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1374–1380, 2000     

Tensile,stress-strain and creep rupture properties of poly (vinyl chloride)/poly(neopentyl glycol adipate)/poly(vinylidene fluoride) blends

Poly (vinyl chloride), PVC, and poly(vinylidene fluoride), PVDF, are incompatible polymers. Poly(neopentyl glycol adipate), PDPA, is miscible with both PVC and PVDF. With PDPA acting as a compatibilizer between PVC and PVDF. compatible PVC/PDPA/PVDF blends can be formed at PVDF content of about less than 50wt%. Above 50wt% PVDF the ternary blends exist in two phases exhibiting two glass transition temperatures, T_g, PVC is the main contributor to the mechanical strength while PDPA and PVDF contribute to the elastic properties of these blends. A compatible blend of 55/22.5/22.5 wt% PVC/PDPA/PVDF exhibiting one single T_g appears to show an interesting balance of the properties of the blend components.     

Porous poly(vinylidene fluoride) membrane with highly hydrophobic surface

The preparation of very hydrophobic poly(vinylidene fluoride) (PVDF) membranes was explored by using two methods. The first one was the modified phase inversion method using a water/N,N‐dimethylacetamide (DMAc) mixture instead of pure water as a soft precipitation bath. The second method was a precipitation‐bath free method, that is, the PVDF/DMAc casting solution underwent gelation in the open air instead of being immersed into a precipitation bath. The morphology of the surface and cross section of the membranes was investigated by using scanning electron microscopy (SEM). It was found that the membranes exhibited certain micro‐ and nanoscale hierarchical roughness on the surface, which brought about an enhanced hydrophobicity of the membrane. The contact angle (CA) of the samples obtained by the second method was as high as 150° with water. The conventional phase inversion method preparing PVDF porous membrane using pure water as precipitation bath usually results in an asymmetric membrane with a dense skin layer having a CA close to that of a smooth PVDF surface. The modified approach avoided the formation of a skin‐layer and resulted in a porous and highly hydrophobic surface of PVDF. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1358–1363, 2005     

Crystal polymorphism in electrospun composite nanofibers of poly(vinylidene fluoride) with nanoclay

We investigated for the first time the morphology and crystal polymorphism of electrospun composite nanofibers of poly(vinylidene fluoride) (PVDF) with two nanoclays: Lucentite™ STN and SWN. Both nanoclays are based on the hectorite structure, but STN has organic modifier in between the layers of hectorite while SWN does not. PVDF/nanoclay was dissolved in N,N-dimethylformamide/acetone and electrospun into composite nanofiber mats with fiber diameters ranging from 50-800 nm. Scanning electron microscopy shows that addition of STN and SWN can greatly decrease the number of beads and make the diameter of the nanofibers more uniform due to the increase of electrospinning solution conductivity brought by the nanoclay. Infrared spectroscopy and X-ray diffraction confirm that both STN and SWN can induce more extended PVDF chain conformers, found in beta and gamma phase, while reducing the alpha phase conformers in electrospun PVDF/Nanoclay composite nanofibers. With the attached organic modifier, even a small amount of STN can totally eliminate the non-polar alpha crystal conformers while SWN cannot. The ionic organic modifier makes STN much more effective than SWN in causing crystallization of the polar beta and gamma phases of PVDF. An ion-dipole interaction mechanism, suggested by Ramasundaram, et al. is utilized to explain the crystal polymorphism behavior in electrospun PVDF/nanoclay composite nanofibers.     

Binary and ternary polymer blends containing poly(vinylidene chloride‐co‐acrylonitrile)

Poly(vinylidene chloride‐co‐acrylonitrile) (Saran F), poly(hydroxy ether of bisphenol A) (phenoxy), poly(styrene‐co‐acrylonitrile) (PSAN), and poly(vinyl phenol) (PVPh) all have the same characteristic: miscibility with atactic poly(methyl methacrylate) (aPMMA). However, the miscibility of Saran F with the other polymer (phenoxy, PSAN, or PVPh) is not guaranteed and was thus investigated. Saran F was found to be miscible only with PSAN but not miscible with phenoxy and PVPh. Because Saran F and PVPh are not miscible, although they are both miscible with aPMMA, aPMMA can thus be used as a potential cosolvent to homogenize PVPh/Saran F. The second part of this report focused on the miscibility of a ternary blend consisting of Saran F, PVPh, and aPMMA to investigate the cosolvent effect of aPMMA. Factors affecting the miscibility were studied. The established phase diagram indicated that the ternary blends with high PVPh/Saran F weight ratio were found to be mostly immiscible. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3068–3073, 2004     

Miscibility and melting behavior of poly(ethylene terephthalate)/poly(trimethylene terephthalate) blends

The miscibility and melting behavior of binary crystalline blends of poly(ethylene terephthalate) (PET)/poly(trimethylene terephthalate) (PTT) have been investigated with differential scanning calorimetry and scanning electron microscope. The blends exhibit a single composition‐dependent glass transition temperature (T_g) and the measured T_g fit well with the predicted T_g value by the Fox equation and Gordon‐Taylor equation. In addition to that, a single composition‐dependent cold crystallization temperature (T_cc) value can be observed and it decreases nearly linearly with the low T_g component, PTT, which can also be taken as a valid supportive evidence for miscibility. The SEM graphs showed complete homogeneity in the fractured surfaces of the quenched PET/PTT blends, which provided morphology evidence of a total miscibility of PET/PTT blend in amorphous state at all compositions. The polymer–polymer interaction parameter, χ₁₂, calculated from equilibrium melting temperature depression of the PET component was ?0.1634, revealing miscibility of PET/PTT blends in the melting state. The melting crystallization temperature (T_mc) of the blends decreased with an increase of the minor component and the 50/50 sample showed the lowest T_mc value, which is also related to its miscible nature in the melting state. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of polymeric flame retardants based on phosphorus‐containing polyesters on morphology and material characteristics of poly(butylene terephthalate)

Flame retarded poly(butylene terephthalate) (PBT) is required for electronic applications and is mostly achieved by low molar mass additives so far. Three phosphorus‐containing polyesters are suggested as halogen‐free and polymeric flame retardants for PBT. Flame retardancy was achieved according to cone calorimeter experiments showing that the peak heat release rate and total heat evolved were reduced because of flame inhibition and condensed‐phase activity. The presented polymers containing derivatives of 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide form immiscible blend systems with PBT. Shear‐rheology shows an increase in storage moduli at low frequencies. This is proposed as quantitative measure for the degree of phase interaction. The phase structure of the blends depends on the chemical structure of the phosphorus polyester and was quite different, depending also on the viscosity ratio between matrix and second phase. A lower viscosity ratio leads to two types of phases with spherical and additionally continuous droplets. Addition of the flame retardants showed no influence on the dielectric properties but on the mechanical behavior. The polymeric flame retardants significantly diminish the impact strength because of several reasons: (1) high brittleness of the phosphorus polyesters themselves, (2) thermodynamic immiscibility, and (3) weak phase adhesion. By adding a copolymer consisting of the two base polymers to the blend, an improvement of impact strength was obtained. The copolymer particularly acts as compatibilizer between the phases and therefore leads to a smaller phase size and to a stronger phase adhesion due to the formation of fibrils. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013