Miscibility studies of hydroxypropyl cellulose/poly(vinyl pyrrolidone) in dilute solutions and solid state

The miscibility of hydroxypropyl cellulose (HPC) and poly(vinyl pyrrolidone) (PVP) blends in aqueous solutions was studied using viscosity, ultrasonic velocity, and refractive index techniques at 30°C. The interaction parameters ΔB, μ, and α calculated from viscosity using Sun and Chee methods indicated the miscibility of this blend. This was further confirmed by ultrasonic and refractive index results. The HPC/PVP blend films are prepared by solution casting method and are analyzed by differential scanning calorimetry, X-ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopic techniques that confirmed the complete miscibility. This miscibility is due to the strong intermolecular H-bonding interactions between  OH groups of HPC and CO groups of PVP. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Super‐tough biodegradable poly(vinyl alcohol)/poly(vinyl pyrrolidone) blends plasticized by glycerol and sorbitol

Tough biodegradable films were prepared using a poly(vinyl alcohol) (PVA)/poly(vinyl pyrrolidone) (PVP) (1:1) blend with plasticizers of glycerol (GLY), sorbitol (SOR), and their (one to one) mixture. We studied the effect of plasticization on the structural, thermal, and mechanical properties of the PVA/PVP blend films. Fourier transform infrared spectra indicated good miscibility of the two components due to the H‐bonding between the PVA and PVP molecules. The addition of plasticizers reduced the interaction between PVA and PVP, evidenced by an increase in the intensity of PVA diffraction peaks observed in the X‐ray diffraction (XRD) characterization. Thermal degradation of the blends increased as a function of the plasticizer used. GLY affected thermal degradation more than SOR and the mixtures. The incorporation of the plasticizers promoted the growth of PVA crystals as evidenced by XRD patterns and the enthalpy of fusion (ΔH_f) obtained by differential scanning calorimetry measurements. The introduction of SOR to the binary blend increased toughness seven times and imparted simultaneous and pronounced improvements to maximum tensile stress and elongation at break. This behavior holds out great promise for the development of a new generation of mechanically robust, yet thoroughly biodegradable materials that could effectively supplant conventional polymers in demanding applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46406.     

Ionomeric blends of poly(ethylene oxide) with poly(styrene‐co‐maleic anhydride) ionomer: Miscibility,crystallization, and melting behavior

The miscibility and crystallization behavior of poly(ethylene oxide) (PEO) and poly(styrene‐co‐maleic anhydride) ionomer (SMAI) blends were studied by the dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC). This study has demonstrated that the presence of ion–dipole interactions enhances the miscibility of otherwise immiscible polymers in the PEO and high molecular weight poly(styrene‐co‐maleic anhydride) (SMA). The effect of ion–dipole interactions on enhancing miscibility is confirmed by the presence of a single glass transition temperature (T_g) and a depression of the equilibrium melting temperature of the PEO component. The equilibrium melting temperature of PEO in the blends are obtained using Hoffman‐Weeks plots. The interaction energy density, β, is calculated from these data using the Nishi‐Wang equation. The results suggest that PEO and SMAI blends are thermodynamically miscible in the melt. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1–7, 2000     

Study of the miscibility and crystallization behavior of poly(ethylene oxide)/poly(vinyl alcohol) blends

The miscibility and crystallization behavior of poly(ethylene oxide)/poly(vinyl alcohol) (PEO/PVA) blends were investigated by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and polarizing optical microscopy. Because the glass‐transition temperature of PVA was near the melting point of PEO crystalline, an uncommon DSC procedure was used to determine the glass‐transition temperature of the PVA‐rich phase. From the DSC and DMA results, two glass‐transition temperatures, which corresponded to the PEO‐rich phase and the PVA‐rich phase, were observed. It was an important criterion to indicate that a blend was immiscible. It was also found that the preparation method of samples influenced the morphology and crystallization behaviors of PEO/PVA blends. The domain size of the disperse phase (PVA‐rich) for the solution‐cast blends was much larger than that for the coprecipitated blends. The crystallinity, spherulitic morphology, and isothermal crystallization behavior of PEO in the solution‐cast blends were similar to those of the neat PEO. On the contrary, these properties in the coprecipitated blends were different from those of the neat PEO. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1562–1568, 2004     

Crystallization behavior and hydrophilicity of poly(vinylidene fluoride)/poly(methyl methacrylate)/poly(vinyl pyrrolidone) ternary blends

Ternary blends composed of matrix polymer poly(vinylidene fluoride) (PVDF) with different proportions of poly(methyl methacrylate) (PMMA)/poly(vinyl pyrrolidone) (PVP) blends were prepared by melt mixing. The miscibility, crystallization behavior, mechanical properties and hydrophilicity of the ternary blends have been investigated. The high compatibility of PVDF/PMMA/PVP ternary blends is induced by strong interactions between the carbonyl groups of the PMMA/PVP blend and the CF₂ or CH₂ group of PVDF. According to the Fourier transform infrared and wide‐angle X‐ray difffraction analyses, the introduction of PMMA does not change the crystalline state (i.e. α phase) of PVDF. By contrast, the addition of PVP in the blends favors the transformation of the crystalline state of PVDF from non‐polar α to polar β phase. Moreover, the crystallinity of the PVDF/PMMA/PVP ternary blends also decreases compared with neat PVDF. Through mechanical analysis, the elongation at break of the blends significantly increases to more than six times that of neat PVDF. This confirms that the addition of the PMMA/PVP blend enhances the toughness of PVDF. Besides, the hydrophilicity of PVDF is remarkably improved by blending with PMMA/PVP; in particular when the content of PVP reaches 30 wt%, the water contact angle displays its lowest value which decreased from 91.4° to 51.0°. Copyright © 2011 Society of Chemical Industry     

Poly (ethylene oxide) (PEO) influence on mechanical,thermal, and degradation properties of PLA/PBSeT blends

Poly (lactic acid) (PLA) is an important biodegradable plastic with unique properties. However, its widespread application is hindered by its low miscibility and suboptimal degradation properties. To overcome these limitations, we investigated the mechanical, thermal, and degradation properties of PLA and poly (butylene sebacate-co-terephthalate) (PBSeT) blends in the presence of poly (ethylene oxide) (PEO). Specifically, this study aimed to identify the effects of PEO as a compatibilizer and hydrolysis accelerator in PLA/PBSeT blends. PLA (80%) and PBSeT (20%) were melt blended with various PEO contents (2–10 phr), and their mechanical, thermal, and hydrolytic properties were analyzed. All PEO-treated blends exhibited a higher elongation at break than that of the control sample, and the tensile strength was slightly reduced. In the PEO 10% sample, the elongation at break increased to 800% of that of the control sample. Differential scanning chromatography (DSC) analysis confirmed that when PEO was added to the PLA/PBSeT blends, the two glass transition temperatures (T_g) narrowed, resulting in improved miscibility of PLA and PBSeT. In addition, the hydrolytic degradation of the PLA/PBSeT/PEO blend accelerated as the PEO content increased. It was confirmed that PEO can act as a compatibilizer and hydrolysis-accelerating agent for PLA/PBSeT blends.     

High molecular weight poly( -lactide) and poly(ethylene oxide) blends: thermal characterization and physical properties

The miscibility of high molecular weight poly( -lactide) PLLA with high molecular weight poly(ethylene oxide) PEO was studied by differential scanning calorimetry. All blends containing up to 50 weight% PEO showed single glass transition temperatures. The PLLA and PEO melting temperatures were found to decrease on blending, the equilibrium melting points of PLLA in these blends decreased with increasing PEO fractions. These results suggest the miscibility of PLLA and PEO in the amorphous phase. Mechanical properties of blends with up to 20 weight% PEO were also studied. Changes in mechanical properties were small in blends with less than 10 weight% PEO. At higher PEO concentrations the materials became very flexible, an elongation at break of more than 500% was observed for a blend with 20 weight% PEO. Hydrolytic degradation up to 30 days of the blends showed only a small variation in tensile strength at PEO concentrations less than 15 weight%. As a result of the increased hydrophilicity, however, the blends swelled. Mass loss upon degradation was attributed to partial dissolution of the PEO fraction and to an increased rate of degradation of the PLLA fraction. Significant differences in degradation behaviour between PLLA/PEO blends and (PLLA/PEO/PLLA) triblock-copolymers were observed.     

Biodegradable blends of high molecular weight poly(ethylene oxide) with poly(3‐hydroxypropionic acid) and poly(3‐hydroxybutyric acid): a miscibility study by DSC,DMTA and NMR spectroscopy

The miscibility of high molecular weight poly(ethylene oxide) blends with poly(3‐hydroxypropionic acid) and poly(3‐hydroxybutyric acid) (P(3HB)) has been investigated by differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA) and high‐resolution solid state ¹³C nuclear magnetic resonance (NMR). The DSC thermal behaviour of the blends revealed that the binary blends of poly(ethylene oxide)/poly(3‐hydroxypropionic acid) (OP blends) were miscible over the whole composition range while the miscibility of poly(ethylene oxide)/poly(3‐hydroxybutyric acid) blends (OB blends) was dependent on the blend composition. OB blends were found to be partly miscible at the middle P(3HB) contents (25 %, 50 %) and miscible at other P(3HB) contents (10 %, 75 % and 90 %). Single‐phase behaviour for OP blends and phase separation behaviour for OB blends were observed from DMTA. The results from NMR spectroscopy revealed that the two components in the OP50 blend were intimately mixed on a scale of about 35 nm, while the domain sizes in the OB blend with a P(3HB) content of 50 % were larger than about 32 nm. © 2000 Society of Chemical Industry     

Structure and properties of fluorinated polymer/poly(ethylene oxide) blends

BACKGROUND: In order to explore ways for improving the toughness of copolymers of vinylidene difluoride and chlorotrifluoroethylene (P(VDF‐CTFE)), polyethylene oxide (PEO) with ultrahigh molecular weight and good mechanical properties was applied for the first time to prepare P(VDF‐CTFE)/PEO blends for adhesives applications. RESULTS: The results show that with an increase of PEO content, the mechanical properties of the blends are improved markedly, and blends with high strength, modulus and toughness are obtained. The difference in the solubility parameters of P(VDF‐CTFE) and PEO is small, and only a single α‐relaxation peak is observed in the high‐temperature zone for the blends, indicating that the blend system is partially miscible. The experimental values for the glass transition temperature of the blend varying with PEO content are always higher than those predicted by the Fox equation, and a strong interaction is supposed to occur between the molecules of P(VDF‐CTFE) and PEO. The relative crystallinity of the blends increases with PEO content, and the PEO particles disperse homogeneously in the P(VDF‐CTFE) matrix, whose average size decreases with increasing PEO content. Phase‐inverted morphologies of the blends are observed above 60 wt% of PEO. CONCLUSION: The partial miscibility of P(VDF‐CTFE)/PEO blends leads to an improvement of the mechanical properties of the blends, which is an effective way to improve the toughness of fluorinated polymers. Copyright © 2009 Society of Chemical Industry     

Kraft lignin/poly(ethylene oxide) blends: Effect of lignin structure on miscibility and hydrogen bonding

Blends of poly(ethylene oxide) (PEO) with softwood kraft lignin (SKL) were prepared by thermal blending. The miscibility behavior and hydrogen bonding of the blends were investigated by differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy. The experimental results indicate that PEO was miscible with SKL, as shown by the existence of a single glass‐transition temperature over the entire composition range by DSC. In addition, a negative polymer–polymer interaction energy density was calculated on the basis of the melting point depression of PEO. The formation of strong intermolecular hydrogen bonding was detected by FTIR analysis. A comparison of the results obtained for the SKL/PEO blend system with those previously observed for a hardwood kraft lignin/PEO system revealed the existence of stronger hydrogen bonding within the SKL/PEO blends but weaker overall intermolecular interactions between components; this suggested that more than just hydrogen bonding was involved in the determination of the blend behavior in the kraft lignin/PEO blends. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1437–1444, 2005     

Effect of tacticity of poly(methyl methacrylate) on the miscibility with poly(vinyl pyrrolidone)

Isotactic, atactic, and syndiotactic poly(methyl methacrylates) (PMMA) (designated iPMMA, aPMMA, and sPMMA) with approximately the same molecular weight were mixed separately with poly(vinyl pyrrolidone) (PVP) primarily in chloroform to make three polymer blend systems. Differential scanning calorimetry (DSC) was used to study the miscibility of these blends. The results showed that the tacticity of PMMA has a definite impact on its miscibility with PVP. The aPMMA/PVP and sPMMA/PVP blends were found to be miscible because all the prepared films showed composition-dependent glass-transition temperatures (T_g). The glass-transition temperatures of the aPMMA/PVP blends are equal to or lower than weight average and can be qualitatively described by the Gordon–Taylor equation. The glass-transition temperatures of the other miscible blends (i.e., sPMMA/PVP blends) are mostly higher than weight average and can be approximately fitted by the simplified Kwei equation. The iPMMA/PVP blends were found to be immiscible or partially miscible based on the observation of two glass-transition temperatures. The immiscibility is probably attributable to a stronger interaction among isotactic MMA segments because its ordination and molecular packing contribute to form a rigid domain. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3190–3197, 2001     

High molecular weight poly(l-lactide) and poly(ethylene oxide) blends: thermal characterization and physical properties

The miscibility of high molecular weight poly(l-lactide) PLLA with high molecular weight poly(ethylene oxide) PEO was studied by differential scanning calorimetry. All blends containing up to 50 weight% PEO showed single glass transition temperatures. The PLLA and PEO melting temperatures were found to decrease on blending, the equilibrium melting points of PLLA in these blends decreased with increasing PEO fractions. These results suggest the miscibility of PLLA and PEO in the amorphous phase. Mechanical properties of blends with up to 20 weight% PEO were also studied. Changes in mechanical properties were small in blends with less than 10 weight% PEO. At higher PEO concentrations the materials became very flexible, an elongation at break of more than 500% was observed for a blend with 20 weight% PEO. Hydrolytic degradation up to 30 days of the blends showed only a small variation in tensile strength at PEO concentrations less than 15 weight%. As a result of the increased hydrophilicity, however, the blends swelled. Mass loss upon degradation was attributed to partial dissolution of the PEO fraction and to an increased rate of degradation of the PLLA fraction. Significant differences in degradation behaviour between PLLA/PEO blends and (PLLA/PEO/PLLA) triblock-copolymers were observed.     

Toughening of poly(lactic acid) with the renewable bioplastic poly(trimethylene malonate)

The aim of this work was to enhance poly(lactic acid)'s (PLA) flexibility and ductility by blending it with another bioplastic. Poly(trimethylene malonate) (PTM), developed as part of this study, was synthesized from 1,3‐propane diol and malonic acid via melt polycondensation. Blend films of PLA and PTM were prepared by solvent casting from chloroform. Differential scanning calorimetry and thermogravimetric analysis were used to show shifted phase transitions and a single glass‐transition temperature, indicating miscibility of PTM in the blend films. Morphology and mechanical characterizations of the PLA/PTM blend films were performed by atomic force microscopy using a quantitative nanomechanical property mapping mode, tensile testing, and scanning electron microscopy. Miscible blends exhibited Young's modulus and elongation at break values that can significantly extend the usefulness of PLA in commercial applications. The blending of PTM with PLA resulted in films with a 27‐fold increase in toughness compared with neat PLA film. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40888.     

Preparation and characterization of konjac glucomannan/poly(diallydimethylammonium chloride) blend films

A novel preservative film was prepared by blending konjac glucomannan (KGM) and poly (diallydimethylammonium chloride) (PDADMAC) in aqueous system. The effects of PDADMAC content on the miscibility, morphology, thermal stability, and mechanical properties of the blend films were investigated by density determination, scanning electron microscopy (SEM), attenuated total reflection infrared spectroscopy (ATR‐IR), X‐ray diffraction (XRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and tensile tests. The results of the density determination predicted that the blends of KGM and PDADMAC were miscible when the PDADMAC content was less than 70 wt %. Moreover, SEM and XRD confirmed the result. ATR‐IR showed that strong intermolecular hydrogen bonds interaction occurred between the negative charge groups of KGM and the quaternary ammonium groups of PDADMAC in the blends. The tensile strength and the break elongation of the blends were improved largely to 106.5 MPa and 32.04%, when the PDADMAC content was 20 wt %. The thermal stability of the blends was higher than pure KGM. Results from the film‐coating preservation experiments with lichi and grapes showed that the blend film had excellent water‐holding and preservative ability. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Interfacial modification mechanism of nanocellulose as a compatibilizer for immiscible binary poly(vinyl alcohol)/poly(ethylene oxide) blends

We undertook this study to understand reinforcement mechanism of short cellulose nanocrystals (CNCs) and long cellulose nanofibrils (CNFs) as compatibility agents for improving the interfacial miscibility of poly(vinyl alcohol) (PVA) and poly(ethylene oxide) (PEO) blends. The effects of the two cellulose nanofibers on the morphological, mechanical, and thermal properties of the polymer blends were compared systematically. The light transparency, scanning electron microscopy, and Fourier transform infrared results show that nanocellulose between PVA and PEO eliminated the negative effects generated by the immiscible interface through increased hydrogen bonding. Thermogravimetric analysis and differential scanning calorimetry results show that crystalline region reorganization around the interface facilitated the shift of the polymer blends from multiple phases to a homogeneous phase. According to the Halpin‐Kardos and Quali models, we assumed that the potential for repairing the immiscible interface would have a larger effect than the potential of reinforcement. At the same concentration, polymer blends with CNCs showed greater light transparency, strength, modulus, and crystal structure than with those with CNFs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45896.     

Preparation and characterization of poly(lactic acid)/poly(ethylene oxide) blend film: effects of poly(ethylene oxide) and poly(ethylene glycol) on the properties

Poly(lactic acid) (PLA) film plasticized with poly(ethylene oxide) (PEO) at various weight percentages (1–5 wt%) was prepared to improve the elongation, thus overcoming the inherent brittleness of the material. After optimization of the amount of PEO (4 wt%) through mechanical analysis, poly(ethylene glycol) (PEG), a well‐established plasticizer of PLA, was added (0.5–1.5 wt%) without hampering the transparency and tensile strength much, and again its amount was optimized (1 wt%). Neat PLA and PLA with the other components were solvent‐cast in the form of films using chloroform as a solvent. Improvement in elongation at break and reduction in tensile strength suggested a plasticizing effect of both PEO and PEG on PLA. Thermal and infrared data revealed that the addition of PEO induced β crystals in PLA. Scanning electron micrographs indicated a porous surface morphology of the blends. PEO alone in PLA exhibited the best optical clarity with higher percentage crystallinity, while PEG incorporation in PLA/PEO resulted in superior barrier properties. Also, the stability of the blends under a wide range of pH means prospective implementation of the films in packaging of food and non‐food‐grade products. © 2018 Society of Chemical Industry     

Poly(ethylene oxide)–polyelectrolyte blends: viscometric and thermal analysis behaviour

The miscibility of binary poly(ethylene oxide) (PEO) and sodium poly(4‐styrene sulphonate) (PSS) or [3,6]‐ionene (ION) systems, was analysed in aqueous solutions and in the solid state by viscometry and thermal analysis, respectively. Both techniques indicate partial miscibility of PEO–PSS and immiscibility of PEO–ION blends. In water solution, the partial miscibility of the PEO–PSS system is probably due to the counterion Na⁺ which can partially provide the driving force association in a similar manner to that observed for PEO–surfactant systems. In blend films, the PEO–polyelectrolyte interaction is also analysed in terms of the effect on the PEO crystallization observed through optical microscopy, and the results indicate compatibility between the components in the PEO–PSS system. © 2000 Society of Chemical Industry     

Blends of poly(ethylene oxide) and poly(4-vinylphenol-co-2-hydroxyethyl methacrylate): thermal analysis, morphological behaviour and specific interactions

DSC and optical microscopy were used to determine the miscibility and crystallinity of blends of poly(ethylene oxide) (PEO) with poly(4-vinylphenol-co-2-hydroxyethyl methacrylate) (PVPh-HEM). A single glass transition temperature was observed for all blends, indicating miscibility. A progressive decrease in the degree of crystallinity and in the size of the PEO spherullites is observed, as PVPh-HEM is added. FTIR was used to probe the intermolecular specific interactions of the blends and the miscibility of the blend is mainly attributed to PVPh-HEM/PEO intermolecular interactions via hydrogen bonding.     

Specific interactions in miscible polymer blends of poly(2‐hydroxypropyl methacrylate) with polyvinylpyrrolidone

The miscibility behaviour and hydrogen‐bonding interaction in blends of poly(2‐hydroxypropyl methacrylate) (PHPMA) with polyvinylpyrrolidone (PVP) were characterized using differential scanning calorimetry and Fourier‐transform infrared spectra. This polymer blend was miscible over the whole composition range and an unusually large positive deviation of T_g from the linearity rule was observed, indicating strong hydrogen bonding between the hydroxyl group of PHPMA and the carbonyl group of PVP. Infrared spectroscopic analysis provided positive evidence for the intra‐molecular hydrogen bonding of PHPMA and inter‐molecular hydrogen bonding between PHPMA and PVP at various compositions and temperatures. Furthermore, equilibrium constants and enthalpies of self‐association and inter‐association between functional groups in the blend of PHPMA and PVP were calculated to explain the results. Copyright © 2004 Society of Chemical Industry     

Conductance investigation of p‐MIECs fabricated by poly(3,4‐ethylenedioxy thiophene), polyacrylic acid,polyethylene oxide,and lithium‐ion salt

Polymer blends and composite films were facilely prepared from their aqueous solutions with varying contents of poly(3,4‐ethylenedioxythiophene) (PEDOT), polyethylene oxide (PEO), and polyacrylic acid (PAA). The physicochemical and electric properties of the composite films were analyzed by Raman spectra, infrared spectra (FT‐IR), scanning electronic microscopy (SEM), thermogravimetric analysis (TGA), and four‐point probe method. PEDOT was successfully incorporated into each blend which was confirmed by spectra analysis. The crystallization of PAA or PEO and the structure of PEDOT should be taken into consideration for the electronic conductivity. According to Raman spectra, in the case of PEDOT–PAA–PEO, conformation of the PEDOT backbone changed from the quinoid to the benzoid structure partly. The ionic conductivities of lithium‐ion salt‐mixed PAA–PEO and ternary blend were characterized by AC impedance spectroscopy. The ternary blend with LiCoO₂ presents good electronic and ionic conductivity, and it appears to be a new candidate for polymeric mixed ionic electronic conductor. POLYM. COMPOS., 36:2076–2083, 2015. © 2014 Society of Plastics Engineer