Phase diagram of polymer blends containing block copolymers

The phase transition and phase separation behavior occurring in mixtures containing an A–B block copolymer and an A homopolymer is discussed. With a pure block copolymer an order-disorder transition can be induced by raising the temperature, whereby the ordered lattice of segregated microdomains becomes unstable and gives way to a homogeneous liquid structure. Small amounts of a homopolymer added to a block copolymer can be accommodated in the microdomains consisting of the same type of monomeric units, up to a solubility limit that depends on the relative lengths of the homopolymer and the copolymer block and on the temperature. The order-disorder transition temperature of the block copolymer is also affected by the added homopolymer. At the other extreme of concentration, spherical micelles of block copolymer are formed when a small amount of the copolymer is added in the bulk homopolymer, and the critical micelle concentration again depends on the relative lengths of the molecules and blocks involved and on the temperature. Measurements were made with light scattering and small-angle X-ray scattering techniques to determine the phase behavior of mixtures containing a styrene-butadiene block copolymer and either a polystyrene or a polybutadiene. The resulting phase diagram exhibits a fascinating complexity. Comparison with recent theories treating these phenomena shows that a good agreement is generally obtained on a qualitative or semi-quantitative level, but a quantitative agreement is often not attained.     

Viscoelastic properties of heterophase blends of homopolymers and block copolymers

Stress relaxation and dynamic mechanical measurements were carried out for two types of heterophase polyblends. One is obtained by blending homopolymers of butadiene and styrene (high impact polystyrene or HIPS); the other by blending homopolymer of butadiene with a triblock copolymer of styrene-butadiene-styrene (SBS/B). It was found that for HIPS, time temperature superposition is difficult, and the shift factors cannot be adequately interpreted by a reasonable model. For SBS/B it is impossible to carry out superposition. Modulus-temperature and loss tangent curves determined by dynamic mechanical experiments indicate the presence of new transition near ?40°C. Possible mechanisms giving rise to this new transition are discussed.     

Morphology and mechanical properties of blends of isotactic or syndiotactic polypropylene with SEBS block copolymers

Blends of poly(styrene)-block-poly(ethene-co-but-1-ene)-block-poly(styrene) (SEBS) with isotactic polypropylene (PP) and syndiotactic PP, respectively, were investigated. The morphology was observed by means of scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The cryofracture surfaces studied by SEM did not show any particles that were pulled out, so that a good compatibility between SEBS and different PPs could be assumed. The multiphase character of the blends could be well detected by TEM of RuO₄ stained samples. TEM micrographs of two-layer specimens revealed that SEBS tends to diffuse into the PP phase under formation of micelles. The block copolymer shows a reorientation phenomenon of large domains at the interface before the diffusion into the PP phase occurs. The interfacial strength as a function of annealing time was measured by a peel test of two-layer specimens. Mechanical properties are studied and related to the blend morphology. © 1996 John Wiley & Sons, Inc.     

Properties of polyurethane oligomeric blends versus high molecular weight block copolymers

Segmental compatibility has been investigated in both oligomeric polyurethane blends and polyurethane block copolymers. The block copolymers are formed by linking a hard segment, composed of three MDI and two butane diol units on average with various macroglycols. The monodisperse oligomeric hard segment, H₃, with its chain ends reacted with ethanol is used as the urethane component in blends with macroglycols. The macroglycols used in both the blend and block copolymer systems include polyethylene oxide (PEO), polypropylene oxide (PPO), polytetramethylene oxide (PTMO), and polybutadiene (PBD). Blends of H₃ and PEO form a eutectic at a weight ratio of $\text{≈20}\text{80}\text{(}\text{H}{}_3\text{/}\text{PEO}\text{)}$ with a T_m,e = 34°C. H₃ and PTMO blends also give rise to a eutectic composition at $\text{≈20}\text{80}\text{(}\text{H}{}_3\text{/}\text{PTMO}\text{)}$ but with a T_m,e = 10°C. Both PPO and PBD mix with H₃ to form a crystalline—amorphous blend. The miscibility of H₃ and the soft segments at the melting point of H₃ is in the order of PEO > PTMO > PPO > PBD. In the block copolymer systems, stress—strain and dynamic mechanical testing indicate that the block copolymerization of a hard segment with each soft segment results in a microphase separated elastomer as expected. The extent of phase separation increases in the order of PBD > PTMO > PPO > PEO which is coincident with the trend predicated by the application of Hilderbrand's solubility parameter concept. All the soft segments used occur in an amorphous phase in the block copolymers while PEO and PTMO crystallize in a blend with H₃. The differences between the properties of the blends and block copolymers suggest that the phase separation, segment crystallization and domain coalescence are substantially restricted by the urethane—polyol junction points.     

Compatibilization of poly(vinyl chloride)/polystyrene blends with epoxidized styrene-butadiene-styrene block copolymers

The effectiveness of epoxidized styrene-butadiene-styrene (ESBS) block copolymer as a polymeric compatibilizer for the incompatible polystyrene/poly(vinyl chloride) (PS/PVC) blend was investigated. ESBS at two epoxidation levels (34 and 49 mol% oxirane units) was used and the study covered mainly compositions with up to 30 wt% PS content in the ternary blends. The results support the view that ESBS can serve as a compatibilizer at these levels of epoxidation and when added in amounts in excess of 5 wt%. Ternary blends may also have good elongation properties due to the thermoplastic elastomer character of ESBS.     

Polycarbonate-polystyrene block copolymers and their application as compatibilzing agents in polymer blends

The synthesis of a block copolymer with polystyrene (PS) and polycarbonate (PC) segments is described. It is produced by anionic polymerization of the styrene and endcapping with a hydroxyl group followed by subsequent reaction with phosgene and bisphenol-A. The polystyrene/polycarbonate block copolymer was used as a compatibilizing agent for blends of poly(ethylene terephthalate) (PET) and poly(p- phenylene oxide) (PPO). The block copolymer reduced the dimensions of the dispersed phase. The uniaxial mechanical properties of the compatibilized blends were improved by 5 to 10 wt% loadings of the copolymer.     

Surface control of hydrophilicity and degradability with block copolymers composed of lactide and cyclic carbonate bearing methoxyethoxyl groups

Block copolymers of L-lactide (LA) and trimethylene carbonate (TMC) derivatives bearing methoxyethyl groups [poly(TMCM-MOE1OM)-block-PLLA] were employed as spin-coated films on substrates, and their hydrophilic and degradation behaviors were investigated. Changing the solvents for film preparation, film thickness, and copolymer composition ratios varied the contact angles in the range of 84.3° ± 2.8° at 269 nm thickness and 18.2° ± 2.5° at 15 nm thickness. These contact angles showed dynamic changes from hydrophobic to hydrophilic properties, probably due to the methoxyethoxyl groups connecting the flexible TMC moieties in the copolymer. Immersion into water or hexane affected the dynamic contact angles. X-ray photoelectron spectroscopy analyses revealed that a large amount of hydrophilic groups was segregated onto the surface, although both LA and TMC units existed. Such dynamic contact angle changes were delayed by the crystallization of polylactide. The hydrolyzed behaviors of these films were examined by quartz cell microbalance, showing a slow degradation process.     

Morphology and micromechanical behavior of binary blends comprising block copolymers having different architectures

Morphology and deformation behavior of binary blends comprising styrene/butadiene block copolymers (polystyrene content, Φ_PS∼0.70) having different molecular architectures were studied by means of transmission electron microscopy and tensile testing. In contrast to the binary diblock copolymer blends discussed in literature, the phase separation behavior of the blends investigated was found to be strongly affected by asymmetric molecular architecture. The blends showed macrophase separated grains, in which the structures resembled the microphase morphology of none of the blend components. Unlike the classical rubber-modified or particle-filled thermoplastics, neither debonding at the particle/matrix interface nor the particle cavitation was observed in these nanostructured blends. The microdeformation of the blends revealed plastic drawing of polystyrene lamellae or PS struts dispersed in rubbery matrix and orientation of the whole deformation structures along the strain direction.     

Solid-state NMR characterization of unsaturated polyester thermoset blends containing PEO-PPO-PEO block copolymers

First, the NMR method proposed in our previous work was improved to provide more accurate measurement of interphase thickness in multiphase polymers. Then the improved method, in combination with other techniques, was applied to elucidate the phase behavior, miscibility, heterogeneous dynamics and microdomain structure in thermoset blends of unsaturated polyester resin (UPR) and amphiphilic poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymer. The experimental results were compared with those of epoxy resin (ER)/PEO-PPO-PEO blends to systematically elucidate the influence of binary polymer-polymer interaction on the phase behavior, domain size and especially the interphase thickness in thermoset blends of UPR and ER, respectively, with the same PEO-PPO-PEO triblock copolymer. It was found that UPR/PEO-PPO-PEO exhibits strong phase separation with considerably small interphase, and only a small fraction of PEO is mixed with UPR. Whereas ER/PEO-PPO-PEO exhibits weak phase separation with thick interphase, and a large amount of PEO is intimately mixed with ER. It was suggested that the thermodynamic interaction between the block copolymer and cross-linked thermoset resin is one of the key factors in controlling the phase behavior, domain size and interphase thickness in these blends. These NMR results are qualitatively in good agreement with the previous theoretical prediction of interphase properties between two immiscible polymers. Our NMR works on different thermoset blend systems with weak and strong microphase separations clearly demonstrate that the improved NMR method is a general and useful method for measuring the interphase thickness and elucidating the phase behavior and subtle microdomain structure in multiphase polymers with detectable heterogeneous dynamics.     

Dynamic mechanical properties and morphology of polypropylene block copolymers and polypropylene/elastomer blends

The relation between the dynamic mechanical properties and the morphology of polypropylene (PP) block copolymers and polypropylene/elastomer blends was studied by dynamic mechanical analysis (DMA), light- and electron microscopy. The latter techniques contributed to an improvement in assignments of relaxation transitions in the DMA spectra. It was established that PP block copolymers had multiphase structure since the ethylene/propylene rubber phase (EPR) formed in the copolymerization contained polyethylene (PE) domains. An identical morphology was found in the case of PP/polyolefin thermoplastic rubber (TPO) blends. Impact modification of PP by styrene/butadiene block copolymers led to a multiphase structure, too, due to the polystyrene (PS) domains aggregated in the soft rubbery polybutadiene phase. In the semicrystalline polyolefinic and in the amorphous styrene/butadienebased thermoplastic rubbers, PE crystallites and PS do mains acted as nodes of the physical network structure, respectively. PP/EPDM/TPO ternary blends developed for replacing high-density PE showed very high dispersion of the modifiers as compared to that of PP block copolymers. This fine dispersion of the impact modifier is a basic regulating factor of impact energy dissipation in the form of shear yielding and crazing.     

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.     

Synthesis, characterization and aggregation behavior of block copolymers containing a polyisocyanopeptide segment

Following up on previous preliminary communications the synthesis of a series of block copolymers by applying amine end-capped polymers as initiators for the nickel(II) catalyzed polymerization of isocyanides is reported. Using a polystyrene derivative as the initiator, superamphiphiles containing a hydrophobic polystyrene tail and a charged helical polyisocyanide headgroup were prepared. Under proper conditions these superamphiphiles self-assembled in water to give a variety of aggregate morphologies, among which are superhelical architectures. Initiators derived from carbosilane dendritic wedges gave block copolymers with a unique combination of structural elements, i.e. a flexible dendritic block and a rigid polyisocyanide block. Block copolymers derived from the 3rd generation dendrimers form well-defined micellar aggregates in the presence of Ag⁺ ions. These aggregates have been used to construct nanoarrays of metallic silver.     

Surface segregation in blends containing poly(dimethylsiloxane)-polystyrene block copolymers

The surface composition of polystyrene blends containing poly(dimethylsiloxane)-polystyrene block copolymers have been analyzed using X-ray photoelectron spectroscopy (XPS), contact angle measurements, and time-of-flight secondary ion mass spectrometry (TOFSIMS). The three techniques showed the surface of the blend samples to be identical to pure poly(dimethylsiloxane) homopolymer, despite the fact that the systems each contained only a 2% bulk concentration of siloxane. The high surface sensitivity of TOFSIMS—which probes the samples to depths of a few angstroms—indicates an enrichment of-Si(CH₃)₃ groups at the surface. These are the terminal groups of the PDMS part of the block. Their enrichment at the surface of the samples is presumably due to their low surface energy, in addition to the tendency for end groups to be at the surface due to free volume considerations.Presented at the XXVIth Silicon Symposium, Indiana University-Purdue University at Indianapolis, March 26–27, 1993.     

Morphology and mechanical properties of polypropylene/polystyrene blends compatibilized with styrene–butadiene block copolymers

The effect of molecular structure of styrene–butadiene block (SB) copolymers on the morphology, tensile properties, impact strength, and microhardness of polypropylene/polystyrene (PP/PS) (80/20) blends was studied. The addition of SB copolymers substantially reduces the size of dispersed PS particles formed at mixing. The distribution of SB copolymers between the interface and bulk phases is controlled by the length of styrene blocks in SB, but a decrease in the size of PS particles at mixing correlates with total molecular weight of SB copolymers. For a substantial part of compatibilized blends, PS particles aggregate rapidly during compression molding and form honeycomb‐like particles split by SB partitions, which persist at further annealing. Aggregation of PS particles continues slowly at further annealing. Blends containing PS particles with well‐developed honeycomb structure show lower yield stress, higher plasticity, and lower tensile impact strength than the blends having PS particles with simple or undeveloped honeycomb structure. Microhardness of PP/PS blends is additive and of PP/PS/SB blends is lower than the additive due to the effect of SB copolymers on crystalline structure of PP matrix. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Thermoplastic blends of physically crosslinked multiblock copolymers and copolymers with uniform grafts

Two multiblock copolymers of styrene and propylene oxide and four acrylate copolymers with uniform polystyrene grafts were prepared and blended. The blends are melt processable and their properties varied from thermoplastic elastomers to toughened plastics. The relationship between mechanical properties and composition of the thermoplastic blends indicated that all the blends exhibited a synergism, which is probably due to the increase of miscibility between the components caused by the same physical crosslinks — the glassy domains aggregated from both the polystyrene grafts and polystyrene blocks. The synergistic effect seemed more evident when two different graft copolymers were blended together than when one multiblock copolymer was blended with one graft copolymer. In all cases a maximum tensile strength appeared at the blend with 90 wt.-% of the component, possessing higher tensile strength and ultimate elongation.     

Morphology and mechanical properties of binary blends of polypropylene with statistical and block ethylene‐octene copolymers

In the present work, statistical (EOCs) and block (OBCs) ethylene‐octene copolymers, with similar densities and crystallinities, were used as impact modifiers of isotactic polypropylene (iPP), and the toughening effects of these two types of elastomers were compared. The viscosity curves of EOCs were similar to those of OBCs with equivalent melt flow rate (MFR), enabling a comparison of the viscosity ratio and elastomer type as independent variables. No distinct differences on the crystal forms and crystal perfection of iPP matrix in various blends were observed by thermal analysis. Morphological examination showed that OBCs form smaller dispersed domains than EOCs with similar MFRs. The flexural modulus, yield stress, stress and strain at break showed the same variation tendency for all the investigated polypropylene/elastomer blends. However, the room temperature Izod impact toughness of iPP/OBC blend was higher than that of iPP/EOC blend containing elastomer with the similar MFRs. The experimental results indicated that the compatibility of iPP/OBCs was much higher than that of iPP/EOCs. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Compatibilization effects of block copolymers in high density polyethylene/syndiotactic polystyrene blends

Three triblock copolymers of poly[styrene-b-(ethylene-co-butylene)-b-styrene] (SEBS) of different molecular weights and one diblock copolymer of poly[styrene-b-(ethylene-co-butylene)] (SEB) were used to compatibilize high density polyethylene/syndiotactic polystyrene (HDPE/sPS, 80/20) blend. Morphology observation showed that phase size of the dispersed sPS particles was significantly reduced on addition of all the four copolymers and the interfacial adhesion between the two phases was dramatically enhanced. Tensile strength of the blends increased at lower copolymer content but decreased with increasing copolymer content. The elongation at break of the blends improved and sharply increased with increments of the copolymers. Drop in modulus of the blend was observed on addition of the rubbery copolymers. The mechanical performance of the modified blends is strikingly dependent not only on the interfacial activity of the copolymers but also on the mechanical properties of the copolymers, particularly at the high copolymer concentration. Addition of compatibilizers to HDPE/sPS blend resulted in a significant reduction in crystallinity of both HDPE and sPS. Measurements of Vicat softening temperature of the HDPE/sPS blends show that heat resistance of HDPE is greatly improved upon incorporation of 20 wt% sPS.     

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     

Reactively formed block and graft copolymers as compatibilizers for polyamide 66/PS blends

Phthalic anhydride terminated polystyrene (PS-An) and styrene-maleic anhydride copolymer (SMA) were compared as a compatibilizer at low loadings (<10 wt%) in 70/30 polyamide 66 (PA66)/polystyrene (PS) blends. Compatibilization efficiency was judged by morphology of the blends and the extent of interfacial coupling to copolymer. Fluorescent labels of functional PS's (anthracene and pyrene for PS-An and SMA, respectively) allowed the detection of small amounts of reactively formed block (PA66-b-PS) or graft copolymer (SMA-g-PA66) in the blends via gel permeation chromatography with a fluorescence detector. Extremely fast reactions giving >60% conversion in 0.5 min mixing were observed regardless of the molecular weight, the structure, and the amount of the functional PS's. Interfacial stability of the reactively formed copolymers was estimated by micelle formation in the bulk phases and the interfacial coverage, Σ. PS-An with higher molecular weight (37 kg/mol) was most effective as a compatibilizer at the interface, showing less tendency to form microemulsions by suppressing interfacial roughening. However, a large portion of PA66-b-PS from low molecular weight PS-An (10 kg/mol) and SMA-g-PA66 from random functional SMA (16 kg/mol) migrated to the bulk phase to form micelles even at <2 wt% loadings. Blends of PA66 with syndiotactic PS compatibilized with PS-An gave very similar morphology to the PA66/PS blends indicating that these conclusions apply also to PA66/sPS blends.     

Preparation and microwave characterization of PTFE/PEEK blends

Present paper describes the preparation and characterization of the PTFE / PEEK blends. The surface morphology of different volume percentage of PTFE/PEEK blends is investigated using Scanning Electron Microscopy. The permittivity and loss tangent of the blends up to 40 MHz are studied using a Precision Impedance Analyzer. The variation of permittivity with respect to temperature (τ_εr) of the composite blends are also measured in the 0–100°C temperature region using a microprocessor controlled hot and cold chamber. The microwave dielectric properties of the polymer blends are studied in the X‐band (8.2–12.4 GHz) region by waveguide cavity perturbation technique using a Vector Network Analyzer. Rectangular cavity resonator is used to measure the complex permittivity of the PTFE/PEEK blends. Different modeling approaches are used to predict the theoretical permittivity of the blends and the results are compared with the experimental values. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers