Compatibilization effects of styrenic/rubber block copolymers in polypropylene/polystyrene blends

Compatibilizing effects of styrene/rubber block copolymers poly(styrene‐b‐butadiene‐b‐styrene) (SBS), poly(styrene‐b‐ethylene‐co‐propylene) (SEP), and two types of poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene) (SEBS), which differ in their molecular weights on morphology and selected mechanical properties of immiscible polypropylene/polystyrene (PP/PS) 70/30 blend were investigated. Three different concentrations of styrene/rubber block copolymers were used (2.5, 5, and 10 wt %). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to examine the phase morphology of blends. The SEM analysis revealed that the size of the dispersed particles decreases as the content of the compatibilizer increases. Reduction of the dispersed particles sizes of blends compatibilized with SEP, SBS, and low‐molecular weight SEBS agrees well with the theoretical predictions based on interaction energy densities determined by the binary interaction model of Paul and Barlow. The SEM analysis confirmed improved interfacial adhesion between matrix and dispersed phase. The TEM micrographs showed that SBS, SEP, and low‐molecular weight SEBS enveloped and joined pure PS particles into complex dispersed aggregates. Bimodal particle size distribution was observed in the case of SEP and low‐molecular weight SEBS addition. Notched impact strength (a_k), elongation at yield (ε_y), and Young's modulus (E) were measured as a function of weight percent of different types of styrene/rubber block copolymers. The a_k and ε_y were improved whereas E gradually decreased with increasing amount of the compatibilizer. The a_k was improved significantly by the addition of SEP. It was found that the compatibilizing efficiency of block copolymer used is strongly dependent on the chemical structure of rubber block, molecular weight of block copolymer molecule, and its concentration. The SEP diblock copolymer proved to be a superior compatibilizer over SBS and SEBS triblock copolymers. Low‐molecular weight SEBS appeared to be a more efficient compatibilizer in PP/PS blend than high‐molecular weight SEBS. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 291–307, 1999     

Effects of the nature and combinations of solvents in the intercalation of clay with block copolymers on the properties of polymer nanocomposites

Polystyrene (PS) nanocomposites were prepared by the free‐radical polymerization of styrene in the presence of organically modified montmorillonite (MMT) clays. MMT clay was modified with a low‐molecular‐weight and quarternized block copolymer of styrene and 4‐vinylpyridine [poly(styrene‐b‐4‐vinylpyridine) (SVP)] with 36.4 wt % PS and 63.6 wt % poly(4‐vinylpyridine) (P4VP). Special attention was paid to the modification, which was carried out in different compositions of a solvent mixture of tetrahydrofuran (THF) and water. The swelling behavior of the MMT clay was studied by an X‐ray diffraction technique. The diffraction peak shifted to lower 2θ angles for all of the modified clays, which indicated the intercalation of the quarternized SVP copolymer into the MMT layers in different degrees. Higher interlayer distances, which showed a high degree of block copolymer insertion, were obtained for solvent compositions with THF in water. The resultant nanocomposites were characterized by X‐ray diffraction, atomic force microscopy, scanning electron microscopy, thermogravimetric analysis, and dynamic mechanical analysis. The desired exfoliated nanocomposite structure was achieved when the MMT modification was conducted in 50 or 66 wt % THF, whereas the other modifications all resulted in intercalated structures. The resulting exfoliated nanocomposite was found to have better thermal stability and dynamic mechanical performance compared to the others, even with 2% clay loading. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

SBS and SEBS block copolymers as impact modifiers for polypropylene compounds

Blends of polypropylene (PP) and thermoplastic elastomers (TPE), namely SBS (styrene‐butadiene‐styrene) and SEBS (styrene‐ethylene/1‐butene‐styrene) block copolymers, were prepared to evaluate the effectiveness of the TPE type as an impact modifier for PP and influence of the concentration of elastomer on the polymer properties. Polypropylene homopolymer (PP‐H) and ethylene–propylene random copolymer (PP‐R) were evaluated as the PP matrix. Results showed that TPEs had a nucleating effect that caused the PP crystallization temperature to increase, with SBS being more effective than SEBS. Microstructure characterization tests showed that in most cases PP/SEBS blends showed the smallest rubber droplets regardless of the matrix used. It was seen that SEBS is a more effective toughening agent for PP than SBS. At 0°C the Izod impact strength of the PP‐H/SEBS 30% b/w blend was twofold higher than the SBS strength, with the PP‐R/SEBS 30% b/w blend showing no break. A similar behavior on tensile properties and flexural modulus were observed in both PP/TPE blends. Yield stress and tensile strength decreased and elongation at break increased by expanding the dispersed elastomeric phase in the PP matrix. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 254–263, 2005     

Self‐assembly of ABA triblock copolymers based on functionalized polydimethylsiloxane and polymethyloxazoline

This study describes the responsive behavior of modified amphiphilic ABA triblock copolymers of polymethyloxazoline‐block‐poly(methylhydrosiloxane‐co‐dimethylsiloxane)‐block‐polymethyloxazoline (PMOX‐b‐P(MHS‐co‐DMS)‐b‐PMOX) when subjected to compression on the water surface or to ions in the water bulk phase. The hydrophobic middle block was functionalized with spacers bearing methyl 2‐hydroxybenzoate (Bz) or 18‐crown‐6 ether (Ce) groups. The behavior at the air–water interface was studied by measuring surface pressure versus mean molecular area (π–mmA) isotherms, and atomic force microscopy (AFM) was employed to investigate the morphology of Langmuir–Blodgett (LB) films after transfer to solid supports. Ion‐responsive self‐assembly was followed using light microscopy and can be understood on a molecular level by employing ¹H NMR spectroscopy. The π‐mmA isotherm of PMOX‐b‐P(MHS‐co‐DMS)‐b‐PMOX‐44Bz at the air–water interface had an extended pseudo‐plateau at a surface pressure of ca 22 mN m^?1 reflecting the coil to loop transformation of the hydrophobic middle block which was absent for the crown ether‐functionalized triblock copolymer. AFM images of LB films of PMOX‐b‐P(MHS‐co‐DMS)‐b‐PMOX‐44Bz showed dewetting effects of the polymer film after transfer to a silicon wafer. LB films of PMOX‐b‐P(MHS‐co‐DMS)‐b‐PMOX‐8Ce formed surface micelles having a size of ca 50–100 nm on the solid support. The ion sensitivities of the crown ether‐derivatized copolymers in solution were investigated by exposing polymeric vesicles to potassium, sodium and magnesium ions. Exposure to K⁺ and Na⁺ led to vesicle rupture and the formation of micro‐tubular structures, while Mg²⁺ had no effect on the vesicular structures as confirmed using light microscopy. Specific interactions between the crown ether‐derivatized polymer and ions were further elucidated from ¹H NMR experiments that indicated that K⁺ coordinated with the crown ether causing the dense packing to subside and leading to solubilization of the polymer in water. 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     

AFM Study on the Interactions Across Interfaces Containing Attached Polymer Chains

Summary: Interactions between surfaces with attached polymers are very common in both biological and engineering fields. These types of interactions are critical in processes such as coagulation and flocculation in mineral processing, biological recognition in metabolic processes and stress transference in polymer composites, among others. Although many mechanisms have been proposed to explain phenomena occurring at the interfaces on a molecular level, few experimental procedures can give direct information about them. In this work, interactions occurring at interfaces containing attached polymer chains, such as the ones that are present in polymer composites, were studied by using AFM. In order to identify the effect of the structure of the interface on phenomena such as stress transference and energy dissipation, polymers with different molar mass, areal density and chemical architecture were synthesized and attached to substrates and AFM cantilevers. Force‐distance curves, obtained by AFM, provided some fundamental information about the mechanisms involved when polymers attached to different surfaces interact. Results showed that chains grafted on different surfaces can interact via entanglements and intersegmental bonding. Based upon the application of the AFM modified technique, interfaces containing polymers, such as in polymer composites, can be designed and optimized through the manipulation of its structure to achieve new roles in the performance of systems.

     

Phase separation in polymer blends comprising copolymers: 6. Effect of molecular architecture of block copolymers

To study the effect of the molecular architecture of a copolymer on its miscibility with corresponding homopolymers a series of block copolymers of styrene and isoprene with diblock, triblock and four-arm star architectures have been prepared and the morphologies of the blends of the copolymers and polyisoprene with different molecular weights have been examined by electron microscopy. The results show that miscibility varies in the sequence diblock>triblock>four-arm star copolymers. This sequence is in the opposite direction to the variation of the architectural complexity of the block copolymers, i.e. the more complex is molecular architecture, the greater is conformation restriction in microdomain formation and the less is solubility of homopolymer in corresponding domains.     

Effect of molecular structure of styrene–butadiene block copolymers on morphology,rheological properties,and impact strength of polystyrene/polyethylene blends

The effect of molecular structure of six model styrene–butadiene (SB) block copolymers with various number of blocks and two lengths of styrene blocks on morphology, rheological properties, and impact strength of polystyrene (PS)/high‐density polyethylene (PE) blends was studied. It was found that location of SB copolymers in the blends is determined by the length of styrene blocks. The length of styrene blocks has similar effects on impact strength and linear viscoelastic properties of the blends. On the other hand, the correlation was not found between the effects of a number of blocks on impact strength and linear viscoelastic properties of the blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2303–2309, 2003     

Deformation and alignment of lamellae in melt extension of blends of a styrene‐butadiene block copolymer with polystyrene

The development of the morphology and the alignment of lamellae in melt elongation of blends of an asymmetric linear styrene‐butadiene block copolymer (LN3) and polystyrene (PS 158K) was investigated. PS 158K and LN3 formed two‐phase polymer blends with PS 158K resp. LN3 inclusions, depending on the concentration of polystyrene. The block copolymer was arranged in a lamellar phase with a lamellae thickness of ～ 13 nm. Our rheological experiments revealed that the complex modulus, the elongational viscosity and the recovered stretch of the blends primarily resulted from a superposition of the properties of the blend components. In melt elongation, pure LN3 started to crumple at a small Hencky strain. In the blends, the presence of the PS 158K inclusions led to a macroscopically more uniform elongation, but with an anisotropic Poisson ratio. The LN3 inclusions in the PS 158K matrix were deformed into a filament‐like shape. In the blends with a LN3 matrix the alignment of the block copolymer lamellae parallel to the loading direction increased with applied extensional strain. In the latter case, the lamellae thickness did not decrease significantly. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Morphology and micromechanical deformation behavior of styrene–butadiene block copolymers. IV. Structure–property correlation in binary block copolymer blends

The structure–property correlation in blends consisting of styrene/butadiene block copolymers forming alternating polystyrene (PS) and polybutadiene (PB) lamellae, and PS domains in rubbery matrix was investigated by different microscopic techniques (transmission electron microscopy, scanning force microscopy, and scanning electron microscopy), uniaxial tensile testing, and dynamic mechanical analysis. Unlike the pure lamellar block copolymer, the blends showed predominantly disordered wormlike morphology formed by the intermolecular mixing. These structures allowed a precise control of stiffness/toughness ratio of the blends over a wide range. The blends showed a gradual transition from predominantly viscoplastic to elastomeric behavior with increasing triblock copolymer content. The results demonstrated that the binary block copolymer blends provide the unique possibility of tailoring mechanical properties on the basis of nanostructured polymeric materials. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1219–1230, 2004     

Effect of diisocyanates and chain extenders on the physicochemical properties and morphology of multicomponent segmented polyurethanes based on poly(l‐lactide), poly(ethylene glycol) and poly(trimethylene carbonate)

Multicomponent segmented polyurethanes (SPUs) based on poly(ethylene glycol), poly(l ‐lactide) and poly(trimethylene carbonate) as macrodiols, 2,4‐toluene diisocyanate (2,4‐TDI) or 1,6‐hexane diisocyanate (HDI) as diisocyanate, and 1,4‐butanediol (BDO) or 2,2‐bis(hydroxymethyl)propionic acid (DMPA) as chain extenders were synthesized. The molecular, thermal, dynamic mechanical and morphological features of this set of uncrosslinked polyurethanes are characterized using ¹H NMR, gel permeation chromatography, differential scanning calorimetry, dynamic mechanical thermal analysis (DMTA) and atomic force microscopy techniques. The lower reaction rate of HDI in comparison with 2,4‐TDI allows for better control of the SPU compositions, so that the intrinsic properties of each block can be better combined and modulated. HDI‐based SPUs are semi‐crystalline, while those based on 2,4‐TDI are amorphous, affecting the mechanical properties of these polyurethanes. All SPUs are heterogeneous, presenting morphologies of a disperse phase in a matrix which varies with the macrodiol ratios as well as with the nature of the diisocyanate and chain extender (a finer dispersion of the disperse phase is observed for SPUs of HDI and BDO). DMTA results indicate that the phases are complex mixtures of the different blocks with at least one rich in PLLA. The PEG content is shown to be the most important factor influencing the water sorption capability, while the incorporation of hindering carboxylic acid groups by the use of DMPA allows the water uptake of SPUs to be controlled by the solution pH. All SPUs show a significant loss of molar mass in hydrolytic degradation experiments and, in general, the PLLA‐rich SPUs are more susceptible to degradation. © 2015 Society of Chemical Industry     

Interfacially polymerized nanofiltration membranes: Atomic force microscopy and salt rejection studies

Interfacial polymerization is one of the main techniques for producing composite nanofiltration (NF) membranes. In this study, five NF membranes were produced through interfacial polymerization under different conditions of reactions, namely varying reaction time, as well as monomer concentrations. The membranes were then imaged using atomic force microscope (AFM). AFM images provided information of the average pore size, pore size distribution, and surface roughness. For some of the membranes, discrete pore sizes were visible. Increasing the reaction time resulted in decreasing water permeabilities but based on AFM imaging the pore size was of similar value. Increasing the monomer concentration also resulted in decreasing water permeabilities. However, based on AFM imaging the pore size differs considerably. Additional permeation experiments were also carried out using NaCl and Na₂SO₄ solutions with membranes identified as NF. By fitting the rejection data using a model such as the Donnan‐steric‐pore model, the variation in effective charge density of the membranes was also determined. The ability to tailor composite NF membranes with the right properties will significantly improve membrane performance. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 605–612, 2005     

Morphology and micromechanical deformation behavior of styrene–butadiene block copolymers. III. Binary blends of asymmetric star block copolymer with general‐purpose polystyrene

The correlation between morphology, mechanical properties, and micromechanical deformation behavior of the blends consisting of an asymmetric styrene/butadiene star block copolymer (ST2‐S74, total styrene volume content Φ_PS = 0.74) and general‐purpose polystyrene (GPPS) was investigated using transmission electron microscopy and uniaxial tensile testing. Addition of 20 wt % of GPPS to the block copolymer resulted in a drastic reduction in strain at break, indicating the existence of critical PS lamella thickness D_c. Above D_c lamellar block copolymers displayed a transition from ductile to brittle behavior, substantiating the mechanism of thin layer yielding proposed for lamellar star block copolymers. The blends showed a variety of deformation structures ranging from classical crazelike zones to those with internal shearlike components. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1208–1218, 2004     

Blends of high density polyethylene and ethylene/1‐octene copolymers: Structure and properties

The morphology formation in the blends comprising a high density polyethylene (HDPE) and selected ethylene/1‐octene copolymers (EOCs) was studied with variation of blend compositions using atomic force microscopy (AFM). The binary HDPE/EOC blends studied showed well phase‐separated structures (macrophase separation) in consistence with individual melting and crystallization behavior of the blend components. For the blends comprising low 1‐octene content copolymers, the lamellar stacks of one of the phases were found to exist side by side with that of the another phase giving rise to leaflet vein‐like appearance. The formation of large HDPE lamellae particularly longer than in the pure state has been explained by considering the different melting points of the blend components. The study of strain induced structural changes in an HDPE/EOC blend revealed that at large strains, the extensive stretching of the soft EOC phase is accompanied by buckling of HDPE lamellar stack along the strain axis and subsequent microfibrils formation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1887–1893, 2007     

Self‐Assembling of SBS Block Copolymers as Templates for Conductive Silver Nanocomposites

Novel nanocomposites based on conductive Ag nanoparticles and a self‐assembled polystyrene‐block‐polybutadiene‐block‐polystyrene (SBS) block copolymer were investigated. Good confinement of the nanoparticles into polystyrene microphase was achieved by the addition of DT as surfactant. The polymeric matrix kept its hexagonal order packed cylindrical structure up to 7 wt.‐% content of Ag nanoparticles. An electrostatic force microscopy (EFM) analysis of well‐dispersed metal‐organic hybrid Ag/SBS films was used to characterize the electric behavior of the conductive nanocomposites.

     

AFM study of crystalline cellulose in the cell walls of straw

Crystalline cellulose in the cell walls of straw was studied by atomic force microscopy (AFM). The samples were first treated and then observed by AFM under dimethylsulfoxide (DMSO). The crystalline regions were located and two allomorphs of crystalline cellulose, triclinic I_α and monoclinic I_β phases, were identified. In most crystalline regions, the I_α and I_β phases are intimately associated, with the I_β phase more abundant than the I_α phase. In some small domains only one phase with long‐range order was observed. It was demonstrated that in these one‐phase domains, I_α phase crystals always have their (010) plane lying parallel to the cell wall surface and I_β phase crystals with (110) plane lying parallel. Copyright © 2005 Society of Chemical Industry     

Surface characterization of quaternized polysulfone films and biocompatibility studies

A novel quaternized polysulfone with N‐dimethyloctylammonium groups was investigated with respect to its surface properties, hydrophobicity, interactions with blood, and morphology. The history of the films formed from N,N‐dimethylformamide/methanol and N,N‐dimethylformamide/water solutions and the compositions of the solvent/nonsolvent mixtures influenced the surface morphology. Thus, atomic force microscopy investigations of the films showed pores and nodules of different sizes and intensities, which depended on the content of methanol or water in the solvent mixtures. Hydrophilicity modification, evidenced by the apolar components and the electron‐acceptor and electron‐donor parameters of the polar components of the surface tension parameters, was correlated with atomic force microscopy data. Surface wettability trends were analyzed on the basis of the free energy of hydration between the prepared films and water and the work of adhesion. The adhesion of red blood cells to the modified polysulfone showed the influence of the hydrophobic properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Study on the morphology of the hydrophobically‐modified polyelectrolyte in aqueous solution by AFM measurements

This work focuses on the AFM study of the aggregation morphology and association mechanism of the hydrophobically‐association water‐soluble polymer P (AM‐AA‐BPAM) in aqueous solution. It shows that the P (AM‐AA‐BPAM) molecule chain, which has hydrophobic and hydrophilic ionic groups, forms the “spherical” aggregations as micelles below 0.2 g · dL^?1, and then connect each other to form the string‐like aggregations, which produce large viscosity for the polymer solution. It is also coincident with the FCS, DLS, and viscosity study result. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1175–1178, 2004     

Local thermal degradation behavior of heterophasic polypropylene copolymers

Polypropylene (PP) impact copolymer is one of the heterophasic PP systems that is improved by rubber modification. Because the copolymer is a complicated polymer blend, which mainly consists of PP and ethylene–propylene rubber (EPR) components, the degradation behavior has hardly been studied. In this study, the thermal degradation of the copolymer was studied through direct observation by atomic force microscopy, which is a powerful tool for observing a local domain in a polymer blend. The degradation behavior was visually captured by the mapping of topological changes. Although the EPR phase was hardly degraded, the neighboring PP matrix was degraded selectively. The degradation behavior of the copolymer was found to be heterogeneous. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1831–1835, 2006     

Surface segregation of polyethylene in low‐density polyethylene/ethylene–propylene–diene rubber blends: Aspects of component structure

Aspects of the molecular weight and its distribution, the branching of low‐density polyethylene (LDPE), and the molecular composition of the ethylene–propylene–diene rubber (EPDM) matrix are presented in this article in terms of their influence on the surface segregation of polyethylene (PE) in elastomer/plastomer blends. All of the PEs studied, despite different weight‐average molecular weights and degrees of branching, segregated to the surface of the LDPE/EPDM blends. Atomic force microscopy pictures demonstrated defective crystalline structures on the surface of the blends, which together with a decrease in the degrees of their bulk crystallinity and a simultaneous increase in their melting temperatures, pointed to a low molecular weight and a defective fraction of PE taking part in the surface segregation. The extent of segregation depended on the molecular structure of the EPDM matrix, which determined the miscibility of the components on a segmental level. The higher the ethylene monomer content in EPDM was, the lower was the PE content in the surface layer of the blends. The composition and structure of the surface layer was responsible for its lower hardness in comparison with the bulk of the blends studied. The surface gradient of the mechanical properties depended on the physicochemical characteristics of the components and the blend composition, which created the possibility of tailoring the LDPE/EPDM blends to dedicated applications. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 625–633, 2006