Preparation and characterization of binary blends composed of poly(dioctylfluorene‐alt‐hexylsulfonylthiophene) and nonconjugated polymers

The solutions and the thin films of poly[9,9‐dioctyl‐2,7‐fluorene‐alt‐2,5–(3‐hexyl‐sulfonylthiophene)] (PFSO₂T) and its binary blends with other nonconjugated polymers such as poly(methyl methacrylate) (PMMA), polycarbonate (PC), and ethylene vinyl acetate copolymer (EVA) can be prepared by different concentrations from a polymer solution. Binary polymer blends can increase the absorbance and photoluminescence intensities in the solid state due to nonconjugated polymers can act as dispersion agents which can reduce the interchain interaction or the aggregation of the conjugated polymers. Photoluminescence intensity of the thin films of fluorescent polymers blending with ethylene vinyl acetate copolymers exhibited six times higher than that of the neat fluorescent polymers. The PFSO₂T/EVA binary blends reveal the least extent of optical degradation of around 20% compared to those binary blends in both absorption and emission intensities after the irradiation under the UV‐light for 20 h. The cross‐sectional morphology of fluorescent polymers blending with ethylene vinyl acetate copolymers reveals little aggregation and better phase separation among the other binary polymer blends. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44969.     

Viscoelastic effects on the phase separation in thermoplastics modified cyanate ester resin

A high temperature thermosetting bisphenol-A dicyanate, BADCy was blended with a thermoplastic poly(ether imide) (PEI). The phase separation behavior of the blend was investigated by scanning electron microscopy (SEM) and time resolved light scattering (TRLS). It was found by SEM that the blend with 20 and 25 wt% PEI had a phase inversion structure. The results of TRLS displayed clearly that the phase separation took place according to a spinodal decomposition (SD) mechanism and the evolution of both scattering vector q_m and the maximum scattering intensity I_m followed Maxwell-type relaxation equation. The temperature-dependent relaxation time τ for the blends can be described by the Williams-Landel-Ferry equation. It demonstrated experimentally that the phase separation behaviors in PEI/BADCy blends were affected by viscoelastic effect.     

Thermal and morphological properties of SA/HPMC blends

Sodium alginate (SA) was blended with varying amounts of hydroxypropyl methylcellulose (HPMC) viz., 10, 20, and 30 wt % by solution casting process. Thus, the obtained blends were characterized by using different analytical techniques such as differential scanning calorimetry (DSC), thermogravimetric analyzer (TGA), Fourier transform infrared spectroscopy (FTIR), and scanning electron microcopy (SEM). FTIR studies reveal the hydrogen bond formation between hydroxyl groups of SA and HPMC polymer chains. DSC analysis shows single glass transition temperature (T_g) for SA/HPMC blends indicating compatibility and physical interaction between SA and HPMC polymer chains. TGA analysis indicates variation of thermal stability of SA with change in compositions of HPMC. SEM studies reveal uniform distribution of second phase in the blends. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effects of the molecular weight of poly(ether imide) on the viscoelastic phase separation of poly(ether imide)/epoxy blends

The phase separation of diglycidyl ether of bisphenol A/methyl tetrahydrophthalic anhydride blends modified with three poly(ether imide)s (PEIs) of different molecular weights was investigated with scanning electron microscopy (SEM) and time‐resolved light scattering (TRLS). The morphologies observed by SEM for the three blends were all close to a cocontinuous structure with different periodic distances. The results of TRLS indicated that the phase separation for the PEI‐modified epoxy blends took place according to the spinodal decomposition mechanism and the onset time of phase separation, with the periodicity of the phase structure depending on the PEI molecular weight and cure temperature. The time‐dependent peak scattering vector was simulated with a Maxwell‐type viscoelastic relaxation equation, indicating that the coarsening process of epoxy droplets was mainly controlled by the viscoelastic flow. Relaxation times obtained at different temperatures for the three blends could be described by the Williams–Landel–Ferry equation. The effects of the PEI molecular weight on the processes of viscoelastic phase separation were investigated, and the observed trends could be explained qualitatively through thermodynamic analysis. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Epifluorescence studies and secondary relaxation processes in immiscible blends of polybutadiene‐poly(2‐vinyl naphthalene) by fluorescence spectroscopy

The development of the morphology of polybutadiene/poly(2‐vinyl naphthalene) blends in five proportions by mass (5, 10, 50, 90, and 95%, w/w) is studied by epifluorescence and scanning electron microscopy (SEM) techniques. The phase separation process of these immiscible polymers produces a primary morphology that is formed by dispersed droplets in a continuous matrix. In the sequence a secondary phase separation inside the primary domains is detected by epifluorescence microscopy of the intrinsically fluorescent domains. Secondary phase separation is confirmed by SEM fracture surface analysis. The relative size of the droplets and the matrix composition depend on the proportion of the components of the blends. The mechanism of the phase separation process is preferentially by nucleation growth for either primary or secondary phase separation processes. Secondary relaxation processes involving the poly(2‐vinyl naphthalene) phase are studied by fluorescence spectroscopy. The profile of the steady‐state excimer fluorescence of poly(2‐vinyl naphthalene) with the temperature in the blend differs from that of the isolated homopolymer and is explained by the contribution from the interface to the radiationless deactivation. The Arrhenius plot for the temperature dependence exhibits slope changes that are related to the polymer relaxation processes. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1637–1649, 2002; DOI 10.1002/app.10389     

Comparison of the phase behaviour of the liquid-crystalline polymer/poly(methyl methacrylate) and poly(vinyl acetate)/poly(methyl methacrylate) blends

The phase behaviour of blends of a liquid-crystalline polymer (LCP) and poly(methyl methacrylate) (PMMA), as well as the phase state of blends of PMMA and poly(vinyl acetate) (PVA) has been investigated using light scattering and phase-contrast optical microscopy. The blends of LCP and PMMA have been obtained by coagulation from ternary solutions. The cloud point curves were determined. It was established that both pairs demix upon heating, ie have an LCST. In the region of intermediate composition, the phase separation proceeds according to a spinodal mechanism; however for LCP/PMMA blends, the decomposition proceeds according to a non-linear regime from the very onset. In the region of small amounts of LCP, the phase separation follows a mechanism of nucleation and growth. For PMMA/PVA blends, the spinodal decomposition proceeds according to a linear regime, in spite of the molecular mobility that PVA chains develop at lower temperatures. Only after prolonged heat treatment does the process transit to a non-linear regime. The data show a similarity between the phase behaviour of blends of liquid-crystalline and of flexible amorphous polymers. The distinction consists of the absence of a linear regime of decomposition for LCP-PMMA blends. © 1999 Society of Chemical Industry     

A study on compatibility of polymer blends of polystyrene/poly(4‐vinylpyridine)

Blends of polystyrene/poly (4‐vinylpyridine) have been prepared by casting from a common solvent. The compatibility of the blends was studied by using dilute solution viscometry (DSV), differential scanning calorimetery (DSC), Fourier transformation‐infrared spectroscopy (FT‐IR), and scanning electron microscopy (SEM). The relative viscosity versus composition plots for the blends are not perfect linear. The corresponding intrinsic viscosity values show negative deviation from ideal behavior when plotted against composition. Also, the modified Krigbaum and Wall interaction parameter, Δb, shows small and negative values for all compositions except for the blend PS/P4VP (25 : 75). The results indicate that the polymers are incompatible but small interaction values predict physically miscible blends which eventually show phase separation, as is observed in the present studies. However, the blends as obtained show a single, composition‐dependent, glass transition temperature that fits the Fox equation well, indicating the presence of homogeneous phase. The constant, k obtained from Gordon‐Taylor equation suggests intermolecular attraction between these polymers. FT‐IR and SEM support the results of DSV and DSC. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of glycerin on structure transition of PVA/SF blends

Blend films of silk fibrion (SF) and poly(vinyl alcohol) (PVA), with glycerin as an additive, were made, and the structure and properties of the blends were investigated by scanning electron microscopy (SEM), Fourier transform infrared (FT‐IR) spectroscopy, differential scanning calorimetry (DSC), and wide‐angle X‐ray diffraction (WAXD) and with an Instron Material Tester. The results showed that SF and PVA are principally incompatible and the blends made by the two polymers were phase‐separated. The results, however, also demonstrated that the blend structure could be changed to some extent by addition of 3–8% glycerin. The boundary of the PVA and SF phases became indistinct, as reported by SEM, a new peak appeared in the WAXD curves, the width of the OH absorption peak in the FT‐IR spectra increased, and the melting points changed in the DSC curves. In particular, the mechanical properties obviously increased, from 350 kg/cm² and 10% of PVA/SF (80/20) film to 832 kg/cm² and 39% of PVA/SF (80/20) film because of the increase in glycerin. It was suggested that glycerin plays a role in building the relationship between PVA and SF, strengthening the interaction between them and improving their compatibility. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2342–2347, 2002     

Rayleigh散射研究非相容聚苯乙烯／顺丁橡胶合金相结构

用光散射在线采集与分析方法完成了熔融混炼过程中非相容高分子共混物的形态结构分析。选择了聚苯乙烯／顺丁橡胶合金体系。使用了小角前向光散射和小角背散射（在线）技术，用Debye-Bueche光散射理论的结构参数如相关蹁ac、平均弦长l、平均旋转半径Rg和积分不变量Q表征了共混物中分散相尺度和均匀性。用扫描电子显微镜（SEM）测定了共混物中分散相尺寸，并与光散射的结果进行了比较。ac,l和Rg的变化规律与显微镜的结果是一致的。用积分不变量Q研究了共混物的均匀性。     

Time-resolved small-angle light scattering for the study of phase separation kinetics in bisphenol-a polycarbonate/poly(methy methacrylate) blends

An automated, solid-state small-angle light scattering apparatus has been constructed for the investigation of polymers; the main features of this system are a bidimensional CCD (charge coupled device) detector with 12-bit resolution and custom-made, user-friendly software for the acquisition and treatment of the scattering data. The miscibility and phase separation kinetics of several bisphenol-A polycarbonate/poly(methyl methacrylate) blends have been investigated using this apparatus. It was found that the rate of phase separation can be altered significantly by replacing part of the polydisperse poly(methyl methacrylate) (PMMA) in the blends by monodisperse PMMA.     

Rubber modified epoxy resin. II: Phase separation behavior

DGEBA (diglycidyl ether of bisphenol A)–ATBN (amine terminated butadiene acrylonitrile copolymer) blends exhibited upper critical solution temperature (UCST) behavior. Triethylene tetramine (TETA) was introduced as an amine curing agent of epoxy. The real-time phase separation behavior of ATBN-added epoxy system during cure was investigated using laser light scattering. SEM (scanning electron microscopy) and optical microscopy were also employed to observe the morphology of the epoxy blends. Since the DGEBA–ATBN blends showed UCST behavior, the degree of phase separation when cured at low temperature was higher than that when cured at high temperature. The domain correlation length increased as the curing temperature was lowered. Dynamic mechanical analysis (DMA) results indicated that the phase inversion occurred above 20 wt% of ATBN composition.     

Analyzing the interactions and miscibility of silk fibroin/mucin blends

Mucin, a glycoprotein with viscoelastic properties, and silk fibroin, a protein excreted from silkworms with properties of thermal and mechanical resistance, have been probed as building blocks in the design of biomaterials. Aiming to evaluate the interaction and miscibility between mucin and fibroin, we synthesized silk fibroin and mucin (SF/MU) blends for biomedical applications. The morphological analysis of the SF/MU blends showed the presence of two phases, suggesting a partial miscibility between the polymers. The degradation temperature of the SF/MU blends increased with an increase in the silk fibroin content, indicating that silk fibroin contributed to the thermal stability of the blends. The glass transition temperature of the SF/MU blends lay between the values of the pure polymers. The Fourier-transform infrared spectroscopy results pointed out that the interaction between fibroin and mucin occurred between the amine group of silk fibroin and mucin carboxyl and hydroxyl groups. The outcomes of this work provided essential information on the miscibility of the SF/MU blends. These findings will be critical for further studies with fibroin and mucin-based biomaterials, especially in mucoadhesive systems and wound healing applications.     

Influence of attapulgites on cure‐reaction‐induced phase separation in epoxy/poly(ether sulfone) blends

The influence of attapulgites (ATTs) on cure‐reaction‐induced phase separation in diglycidyl ether of bisphenol A/poly(ether sulfone) (PES) blends has been studied with scanning electron microscopy (SEM), transmission electron microscopy (TEM), optical microscopy, time‐resolved light scattering, and dynamic mechanical analysis at different ATT and PES concentrations. The SEM results show that the incorporation of a small amount of ATT into the blends can change the final phase morphology markedly and affect the secondary phase separation. The TEM results show that ATT particles are pinned down by the interfacial tension at the phase interfaces, and this slows the interfacial motion. In addition, the incorporation of a small amount of ATT particles can improve the modulus because of the increased interfacial interaction of the PES‐rich and epoxy‐rich phases. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Properties of extrusion cast sheets of blends of natural and aliphatic polyesters

Natural and synthetic polymers of various compositions were blended in a twin‐screw extruder. These blends were then sheeted into thin sheets with a coat hanger die attached to a single‐screw extruder. The natural content in the blend was varied between 5 and 50 wt %, and the mechanical and morphological properties of the blends were evaluated. At 50 wt % natural content, the tensile strength decreased to a third of that of the synthetic polymer. The use of a compatibilizer doubled the tensile strength for the 50 wt % natural content blend. The sheets displayed equal strengths in the machine and transverse direction. The tear strength decreased as the natural content increased, and the decrease was greater in the anhydride‐compatibilized blends than in the uncompatibilized blends. The blends displayed two distinct glass transitions, one for each component, indicating phase separation. The crystallinity of the blends decreased as the starch content increased. This result was confirmed by differential scanning calorimetry (DSC), which showed that the melting endotherm decreased as the starch content increased. Gel permeation chromatography (GPC) results showed that the peak position was at the same location irrespective of blend composition, indicating minimal degradation of starch moieties. The water absorption was diffusion controlled, with a sharp initial burst of water uptake. Scanning electron microscopy (SEM) showed melting of starch granules that formed a co‐continuous phase with the synthetic polyester. Increasing the natural content also increased the surface roughness of the sheets. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1545–1554, 2003     

Liquid–liquid phase separation and crystallization of polydisperse isotactic polypropylene solutions

Phase diagrams were calculated based on Flory-Huggins solution thermodynamics to investigate the effects of polydispersity of polymer molecules and interaction parameter on the phase equilibria of crystallizable polymer solutions. The polydispersity was modeled with blends of two monodisperse polymers differing in chain lengths as a simplification. It was found that a longer chain length component could be separated easily to a polymer-rich phase by liquid demixing, but a shorter chain length component might exist at relatively constant concentration in each phase on fractionation. The influence of polydispersity on the liquid–solid phase equilibrium was small, and the phase boundary could be moved significantly in the region of low concentration of polymer by a small change of temperature. Liquid–liquid phase separation was more sensitive to the interaction between polymer and solvent than liquid–solid phase transition. Numerical calculations showed that the temperature at which liquid–liquid phase separation was coupled with liquid–solid phase equilibrium increased with a lower concentration of the polymer due to polydispersity of polymer chain lengths, and this phenomenon was observed at a lower temperature with more favorable interaction. The results were consistent with the experimental observations of isotactic polypropylene solutions. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 849–857, 1998     

Miscibility behavior of blend of polyesteramides of linseed oil and dehydrated castor oil with poly(methacrylic acid)

Blending of two polymers in solution is a simple and cost‐effective technique to improve upon the physical and mechanical properties of the component polymers through synergism. To obtain maximum synergy in their properties, the component polymers should be miscible with each other on molecular scale. Polymer blends of complex physicomechanical properties are being actively investigated. Poly(methacrylic acid) (PMAA), a commercial polymer, yields transparent, hard, brittle, and water‐sensitive films. It has been blended with natural polymers like dextran, collagen, and gelatin to obtain films with improved physical and mechanical characteristics. Polyesteramides, which are easily synthesized from vegetable seeds oil, a sustainable resource, have found application in surface coatings. These oligomeric products do not make free standing films in the ambient condition. The polyesteramides from vegetable seeds oil can be used to obtain blend with PMMA of improved mechanical and water absorption properties. In this study, linseed oil polyesteramide (LOPEA) and dehydrated castor oil polyesteramide (DCPEA), the source oils with different unsaturation in their fatty acid chains, were blended with PMAA through mixing in solution in the ratio DCPEA/LOPEA: PMAA as 80/20, 70/30, 60/40, 50/50, 40/60, 30/70, and 20/80. In the first instance, the miscibility of the two components was investigated in solution by viscosity and ultrasonic measurements and in solid phase through differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). Moisture absorption by the blend was also studied. DCPEA and LOPEA show immiscibility with PMAA in solution phase while LOPEA with more unsaturation in the fatty acid chain of the oil was found more immiscible than DCPEA. DCPEA shows a narrow miscibility window in the solid phase while LOPEA was found immiscible with PMAA in the solid phase too. Uptake of moisture was found to be markedly reduced in the blends of DCPEA/LOPEA with PMAA. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1367–1374, 2007:     

On the deformation of poly(methyl methacrylate) poly(ethylene oxide) blends: A molecular characterization by small-angle neutron scattering

The deformation behavior of miscible amorphous/amorphous PMMA/PEO poly(methyl methacrylate)/poly(ethylene oxide) blends was compared with that of pure PMMA. Small-angle neutron scattering experiments were performed on labeled systems made of PEO + D-PMMA + HPMMA. Characteristic molecular parameters such as radius of gyration, Rg, molecular weight, M_w, and interaction parameter, X, were extracted from the coherent scattering cross sections, Molecular anisotropy was measured on the solid state coextruded samples, and the observed drawing efficiency is compared with, the results of shrinkage tests. In the case of PMMA/PEO blends, anomalous scattering behavior precludes any quantitative Interpretation of the scattering patterns, but revealed important structural changes upon drawing, namely a deformation-induced phase separation.     

Morphological properties,rheological behaviors,and phase interaction of nylon 11/polypropylene blends by in situ reactive compatibilization and dispersion through polyhydroxybutyrate

The current research discusses the reactive compatibilization of nylon 11 (PA11) and polypropylene (PP) using maleic anhydride grafted PP (PP-g-MA) through an extruder. PP phase is dispersed in PA11 by coalescence and droplet break-up mechanism by using polyhydroxybutyrate (PHB) as a dispersion agent that induces uniform interaction between the blend components. The reactive compatibilization ensures the mixing of polymers, and the consistent interaction of phases is controlled by dispersion. All of the blends were processed through melt processing at different compositions using a twin-screw extruder. Scanning electron microscopy was used to determine the morphologies of the binary and ternary blends. Surface tension and interfacial tension of the homopolymer characterizes the interaction of the polymers at interphase. The interaction of PHB/PA11 appeared preferable than that of PHB/PP, elaborating on the efficient dispersion and droplet formation of the PP phase. The compatibilizer maleic anhydride grafted PP (PP-g-MA) imparts a drastic effect on the compatibility of PA11-PP and PA11-PHB-PP blends and reduces PP phase particle size, which indicates the affinity of PHB and PP. The encapsulation of PP by PHB was seen in the expectation of minimum free energy models. The rheological measurements were used to understand the phase separation within blends. These measurements were also applied to understand the interaction between PA11-PP-PHB phases. The modulus values and viscosity ratio of the blends were measured to follow the chain relaxation in the melt. In the Cole–Cole plot, it was found that the reduction in PP phase size influences the relaxation of chains of blends.     

Formation of phase structure and crystallization behavior from disordered melt for ethylene-isoprene block copolymers and their blends

The structure formation and crystallization kinetics in crystallization from a disordered melt were investigated for a polyethylene-polyisoprene block copolymer (LEI) having M_n = 3.2 × 10⁴ and 53 wt% of polyethylene content and for its blends with the corresponding homopolymers, polyethylene (PE) and polyisoprene (PIp), using synchrotron small-angle X-ray scattering techniques (SAXS) and differential scanning calorimetry (DSC). For LEI copolymer and the blends, no microphase separation structure was observed in the molten state. In the crystalline state of the neat LEI, the first and higher order scattering peaks were clearly observed, in which the intensity of the higher order peaks was considerably strong. This unusual behavior of the higher order peaks was explained by the lamellar insertion model of Hama and Tashiro. From the analyses based on this model and one-dimensional electron density correlation function with a three phase model, the phase structure in the crystalline state of the neat LEI was concluded to be a regular lamellar structure consisting of crystalline lamella of PE block and amorphous layers of PE and PIp blocks. This phase structure was quite different from that reported previously for a polyethylene-polyisoprene block copolymer (HEI) with a higher molecular weight in which HEI crystallized with keeping the microphase separation structure in the melt. For the blends of LEI with PIp homopolymer, the phase structure is affected by the blend composition, while for the blends with PE homopolymer, the phase structure depended on the crystallization temperature as well as the molecular weight and composition of the added PE. The Avrami index was 2-3 for neat LEI, all blends and PE homopolymers.     

Miscibility,morphology and thermal properties of poly(para‐dioxanone)/poly(D,L‐lactide) blends

BACKGROUND: Poly(para‐dioxanone) (PPDO) is a biodegradable polyester with excellent biodegradability, bioabsorbability, biocompatibility and mechanical flexibility. However, its high cost and relatively fast degradation rate have hindered the development of commercial applications. Blending with other polymers is a simple and convenient way of modifying the properties of aliphatic polyesters. Poly(D ,L ‐lactide) (PDLLA) is another polyester that has been extensively studied for biomedical applications due to its biocompatibility and suitable degradation rate. However, to our knowledge, blends of PPDO/PDLLA have not been reported in the literature. RESULTS: A series of biodegradable polymers were blended by solution co‐precipitation of PPDO and PDLLA in various blend ratios. The miscibility, morphology and thermal properties of the materials were investigated. DSC curves for all blends revealed two discrete glass transition temperatures which matched the values for pure PPDO and PDLLA. SEM images of fracture surfaces displayed evidence of phase separation consistent with the DSC results. The contact angles increased with the addition of PDLLA. CONCLUSION: PPDO/PDLLA blends exhibit two distinct glass transition temperatures that remain nearly constant and correspond to the glass transition temperatures of the homopolymers for all blend compositions, indicating that blends of PPDO and PDLLA are immiscible. Images of the surface obtained using SEM were also suggestive of a two‐phase material. The crystallinity of the PPDO phase in the blends was affected by the PDLLA content. The mechanical properties of the blends changed dramatically with composition. Adding PDLLA makes the blends less hydrophilic than PPDO. Copyright © 2008 Society of Chemical Industry