Miscibility and phase structure of binary blends of polylactide and poly(vinylpyrrolidone)

The miscibility, crystallization behavior, and component interactions of two binary blends, poly(L ‐lactide) (L ‐PLA)/poly(vinylpyrrolidone) (PVP) and poly(D ,L ‐lactide) (DL ‐PLA)/PVP, were studied with differential scanning calorimetry and Fourier transform infrared (FTIR) spectroscopy. The composition‐dependent changes of the glass‐transition temperature (T_g) and degree of crystallinity (X_c) of the L ‐PLA phase indicated that L ‐PLA and PVP were immiscible over the composition range investigated. However, the sharp decrease of X_c with increasing PVP content in the second heating run demonstrated that the cold crystallization process of L ‐PLA was remarkably restricted by PVP. In DL ‐PLA/PVP blends, the existence of two series of isolated T_g's indicated that DL ‐PLA and PVP were phase‐separated, but evidence showed that there was some degree of interaction at the interface of the two phase, especially for the blends with low DL ‐PLA contents. FTIR measurements showed that there was no appreciable change in the spectra of L ‐PLA/PVP with respect to the coaddition of each component spectrum, implying the immiscibility of the two polymers. In contrast to L ‐PLA, the intermolecular interaction between DL ‐PLA and PVP was detected by FTIR; this was evidenced by the observation of a high‐frequency shift of the C?O stretching vibration band of PVP with increasing DL ‐PLA content, which suggested some degree of miscibility. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 973–979, 2003     

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     

Miscibility and enthalpy relaxations in polysulfone—Carboxylated polysulfone blends

Phase behavior in polysulfone-carboxylated polysulfone (PSf-CPSf) blends was studied by glass transition observations in conjunction with enthalpy relaxation technique. Miscibility in all proportions was detected in blends where CPSf has a degree of carboxylation (DC, i.e. number of carboxyl groups per repeat unit) less than about 1.3. Partial miscibility was detected in blends for DC > 1.4 and up to DC = 1.9, probably as a result of decreasing intermolecular interactions with increase in DC.     

Miscibility, crystallization and melting behaviour, and semicrystalline morphology of binary blends of polycaprolactone with poly(hydroxy ether of bisphenol A)

Blends of poly(hydroxy ether of bisphenol A) (Phenoxy) with polycaprolactone (PCL) were prepared by the coprecipitation technique. The melt miscibility of the polymers was studied by optical microscopy, light transmission measurements and dynamic mechanical analysis. The crystallization kinetics of PCL in the miscible Phenoxy/PCL blends were studied using optical microscopy and the segregation behaviour of Phenoxy due to the crystallization of PCL was examined by means of optical microscopy and small-angle X-ray diffraction, while the melting behaviour of PCL in the blend was explored by differential scanning calorimetry. The polymers were found to be miscible over the entire composition and temperature range (up to 200°C), while Phenoxy is segregated interlamellarly as well as interfibrillarly and interspherulitically during the crystallization process of PCL.     

Phenoxy/Hytrel blends. I. Miscibility and melt-state reactions

Polyhydroxy ether of bisphenol A (phenoxy)/Hytrel (Hy) blends were obtained by melt mixing throughout the composition range and at several processing times. Interchange reactions took place and were followed by the torque behavior, solubility tests, and FTIR spectra. After a mixing time of 15 min, they gave rise to basically unreacted products, but at longer mixing times, they produced both branched and crosslinked products. The blends were miscible at all compositions due to the presence of specific interactions, as was seen because of the presence of a single T_g by DSC that was confirmed by DMTA. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 185–193, 1998     

Miscibility of blends of Aeromonas gum or Erwinia gum with other polysaccharides

Aeromonas (A) gum and Erwinia (E) gum are acidic heteropolysaccharides, which exist in water as expanded chains caused by the electrostatic repulsion between the charged groups. A modified approach, which was suggested to estimate miscibility of stiff polymer in our previous study, was used to determine miscibility parameter μ for blends between A gum or E gum with other polysaccharides, by using viscometry in aqueous 0.1M NaCl solution. When weight ratios of E gum/pectin were in the range of 3 : 7 ∼ 7 : 3, the blends in aqueous solution are miscible. The blends of A gum/xanthan, A gum/pectin, and E gum/xanthan in aqueous solution are obviously immiscible. When the weight fraction (w₂) of A gum or E gum in the mixture solution is 0.7, the μ predicts that the miscibility of blend films was on the order of E gum/pectin > E gum/xanthan > A gum/pectin > A gum/xanthan. These results are in good agreement with those observed by scanning electron microscopy and Fourier transform IR. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1387–1395, 1999     

Miscibility of polymethylmethacrylate and polyethyleneglycol blends in tetrahydrofuran

The miscibility of polymethylmethacrylate (PMMA) and polyethyleneglycol (PEG) blends in tetrahydrofuran (THF) has been investigated by viscosity, density, refractive index, and ultrasonic velocity studies. Various interaction parameters such as polymer–solvent and blend–solvent interaction parameters and heat of mixing have been calculated using the viscosity, density, and ultrasonic velocity data. The results indicated the existence of positive interactions in the blend polymer solutions and that they are miscible in THF in the entire composition range. The study also revealed that variation in the temperature does not affect the miscibility of PMMA and PEG blends in THF significantly. The presence of hydrogen bonding in the blends in the solid state has also been indicated by FTIR studies. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

Miscibility in crystalline polymer blends: Isotactic polypropylene and linear low‐density polyethylene

The phase behavior and the crystallization kinetics of blends composed of isotactic polypropylene (iPP) and linear low‐density polyethylene (LLDPE) were investigated by differential scanning calorimetry. The phase behavior indicates the formation of separate crystals of iPP and LLDPE at each investigated blend composition. The crystallization trace reveals that iPP crystallizes in its normal range of temperatures (i.e., at temperatures higher than that of LLDPE), when its content in the blend is higher than 25% by weight. In the blend whose iPP content is as high as 25%, at least a portion of iPP crystallizes at temperatures lower than that of LLDPE. This behavior has been proposed by Bassett to be attributed to a change in the kind of nucleation from heterogeneous to homogeneous. From the Avrami analysis of the isothermal crystallization of iPP in the presence of molten LLDPE, n values close to 2 are always obtained. According to our previously proposed interpretation of the Avrami coefficient, it can be related to the crystallite fractal dimension, through d = n + 1, which gives values close to 3, according to the spherulitic observed morphology. The kinetics parameter, i.e., the half‐time of crystallization, and the kinetic constant k show that a decrease in the overall rate of crystallization of iPP occurs on blending. Optical microscopy photographs, taken during the cooling of the samples from the melt, confirm the above results and show increasingly less resolved spherulite texture on increasing LLDPE content in the blend. The diffusion parameters evaluated for the neat polymers and for the blends in dichloromethane, which give information on the miscibility in the amorphous state, show that the diffusional behavior of the blends is governed by iPP, suggesting a two‐phase amorphous state. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3338–3346, 2003     

Nonisothermal crystallization of polyamide 66/poly(phenylene sulfide) blends

The crystalline morphologies of isothermally and nonisothermally crystallized poly(phenylene sulfide) (PPS) and its blend with polyamide 66 (PA66) were investigated by polarized optical microscopy with a hot stage. The spherulite superstructure of PPS was greatly affected by crystallizable PA66; a Maltese cross was not clear, and the impingement between spherulites disappeared. This could be ascribed to the formation of small crystals of PA66, which filled in the PPS lamellae. The nonisothermal crystallization behavior was also measured by differential scanning calorimetry. The presence of PA66 changed the nonisothermal crystallization process of PPS. The maximum crystallization temperature of the PPS phase in the blend was higher that that of neat PPS, and this indicated that PA66 acted as a nucleus for PPS. Also, the compatibilizer poly(ethylene‐stat‐methacrylate) (EMA) was added to modify the interfacial interplay of the PA66/PPS blend system. The addition of EMA greatly influenced the nonisothermal crystallization process of the PPS phase in the blend system. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Miscibility study of chitosan/polyethylene glycol fumarate blends in dilute solutions

Solution miscibility of chitosan/polyethylene glycol fumarate blends dissolved in acetate buffer solution was investigated in different blend compositions by viscosity, density, and refractive index measurement techniques at 30, 40, and 50°C. In order to quantify the miscibility of the polymer pair, degree of miscibility was studied by means of two criteria known as interaction parameters i.e., μ and α. On the basis of the sign convention involved in these criteria, these values revealed that the blend solution was miscible when the chitosan content was more than 80% (w/w) of the composition. The results were confirmed by density, and refractive index measurements. Furthermore, the results showed that the miscibility window of chitosan/polyethylene glycol fumarate blends was independent with respect to the changes in solution temperature. Therefore, these results suggested due to intermolecular hydrogen‐bonding interaction between amino and hydroxy groups of chitosan and hydroxy groups of polyethylene glycol fumarate which play an important role in the formation of miscible phase. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Phase separation in polymer blends comprising copolymers: 6. Effect of molecular architecture of block copolymers

To study the effect of the molecular architecture of a copolymer on its miscibility with corresponding homopolymers a series of block copolymers of styrene and isoprene with diblock, triblock and four-arm star architectures have been prepared and the morphologies of the blends of the copolymers and polyisoprene with different molecular weights have been examined by electron microscopy. The results show that miscibility varies in the sequence diblock>triblock>four-arm star copolymers. This sequence is in the opposite direction to the variation of the architectural complexity of the block copolymers, i.e. the more complex is molecular architecture, the greater is conformation restriction in microdomain formation and the less is solubility of homopolymer in corresponding domains.     

Miscibility of chitosan–hydroxyethylcellulose blends in aqueous acetic acid solutions at 35°C

The miscibility of blends of chitosan and hydroxyethylcellulose in a 2% acetic acid solution was studied by viscometry, densitometry, and refractometry at 35°C. The data suggest that the blends were completely miscible in all proportions. Further, the membranes were fabricated from concentrated blend solutions. The solid‐state compatibility of the blends was confirmed by scanning electron microscopy. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1996–1998, 2005     

Miscibility and crystallization behaviors of biodegradable poly(butylene succinate‐co‐butylene terephthalate)/phenoxy blends

Miscibility and crystallization behaviors of biodegradable poly(butylene succinate‐co‐butylene terephthalate) (PBST)/poly(hydroxyl ether biphenyl A) (phenoxy) blends were investigated with various techniques in this work. PBST and phenoxy are completely miscible as evidenced by the single composition‐dependent glass transition temperature over the entire blend compositions. Nonisothermal melt crystallization peak temperature is higher in neat PBST than in the blends at a given cooling rate. Isothermal melt crystallization kinetics of neat and blended PBST was studied and analyzed by the Avrami equation. The overall crystallization rate of PBST decreases with increasing crystallization temperature and the phenoxy content in the PBST/phenoxy blends; however, the crystallization mechanism of PBST does not change. Moreover, blending with phenoxy does not modify the crystal structure but reduces the crystallinity degree of PBST in the PBST/phenoxy blends. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Miscibility and mechanical properties of sulfonated polystyrene–polyurethane blends

A sulfonated polystyrene (SPS) and a polyurethane containing a tertiary amine group (NPU) were blended in solution. The effect of blend composition was studied in the blend of SPS with 9.83 mol % of sulfonation (SPS-9.83) and NPU with 33 mol % of MDEA (NPU-33). As the SPS concentration increases, a significant improvement of miscibility is observed. The tensile strength of the blends is greater than either pure NPU or SPS. A maximum strength and a maximum density occur at 50 wt % SPS. The stress–strain curve shows a well-defined yield when the SPS concentration in the blend is 30 or 50 wt %. The yield is more dramatic in the blend with 50 wt % SPS than that of 30 wt % SPS. At a lower SPS concentration, the blend behaves like a rubber, while a higher SPS concentration in the blend results in a brittle failure before yield. An increase in the sulfonation level of SPS in the SPS–NPU-33 (30/70) blends leads to an improved miscibility. A significant enhancement of tensile strength is observed as the sulfonation increases. A clear yield point on the stress–strain curves occurs when the sulfonation of SPS in the blend is 4.79 mol % or greater. Increasing the MDEA content of NPU up to 8.3 mol % can lead to an enhancement of tensile strength. A further increase in the MDEA content has little influence on the tensile strength, but a clear yield on the stress–strain curve occurs. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:2035–2045, 1998     

Miscibility of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and poly(vinyl chloride) blends

The miscibility behaviour of biodegradable poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHB-HV) blended with poly(vinyl chloride) (PVC) was investigated by using differential scanning calorimetry, dynamic mechanical thermal analysis, Fourier-transform infra-red spectroscopy and a mechanical testing system. A blend of PHB-HV containing 8% HV (PHB-8HV) with PVC was immiscible, showing two separate T_g values in all compositions: whereas a blend of PHB-HV containing 18% HV (PHB-18HV) with PVC was miscible, showing a melting-point depression and a single T_g in the whole range of compositions. For the PHB-18HV/PVC system, the C-O-C stretching vibration at 1183 cm⁻¹ of PHB-18HV and the CHCl deformation at 1254cm⁻¹ of PVC were shifted, indicating that there exists a specific intermolecular interaction between the two components. In addition, as the PVC component was increased, tensile strength and Young's modulus were increased, while the inverse behaviour was observed in elongation at break.     

Miscibility characterization of SMA/SAN and SMA/PMMA blends by differential scanning calorimetry and fluorescence techniques

In this study, styrene‐maleic anhydride (SMA) copolymer was modified by monoesterification method with 9‐(hydroxymethyl)anthracene fluorophore to prepare a fluorescent anthracene labeled SMA (SMA‐An) material. The latter was then characterized by attenuated total reflection (ATR) and thermogravimetric analysis (TGA) techniques. In the second step of this work, SMA‐An was added to SMA/[Styrene‐Acrylonitrile Copolymer (SAN)] and SMA/[Poly(methyl methacrylate) (PMMA)] blends to investigate the miscibility of these blends at the molecular level. The miscibility of SMA/PMMA blends was characterized using fluorescence quenching of anthracene by the succinic anhydride and succinic acid functions on SMA macromolecule itself. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Miscibility of segmented polyurethane/poly(vinyl chloride) blends

Miscibilities of segmented polyurethanes (SPUs) and poly(vinyl chloride) (PVC) or functionalized poly(vinyl chloride) (FPVC) were studied with dynamic mechanical analysis, differential scanning calorimetry, and X‐ray diffraction. Mechanical properties of the blends were also studied with tensile measurements. The miscibility of the blends depended greatly on the hard‐segment content of SPU and the existence of the functional groups. The combination of SPU with a low hard‐segment content and PVC with functional groups made the blend system miscible. Moreover, controlling the blend composition of SPU/FPVC allowed us to modify the mechanical properties of SPU, where the elongation at break was multiplied without a significant change in its tensile strength. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3022–3029, 2001     

Phase separation in polymer blends comprising copolymers: 4. Polycarbonate/polystyrene ABCP system

An AB-crosslinked copolymer (ABCP) with polycarbonate as A-chain and polystyrene as B-chain was prepared and characterized. A series of blends of the ABCP and homopolystyrene fractions with different molecular weights were prepared and examined by electron microscopy. The results show that the miscibility between the homopolymer and the like chains in the copolymer is limited even if the molecular weight of the former is much less than that of the latter. Considering the relatively large miscibility in diblock copolymer/homopolymer blends and the limited miscibility in ABCP/homopolymer-A blends reported in literature, this study leads to an argument that the molecular architecture of a copolymer is an important factor governing its miscibility with homopolymer. The relatively complicated architecture of ABCPs causing more restriction to the chain conformation might be one of the main reasons for its low miscibility with homopolymers.     

Poly(L‐lactide)/polypropylene blends: Evaluation of mechanical,thermal, and morphological characteristics

Poly(L lactide) (PLA) was blended with polypropylene (PP) at various ratios (PLA:PP = 90 : 10, 80 : 20, 70 : 30, and 50 : 50) with a melt‐blending technique in an attempt to improve the melt processability of PLA. Maleic anhydride (MAH)‐grafted PP and glycidyl methacrylate were used as the reactive compatibilizers to induce miscibility in the blend. The PLA/PP blend at a blend ratio of 90 : 10, exhibited optimum mechanical performance. Differential scanning calorimetry and thermogravimetric analysis studies showed that the PLA/PP/MAH‐g‐PP blend had the maximum thermal stability with the support of the heat deflection temperature values. Furthermore, dynamic mechanical analysis findings revealed an increase in the glass‐transition temperature and storage modulus with the addition of MAH‐g‐PP compatibilizer. The interaction between the compatibilizers and constituent polymers was confirmed from Fourier transform infrared spectra, and scanning electron microscopy of impact‐fractured samples showed that the soft PP phase was dispersed within the PLA matrix, and a decrease in the domain size of the dispersed phase was observed with the incorporation of MAH‐g‐PP, which acted as a compatibilizer to improve the compatibility between PLA and PP. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011