Structural and ordering behavior of lamellar polystyrene‐block‐polybutadiene‐block‐polystyrene triblock copolymer containing layered silicates

Nanocomposites based on organically modified montmorillonites (OMMTs) and sodium montmorillonite (CLO‐Na⁺) with poly(styrene‐b‐butadiene‐b‐styrene) (SBS) diblock copolymer have been investigated. Solution blending of OMMT suspension in toluene with SBS and subsequent static casting and annealing resulted in transparent films. Final samples were processed by compression molding. The intercalation spacing in the nanocomposites, microphase separation of the SBS, and the degree of dispersion of nanocomposites were investigated by X‐ray diffraction (Wide and small‐angle X‐ray scattering), transmission optical microscopy (TOM), atomic force microscopy (AFM), and transmission electron microscopy (TEM). The increase of basal spacing of OMMT in the nanocomposites suggested the intercalation of SBS. The lamellar structure perfection was extensively affected by both OMMT. AFM images and TOM micrographs only showed well dispersed but not exfoliated nanocomposites. On the other hand, TEM showed inserted tactoids into both blocks depending on the surfactant used (stained samples) and the dispersion of those tactoids (unstained samples). Fourier transform infrared spectroscopy indicated only the presence of the OMMT into the SBS. Deviations of the decomposition pathway of pristine SBS with addition of the OMMT were found by thermogravimetric analysis. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Self‐assembled structures in polystyrene‐block‐polyisoprene‐blend‐polystyrene and polystyrene‐block‐poly(methyl methacrylate)‐blend‐polystyrene or ‐blend‐poly(methyl methacrylate) in the strong segregation regime

This study deals with the investigation of microphase‐separated morphology and phase behaviour in blends of polystyrene‐block‐polyisoprene with homopolystyrene and blends of polystyrene‐block‐poly(methyl methacrylate) with homopoly(methyl methacrylate) or homopolystyrene in the strong segregation regime using small‐angle X‐ray scattering and transmission electron microscopy as a function of composition, molecular weight of homopolymers, r_M and temperature. Parameter r_M = M_H/M_C (where M_H is the molecular weight of homopolymer and M_C that of the corresponding block copolymer) was selected to encompass behaviour of the chains denoted as a ‘wet brush’ (i.e. r_M < 1). The relative domain spacing D/D_o increases in the regime 0 < r_M?1 with increasing concentration of homopolymer w_P and increasing r_M but depends on the specific implemented morphology. We tested a new approximate D/D_o versus w_P relation in the strong segregation regime using block copolymers of high molecular weights. It is shown that the parameters r_M and χ^3/2N determine the slope of the D/D_o versus w_P relation in the strong segregation regime and the new approximation generally matches the experimental data better than the approximations used so far. Copyright © 2010 Society of Chemical Industry     

Nanostructured polymer blends based on polystyrene‐b‐polybutadiene‐b‐poly(methyl methacrylate) triblock copolymers modified with polystyrene and/or poly(methyl methacrylate) homopolymers

Morphologies of polymer blends based on polystyrene‐b‐ polybutadiene‐b ‐poly(methyl methacrylate) (SBM) triblock copolymer were predicted, adopting the phase diagram proposed by Stadler and co‐workers for neat SBM block copolymer, and were experimentally proved using atomic force microscopy. All investigated polymer blends based on SBM triblock copolymer modified with polystyrene (PS) and/or poly(methyl methacrylate) (PMMA) homopolymers showed the expected nanostructures. For polymer blends of symmetric SBM‐1 triblock copolymer with PS homopolymer, the cylinders in cylinders core?shell morphology and the perforated lamellae morphology were obtained. Moreover, modifying the same SBM‐1 triblock copolymer with both PS and PMMA homopolymers the cylinders at cylinders morphology was reached. The predictions for morphologies of blends based on asymmetric SBM‐2 triblock copolymer were also confirmed experimentally, visualizing a spheres over spheres structure. This work presents an easy way of using PS and/or PMMA homopolymers for preparing nanostructured polymer blends based on SBM triblock copolymers with desired morphologies, similar to those of neat SBM block copolymers. © 2017 Society of Chemical Industry     

Preparation and mechanical properties of clay/polystyrene‐block‐polybutadiene‐block‐polystyrene triblock copolymer (SBS) intercalated nanocomposites using organoclay containing stearic acid

Organoclays containing various amounts of stearic acid (SA) were synthesized, and clay/polystyrene‐block‐polybutadiene‐block‐polystyrene triblock copolymer (SBS) intercalated nanocomposites were prepared using organoclays containing SA by melt‐blending. Montmorillonite was the clay used, and both stearylamine and SA were used as surface modifiers. The amount of SA added was 0, 20, 50 and 100% of the cation‐exchange capacity (CEC). In this study, the effects of SA on the microstructure and mechanical properties of the clay/SBS nanocomposites were investigated. In clay/SBS with 100% CEC of SA, although no exfoliation of the clay occurred, the stacked clay layers were uniformly dispersed at the nanometer level (100–800 nm) without agglomeration. Clay/SBSs containing SA exhibited superior mechanical properties compared to clay/SBS without SA. It was found that SA effectively improved the clay dispersion in the SBS matrix and the mechanical properties of the clay/SBSs. Copyright © 2006 Society of Chemical Industry     

Self‐assembled structures in d8‐polystyrene‐block‐polyisoprene/polystyrene blends in the weak segregation regime: SAXS and TEM study

BACKGROUND: This paper reports an investigation of the microphase‐separated morphology and phase behaviour in blends of d‐polystyrene‐block‐polyisoprene with homopolystyrene in the weak segregation regime, using small‐angle X‐ray scattering and transmission electron microscopy, as a function of composition, weight‐average molecular weight and temperature. The chain length ratio parameter r_M = M_H/M_C (where M_H and M_C are the weight‐average molecular weights of the homopolymer and corresponding block copolymer chain) was selected to encompass all possible types of mutual homopolymer/block copolymer sizes. RESULTS: In the weak segregation regime the polystyrene block chains behave as a ‘wet brush’ for r_M < 1 similarly to the intermediate and strong segregation regimes. For r_M > 1 a macroscopic phase separation occurs. The domain spacing D increases systematically in the range 0 < r_M ≤ 1 with increasing concentration of homopolymer w_P and increasing r_M regardless of the implemented specific morphology, but the slope of the periodicity D versus w_P relation is smaller than in the intermediate and strong segregation regimes. CONCLUSION: The criterion for ‘wet and dry brush’ morphologies has been applied to explain the changes in microdomain morphology during the self‐assembly process. It has been shown that the parameters r_M and χ^3/2N (where χ is the Flory–Huggins parameter and N the number of segments per chain) characterize the slope of the D versus w_P relation in the weak and intermediate segregation regimes. Copyright © 2009 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     

Viscosity and shear strength of natural‐rubber‐based adhesives in the presence of gum rosin and petroresin

The viscosity and shear strength of pressure‐sensitive adhesives based on natural rubber (standard Malaysian rubber grade L) were studied with gum rosin and petroresin as the tackifying resins. Effects of the concentration of the tackifying resin and the molecular weight of rubber on the two properties were systematically investigated. Toluene was used as the solvent throughout the study to prepare the adhesives. The viscosity and shear strength of the adhesives were determined with a rotary viscometer and a texture analyzer, respectively. For the shear test, a hand coater was used to coat the adhesives on the release paper substrate to provide coating thicknesses of 60 and 120 μm. The results indicated that the viscosity increased with the resin loading and molecular weight of rubber increasing. The viscosity of the adhesive prepared from petroresin had a higher value than that of the gum‐rosin‐based adhesive. The shear strength of the adhesives decreased gradually with increasing resin content for both tackifying resins and coating thicknesses, and this observation was attributed to the decrease in the cohesive strength due to the dilution effect of the resins. However, the shear strength passed through a maximum at a molecular weight of rubber of 8.5 × 10⁴ for both resins. The gum‐rosin‐based adhesive consistently showed higher shear strength than that of the petroresin/natural rubber adhesive because of the better cohesiveness and compatibility of the former system. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Wetting behaviour and direct observation of thermally responsive polystyrene‐block‐poly(N‐isopropylacrylamide)‐block‐polystyrene electrospun fibres in aqueous environment

Electrospun fibres of thermally responsive triblock copolymer polystyrene‐block‐poly(N‐isopropylacrylamide)‐block‐polystyrene were prepared. Fibre morphology and swelling were studied below and above the lower critical solution temperature of poly(N‐isopropylacrylamide) (PNIPAM) using cryo‐electron microscopy. Cryo‐transmission electron microscopy showed that the fibre diameter increased up to 150% after immersion in water at 20 °C. In contrast, at 45 °C the fibre diameter increased considerably less. The sessile drop technique was used to characterize temperature‐dependent wetting of fibre mats. Contact angle (θ_CA) measurements revealed that a block copolymer fibre mat changed from hydrophobic (θ_CA > 90°) to hydrophilic (θ_CA < 90°) state within seconds after applying a water droplet on it at 20 °C. At 40 °C the initial contact angle was measured to be higher (135°) and it decreased much less than at 20 °C during the first minute of measurement. We observed using scanning electron microscopy that the electrospun fibres of the block copolymer having 77 wt% of PNIPAM lost their cylindrical shape and changed from fibres to thin sheets at both 20 and 40 °C within seconds after applying water on the fibres. Fibres having 55 wt% of PNIPAM were observed to be stable in water at both 20 and 40 °C, which resulted, surprisingly, in fibre mats with the strongest effects on thermally sensitive wetting. We discuss the surprising results and the implications that the evolution of fibre surface roughness has on the long‐term wetting behaviour, demonstrating a self‐adaptable hydrophilicity/hydrophobicity nature of the fibre mats. © 2013 Society of Chemical Industry     

Polymer nanocomposites containing carbon nanotubes and miscible polymer blends based on poly[ethylene‐co‐(acrylic acid)]

Four binary polymer blends containing poly [ethylene‐co‐(acrylic acid)] (PEAA) as one component, and poly(4‐vinyl phenol‐co‐2‐hydroxy ethyl methacrylate) (P4VPh‐co‐2HEMA) or poly(2‐ethyl‐2‐oxazoline) (PEOx) or poly(vinyl acetate‐co‐vinyl alcohol) (PVAc‐co‐VA) or poly (vinylpyrrolidone‐co‐vinyl acetate) (PVP‐co‐VAc) as the other component were prepared and used as a matrix of a series of composite materials. These binary mixtures were either partially or completely miscible within the composition range studied and were characterized by differential scanning calorimetry (DSC) and Fourier transformed infrared spectroscopy (FTIR). Carbon nanotubes (CNTs) were prepared by a thermal treatment of polyester synthesized through the chemical reaction between ethylene glycol and citric acid over an alumina boat. High resolution transmission electron microscopy (HRTEM) was used to characterize the synthesized CNTs. Films of composite materials containing CNTs were obtained after evaporation of the solvent used to prepare solutions of the four types of binary polymer blends. Young's moduli of the composites were obtained by thermomechanical analysis at room temperature. Only one glass transition temperature was detected for several compositions on both binary blends and the composite material matrices. Evidence of hydrogen bond formation was recorded for both miscible blends and composite materials. The degree of crystallinity and Young's moduli of the CNT‐polymer composites increased compared to the single polymer blends. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Evaluation of disposable diaper construction hot melt pressure‐sensitive adhesives using blends of olefinic block copolymer and amorphous polyolefin polymers—Adhesive performance,sprayability, and viscoelastic characteristics

Pressure‐sensitive adhesives (PSAs) used in disposable diaper construction have been formulated using blends of olefinic block copolymer (OBC) and an ethylene–propylene (PE‐PP) amorphous polyolefin (APO) polymer, with three different unsaturated hydrocarbon resins (with varying aromatic content), and also with two different saturated aliphatic hydrocarbon resin (with varying cycloaliphaticity). The viscoelastic properties of theses PSA formulations were studied using dynamic mechanical analysis (DMA). Viscosity profiles at five different temperatures were generated to better understand the application window for the resulting adhesive formulation. Rheology master curves were generated using time–temperature–superposition analysis and correlated with the processability characteristics. Adhesives used in disposable diaper construction were applied between a polyethylene backing and a nonwoven substrate with an air‐assisted spiral spray application technique on an Acumeter Spray Coater. After the adhesive was applied, peel adhesion testing on the samples was performed. It has been observed that the OBC/PE–PP‐based disposable diaper construction PSA has a lower application temperature along with wider tolerance for hydrocarbon resin chemistries, especially for the saturated aliphatic resin‐based PSA formulations. Based on the coating parameters used, it has been learned that the adhesive formulations seem to show a higher shear rate at the nozzle, but Reynolds number calculated indicated no major turbulence occurring at the nozzle during spraying. Very good spray patterns were obtained for the olefinic polymer‐based PSA formulations. Disposable diaper construction article showed good adhesive peel properties, especially for the adhesive formulations containing saturated aliphatic hydrocarbon resin, which were comparable to the SBS‐based control. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3311–3318, 2013     

Phase behavior of ternary blends containing dimethylpolycarbonate,tetramethylpolycarbonate and poly[styrene‐co‐(methyl methacrylate)] copolymers (or polystyrene)

The miscibility and phase behavior of ternary blends containing dimethylpolycarbonate (DMPC), tetramethylpolycarbonate (TMPC) and poly[styrene‐co‐(methyl methacrylate)] copolymer (SMMA) have been explored. Ternary blends containing polystyrene (PS) instead of SMMA were also examined. Blends of DMPC with SMMA copolymers (or PS) did not form miscible blends regardless of methyl methacrylate (MMA) content in copolymers. However, DMPC blends with SMMA (or PS) blends become miscible by adding TMPC. The miscible region of ternary blends is compared with the previously determined miscibility region of binary blends having the same chemical components and compositions. The region where the ternary blends are miscible is much narrower than that of binary blends. Based on lattice fluid theory, the observed phase behavior of ternary blends was analyzed. Even though the term representing the Gibbs free energy change of mixing for certain ternary blends had a negative value, blends were immiscible. It was revealed that a negative value of the Gibbs free energy change of mixing was not a sufficient condition for miscible ternary blends because of the asymmetry in the binary interactions involved in ternary blends. Copyright © 2004 Society of Chemical Industry     

Preparation,morphology, and mechanical properties of elastomers based on α,ω‐dihydroxy‐polydimethylsiloxane/polystyrene blends

α,ω‐Dihydroxy‐polydimethylsiloxane/polystyrene (PDMS/PS) blends were prepared by the solution polymerization of styrene (St) in the presence of α,ω ‐dihydroxy‐polydimethylsiloxane (PDMS), using toluene as solvent and benzoyl peroxide (BPO) as initiator. The PDMS/PS blends obtained by this method are a series of stable, white gums, which were vulcanized to elastomers at room temperature with methyl‐triethoxysilicane (MTES). The use level of MTES was far more than the necessary amount used to end‐link hydroxy‐terminated chains of PDMS, with the excess being hydrolyzed to crosslinked networks, which were similar to SiO₂ and acted as filler. Investigations were carried out on the elastomeric materials by extraction measurement, swelling measurement, and scanning electron microscopy. The extraction data show that at each composition the amount of soluble fraction is less than expected and the difference between experimental and theoretical values becomes more and more significant as PS content increases. This is mainly due to the grafting of PS onto PDMS and the entanglement of PS in the interpenetrating polymer network (IPN), which consists of either directly linked PDMS chains or chains linked via PS grafts and is formed by free radical crosslinking of PDMS during the radical polymerization of St. PS grafted on PDMS is insoluble and PS entangled in the IPN is difficult to extract. Both render the soluble fraction to be less than expected. As the St content in preparing PDMS/PS blends increases, the probability of grafting PS onto PDMS also increases, which may subsequently produce a higher crosslinking level of PDMS networks that linked via PS grafts by radical crosslinking. As a result, not only the amount of insoluble PS increases but also PS entangled in the IPN is more difficult to extract. Scanning electron microscopy demonstrates that the elastomer system has a microphase‐separated structure and a certain amount of PS remains in the PDMS networks after extraction, which is in accordance with the extraction data. Moreover, the mechanical properties of the elastormeric materials have been studied in detail. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3542–3548, 2004     

Miscibility windows in ternary polymer blends of a polyester,polymethacrylate and poly(styrene‐co‐acrylonitrile)

Miscibility, phase diagrams and morphology of poly(ε‐caprolactone) (PCL)/poly(benzyl methacrylate) (PBzMA)/poly(styrene‐co‐acrylonitrile) (SAN) ternary blends were investigated by differential scanning calorimetry (DSC), optical microscopy (OM), and scanning electron microscopy (SEM). The miscibility window of PCL/PBzMA/SAN ternary blends is influenced by the acrylonitrile (AN) content in the SAN copolymers. At ambient temperature, the ternary polymer blend is completely miscible within a closed‐loop miscibility window. DSC showed only one glass transition temperature (T_g) for PCL/PBzMA/SAN‐17 and PCL/PBzMA/SAN‐25 ternary blends; furthermore, OM and SEM results showed that PCL/PBzMA/SAN‐17 and PCL/PBzMA/SAN‐25 were homogeneous for any composition of the ternary phase diagram. Hence, it demonstrated that miscibility exists for PCL/PBzMA/SAN‐17 and PCL/PBzMA/SAN‐25 ternary blends, but that the ternary system becomes phase‐separated outside these AN contents. Copyright © 2003 Society of Chemical Industry     

Morphology,structure, and photovoltaic properties of poly(3‐hexylthiophene) and [6,6]‐phenyl‐C61‐butyric acid methyl ester‐based ternary blends doping with polystyrene of different tacticities

The influence of the polystyrene of different tacticities on the morphology, phase structure, and photovoltaic properties of poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) blend has been extensively investigated. The atactic polystyrene (aPS) immiscible with P3HT tended to form the phase‐separated and columnar structure at low aPS weight ratio. Besides, the aPS could migrate to the surface of the films with PCBM phase distributing in the interfaces between P3HT and aPS domains at high aPS weight ratio of 75 wt %. The syndiotactic polystyrene (sPS) immiscible with P3HT could induce the crystallization of P3HT at low weight ratio of 3 wt %. The device based on aPS/P3HT/PCBM ternary blend showed of power conversion efficiency (PCE) of 1.2% even at aPS weight ratio of 50 wt %. However, the device based on sPS/P3HT/PCBM exhibited a sharp decrease in PCE value from 2.3% to 0.6% at sPS weight ratio of 3 wt %, due to the change in film morphology. The performance of the solar cell is believed to be determined by the morphology and phase structure of the ternary blends as revealed by the atomic force microscopy and UV‐vis spectra analysis. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41823.     

Effect of silica on viscosity,tack, and shear strength of epoxidized natural rubber‐based pressure‐sensitive adhesives in the presence of coumarone‐indene resin

The viscosity, loop tack, and shear strength of silica‐filled epoxidized natural rubber (ENR 25 and ENR 50 grade) adhesive were investigated using coumarone‐indene as the tackifying resin. Silica loading was varied from 10–50 parts per hundred parts of rubber (phr), whereas the coumarone‐indene concentration was fixed at 40 phr. Toluene was used as the solvent throughout the study. Polyethylene terephthalate substrate was coated at various adhesive coating thicknesses, i.e., 30, 60, 90, and 120 μm using a SHEEN Hand Coater. Viscosity of the adhesive was determined by a HAAKE Rotary Viscometer whereas loop tack and shear strength were measured by a Llyod Adhesion Tester operating at 30 cm/min. Result shows that viscosity of the adhesive increases gradually with increase of silica loading due to the concentration effect of the filler. Both loop tack and shear strength show maximum value at 40 phr silica for ENR 25. However, the respective values for ENR 50 are 20 and 40 phr of filler. This observation is attributed to the maximum wettability and compatibility of adhesive on the substrate at the respective silica loadings. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010