Blends of the alternating ethylene–tetrafluoroethylene copolymer with poly(vinylidene fluoride)

Blends of the alternating ethylene–tetrafluoroethylene copolymer (ETFE) with poly(vinylidene fluoride) (PVF₂) were prepared by melt-mixing. Compatibility, morphology, thermal behavior, and mechanical properties of the ETFE/PVF₂ blends with various compositions were studied by using differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), dynamic mechanical analysis (DMA), thermogravimetric analysis (TGA), tensile tests, and scanning electron microscopy (SEM). DMA studies showed that the blends have separate glass transition temperatures (T_g) close to those of the pure polymers. ETFE and PVF₂ are incompatible. Marked negative deviations from simple additivity were observed for both the ultimate strength and the elongation at break over the entire composition range. The interfaces between ETFE and PVF₂ are weakly bonded with rather poor interaction. SEM observations revealed that the blends have a two-phase structure and the adhesion between the phases is poor. © 1997 John Wiley & Sons, Inc. J Appl Polm Sci 65:295–304, 1997     

Phase separation,cure kinetics,and morphology of epoxy/poly(vinyl acetate) blends

Epoxy based on diglycidyl ether of bisphenol A + 4,4′diaminodiphenylsulfone blended with poly(vinyl acetate) (PVAc) was investigated through differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA) and environmental scanning electron microscopy (ESEM). The influence of PVAc content on reaction induced phase separation, cure kinetics, morphology and dynamic‐mechanical properties of cured blends at 180°C is reported. Epoxy/PVAc blends (5, 10 and 15 wt % of PVAc content) are initially miscible but phase separate upon curing. DMTA α‐relaxations of cured blends agree with T_g results by DSC. The conversion‐time data revealed the cure reaction was slower in the blends than in the neat system, although the autocatalytic cure mechanism was not affected by the addition of PVAc. ESEM showed the cured epoxy/PVAc blends had different morphologies as a function of PVAc content: an inversion in morphology took place for blends containing 15 wt % PVAc. The changes in the blend morphology with PVAc content had a clear effect on the DMTA behavior. Inverted morphology blends had low storage modulus values and a high capability to dissipate energy at temperatures higher than the PVAc glass‐transition temperature, in contrast to the behavior of neat epoxy and blends with a low PVAc content. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1507–1516, 2007     

Effect of poly(epichlorohydrin) on the thermal and mechanical properties of poly(vinyl chloride)

Five kinds of polyepichlorohydrin (PECH) of different molecular weights were synthesized and characterized by gel permeation chromatography (GPC). Mechanical blending was used to mix PECH and poly(vinyl chloride) (PVC) together. The blends of different PVC/PECH ratios were characterized by thermogravimetric analysis (TGA), tensile tests, differential scanning calorimetry (DSC), and dynamic mechanical analysis (DMA). TGA results show the thermal stability of PVC/PECH blends is desirable. Tensile tests indicate elongation at break is raised by increasing both the amount and the molecular weight of PECH. DSC is used to determine the glass transition temperature of PECH, and a quite low T_g is obtained. DMA results indicate that PECH has a perfect compatibility with PVC, when PECH concentration is below 20 wt %. There is only one peak in each tan δ curve, and the corresponding T_g decreases as PECH amount increases. However, above 20 wt %, phase separation takes place. The molecular weight of PECH also has a great influence on the glass transition temperature of the blends. This study shows that PECH is an excellent plasticizer for PVC, and one can tailor the glass transition temperature and tensile properties by changing the amount and the molecular weight of PECH. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Miscibility and properties of completely biodegradable blends of poly(propylene carbonate) and poly(butylene succinate)

Completely biodegradable blends of poly (propylene carbonate) (PPC) and poly(butylene succinate) (PBS) were melt‐prepared and then compression‐molded. The miscibilities of the two aliphatic polyesters, that is, PPC and PBS, were investigated by dynamic mechanical analysis (DMA) and scanning electron microscopy (SEM). The static mechanical properties, thermal behaviors, crystalline behavior, and melt flowability of the blends were also studied. Static tensile tests showed that the yield strength and the strength at break increased remarkably up to 30.7 and 46.3 MPa, respectively, with the incorporation of PBS. The good ductility of the blends was maintained in view of the large elongation at break. SEM observation revealed a two‐phase structure with good interfacial adhesion. The immiscibility of the two components was verified by the two independent glass‐transition temperatures obtained from DMA tests. Moreover, thermogravimetric measurements indicated that the thermal decomposition temperatures (T_?5% and T_?10%) of the PPC/PBS blends increased dramatically by 30–60°C when compared with PPC matrix. The melt flow indices of the blends showed that the introduction of PBS improved the melt flowability of the blends. The blending of PPC with PBS provided a practical way to develop completely biodegradable blends with applicable comprehensive properties. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Morphology,dynamic mechanical,and electrical properties of bio‐based poly(trimethylene terephthalate) blends,part 2: Poly(trimethylene terephthalate)/poly(ether esteramide)/polycarbonate blends

Bio‐based poly(trimethylene terephthalate) (PTT) and poly(ether esteramide) (PEEA) blends were prepared by melt processing with varying weight ratios (0–20 wt %) of polycarbonate (PC). The blends were characterized by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), polarized light microscopy (PLM), and transmission electron microscopy (TEM). Electrostatic performance was also investigated for those PTT blends since PEEA is known as an ion conductive polymer. DMA suggests that PC is miscible with PEEA and selectively goes into PEEA phase in case of ternary blends of PTT/PEEA/PC. The glass transition temperature (T_g) for PC/PEEA is well predicted by Gordon Taylor equation. Addition of PC retards the electrostatic decay performance of PTT/PEEA blends by restricting the motion of ions in PEEA through increasing the T_g of PEEA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Miscibility,phase behavior,and mechanical properties of ternary blends of poly(vinyl chloride)/polystyrene/chlorinated polyethylene-graft-polystyrene

The effectiveness of chlorinated polyethylene-graft-polystyrene (CPE-g-PS) as a polymeric compatibilizer for immiscible poly(vinyl chloride)/polystyrene (PVC/PS) blends was investigated. The miscibility, phase behavior, and mechanical properties were studied using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), Izod impact tests, tensile tests, and scanning electron microscopy (SEM). DSC and DMA studies showed that PVC is immiscible with chlorinated polyethylene (CPE) in CPE-g-PS, whereas the PS homopolymer is miscible with PS in CPE-g-PS. The PVC/PS/CPE-g-PS ternary blends exhibit a three-phase structure: PVC phase, CPE phase, and PS phase that consisted of a PS homopolymer and PS in CPE-g-PS. The mechanical properties showed that CPE-g-PS interacts well with both PVC and PS and can be used as a polymeric compatibilizer for PVC/PS blends. CPE-g-PS can also be used as an impact modifier for both PVC and PS. SEM observations confirmed, after the addition of CPE-g-PS, improvement of the interfacial adhesion between the phases of the PVC/PS blends. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 995–1003, 1998     

Mechanical and morphological properties of epoxy resins modified by poly(phthalazinone ether sulfone ketone)

A series of blends have been prepared by adding a novel thermoplastic poly(phthalazinone ether sulfone ketone) (PPESK) in varying proportions to diglycidyl ether of bisphenol A epoxy resin (DGEBA) cured with p‐diaminodiphenylsulfone (DDS). All the blends showed two‐phase structures characterized by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). Addition of the PPESK resulted in great enhancement of glass transition temperatures (T_g) both in the epoxy‐rich phase and in the PPESK‐rich phase by reason of the special structure of PPESK. There was moderate increase in the fracture toughness as estimated by impact strength. Fracture mechanisms such as crack deflection and branches, ductile microcracks, ductile tearing of the thermoplastic, and local plastic deformation of the matrix were responsible for the increase in the fracture toughness of the blends. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Studies on the miscibility and phase structure in blends of poly(epichlorohydrin) and poly(vinyl acetate)

The miscibility of atactic poly(epichlorohydrin) (aPECH) with poly(vinyl acetate) (PVAc) was examined under two different conditions: (i) in dilute solution, using vicometeric measurements and (ii) as cast films, using differential scanning calorimetric (DSC) and FT-infrared spectroscopy. Phase separation on heating, i.e. lower critical solution temperature (LCST) behavior of the aPECH/PVAc blends was examined by the measurement of transmitted light intensity against temperature. From viscosity measurements, the Krigbaum-Wall polymer-polymer interaction (ΔB) was evaluated. The DSC results show that the aPECH/PVAc blends are miscible as evidenced by the observation of a single composition-dependent glass-transition temperature (T_g) which is well described by the Couchman and Gordon Taylor models. The Flory-Huggins interaction parameter (χ₁₂) calculated from the T_g-method was negative and equal to −0.01, indicating a relatively low interaction strength. The FT-IR results match very well with those of DSC. The cloud point phenomenon is thermodynamically driven but phase separation, once taken place, is diffusion controlled in normal accessible time.     

Thermal properties and non‐isothermal crystallization behavior of biodegradable poly(p‐dioxanone)/poly(vinyl alcohol) blends

Blends of two biodegradable semicrystalline polymers, poly(p‐dioxanone) (PPDO) and poly(vinyl alcohol) (PVA) were prepared with different compositions. The thermal stability, phase morphology and thermal behavior of the blends were studied by using thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). From the TGA data, it can be seen that the addition of PVA improves the thermal stability of PPDO. DSC analysis showed that the glass transition temperature (T_g) and the melting temperature (T_m) of PPDO in the blends were nearly constant and equal to the values for neat PPDO, thus suggesting that PPDO and PVA are immiscible. It was found from the SEM images that the blends were phase‐separated, which was consistent with the DSC results. Additionally, non‐isothermal crystallization under controlled cooling rates was explored, and the Ozawa theory was employed to describe the non‐isothermal crystallization kinetics. Copyright © 2006 Society of Chemical Industry     

Cure kinetics and morphology of blends of epoxy resin with poly (ether ether ketone) containing pendant tertiary butyl groups

The cure kinetics and morphology of diglycidyl ether of bisphenol-A (DGEBA) epoxy resin modified with a poly (ether ether ketone) based on tertiary butyl hydroquinone (PEEK-T) cured with diamino diphenyl sulphone (DDS) were investigated using differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and dynamic mechanical thermal analysis (DMTA). The results obtained from DSC were applied to autocatalytic and diffusion controlled kinetic models. The reaction mechanism broadly showed autocatalytic behaviour regardless of the presence of PEEK-T. At higher PEEK-T concentration, more diffusion controlled mechanism was observed. The rate of curing reaction decreased with increase in thermoplastic content and also with the lowering of curing temperature. The activation energies of the blends are higher than that of the neat resin. The blends showed a phase separated morphology. The dispersed phase showed a homogeneous particle size distribution. The T_g of the neat resin decreased with the decrease in cure temperature. Two T_g's corresponding to the epoxy rich and thermoplastic rich phases were observed in the dynamic mechanical spectrum. The storage modulus of 10 and 20 phr PEEK-T blends are found to be greater than the neat resin.     

Miscibility and mechanical properties of tetrafunctional epoxy resin/phenolphthalein poly(ether ether ketone) blends

Phenolphthalein poly(ether ether ketone) (PEK‐C) was found to be miscible with uncured tetraglycidyl 4,4′‐diaminodiphenylmethane (TGDDM), which is a type of tetrafunctional epoxy resin (ER), as shown by the existence of a single glass transition temperature (T_g) within the whole composition range. The miscibility between PEK‐C and TGDDM is considered to be due mainly to entropy contribution. Furthermore, blends of PEK‐C and TGDDM cured with 4,4′‐diaminodiphenylmethane (DDM) were studied using dynamic mechanical analysis (DMA), Fourier‐transform infrared (FTIR) spectroscopy, and scanning electron microscopy (SEM). DMA studies show that the DDM‐cured TGDDM/PEK‐C blends have only one T_g. SEM observation also confirmed that the blends were homogeneous. FTIR studies showed that the curing reaction is incomplete due to the high viscosity of PEK‐C. As the PEK‐C content increased, the tensile properties of the blends decreased slightly and the fracture toughness factor also showed a slight decreasing tendency, presumably due to the reduced crosslink density of the epoxy network. SEM observation of the fracture surfaces of fracture toughness test specimens showed the brittle nature of the fracture for the pure ER and its blends with PEK‐C. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 598–607, 2001     

Melt blending of polylactide and poly(methyl methacrylate): Thermal and mechanical properties and phase morphology characterization

Blends of polylactide with poly(methyl methacrylate), PLA/PMMA, were prepared by a semi‐industrial twin screw extruder and afterwards were injection molded. Blends were studied using different techniques as Fourier Transform Infrared Spectroscopy (FTIR), Dynamic Mechanical Analysis (DMA), Differential Scanning Calorimetry (DSC), Scanning Electron Microscopy (SEM), and mechanical properties by means of tensile and impact tests, were also studied. This work helped better understanding of apparently contradictory results reported in the literature for PLA/PMMA blends prepared by melt compounding. DSC first heating scan and DMA results showed partially miscible blends, whereas the second DSC heating scan showed miscible blends. For miscible blends, T_g values were predicted using Gordon‐Taylor equation. On the other hand, Small and Van Krevelen approaches were used to estimate the solubility parameters of neat PLA and neat PMMA, and Flory‐Huggins interaction parameter was calculated from solubility parameters. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42677.     

Physical aging in poly(methyl methacrylate)poly(styrene-co-acrylonitrile) blends. Part II: Enthalpy relaxation

An investigation of the effect of physical aging on excess enthalpy of compatible polymer blends was carried out. Poly(methyl methacrylate) (PMMA) and poly(styrene-co-acrylonitrile) (SAN) were chosen for this study. Blends of different ratios of PMMA and SAN were physically aged at different times and temperatures below their glass transition (T_g) and then subjected to enthalpy relaxation measurement in a differential scanning calorimeter (DSC). An improved procedure was developed and, employed to analyze the data. The error associated with the calculation of the normalized deviation in enthalpy, known as the “Φ” function, was below 4%. The relaxation was observed to proceed faster at higher aging temperature. It was also found that at higher aging temperatures of T_g – 20 and T_g– 35°C, enthalpy relaxation in SAN-rich blends proceeds faster than in PMMA rich blends, while at the low aging temperature of T_g– 50°C the rate of relaxation becomes independent of the composition.     

Miscibility in poly(vinyl chloride)/chlorinated poly(vinyl chloride) blends,and blends of different chlorinated poly(vinyl chlorides)

Blends of poly(vinyl chloride) with chlorinated poly(vinyl chloride) (PVC), and blends of different chlorinated poly(vinyl chlorides) (CPVC) provide an opportunity to examine systematically the effect that small changes in chemical structure have on polymer-polymer miscibility. Phase diagrams of PVC/CPVC blends have been determined for CPVC's containing 62 to 38 percent chlorine. The characteristics of binary blends of CPVC's of different chlorine contents have also been examined using differential calorimetry (DSC) and transmission electron microscopy. Their mutual solubility has been found to be very sensitive to their differences in mole percent CCl₂ groups and degree of chlorination. In metastable binary blends of CPVC's possessing single glass transition temperatures (T_g) the rate of phase separation, as followed by DSC, was found to be relatively slow at temperatures 45 to 65° above the T_g of the blend.     

Crystallization,morphology, and mechanical behavior of polylactide/poly(ε‐caprolactone) blends

Optically pure polylactides, poly(L ‐lactide) (PLLA) and poly(D ‐lactide) (PDLA), were blended across the range of compositions with poly(ε‐caprolactone) (PCL) to study their crystallization, morphology, and mechanical behavior. Differential scanning calorimetry and dynamic mechanical analysis (DMA) of the PLA/PCL blends showed two T_gs at positions close to the pure components revealing phase separation. However, a shift in the tan δ peak position by DMA from 64 to 57°C suggests a partial solubility of PCL in the PLA‐rich phase. Scanning electron microscopy reveals phase separation and a transition in the phase morphology from spherical to interconnected domains as the equimolar blend approaches from the outermost compositions. The spherulitic growth of both PLA and PCL in the blends was followed by polarized optical microscopy at 140 and 37°C. From tensile tests at speed of 50 mm/min Young's modulus values between 5.2 and 0.4 GPa, strength values between 56 and 12 MPa, and strain at break values between 1 and 400% were obtained varying the blend composition. The viscoelastic properties (E′ and tan δ) obtained at frequency of 1 Hz by DMA are discussed and are found consistent with composition, phase separation, and crystallization behavior of the blends. POLYM. ENG. SCI., 46:1299–1308, 2006. © 2006 Society of Plastics Engineers     

Compatibility study of chlorinated polyethylene/ethylene methacrylate copolymer blends using thermal,mechanical, and chemical analysis

Blends of chlorinated polyethylene (CPE) elastomer and ethylene methacrylate copolymer (EMA) in various compositions were studied for their compatibility using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and Fourier transform infrared (FTIR) spectroscopy techniques. Irrespective of measurement techniques used, all blends showed a single glass transition temperature (T_g) lying in between the T_g of control polymers in both DSC and DMA. Glass transition temperatures of blends obtained from DSC were in consistency with Couchman–Karasz equation. Also, the T_g obtained from both DSC and DMA are above the “rule of mixing” line of the two control polymers. These results from thermal analysis clearly indicate some compatibility between the two polymers. Furthermore, compatibility of CPE/EMA blends were also been investigated by FTIR spectroscopy and scanning electron microscopic analysis. A shifting of characteristic C? Cl stretching peak of CPE and C?O stretching peak of EMA toward lower wave number indicate the presence of specific interaction between the two polymers. Mechanical properties like tensile strength, modulus at 100% elongation, elongation at break, and hardness were observed above the line of additivity drawn between the two control polymers, which corroborate compatibility between CPE and EMA. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40316.     

Miscibility and hydrogen bonding in blends of poly(vinyl acetate) with phenolic resin

The miscibility of phenolic resin and poly(vinyl acetate) (PVAc) blends was investigated by differential scanning calorimeter (DSC), Fourier transform infrared spectroscopy (FT-IR) and solid state ¹³C nuclear magnetic resonance (NMR). This blend displays single glass transition temperature (T_g) over entire compositions indicating that this blend system is miscible in the amorphous phase due to the formation of hydrogen bonding between hydroxyl groups of phenolic resin and carbonyl groups of PVAc. Quantitative measurements on fraction of hydrogen-bonded carbonyl group using both ¹³C solid-state NMR and FT-IR analyses result in good agreement between these two spectroscopic techniques. According to the proton spin-lattice relaxation time in the rotating frame (T_1ρ^H), the phenolic/PVAc blend is intimately mixed on a scale less than 2-3 nm. Furthermore, the inter-association equilibrium constant and its related enthalpy of phenolic/PVAc blends were determined as a function of temperatures by infrared spectra based on the Painter-Coleman association model.     

Miscibility and crystallization behavior of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)/poly(vinyl acetate) blends

The miscibility and crystallization behavior of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (P(HB‐co‐HV))/poly(vinyl acetate) (PVAc) blends have been investigated by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). It was found that P(HB‐co‐HV)/PVAc blends were miscible in the melt over the whole compositions. Thus the blend exhibited a single glass transition temperature (T_g), which increased with increasing PVAc composition. The spherulitic morphologies of P(HB‐co‐HV)/PVAc blends indicated that the PVAc was predominantly segregated into P(HB‐co‐HV) interlamellar or interfibrillar regions during P(HB‐co‐HV) crystallization because of the volume‐filled spherulites. As to the crystallization kinetics study, it was found that the overall crystallization and crystal growth rates decreased with the addition of PVAc. The kinetics retardation was primarily attributed to the reduction of chain mobility and dilution of P(HB‐co‐HV) upon mixing with higher T_g PVAc. The overall crystallization rate was predominantly governed by the spherulitic growth rate and promoted by the samples treated with the quenched state because of the higher nucleation density. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 980–988, 2006     

The effect of citrate ester plasticizers on the thermal and mechanical properties of poly(DL‐lactide)

Citrate esters triethyl citrate, tributyl citrate, and acetyl tributyl citrate were used as plasticizers for amorphous poly(D,L ‐lactide) (PDLLA). The resultant compositions were analyzed by means of differential scanning calorimetry (DSC), dynamic mechanical thermal analysis, and tensile testing to investigate the properties of the blends. Glass transition temperatures (T_gs) obtained by DSC were also compared to theoretically calculated T_gs. Increasing plasticizer content decreased the resultant T_g of the blend with plasticizer efficiency enhanced as the molecular weight of the citrate ester increased. However, in blends with high plasticizer content, a lack of miscibility also occurred with increased molecular weight. Theoretical results were comparable with those obtained experimentally at compositions, which were miscible. Increasing plasticizer content increased the ductility and decreased the strength of the polymer. The addition of 10 wt % plasticizer to PDLLA decreased tensile strength by over 50% with the deterioration larger at higher concentrations of plasticizer. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Study of miscibility of poly(vinyl acetate) and poly(vinyl alcohol) blends by fluorescence spectroscopy

Secondary relaxation of poly(vinyl alcohol) (PVA), poly(vinyl acetate) (PVAc), and their blends in different proportions (9 : 1, 1 : 1, and 1 : 9) were studied by photoluminescence of anthracene, fluorescein, and both probes dissolved in the polymer blends. The temperature of the glass transition in the homopolymers was determined by the radiationless deactivation of anthracene as T_g(PVAc) ? 304 K and the photobleaching of fluorescein as T_g(PVA) ? 350 K. The relaxation processes of the different phases of the polymer blends occur at temperatures close to the homopolymers, which may be explained by the localization of each molecular probe within the matrix. These deactivation curves, however, are not similar to those of the individual homopolymers, suggesting a partial miscibility between these polymers. © 1995 John Wiley & Sons, Inc.