Morphology and mechanical properties of binary triblock copolymer blends

The influence of the morphology on the mechanical properties of binary styrene–butadiene (SB) triblock copolymer blends of a thermoplastic block copolymer and a thermoplastic elastomer (TPE) with different molecular architectures was studied with bulk samples prepared from toluene. Both block copolymers contained SB random copolymer middle blocks, that is, the block sequence S–SB–S. The two miscible triblock copolymers were combined to create a TPE with increased tensile strength without a change in their elasticity. The changes in the equilibrium morphology of the miscible triblock copolymer blends as a function of the TPE content (lamellae, bicontinuous morphology, hexagonal cylinders, and worms) resulted in a novel morphology–property correlation: (1) the strain at break and Young's modulus of blends with about 20 wt % TPE were larger than those of the pure thermoplastic triblock copolymer; (2) at the transition from bicontinuous structures to hexagonal structures (～35 wt % TPE), a change in the mechanical properties from thermoplastic to elastomeric was observed; and (3) in the full range of wormlike and hexagonal morphology (60–100 wt % TPE), elastomeric properties were observed, the strength greatly increasing and high‐strength elastomers resulting. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 429–438, 2005     

Determining the phase behavior of nanoparticle‐filled binary blends

Nanoparticle additives provide a means of imparting the desired electrical, optical, or mechanical properties to a polymeric matrix. The difficulty faced in creating these composites is determining the optimal conditions for forming a thermodynamically stable mixture, where the particles will not phase separate from the matrix material. This challenge is even more daunting when the polymeric matrix is itself a multicomponent mixture, as is often the case in advanced materials. Ideally, the nanoparticles would not only contribute the needed physical properties, but also stabilize the mixture so that the entire system forms a single‐phase system. In this study, we use a free energy expression for a binary blend that contains nanoparticles and take the interaction parameters between the different species to be independent variables. Thus, the particles can have distinct enthalpic interactions with each of the polymeric components. Using this expression, we determine the conditions under which the mixture forms a stable, single‐phase material. In particular, we isolate how variations in the system's parameters (e.g., polymer composition, particle volume fraction, particle size, interaction energies) affect the phase diagrams. The findings provide guidelines for creating effective formulations and can allow researchers to understand how choices made in the nature of the components affect the overall macroscopic properties. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2389–2403, 2006     

Ageing of different biodegradable polyesters blends mechanical and hygrothermal behavior

The aim of this study is to better understand the performance of binary blends of biodegradable polyesters when exposed to hygrothermal ageing, in order to overcome some of their limitations such as water resistance. For this, blends have been prepared by extrusion using two P(L)LA (l-poly-(lactic acid)) of different molecular weights and P?CL (poly-?-caprolactone). Mechanical properties over ageing are reported and compared to pure P(L)LA. Blending P?CL to P(L)LA allowed to improve P(L)LA initial resilience. During ageing, crystallinity increase seemed to lower water uptake at short ageing times, while osmotic cracking was found to possibly occur in pure P(L)LA for long ageing times, thus increasing water uptake. Besides, P(L)LA/P?CL blends water uptake remained constant over ageing. Finally, while P(L)LA resilience decrease could be related to chain scission, blend aptitude to elongation decrease was related to interphase decohesion, at long ageing times. Results showed P(L)LA molecular weight influence on both initial mechanical properties and water uptake.     

Effect of melt temperature on the phase morphology, thermal behavior and mechanical properties of injection-molded PP/LLDPE blends

<正>The phase morphology and thermal behavior of various isotactic polypropylene(PP)/linear low density polyethylene(LLDPE) blends were investigated with aid of scanning electron microscopy(SEM) and differential scanning calorimetry(DSC),respectively.The effect of barrel(melt) temperature on the morphology,thermal behavior and the resultant mechanical properties of the injection molded bars was the research focus,and the influence of LLDPE composition was also taken into account.It was found that the mechanical properties,especially the tensile ductility and the impact strength,were greatly affected by the processing temperature.The samples obtained at low temperatures had the highest elongation at break and impact strength,while those molded at high temperatures had the poorest toughness.Two reasons were responsible for that:first,the phase size in the samples increased with the processing temperature;second, possible orientation existed in the samples obtained at low processing temperatures.     

Phase behavior,morphology, and mechanical properties of polyethylene-copolymer blends

Binary blends of unbranched polyethylene (PE) and 5-10% model ethylene-butene random copolymers are used to determine the effects of composition heterogeneity on phase separation in the melt, semicrystalline morphology, plane strain fracture toughness J_C and tensile modulus and yield strength. Slowly cooled samples of melt-miscible blends are appreciably tougher (J_C = 5.2 kJ/m²) than unblended PE (J_C = 2.7 kJ/m²). A blend with the same average short chain branch concentration, but which is phase separated in the melt state, has J_C= 3.3 kJ/m²; dispersed domains of amorphous polymer have little effect on toughness. Enhanced toughness is associated with nonuniform morphology formed on slow cooling “one phase” melts composed of chains with different amounts of branching. The relative number of chemically different chains, as opposed to absolute branch concentrations, seems most important. Tensile properties are relatively unaffected by blending at these levels. Results from these model blends are used to consider the properties of compositionally heterogeneous ethylene copolymers. © 1994 John Wiley & Sons, Inc.     

Conductivity and structure of melt‐processed polyaniline binary and ternary blends

In the present study, conductive binary and ternary blends containing polyaniline (PANI) were developed through melt blending. The binary blends' investigation focused on the morphology, in light of the components' interaction, and the resulting electrical conductivity. Similar solubility parameters of a given doped PANI and a matrix polymer lead to dispersion of fine PANI particles within the matrix, and to formation of conducting paths at low PANI contents. A plasticizer acting also as a compatibilizer improves the matrix polymer/PANI interactions. In ternary blends consisting of PANI and two immiscible polymers, the PANI preferrentially locates in one of the components, affecting the blend's morphology. This “concentrating” effect leads to relatively high electrical conductivity at a low PANI content. The electrical conductivity of the studied ternary blends is almost independent of the components' sequence of addition into the hot melt mixing device, exhibiting the selectivity of PANI towards one of the components. Copyright © 2000 John Wiley & Sons, Ltd.     

A preliminary study on the initial elastic adhesion behavior of leucocytes

By treating the cell body as an elastic colloid and applied with the Hertz contact theory of linear elasticity and the lubrication equation of fluid dynamics, the elastic adhesion behavior of leucocytes in close motion toward a plane surface is investigated. The effect of the Stokes number on the deformation profile of the cell is considered during the adhesion period. From the results of numerical simulation, it is found that under certain conditions (i.e. regardless of the magnitude of F for the cases of ST=1 and 3 and ε0.0055 for ST=10), after exhausting all of the incoming kinetic energy, the cell can rest at an equilibrium separation which is close to the ligand–receptor bond length formed between two interacting surfaces.     

Effect of molecular interactions on the miscibility and structure of polymer blends

The effect of polymer-polymer interactions on the miscibility and macroscopic properties of PVC/PMMA, PVC/PS and PMMA/PS blends were studied in the entire composition range. The miscibility of the components was characterized by the Flory-Huggins interaction parameter or by quantities related to it. Thermal analysis, light transmittance measurements, and scanning electron microscopy were carried out on the blends and their mechanical properties were characterized by tensile tests. Interactions were analyzed by infrared spectroscopy and contact angle measurements. All three polymer pairs form heterogeneous blends, but the strength of molecular interactions is different in them, the highest is in PVC/PMMA system resulting in partial miscibility of the components and beneficial mechanical properties. The structure of these blends depends strongly on composition. A phase inversion can be observed between 0.5 and 0.6 PMMA content accompanied with a significant change in structure and properties. The PVC/PS and the PMMA/PS pairs are immiscible, though the results indicate the partial solubility of the components. The analysis of the surface characteristics of the components and the comparison of quantities derived from them with miscibility as well as with the macroscopic properties of blends revealed that blend properties cannot be predicted in this way, since they are affected by several factors.     

溶剂对SBS溶液浇铸膜形态结构及性能影响

聚苯乙烯 聚丁二烯 聚苯乙烯 (ＳＢＳ)嵌段共聚物所兼具的高弹性与热塑性来源于其独特的微观相分离结构 ,其形态结构与性能的关系长期以来一直倍受人们的关注 .对于这种微相分离体系 ,除了传统意义上的良溶剂 (对两种嵌段均具有良好的溶解性 ,又称非选择性溶剂 )与不良溶剂外 ,还存在着对两种嵌段中的一种溶解性较好 ,对另一种溶解性较差的选择性溶剂[1,2 ].在溶液浇铸成膜过程中 ,不同溶剂与组成共聚物的两种嵌段的相互作用参数的差异将导致溶液中大分子构象的差异以及微观相分离过程的差异 ,从而影响浇铸膜的形态以及性能[3].本文首先利用…     

Phase behavior and structure formation in ternary blends: studies on blends of PVDF/PMMA/PVAC

The phase behavior of ternary blends was analyzed on the basis of the lattice approach. Both compatibilization and incompatibilization effects are predicted to occur depending on the relative magnitudes and the sign of the interaction parameters of the binary subsystems. Thermodynamic, structural and kinetic properties were investigated for a ternary model blend composed of poly(vinylidene fluoride), poly(methyl methacrylate) and poly(vinyl acetate). This particular ternary system is characterized by a specific symmertry with respect to the interactions in the binary subsystems. This symmetry affects both thermodynamic and structural properties. The experimentally determined interaction parameters were used to model the phase diagram on the basis of the lattice model: the theoretical phase diagram was found to be close to the experimental one. The crystallization processes were analyzed both for the binary and the ternary systems on the basis of a modified Turnbull–Fisher equation. The conclusions are that the properties of the ternary systems can be understood to a first approximation on the basis of those of the corresponding binary systems and the symmetry of the interactions.     

Towards quantification of butadiene content in styrene-butadiene block copolymers and their blends with general purpose polystyrene (GPPS) and the relation between mechanical properties and NMR relaxation times

The properties of styrene-butadiene-styrene (SBS) block copolymers do not only depend on the butadiene content and the degree of polymerisation but also on their chain architecture. In this contribution we present the results of a low-field time domain (TD) NMR study in which the transverse relaxation behaviour of different SBS block copolymers was analysed and correlated with findings from mechanical testing on pure and blended materials and transmission electron microscopy data which provide information on the microphase separation.The results indicate that while a straightforward determination of the butadiene content as in blended materials like ABS is not possible for these materials, the TD-NMR results correlate quite well with the mechanical performance of blends from SBS block copolymers with general purpose polystyrene (GPPS), i.e. industrial grade homopolymer polystyrene. Temperature-dependent experiments on pure and blended materials revealed a slight reduction in the softening temperature of the GPPS fraction in the blends.     

Influence of a liquid crystalline block on the microdomain structure of block copolymers

We report on the phase behavior and microdomain structure of two types of diblock copolymers containing a liquid crystal (LC) block joined to a flexible coil block. Consideration of the symmetry groups of the liquid crystalline phases and of the block copolymer microdomain structures provides a rationale for predicting the possible types of liquid crystalline block copolymer morphologies. Both previously reported and newly discovered structural types are identified. Possible organizational schemes are developed for the mesogens and periodic disclination defects with respect to the intermaterial dividing surfaces separating the liquid crystalline and flexible coil domains. The first type of copolymer investigated has a rod-like LC block whereas the second type copolymer has a side chain LC block. Five different rod-coil diblocks based on poly(hexyl isocyanate-b-styrene) P(HIC-b-S) were synthesized by anionic polymerization. Wavy lamellae, zig-zag and arrowhead microdomain morphologies corresponding to smectic-C and smectic-O structures were observed depending on the composition. These layered phases have the director (PHIC chain axis) tilted at various orientations with respect to the layer normal. Side-chain LC diblocks based on functionalized poly(isoprene-b-styrene) P(I-b-S) were also investigated. These polymers were synthesized using polymer analogous chemistry from P(I-b-S) precursors. Three different mesogenic groups were attached to the PI blocks: one based on biphenyl benzoate and two based on azobenzene. The microdomain structures found for the functionalized poly(isoprene side-chain LC-b-styrene) P(ILC-b-S) diblocks are typical of traditional coil-coil diblocks (lamellae and cylinders). However, these morphologies possess an additional smectic layering of the mesogens within the microdomains of the LC block. In the case of the rod-coil diblocks, the transformation from an initially isotropic state to the final microphase separated solid state occurs via nematic and then smectic liquid crystalline states, whereas for the side-chain LC-coil cases, the microphase separation transition occurs prior to development of orientational order. The long-range microdomain order of LC block-coil block copolymers can extend over very large distances due to the influence of the orientational ordering of the LC block.     

Effect of polymer and ion concentration on mechanical and drug release behavior of gellan hydrogels using factorial design

Developing optimized hydrogel products requires an in-depth understanding of the mechanisms that drive hydrogel tunability. Here, we performed a full 4 × 4 factorial design study investigating the impact of gellan, a naturally derived polysaccharide (1%, 2%, 3%, or 4% w/v) and CaCl₂ concentration (1, 3, 7, or 10 mM) on the viscoelastic, swelling, and drug release behavior of gellan hydrogels containing a model drug, vancomycin. These concentrations were chosen to specifically provide insight into gellan hydrogel behavior for formulations utilizing polymer and salt concentrations expanding beyond those commonly reported by previous studies exploring gellan. With increasing gellan and CaCl₂ concentration, the hydrogel storage moduli (0.1–100 kPa) followed a power-law relationship and on average these hydrogels had higher liquid absorption capability and greater total drug release over 6 days. We suggest that the effects of gellan and CaCl₂ concentration and their interactions on hydrogel properties can be explained by various phenomena that lead to increased swelling and increased resistance to network expansion.     

High density polyethylene/hydrogenated oligo(cyclopentadiene) blends: Phase structure,thermal and mechanical properties

The article discusses the influence of an oligomeric resin, hydrogenated oligo (cyclopentadiene) (HOCP), on the morphology and properties of its blends with high density polyethylene (HDPE). HDPE/HOCP blends after solidification contain three phases: the crystalline phase of HDPE and two amorphous phases, one rich in amorphous HDPE and the other in HOCP. DSC thermograms and the loss modulus behaviors show that the γ transition is influenced by HOCP molecules and, in addition to the α_c transition of HDPE, there is another transition that is attributed to the HOCP-rich phase. The hypothesis of the two amorphous phases is confirmed by the optical microscopy observations performed on isothermally crystallized blend films. © 1994 John Wiley & Sons, Inc.     

Effect of diblock copolymers on dynamic mechanical properties of polyethylene/polystyrene blends

A systematic investigation of the dynamic mechanical properties of high-density polyethylene (HDPE)/high-impact polystyrene (HIPS)/copolymer blends was carried out. Blends of 80/20 weight percent of HDPE/HIPS were prepared in the melt state at 180°C in a batch mixer. Synthesized pure diblock (H77) and tapered diblock (H35) copolymers of hydrogenated polybutadiene (HPB) and polystyrene (PS) were added at different concentrations (1, 3, and 5 wt %), and the dynamic mechanical properties were investigated. The results show that: (1) both the tapered and the pure diblock copolymers enhance the phase dispersion and the interphase interactions; (2) structure and molecular weight are both important parameters in the molecular design of copolymers; (3) important effects occur when only small amounts of copolymer are added (up to the interface saturation concentration SC); (4) a micellar structure formation is possible when the copolymer is in excess in the blend; (5) the effect of the copolymer structure on the SC and the critical micellar concentration (CMC) is more pronounced than the effect of molecular weight. These concentrations are found to be lower for the tapered diblock copolymer. The analysis of the dynamic mechanical thermal analysis (DMTA) results obtained for the 20/80 HDPE/HIPS blend leads to the conclusion that the copolymers also enhance the interactions between heterogeneous phases. Similar conclusions based on electron microscopy were reported in the literature. DMTA shows great potential to relate macroscopic observations to the state of a copolymer in an immiscible blend.     

Influence of compatibilization on the mechanical behavior of poly(trimethylene terephthalate)/poly(ethylene-octene) blends

Poly(trimethylene terephthalate) (PTT) based blends toughened with up to 30 wt.% of a partially maleinized poly(ethylene-octene) copolymer (mPEO) were obtained by melt mixing. The blends were composed of two pure amorphous phases and a partially crystalline PEO phase. The rubber modification clearly compatibilized the blends leading to a decrease in the dispersed phase size. The decrease was not enough to attain the brittle-tough transition, but an increase in the shear rate gave rise to an additional decrease in the dispersed phase size and in the interparticle distance (IDc) that led to very high toughness values (15-fold the notched impact strength of the matrix) at rubber contents above 25 wt.%. The critical interparticle distance of the blends was 0.17 μm. A comparison between this IDc and those of PBT/mPEO and PET/mPEO blends was explained in terms of their interfacial tensions.     

Effects of SEBS-g-BTAI on the morphology, structure and mechanical properties of PA6/SEBS blends

Styrene-b-(ethylene-co-1-butene)-b-styrene (SEBS) triblock copolymer functionalized with ε-caprolactam blocked allyl (3-isocyanate-4-tolyl) carbamate (SEBS-g-BTAI) was used to toughen polyamide 6 (PA6) via reactive blending. Compared to the PA6/SEBS blends, mechanical properties such as tensile strength, Young’s modulus, especially Izod notched strength of PA6/SEBS-g-BTAI blends were improved distinctly. Both rheological and FTIR results indicated a new copolymer formed by the reaction of end groups of PA6 and isocyanate group regenerated in the backbone of SEBS-g-BTAI. Smaller dispersed particle sizes with narrower distribution were found in PA6/SEBS-g-BTAI blends, via field emitted scanning electron microscopy (FESEM). The core-shell structures with PS core and PEB shell were also observed in the PA6/SEBS-g-BTAI blends via transmission electron microscopy (TEM), which might improve the toughening ability of the rubber particles.     

Chain structure and thermal behavior of reactive blends of PET/LCP with bis(2-oxazoline)

The sequence structure and thermal behavior of reactive blends of poly(ethylene terephthalate) (PET) with the liquid crystalline copolyester 60 PHB/PET containing 60 mol % of p-hydroxybenzoic acid (PHB) with addition of bis(2-oxazoline) (BOZ) were studied in detail. ¹H NMR results indicate that both the number average sequence length of PET and PHB segments (L _PET and L _PHB) decrease with increasing mixing time and temperature via transesterification between PET and LCP. The transesterification is promoted in the presence of BOZ. As a consequence, the sequence structure and in turn the crystallization both from the glassy and the melt state and the melting behavior are markedly affected.     

Monte Carlo simulation of adsorption of binary and quaternary alkane isomers mixtures in zeolites: Effect of pore size and structure

Grand canonical Monte Carlo and configurational bias Monte Carlo techniques were employed to simulate the adsorption of binary mixtures of butane isomers and quaternary mixtures in nine zeolites at 300 K. For binary mixtures the results show there is a critical pore size, which is 10-membered-ring about 5.6 Å. The channel sizes of BEA, ISV, MOR and CFI are larger than this critical pore size, they prefer i-butane than n-butane, whereas TON with smaller channel size than critical pore size prefers n-butane than i-butane, but its selectivity decreases with pressure increasing. MFI, MEL and TER prefer i-butane than n-butane at low pressure, but with pressure increasing, the selectivity is reversed. BOG prefers i-butane than n-butane but the selectivity decreased with pressure increasing. It demonstrates that the adsorption and selectivity are controlled by both pore size and pore structure. The n-butane–i-butane–n-pentane–2-methylbutane quaternary mixtures adsorbed in these nine zeolites were studied, and the results show alkane chain length dependence at low pressure, but the adsorption is controlled by pore size and structure with pressure increasing in all the zeolites except for TON and BOG.     

Miscibility and phase structure of binary blends of polylactide and poly(methyl methacrylate)

Blends of amorphous poly(DL‐lactide) (DL‐PLA) and crystalline poly(L‐lactide) (PLLA) with poly(methyl methacrylate) (PMMA) were prepared by both solution/precipitation and solution‐casting film methods. The miscibility, crystallization behavior, and component interaction of these blends were examined by differential scanning calorimetry. Only one glass‐transition temperature (T_g) was found in the DL‐PLA/PMMA solution/precipitation blends, indicating miscibility in this system. Two isolated T_g's appeared in the DL‐PLA/PMMA solution‐casting film blends, suggesting two segregated phases in the blend system, but evidence showed that two components were partially miscible. In the PLLA/PMMA blend, the crystallization of PLLA was greatly restricted by amorphous PMMA. Once the thermal history of the blend was destroyed, PLLA and PMMA were miscible. The T_g composition relationship for both DL‐PLA/PMMA and PLLA/PMMA miscible systems obeyed the Gordon–Taylor equation. Experiment results indicated that there is no more favorable trend of DL‐PLA to form miscible blends with PMMA than PLLA when PLLA is in the amorphous state. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 23–30, 2003