Miscibility and crystallization of poly(ethylene succinate)/poly(vinyl phenol) blends

Miscibility of biodegradable poly(ethylene succinate) (PES)/poly(vinyl phenol) (PVPh) blends has been studied by differential scanning calorimetry (DSC) in this work. PES is found to be miscible with PVPh as shown by the existence of single composition dependent glass transition temperature over the entire composition range. Spherulitic morphology and the growth rates of neat and blended PES were investigated by optical microscopy (OM). Both neat and blended PES show a maximum growth rate value in the crystallization temperature range of 45-65 °C, with the growth rate of neat PES being higher than that of blended PES at the same crystallization temperature. The overall crystallization kinetics of neat and blended PES was also studied by DSC and analyzed by the Avrami equation at 60 and 65 °C. The crystallization rate decreases with increasing the temperature for both neat and blended PES. The crystallization rate of blended PES is lower than that of neat PES at the same crystallization temperature. However, the Avrami exponent n is almost the same despite the blend composition and crystallization temperature, indicating that the addition of PVPh does not change the crystallization mechanism of PES but only lowers the crystallization rate.     

Poly(butylene succinate)/poly(vinyl phenol) blends. Part 1. Miscibility and crystallization

Miscibility has been investigated in blends of poly(butylene succinate) (PBSU) and poly(vinyl phenol) (PVPh) by differential scanning calorimetry in this work. PBSU is miscible with PVPh as shown by the existence of single composition dependent glass transition temperature over the entire composition range. In addition, the polymer–polymer interaction parameter, obtained from the melting depression of PBSU using the Nishi–Wang equation, is composition dependent, and its value is always negative. This indicates that PBSU/PVPh blends are thermodynamically miscible in the melt. Preliminary morphology study of PBSU/PVPh blends was also studied by optical microscopy (OM). OM experiments show the spherulites of PBSU become larger with the PVPh content, indicative of a decrease in the nucleation density, and the coarseness of PBSU spherulites increases too with increasing the PVPh content in the blends.     

Fully biodegradable blends of poly(l-lactide) and poly(ethylene succinate): Miscibility, crystallization, and mechanical properties

Both poly(l-lactide) (PLLA) and poly(ethylene succinate) (PES) are biodegradable semicrystalline polyesters. The disadvantages of poor mechanical properties and slow crystallization rate of PLLA limit its wide application. Fully biodegradable polymer blends were prepared by blending PLLA with PES. Miscibility, crystallization behavior, and mechanical properties of PLLA/PES blends were investigated by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), wide angle X-ray diffraction (WAXD), scanning electron microscopy (SEM), and tensile tests in this work. Experimental results indicated that PLLA was immiscible with PES. Crystallization of PLLA/PES blends was studied by DSC using two-step crystallization condition and analyzed by the Avrami equation. The crystallization rate of PLLA at 100 °C was accelerated with the increase of PES in the blends while the crystallization mechanism did not change. In the case of the isothermal crystallization of PES at 67.5 °C, the crystallization mechanism did not change, and the crystallization rate decreased with the increase of PLLA. The mechanical properties of PLLA/PES blends were examined by tensile testing. The elongation at break of PLLA was improved significantly in the blends, while its considerably high Young's modulus was still kept. SEM images of fracture surfaces indicated that the fracture behavior of PLLA/PES blends changed from brittle fracture to ductile fracture behavior in the blends.     

Miscibility and crystallization in crystalline/crystalline blends of poly(butylene succinate)/poly(ethylene oxide)

Miscibility and crystallization behavior have been investigated in blends of poly(butylene succinate) (PBSU) and poly(ethylene oxide) (PEO), both semicrystalline polymers, by differential scanning calorimetry and optical microscopy. Experimental results indicate that PBSU is miscible with PEO as shown by the existence of single composition dependent glass transition temperature over the entire composition range. In addition, the polymer-polymer interaction parameter, obtained from the melting depression of the high-T_m component PBSU using the Flory-Huggins equation, is composition dependent, and its value is always negative. This indicates that PBSU/PEO blends are thermodynamically miscible in the melt. The morphological study of the isothermal crystallization at 95 °C (where only PBSU crystallized) showed the similar crystallization behavior as in amorphous/crystalline blends. Much more attention has been paid to the crystallization and morphology of the low-T_m component PEO, which was studied through both one-step and two-step crystallization. It was found that the crystallization of PEO was affected clearly by the presence of the crystals of PBSU formed through different crystallization processes. The two components crystallized sequentially not simultaneously when the blends were quenched from the melt directly to 50 °C (one-step crystallization), and the PEO spherulites crystallized within the matrix of the crystals of the preexisted PBSU phase. Crystallization at 95 °C followed by quenching to 50 °C (two-step crystallization) also showed the similar crystallization behavior as in one-step crystallization. However, the radial growth rate of the PEO spherulites was reduced significantly in two-step crystallization than in one-step crystallization.     

Nonisothermal crystallization kinetics of biodegradable poly(butylene succinate)/poly(vinyl phenol) blend

Nonisothermal melt crystallization kinetics of biodegradable PBSU/PVPh blend was investigated with differential scanning calorimetry (DSC) from the viewpoint of practical application. PBSU/PVPh blends were cooled from the melt at various cooling rates ranging from 2.5 to 40°C/min. The crystallization peak temperature decreased with increasing the cooling rate for both neat and blended PBSU. Furthermore, the crystallization peak temperature of PBSU in the blend was lower than that of neat PBSU at a given cooling rate. Two methods, namely the Avrami equation and the Tobin method, were used to describe the nonisothermal crystallization of PBSU/PVPh blend. It was found that the Avrami equation was more suitable to predict the nonisothermal crystallization of PBSU/PVPh blend than the Tobin method. The effects of cooling rate and blend composition on the crystallization behavior of PBSU were studied in detail. It was found that the crystallization rate decreased with decreasing the cooling rate for both neat and blended PBSU. However, the crystallization of PBSU blended with PVPh was retarded compared with that of neat PBSU at the same cooling rate. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 972–978, 2007     

Poly(hydroxybutyrate)/poly(butylene succinate) blends: miscibility and nonisothermal crystallization

Four blends of poly(hydroxybutyrate) (PHB) and poly(butylene succinate) (PBSU), both biodegradable semicrystalline polyesters, were prepared with the ratio of PHB/PBSU ranging from 80/20 to 20/80 by co-dissolving the two polyesters in N,N-dimethylformamide and casting the mixture. Differential scanning calorimetry (DSC) and optical microscopy (OM) were used to probe the miscibility of PHB/PBSU blends. Experimental results indicated that PHB showed some limited miscibility with PBSU for PHB/PBSU 20/80 blend as evidenced by the small change in the glass transition temperature and the depression of the equilibrium melting point temperature of the high melting point component PHB. However, PHB showed immiscibility with PBSU for the other three blends as shown by the existence of unchanged composition independent glass transition temperature and the biphasic melt. Nonisothermal crystallization of PHB/PBSU blends was investigated by DSC using various cooling rates from 2.5 to 10 °C/min. During the nonisothermal crystallization, despite the cooling rates used two crystallization peak temperatures were found for PHB/PBSU 40/60 and 60/40 blends, corresponding to the crystallization of PHB and PBSU, respectively, whereas only one crystallization peak temperature was observed for PHB/PBSU 80/20 and 20/80 blends. However, it was found that after the nonisothermal crystallization the crystals of PHB and PBSU actually co-existed in PHB/PBSU 80/20 and 20/80 blends from the two melting endotherms observed in the subsequent DSC melting traces, corresponding to the melting of PHB and PBSU crystals, respectively. The subsequent melting behavior was also studied after the nonisothermal crystallization. In some cases, double melting behavior was found for both PHB and PBSU, which was influenced by the cooling rates used and the blend composition.     

Miscibility and crystallization behaviour of biodegradable blends of two aliphatic polyesters. Poly(3-hydroxybutyrate-co-hydroxyvalerate) and poly(butylene succinate) blends

Blends of poly(3-hydroxybutyrate-co-hydroxyvalerate) (PHBV) and poly(butylene succinate) (PBSU), both biodegradable semicrystalline polyesters, were prepared with the ratio of PHBV/PBSU ranging from 80/20 to 20/80 by co-dissolving the two polyesters in chloroform and casting the mixture. Differential scanning calorimetry (DSC) and optical microscopy (OM) were used to study the miscibility and crystallization behaviour of PHBV/PBSU blends. Experimental results indicate that PHBV is immiscible with PBSU as shown by the almost unchanged glass transition temperature and the biphasic melt. Crystallization of PHBV/PBSU blends was studied by DSC using two-step crystallization and analyzed by the Avrami equation. The crystallization rate of PHBV decreases with the increase of PBSU in the blends while the crystallization mechanism does not change. In the case of the isothermal crystallization of PBSU, the crystallization mechanism does not change. The crystallization rate of PBSU in the blends is lower than that of neat PBSU; however, the change in the crystallization rate of PBSU was not so big in the blends. The different content of the PHBV in the blends does not make a significant difference in the crystallization rate of PBSU.     

Miscibility and crystallization of poly(ethylene oxide) and poly(ε-caprolactone) blends

Blends of poly(ethylene oxide) (PEO) with poly(ε-caprolactone) (PCL), both semicrystalline polymers, were prepared by co-dissolving the two polyesters in chloroform and casting the mixture. Phase contrast microscopy was used to probe the miscibility of PEOB/PCL blends. Experimental results indicated that PEO was immiscible with PCL because the melt was biphasic. Crystallization of PEO/PCL blends was studied by differential scanning calorimetry and analyzed by the Avrami equation. The crystallization rate of PEO decreased with the increase of PCL in the blends while the crystallization mechanism did not change. In the case of the isothermal crystallization of PCL, the crystallization mechanism did not change, and the change in the crystallization rate was not very big, or almost constant with the addition of PEO, compared with the change of the crystallization rate of PEO.     

Miscibility and crystallization behavior of biodegradable blends of two aliphatic polyesters. Poly(butylene succinate) and Poly(ε-caprolactone)

Poly(butylene succinate) (PBSU) and poly(ε-caprolactone) (PCL) blends, both biodegradable chemosynthetic semicrystalline polyesters, were prepared with the ratio of PBSU/PCL ranging from 80/20 to 20/80 by co-dissolving the two polyesters in chloroform and casting the mixture. The miscibility and crystallization behavior of PBSU/PCL blends were investigated by differential scanning calorimetry and optical microscopy. Experimental results indicated that PBSU was immiscible with PCL as evidenced by the composition independent glass transition temperature and the biphasic melt. However, during the crystallization from the melt at a given cooling rate, the crystallization peak temperature of PBSU in the blends decreased slightly with the increase of PCL, while that of PCL in the blends first increased and then decreased with the increase of PBSU. Moreover, both the crystallization peak temperature of PBSU and PCL shifted to the low temperature range with the increase of the cooling rate for a given blend composition. Double melting peaks or one main melting peak with a shoulder were found for both PBSU and PCL after the complete crystallization cooled from the melt, and were ascribed to the melting-recrystallization mechanism. It was found that the subsequent melting behavior of PBSU/PCL blends was influenced apparently by the blend composition and the cooling rate used.     

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     

Crystallization kinetics and morphology of poly(butylene succinate)/poly(vinyl phenol) blend

Biodegradable crystalline poly(butylene succinate) (PBSU) can form miscible polymer blends with amorphous poly(vinyl phenol) (PVPh). The isothermal crystallization kinetics and morphology of neat and blended PBSU with PVPh were studied by differential scanning calorimetry (DSC), optical microscopy (OM), wide angle X-ray diffraction (WAXD), and small angle X-ray scattering (SAXS) in this work. The overall isothermal crystallization kinetics of neat and blended PBSU was studied with DSC in the crystallization temperature range of 80-88 °C and analyzed by applying the Avrami equation. It was found that blending with PVPh did not change the crystallization mechanism of PBSU, but reduced the crystallization rate compared with that of neat PBSU at the same crystallization temperature. The crystallization rate decreased with increasing crystallization temperature, while the crystallization mechanism did not change for both neat and blended PBSU irrespective of the crystallization temperature. The spherulitic morphology and growth were observed with hot stage OM in a wide crystallization temperature range of 75-100 °C. The spherulitic morphology of PBSU was influenced apparently by the crystallization temperature and the addition of PVPh. The linear spherulitic growth rate was measured and analyzed by the secondary nucleation theory. Through the Lauritzen-Hoffman equation, some parameters of neat and blended PBSU were derived and compared with each other including the nucleation parameter (K_g), the lateral surface free energy (σ), the end-surface free energy (σ_e), and the work of chain folding (q). Blending with PVPh decreased all the aforementioned parameters compared with those of neat PBSU; however, the decrease extent was limited. WAXD result showed that the crystal structure of PBSU was not modified after blending with PVPh. SAXS result showed that the long period of blended PBSU increased, possibly indicating that the amorphous PVPh might reside mainly in the interlamellar region of PBSU.     

Miscibility and interactions in poly(n-propyl methacrylate)/poly(vinyl alcohol) blends

Poly(n-propyl methacrylate) (PPMA) is miscible with poly(vinyl alcohol) (PVA) over the whole composition range as shown by the existence of a single glass transition temperature in each blend. The interaction between PPMA and PVA was examined by Fourier transform infrared spectroscopy and solid-state nuclear magnetic resonance spectroscopy. The interactions mainly involve the hydroxyl groups of PVA and the carbonyl groups of PPMA. The measurements of proton spin-lattice relaxation time reveal that PPMA and PVA do not mix intimately on a scale of 1-3 nm, but are miscible on a scale of 20-30 nm. A small negative interaction parameter value has been obtained by melting point depression measurement.     

Miscibility and interactions in poly(2,2,3,3,3-pentafluoropropyl methacrylate-co-4-vinylpyridine)/poly(p-vinylphenol) blends

The miscibility and specific interactions in poly(2,2,3,3,3-pentafluoropropyl methacrylate-co-4-vinylpyridine) (PFX, X=0, 28, 40 or 54, denoting the mol% of 4-vinylpyridine unit in the copolymer)/poly(p-vinylphenol) (PVPh) blends have been studied by differential scanning calorimetry (DSC), atomic force microscopy (AFM), Fourier transform infrared (FTIR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). DSC studies show that PF0 is immiscible with PVPh, and the presence of a sufficient amount of 4-vinylpyridine units in the copolymer produces miscible blends. AFM images also clearly show that the blends change from heterogeneous to homogeneous upon the incorporation of 4-vinylpyridine unit into the copolymer. FTIR and XPS show the existence of inter-polymer hydrogen bonding between PFX and PVPh. The intensity of the inter-polymer hydrogen bonding increases with increasing 4-vinylpyridine content in the copolymer.     

Miscibility and crystallization behavior of biodegradable blends of two aliphatic polyesters. Poly(3-hydroxybutyrate-co-hydroxyvalerate) and poly(ε-caprolactone)

Biodegradable polymer blends of poly(3-hydroxybutyrate-co-hydroxyvalerate) (PHBV) and poly(ε-caprolactone) (PCL) blends were prepared with the ratio of PHBV/PCL ranging from 80/20-20/80 by co-dissolving the two polyesters in chloroform and casting the mixture. Differential scanning calorimetry (DSC) and optical microscopy (OM) were used to investigate the miscibility and crystallization of PHBV/PCL blends. Experimental results indicated that PHBV showed no miscibility with PCL for PHBV/PCL blends as evidenced by the existence of unchanged composition independent glass transition temperature and the biphasic melt. Crystallization of PHBV and PCL was studied with DSC and analyzed by the Avrami equation by using two-step crystallization in the PHBV/PCL blends. The crystallization rate of PHBV at 70 °C decreased with the increase of PCL in the blends, while the crystallization mechanism did not change. In the case of the isothermal crystallization of PCL at 42 °C, the crystallization rate increased with the addition of PHBV, and the crystallization mechanism changed, too, indicating that the crystallization of PHBV at 70 °C had an apparent influence on the crystallization of PCL at 42 °C.     

Studies on blends of binary crystalline polymers: Miscibility and crystallization behavior in PBT/PAr(I27-T73)

The miscibility and crystallization behavior of binary crystalline blends of poly(butylene terephthalate) [PBT] and polyarylate based on Bisphenol A and a 27/73 mole ratio of isophthalic and terephthalic acids [PAr(I27-T73)] have been investigated by differential scanning calorimetry (DSC). This blend system exhibits a single composition-dependent glass transition temperature over the entire composition range. The equilibrium melting point depression of PBT was observed, and Flory interaction parameter χ₁₂ = −0.96 was obtained. These indicate that the blends are thermodynamically miscible in the melt. The crystallization rate of PBT decreased as the amount of PAr(I27-T73) increased, and a contrary trend was found when PAr(I27-T73) crystallized with the increase of the amount of PBT. The addition of high-T_g PAr(I27-T73) would suppress the segmental mobility of PBT, while low-T_g PBT would have promotional effect on PAr(I27-T73). The crystallization rate and melting point of PBT were significantly influenced when the PAr(I27-T73) crystallites are previously formed. It is because not only does the amorphous phase composition shift to a richer PBT content after the crystallization of PAr(I27-T73), but also the PAr(I27-T73) crystal phase would constrain the crystallization of PBT. Thus, effects of the glass transition temperature, interaction between components, and previously formed crystallites of one component on the crystallization behavior of the other component were discussed and compared with blends of PBT and PAr(I-100) based on Bisphenol A and isophthalic acid.     

Miscibility and interactions in poly(methylthiomethyl methacrylate)/poly(vinyl alcohol) blends

Poly(methylthiomethyl methacrylate) (PMTMA) is miscible with poly(vinyl alcohol) (PVA) over the whole composition range as shown by the existence of a single glass transition temperature in each blend. The interaction between PMTMA and PVA was examined by Fourier transform infrared spectroscopy, solid-state nuclear magnetic resonance spectroscopy and X-ray photoelectron spectroscopy. The interactions mainly involve the hydroxyl groups of PVA and the thioether sulfur atoms of PMTMA, and the involvement of the carbonyl groups of PMTMA in interactions is not significant. The measurements of proton spin-lattice relaxation time reveal that PMTMA and PVA do not mix intimately on a scale of 1-3 nm, but are miscible on a scale of 20-30 nm. In comparison, we have previously found that PMTMA is miscible with poly(p-vinylphenol) and the two polymers mix intimately on a scale of 1-3 nm.     

Miscibility and crystallisation behaviour of poly(ethylene terephthalate)/polycarbonate blends

Poly(ethylene terephthalate)/polycarbonate blends were produced in a twin-screw extruder with and without added transesterification catalyst, lanthanum acetyl acetonate. The miscibility of the blends was studied from their crystallisation behaviour and variation in glass transition temperature with composition using differential scanning calorimetry, scanning electron microscopy and change in mechanical properties. The blends prepared without the catalyst showed completely immiscible over all compositions, while those prepared in the presence of the catalyst showed some limited miscible. The presence of PC inhibited the crystallisation of PET but this was much greater in the blends prepared in the presence of catalyst suggesting that some reaction had taken place between the two polyesters. The tensile properties showed little differences between the two types of blends.     

Miscible blends of poly(4‐vinyl phenol)/poly (trimethylene terephthalate)

A new miscible blend of all compositions comprising poly(4‐vinyl phenol) (PVPh) and poly(trimethylene terephthalate) (PTT) was discovered and reported. The blends exhibit a single composition‐dependent glass transition and homogeneous phase morphology, with no lower critical solution temperature (LCST) behavior upon heating to high temperatures. Interactions and spherulite growth kinetics in the blends were also investigated. The Flory–Huggins interaction parameter (χ₁₂) and interaction energy density (B) obtained from analysis of melting point depression are negative (χ₁₂ = ?0.74 and B = ?32.49 J cm^?3), proving that the PVPh/PTT blends are miscible over a wide temperature range from ambient up to high temperatures in the melt state. FTIR studies showed evidence of hydrogen‐bonding interactions between the two polymers. The miscibility of PVPh with PTT also resulted in a reduction in spherulite growth rate of PTT in the miscible blend. The Lauritzen–Hoffman model was used to analyze the spherulite growth kinetics, which showed a lower fold‐surface free energy (σ_e) of the blends than that of the neat PTT. The decrease in the fold‐surface free energy has been attributed to disruption of the PTT lamellae exerted by PVPh in an intimately interacted miscible state. Copyright © 2004 Society of Chemical Industry     

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     

Novel miscible poly(ethylene sebacate)/poly(4-vinyl phenol) blends: Miscibility, melting behavior and crystallization study

High molecular weight samples of the novel biodegradable polyester poly(ethylene sebacate) (PESeb) were synthesized. Miscible poly(ethylene sebacate)/poly(4-vinyl phenol) semicrystalline/amorphous blends were prepared by applying the solvent casting method. Miscibility was proved by the single composition dependent glass transition temperature over the entire composition range observed in DSC traces of the quenched blend samples and also by the melting point depression. The Flory-Huggins interaction parameter was found to be x₁₂ = −1.3. Also, FTIR spectra supported the hypothesis of intermolecular interactions due to hydrogen bonding. The crystallization of PESeb in blends was studied. As expected, isothermal crystallization rates decreased in the blends with increasing the PVPh content. The Lauritzen-Hoffman analysis was tested. The values of nucleation constant K_g did not show any substantial variation. The non-isothermal crystallization of the blends was also tested. It was found that the crystallization is retarded in the case of blends, compared to the neat PESeb.