Nanophase morphology and crystallization in poly(vinylidene fluoride)/polydimethylsiloxane‐block‐poly(methyl methacrylate) blends

A polydimethylsiloxane‐block‐poly(methyl methacrylate) (PDMS‐b‐PMMA) diblock copolymer was synthesized by the atom transfer radical polymerization method and blended with a high‐molecular‐weight poly(vinylidene fluoride) (PVDF). In this A‐b‐B/C type of diblock copolymer/homopolymer system, semi‐crystallizable PVDF (C) and PMMA (B) block are miscible due to favorable intermolecular interactions. However, the A block (PDMS) is immiscible with PVDF and therefore generates nanostructured morphology via self‐assembly. Crystallization study reveals that both α and γ crystalline phases of PVDF are present in the blends with up to 30 wt% of PDMS‐b‐PMMA block copolymer. Adding 10 wt% of PVDF to PDMS‐b‐PMMA diblock copolymer leads to worm‐like micelle morphology of PDMS of 10 nm in diameter and tens of nanometers in length. Moreover, morphological results show that PDMS nanostructures are localized in the inter‐fibrillar region of PVDF with the addition of up to 20 wt% of the block copolymer. Increase of PVDF long period by 45% and decrease of degree of crystallization by 34% confirm the localization of PDMS in the PVDF inter‐fibrillar region. © 2018 Society of Chemical Industry     

Nanophase morphology and crystallization in poly(vinylidene fluoride)/polydimethylsiloxane‐block‐poly(methyl methacrylate)‐block‐polystyrene blends

An approach to achieve confined crystallization of ferroelectric semicrystalline poly(vinylidene fluoride) (PVDF) was investigated. A novel polydimethylsiloxane‐block‐poly(methyl methacrylate)‐block‐polystyrene (PDMS‐b‐PMMA‐b‐PS) triblock copolymer was synthesized by the atom‐transfer radical polymerization method and blended with PVDF. Miscibility, crystallization and morphology of the PVDF/PDMS‐b‐PMMA‐b‐PS blends were studied within the whole range of concentration. In this A‐b‐B‐b‐C/D type of triblock copolymer/homopolymer system, crystallizable PVDF (D) and PMMA (B) middle block are miscible because of specific intermolecular interactions while A block (PDMS) and C block (PS) are immiscible with PVDF. Nanostructured morphology is formed via self‐assembly, displaying a variety of phase structures and semicrystalline morphologies. Crystallization at 145 °C reveals that both α and β crystalline phases of PVDF are present in PVDF/PDMS‐b‐PMMA‐b‐PS blends. Incorporation of the triblock copolymer decreases the degree of crystallization and enhances the proportion of β to α phase of semicrystalline PVDF. Introduction of PDMS‐b‐PMMA‐b‐PS triblock copolymer to PVDF makes the crystalline structures compact and confines the crystal size. Moreover, small‐angle X‐ray scattering results indicate that the immiscible PDMS as a soft block and PS as a hard block are localized in PVDF crystalline structures. © 2019 Society of Chemical Industry     

Influence of composition and molecular mass on the morphology,crystallization and melting behaviour of poly(ethylene oxide)/poly(methyl methacrylate) blends

Results are reported on the influence of composition and molecular mass of components on the isothermal growth rate of spherulites, on the overall kinetic rate constant, on the primary nucleation and on the thermal behaviour of poly(ethylene oxide)/poly(methyl methacrylate) blends. The growth rate of PEO spherulites as well as the observed equilibrium melting temperatures decrease, for a given T_c or ΔT, with the increase of PMMA content.Such observations are interpreted by assuming that the polymers are compatible in the undercooled melt, at least in the range of crystallization temperatures investigated. Thermodynamic quantities such as the surface free energy of folding σ_e and the Flory-Huggins parameter χ₁₂ have been obtained by studying the dependence of the radial growth rate G and of the overall kinetic rate constant K from temperature and composition and the dependence of the equilibrium melting temperature depression ΔT_m upon composition, respectively.     

Nonisothermal crystallization kinetics of poly(ethylene terephthalate) and poly(methyl methacrylate) blends

The nonisothermal crystallization kinetics of poly(ethylene terephthalate) (PET) and poly(methyl methacrylate) (PMMA) blends were studied. Four compositions of the blends [PET 25/PMMA 75, PET 50/PMMA 50, PET 75/PMMA 25, and PET 90/PMMA 10 (w/w)] were melt‐blended for 1 h in a batch reactor at 275°C. Crystallization peaks of virgin PET and the four blends were obtained at cooling rates of 1°C, 2.5°C, 5°C, 10°C, 20°C, and 30°C/min, using a differential scanning calorimeter (DSC). A modified Avrami equation was used to analyze the nonisothermal data obtained. The Avrami parameters n, which denotes the nature of the crystal growth, and Z_t, which represents the rate of crystallization, were evaluated for the four blends. The crystallization half‐life (t_½) and maximum crystallization (t_max) times also were evaluated. The four blends and virgin polymers were characterized using a thermogravimetric analyzer (TGA), a wide‐angle X‐ray diffraction unit (WAXD), and a scanning electron microscope (SEM). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3565–3571, 2006     

Crystallization of poly(tetramethylene succinate) in blends with poly(ϵ‐caprolactone) and poly(ethylene terephthalate)

The crystallization behavior of polymer blends of poly(tetramethylene succinate) (PTMS) with poly(?‐caprolactone) (PCL) or poly(ethylene terephthalate) (PET) was investigated with differential scanning calorimetry under isothermal and nonisothermal conditions. The blends were prepared by solution casting and precipitation, respectively. The constituent polymers were semicrystalline materials and crystallized nearly independently in the blends. The addition of the second component to PTMS showed that PCL did not significantly influence the crystallinity of the constituents in the blends under isothermal conditions, whereas the crystallization of PTMS was slightly suppressed by crystalline PET. Nonisothermal crystallization under constant cooling rates was examined in terms of a quasi‐isothermal Avrami approach. In blends, the rates of crystallization were differently influenced by the second component. The rate of the constituent that crystallized at the higher temperature was barely influenced by the second component being in the molten state, whereas the rate of the second component, crystallizing when the first component was already crystalline, was altered differently under isothermal and nonisothermal conditions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 149–160, 2004     

Poly(ethylene glycol)/poly(methyl methacrylate) blends as novel form‐stable phase‐change materials for thermal energy storage

In this study, we focused on the preparation and characterization of poly(ethylene glycol) (PEG)/poly(methyl methacrylate) (PMMA) blends as novel form‐stable phase‐change materials (PCMs) for latent‐heat thermal energy storage (LHTES) applications. In the blends, PEG acted as a PCM when PMMA was operated as supporting material. We subjected the prepared blends at different mass fractions of PEG (50, 60, 70, 80, and 90% w/w) to leakage tests by heating the blends over the melting temperature of the PCM to determine the maximum encapsulation ratio without leakage. The prepared 70/30 w/w % PEG/PMMA blend as a form‐stable PCM was characterized with optical microscopy and Fourier transform infrared spectroscopy. The thermal properties of the form‐stable PCM were measured with differential scanning calorimetry (DSC). DSC analysis indicated that the form‐stable PEG/PMMA blend melted at 58.07°C and crystallized at 39.28°C and that it had latent heats of 121.24 and 108.36 J/g for melting and crystallization, respectively. These thermal properties give the PCMs potential LHTES purposes, such as for solar space heating and ventilating applications in buildings. Accelerated thermal cycling tests also showed that the form‐stable PEG/PMMA blend as PCMs had good thermal reliability and chemical stability. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

First results of small and wide angle X-ray scattering of poly(ethylene oxide)/poly(methyl methacrylate) binary blends

Some preliminary small and wide angle X-ray scattering results are reported from isothermally crystallized samples of poly(ethylene oxide)/(methyl methacrylate) binary blends.     

A high‐resolution solid‐state NMR investigation of molecular mobility of poly(methyl methacrylate)/poly(vinyl pyrrolidone)/poly(ethylene oxide) ternary blends

The ternary blends of poly(methyl methacrylate)/poly(vinyl pyrrolidone)/poly(ethylene oxide), PMMA/PVP/PEO, were prepared by melting process, using a Haake plastograph, and nuclear magnetic resonance spectroscopy (NMR) was used as a methodology to characterize the molecular mobility of blend components, because NMR has several techniques that allow us to evaluate polymeric materials in different time scales. The NMR results showed that the blends were miscible on a molecular level. The values of proton lattice relaxation time in the rotating frame (T₁ρH) indicate that the ternary blend interaction did not reduce the intermolecular distance, because it is dipole–dipole. The molecular motion of each component, even in the miscible amorphous phase and the addition of PEO, has a definitive effect on the PMMA molecular mobility. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1492–1495, 2006     

Crystallization,morphology, and electrical properties of bio‐based poly(trimethylene terephthalate)/poly(ether esteramide)/ionomer 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 ionomers such as lithium‐neutralized poly(ethylene‐co‐methacrylic acid) copolymer (EMAA‐Li) and sodium‐neutralized poly(ethylene‐co‐methacrylic acid) copolymer (EMAA‐Na). The blends were characterized by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), polarized light microscopy (PLM), and transmission electron microscopy (TEM). DSC and PLM results showed that EMAA‐Na increased the crystallization rate for PTT significantly, whereas EMAA‐Li did not enhance the crystallization rate at all. Specific interactions between PEEA and ionomers were confirmed by DSC and TEM. Electrostatic performance was also investigated for those PTT blends because PEEA is known as an ion‐conductive polymer. Here, we confirmed that both sodium and lithium ionomers work as a synergist to enhance the static decay performance of PTT/PEEA blends. Morphological study of these ternary blends systems was conducted by TEM. Dispersed ionomer domains were encapsulated by PEEA, which increases the interfacial surface area between PEEA and the PTT matrix. This encapsulation effect explains the unexpected synergy for the static dissipation performance on addition of ionomers to PTT/PEEA blends. This core–shell morphology can be predicted by calculating spreading coefficient for the ternary blends. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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

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

Morphology and spherulitic growth kinetics in poly(ethylene oxide)/poly(n‐butyl methacrylate) blends

Results of a study concerning the morphology and the spherulite growth rates of poly(ethylene oxide) (PEO) in binary blends with poly(n‐butyl methacrylate) (PnBMA) are reported. Microscopic observations show that blending causes the spherulite structure to become coarser and less birefringent and confirms that the spherulitic growth rates of PEO were reduced by the addition of PnBMA. X‐ray diffraction studies show no change in the unit cell dimensions and a decrease in the degree of crystallinity upon blending. Analysis of the spherulite radial growth rate data by using Lauritzen–Hoffman theory indicates that crystallization in the range of 300 to 330 K occurs solely within regime III. The calculated surface free energy of folding, σ_e, for pure PEO is 57 erg cm^?2 and decreases with increasing the content of PnBMA in the blend. Copyright © 2004 Society of Chemical Industry     

Effects of compatibilizer on the morphological,mechanical, and rheological properties of poly(methyl methacrylate)/poly(N‐methyl methacrylimide) blends

The effects of compatibilizer on the morphological, thermal, mechanical, and rheological properties of poly(methyl methacrylate) (PMMA)/poly(N‐methyl methacrylimide) (PMMI) (70/30) blends were investigated. The compatibilizer used in this study was styrene–acrylonitrile–glycidyl methacrylate (SAN‐GMA) copolymer. Morphological characterization of the PMMA/PMMI (70/30) blend with SAN‐GMA showed a decrease in PMMI droplet size with an increase in SAN‐GMA. The glass‐transition temperature of the PMMA‐rich phase became higher when SAN‐GMA was added up to 5 parts per hundred resin by weight (phr). The flexural and tensile strengths of the PMMA/PMMI (70/30) blend increased with the addition of SAN‐GMA up to 5 phr. The complex viscosity of the PMMA/PMMI (70/30) blends increased when SAN‐GMA was added up to 5 phr, which implies an increase in compatibility between the PMMA and PMMI components. From the weighted relaxation spectrum, which was obtained from the storage modulus and loss modulus, the interfacial tension of the PMMA/PMMI (70/30) blend was calculated using the Palierne emulsion model and the Choi‐Schowalter model. The results of the morphological, thermal, mechanical, and rheological studies and the values of the interfacial tension of the PMMA/PMMI (70/30) blends suggest that the optimum compatibilizer concentration of SAN‐GMA is 5 phr. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43856.     

Cocontinuous morphology in vinylidene fluoride based polymers/poly(ethylene oxide) blends

In this work, blends of three different vinylidene fluoride (VdF) based homopolymers and copolymers with poly(ethylene oxide) were investigated. We focused on the continuity domain and, more particularly, on the cocontinuous morphology of these systems. The melt‐mixed blends were characterized by different techniques. The morphology was identified through a selective extraction technique and was confirmed by scanning electron microscopy. Dynamic oscillatory shear measurements were performed with a constant stress rheometer in the linear viscoelastic domain in the whole composition range. Because of the high viscosities and long relaxation times of the VdF‐based polymers, the interfacial effects were hidden by the intrinsic behavior of the neat components. Nevertheless, the combination of the different techniques highlighted the similarity of the systems toward morphological development, whatever the VdF monomers. The experiments and theoretical analysis indicated that the rheological behavior dominated the interfacial effects in such systems with a large viscosity ratio and that it also dictated the boundaries of the continuity domain. The originality of this study came from the use of three different VdF‐based polymers. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Morphology and barrier mechanism of biaxially oriented poly(ethylene terephthalate)/poly(ethylene 2,6‐naphthalate) blends

To improve the barrier properties of poly(ethylene terephthalate) (PET), PET/poly(ethylene 2,6‐naphthalate) (PEN) blends with different concentrations of PEN were prepared and were then processed into biaxially oriented PET/PEN films. The air permeability of bioriented films of pure PET, pure PEN, and PET/PEN blends were tested by the differential pressure method. The morphology of the blends was studied by scanning electron microscopy (SEM) observation of the impact fracture surfaces of extruded PET/PEN samples, and the morphology of the films was also investigated by SEM. The results of the study indicated that PEN could effectively improve the barrier properties of PET, and the barrier properties of the PET/PEN blends improved with increasing PEN concentration. When the PEN concentration was equal to or less than 30%, as in this study, the PET/PEN blends were phase‐separated; that is, PET formed the continuous phase, whereas PEN formed a dispersed phase of particles, and the interface was firmly integrated because of transesterification. After the PET/PEN blends were bioriented, the PET matrix contained a PEN microstructure consisting of parallel and extended, separate layers. This multilayer microstructure was characterized by microcontinuity, which resulted in improved barrier properties because air permeation was delayed as the air had to detour around the PEN layer structure. At a constant PEN concentration, the more extended the PEN layers were, the better the barrier properties were of the PET/PEN blends. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1309–1316, 2006     

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

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

Solution and solid‐state NMR investigation of poly(methyl methacrylate)/poly(vinyl pyrrolidone) blends

The development of polymer blends has become very important for the polymer industry because these blends have shown to be a successful and versatile alternative way to obtain a new polymer. In this study, binary blends formed by poly(methyl methacrylate) (PMMA) and poly(vinyl pyrrolidone) were prepared by solution casting and evaluated by solution and solid‐state NMR. Variations in the microstructure of PMMA were analyzed by ¹³C solution NMR. Solid‐state NMR promotes responses on physical interaction, homogeneity, and compatibility to use these blends to understand the behavior of the ternary blends. The NMR results led‐us to acquire information on the polymer blend microstructure and molecular dynamic behavior. From the NMR solution, it was possible to evaluate the microstructure of both polymer blend components; they were atactic. From the solid state, good compatibility between both polymer components was characterized. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 372–377, 2004     

Hydrolytic degradation of poly(l‐lactic acid)/poly(methyl methacrylate) blends

The hydrolytic degradation of poly(l ‐lactic acid)/poly(methyl methacrylate) (PLLA/PMMA) blends was carried out by the immersion of thin films in buffer solutions (pH = 7.24) in a shaking water bath at 60 °C for 38 days. The PLA/PMMA blends (0/100; 30/70; 50/50; 70/30; 100/0) were obtained by melt blending using a Brabender internal mixer and shaped into thin films of about 150 µm in thickness. Considering that PMMA does not undergo hydrolytic degradation, that of PLLA was followed via evolution of PLA molecular weight (recorded by size exclusion chromatography), thermal parameters (differential scanning calorimetry (DSC)) and morphology of the films (scanning transmission electron microscopy). The results reveal a completely different degradation pathway of the blends depending on the polymethacrylate/polyester weight ratio. DSC data suggest that, during hydrolysis at higher PMMA content, the polyester amorphous chains, more sensitive to water, are degraded before being able to crystallize, while at higher PLLA content, the crystallization is favoured leading to a sample more resistant to hydrolysis. In other words, and quite unexpectedly, increasing the content of water‐sensitive PLLA in the PLLA/PMMA blends does not mean de facto faster hydrolytic degradation of the resulting materials. © 2018 Society of Chemical Industry     

Control and development of crystallinity and morphology in poly(β‐hydroxybutyrate‐co‐β‐hydroxyvalerate)/poly(propylene carbonate) blends

Two different methodologies (reactive blending and mechanical blending) for preparing blends of poly(β‐hydroxybutyrate‐co‐β‐hydroxyvalerate) (PHBV) and poly(propylene carbonate) (PPC) were used. The miscibility, chemical structure, thermal behavior, crystallinity, morphology, and mechanical properties of the blends were investigated with Fourier transform infrared spectroscopy, differential scanning calorimetry, polarized optical microscopy, scanning electron microscopy, and tensile tests. A certain extent of hydrogen‐bonding interactions between PHBV and PPC took place in the blends. The graft copolymerization was confirmed in the reactive system. The incorporation of PPC hampered the crystallization process of PHBV and evidently altered the morphology, and the effect was enhanced in the reactive blend. The mechanical properties of PHBV could be changed by 1–2 orders of magnitude by blending modification. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1427–1436, 2005     

Crystallization of poly(ethylene oxide) in i-polypropylene–poly(ethylene oxide) blends

A two-stage stable system of isotactic polypropylene–poly(ethylene oxide) blend, in which poly(ethylene oxide) can be permanent either in molten or in crystallized states in the temperature range from 280 to 327 K, was described. The behavior of that blend was explained in terms of fractionated crystallization. A fine dispersion of poly(ethylene oxide) inclusions is required for efficient suppression of crystallization initiated by heterogeneous nuclei. The application of a thin film of polypropylene-poly(ethylene oxide) 9 : 1 blend obtained by quenching for multiuse erasable and rewritable carriers for visible information has been demonstrated. The same sample exhibits different dynamic mechanical properties when poly(ethylene oxide) inclusions are molten or crystallized. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2047–2057, 1997     

Crystallization of poly(butylene terephthalate)/poly(ethylene octene) blends: Isothermal crystallization

Poly(ethylene‐octene) (POE), maleic anhydride grafted poly(ethylene‐octene) (mPOE), and a mixture of POE and mPOE were added to poly(butylene terephthalate) (PBT) to prepare PBT/POE, PBT/mPOE, and PBT/mPOE/POE blends by a twin‐screw extruder. Observation by scanning electron microscopy revealed improved compatibility between PBT and POE in the presence of maleic anhydride groups. The melting behavior and isothermal crystallization kinetics of the blends were studied by wide‐angle X‐ray diffraction and differential scanning calorimeter; the kinetics data was delineated by kinetic models. The addition of POE or mPOE did not affect the melting behavior of PBT in samples quenched in water after blending in an extrude. Subsequent DSC scans of isothermally crystallized PBT and PBT blends exhibited two melting endotherms (T_mI and T_mII). T_mI was the fusion of the crystals grown by normal primary crystallization and T_mII was the melting peak of the most perfect crystals after reorganization. The dispersed second phase hindered the crystallization; on the other hand, the well dispersed phases with smaller size enhanced crystallization because of higher nucleation density. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008