Dissipative particle dynamics study on the interfaces in incompatible A/B homopolymer blends and with their block copolymers

Dissipative particle dynamics, a simulation technique appropriate at mesoscopic scales, has been applied to investigate the interfaces in immiscible binary A/B homopolymer blends and in the ternary systems with their block copolymers. For the binary blends, the interfacial tension increases and the interface thickness decreases with increasing Flory-Huggins interaction parameter chi while the homopolymer chain length is fixed. However, when the chi parameter and one of the homopolymer chain length is fixed, increasing another homopolymer chain length will induce only a small increase on interfacial tension and slight decrease on interface thickness. For the ternary blends, adding the A-b-B block copolymer will reduce the interfacial tension. When the mole number of the block copolymer is fixed, longer block chains have higher efficiency on reducing the interfacial tension than the shorter ones. But for the block copolymers with fixed volume fraction, shorter chains will be more efficient than the longer ones on reducing the interfacial tension. Increasing the block copolymer concentration reduces interfacial tension. This effect is more prominent for shorter block copolymer chains.     

Use of block copolymer-stabilized cadmium sulfide quantum dots as novel tracers for laser scanning confocal fluorescence imaging of blend morphology in polystyrene/poly(methyl methacrylate) films

This paper describes the first use of polymer-coated quantum dots (QDs) as fluorescent tracers for LSCFM imaging of phase morphology in polymer blends. Cadmium sulfide (CdS) QDs stabilized at the surface with a PS-b-PAA block copolymer are shown to be well dispersed via their polystyrene (PS) brush layer in the PS phase of solvent-cast 40/60 (w/w) PS/PMMA blends. The QDs are excluded from the PMMA phase, providing excellent fluorescence contrast for LSCFM imaging of the phase-separated blends. The presence of PS-b-PAA-stabilized QDs does not appear to affect the blend morphology, since the observed morphologies are the same when the percentage of QDs within the PS phase is varied from 10 to 50 wt %. These QD fluorescent tracers are used to characterize several aspects of blend morphology in solvent-cast 40/60 PS/PMMA blends containing PS homopolymer with either 100 (low molecular weight) or 1250 (high molecular weight) repeat units. In the PS(1250)/PMMA blends, a percolating distribution of PMMA droplets (2-25 mum) in a PS matrix is observed in the bulk, and a distinct inversion in the continuous phase is found near the glass substrate. In the PS(100)/PMMA blends, a "phase-in-phase" morphology is found, consisting of large PS domains (20-100 mum) dispersed in a PMMA continuous phase and small PMMA domains (1-2 mum) scattered throughout the larger PS droplets. The observed change in blend structure is attributed to a lower interfacial tension for the lower molecular weight PS.     

Phase behavior of binary blends of diblock copolymer/homopolymer confined in spherical nanopores

Binary blends of a diblock copolymer (AB) and an incompatible homopolymer (C) confined in spherical cavities are studied using a simulated annealing technique. The phase behavior of the blends is examined for four typical cases, representing the different selectivity of the pore surface to the A, B, and C species. The internal morphology of the spherical polymeric particles is controlled by the homopolymer volume fraction, the degree of confinement, and the composition of the copolymer. Inside a particle, the homopolymers segregate to form one or, under some conditions, two domains; thus, the homopolymers may act as an additional controlling parameter of the shape and symmetry of the copolymer domain. A rich array of confinement-induced novel diblock copolymer morphologies is predicted. In particular, core-shell particles with the copolymers as the shell wrapping around a homopolymer core or a copolymer-homopolymer combined core and Janus-like particles with the copolymers and the homopolymers on different sides are obtained.     

最有效的相容剂是两嵌段还是多嵌段聚合物?

Monte Carlo simulations were used to investigate the compatibilizing behaviors of multi-block copolymers with different architectures in A/B/(block copolymer) ternary blends. The volume fraction of homopolymer A, employed as the dispersed phase, was 19%. The simulations illustrate how a di- or multi-block copolymer aggregates at the interfaces and influences the phase behaviour of such incompatible polymer blends. The di-block copolymer chains tend to "stand" on the interface whereas the multi-block chains lie on the interface.In comparison with the dj-block copolymer, the block copolymers with 4, or 10 blocks can occupy more areas on the interface, and thus the multi-block copolymers have higher efficiency for the retardation of the phase separation.     

Phase separation in semicrystalline blends of poly(phenylene sulfide) and poly(ethylene terephthalate). II. Effect of poly(phenylene sulfide) homopolymer solubilization of PPS‐graft‐PET copolymer on morphology and crystallization behavior

The morphology and crystallization behavior of poly(phenylene sulfide) (PPS) and poly(ethylene terephthalate) (PET) blends compatibilized with graft copolymers were investigated. PPS‐blend‐PET compositions were prepared in which the viscosity of the PPS phase was varied to assess the morphological implications. The dispersed‐phase particle size was influenced by the combined effects of the ratio of dispersed‐phase viscosity to continuous‐phase viscosity and reduced interfacial tension due to the addition of PPS‐graft‐PET copolymers to the blends. In the absence of graft copolymer, the finest dispersion of PET in a continuous phase of PPS was achieved when the viscosity ratio between blend components was nearly equal. As expected, PET particle sizes increased as the viscosity ratio diverged from unity. When graft copolymers were added to the blends, fine dispersions of PET were achieved despite large differences in the viscosities of PPS and PET homopolymers. The interfacial activity of the PPS‐graft‐PET copolymer appeared to be related to the molecular weight ratio of the PPS homopolymer to the PPS segment of the graft copolymer (M_H/M_A). With increasing solubilization of the PPS graft copolymer segment by the PPS homopolymer, the particle size of the PET dispersed phase decreased. In crystallization studies, the presence of the PPS phase increased the crystallization temperature of PET. The magnitude of the increase in the PET crystallization temperature coincided with the viscosity ratio and extent of the PPS homopolymer solubilization in the graft copolymer. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 599–610, 2000     

Scanning electron microscopy methods for studying interfacial interaction in polymer blends

The scanning electron microscopy method in combination with the selective etching technique for polymer blends have been used to evaluate interfacial interaction in natural rubber and low density polyethylene blends. The morphology of the polymer blends, studied under externally applied strain, has been investigated to understand the role of interface adhesion between natural rubber and polyethylene phases, for two separate crosslinking systems, i.e. sulphur and peroxide.

Externally induced strain which facilitates phase separation in sulphur cured blends by initiating cracks at the interface; peroxide curing prevents separating out of the polyethylene phase from the natural rubber matrix. In the latter case, induced stress is distributed predominantly by developing fine flaw paths in the rubber matrix.

The method which has been developed for natural rubber and polyethylene blend systems may be used to evaluate the degree of interfacial adhesion between the dispersed phase and the dispersion medium for other kinds of polymer-polymer, polymer-filler as well as polymer-fibre composites.     

Reactive compatibilization of PA12/plasticized starch blends: Towards improved mechanical properties

Glycerol-plasticized starch (TPS)/polyamide 12 (PA12) blends were processed by melt mixing using two types of interfacial agent, i.e. diglycidyl ether of bisphenol A and a poly(ethylene-co-butyl acrylate-co-maleic anhydride) copolymer. Morphologies of the blends were tailored from the nature and amount of the interfacial agents. The average size of the dispersed phase was shown to decrease with the incorporation of the reactive agents and was proved to respect models, usually employed for conventional blends, for size predictions of the dispersed phase. By means of rheological experiments, it has been investigated whether the size reduction of the dispersed phase was coming from the compatibilization of the blend or from the viscosity changes due to chain extension in the matrix. The influence of the coupling agents on the viscoelastic behavior of the blend was characterized. Both interfacial agents led to increase the absolute complex viscosity but in the case of diepoxy reactive agent, the Newtonian flow behavior of complex viscosity totally disappeared in the low-frequency region. Mechanical properties of the TPS/PA12 blends were characterized and were proved to be strongly impacted by the use of interfacial agents. Elongation at break was enhanced as a consequence of a better adhesion between the matrix and the dispersed phase, whereas a decrease of the Young’s modulus was observed with increasing DGEBA content. Polyamide 12 crystallization in TPS/PA12 blends was found to be strongly dependent on DGEBA content while the introduction of maleic anhydride-grafted copolymer had no influence.     

Phase morphology development in PP/PA6 blends induced by a maleated thermoplastic elastomer

The effects of maleated thermoplastic elastomer (TPEg) on morphological development of polypropylene (PP)/polyamide 6 (PA6) blends with a fixed PA6 content (30 wt %) were investigated. For purpose of comparison, nonmaleated thermoplastic elastomer (TPE) was also added to the above binary blends. A comparative study of FTIR spectroscopy in above both ternary blends confirmed the formation of in situ graft copolymer in the PP/PA6/TPEg blend. Dynamic mechanical analysis (DMA) indicated that un‐like TPE, the incorporation of TPEg remarkably affected both intensity and position of loss peaks of blend components. Scanning electron microscopy (SEM) demonstrated that PP/PA6/TPE blends still exhibited poor interfacial adhesion between the dispersed phase and matrix. However, the use of TPEg induced a finer dispersion and promoted interfacial adhesion. Transmission electron microscopy (TEM) for PP/PA6/TPEg blends showed that a core‐shell structure consisting of PA6 particles encapsulated by an interlayer was formed in PP matrix. With the concentration of TPEg increasing, the dispersed core‐shell particles morphology was found to transform from discrete acorn‐type particles to agglomerate with increasing degree of encapsulation. The modified Harkin's equation was applied to illustrate the evolution of morphology with TPEg concentration. “Droplet‐sandwiched experiments” further confirmed the encapsulation morphology in PP/PA6/TPEg blends. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1050–1061, 2006     

Block copolymer compatibilizers for polystyrene/poly(dimethylsiloxane) blends

Symmetric polystyrene (PS)–poly(dimethylsiloxane) (PDMS) diblock copolymers were mixed into a 20% dispersion of PDMS in PS. The effect of adding the block copolymer on the blend morphology was examined as a function of the block copolymer molecular weight (M_n,bcp), concentration, and viscosity ratio (η_r). When blended together with the PS and PDMS homopolymers, most of the block copolymer appeared as micelles in the PS matrix. Even when the copolymer was preblended into the PDMS dispersed phase, block copolymer micelles in the PS matrix phase were observed with transmission electron microscopy after mixing. Adding 16 kg/mol PS–PDMS block copolymer dramatically reduced the PDMS particle size, but the morphology, as examined by scanning electron microscopy, was unstable upon thermal annealing. Adding 156 kg/mol block copolymer yielded particle sizes similar to those of blends with 40 or 83 kg/mol block copolymers, but only blends with 83 kg/mol block copolymer were stable after annealing. For a given value of M_n,bcp, a minimum PDMS particle size was observed when η_r ～ 1. When η_r = 2.6, thermally stable, submicrometer particles as small as 0.6 μm were observed after the addition of only 3% PS–PDMS diblock (number‐average molecular weight = 83 kg/mol) to the blend. As little as 1% 83 kg/mol block copolymer was sufficient to stabilize a 20% dispersion of 1.1‐μm PDMS particles in PS. Droplet size reduction was attributed to the prevention of coalescence caused by small amounts of block copolymer at the interface. The conditions under which block copolymer interfacial adsorption and interpenetration were facilitated were explained with Leibler's brush theory. © 2002 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 346–357, 2002; DOI 10.1002/polb.10098     

Compatabilization of polystyrene/polypropylene blends by styrene–butadiene block copolymers with differing polystyrene block lengths

Compatibilization of polystyrene/polypropylene (PS/PP) blends, by use of a series of butadiene–styrene block copolymers was studied by means of small‐angle X‐ray scattering (SAXS) and transmission electron microscopy (TEM). The compatibilizers used differ in molar mass and the number of blocks. It was shown that the ability of a block copolymer (BC) to participate in the formation of an interfacial layer (and hence in compatibilization) is closely associated with the molar mass of styrene blocks. If the styrene blocks are long enough to form entanglements with the styrene homopolymer in the melt, then the BC is trapped inside this phase of the PS/PP blends, and its migration to the PS/PP interface is difficult. In this case, the BC does not participate in the formation of the interfacial layer nor, consequently, in the compatibilization process. On the other hand, the BC's with the molar mass of the PS blocks below the critical value are proved to be localized at the PS/PP interface. This preferable entrapping of some styrene–butadiene BC's in the PS phase of the PS/PP blend is, of course, connected to the differing miscibility of the BC blocks with corresponding components of this blend. Although the styrene block is chemically identical to the styrene homopolymer in the blend, the butadiene block is similar to the PP phase. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1647–1656, 1999     

Reactively and physically compatibilized immiscible polymer blends: stability of the copolymer at the interface

This paper reports on the interfacial behaviour of block and graft copolymers used as compatibilizers in immiscible polymer blends. A limited residence time of the copolymer at the interface has been shown in both reactive blending and blend compatibilization by preformed copolymers. Polystyrene (PS)/polyamide6 (PA6), polyphenylene oxide (PPO)/PA6 and polymethylmethacrylate (PMMA)/PA6 blends have been reactively compatibilized by a styrene-maleic anhydride copolymer SMA. The extent of miscibility of SMA with PS, PPO and PMMA is a key criterion for the stability of the graft copolymer at the interface. For the first 10 to 15 minutes of mixing, the in situ formed copolymer is able to decrease the particle size of the dispersed phase and to prevent it from coalescencing. However, upon increasing mixing time, the copolymer leaves the interface which results in phase coalescence. In PS/LDPE blends compatibilized by preformed PS/hydrogenated polybutadiene (hPB) block copolymers, a tapered diblock stabilizes efficiently a co-continuous two-phase morphology, in contrast to a triblock copolymer that was unable to prevent phase coarsening during annealing at 180°C for 150 minutes.     

Effect of homopolymer matrix on diblock copolymer grafted nanoparticle conformation and potential of mean force: A molecular simulation study

We study the effect of homopolymer A or B matrix on the conformations and effective interactions of AB diblock copolymer grafted particles using coarse‐grained molecular dynamics simulations. In an A homopolymer matrix we observe patchy conformations within the AB diblock copolymer grafted layer, where the number of B patches is controlled by the A‐A attractive interaction strength. In a B homopolymer matrix the grafted particle takes on a core‐corona conformation, where the inner A block aggregates near the particle surface and the outer B block forms a corona that interacts with the B matrix. The potential of mean force (PMF) between two particles in an A homopolymer matrix has a long‐ranged attractive well with a minima at intermediate distances corresponding to the location of the outer B block patches. The PMF between two particles in a B homopolymer matrix has an attractive well at short interparticle distances corresponding to the size of the inner A block. We isolate the contribution of the homopolymer matrix on the PMF between the two diblock copolymer grafted particles, by deducting the PMF in the absence of a matrix, assuming the contributions of the grafted particle and matrix to the PMF to be additive. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 76–88     

Viscoelastic interfacial properties of compatibilized poly(ε‐caprolactone)/polylactide blend

Poly(ε‐caprolactone)/polylactide blend (PCL/PLA) is an interesting biomaterial because the two component polymers show good complementarity in their physical properties. However, PCL and PLA are incompatible thermodynamically and hence the interfacial properties act as the important roles controlling the final properties of their blends. Thus, in this work, the PCL/PLA blends were prepared by melt mixing using the block copolymers as compatibilizer for the studies of interfacial properties. Several rheological methods and viscoelastic models were used to establish the relations between improved phase morphologies and interfacial properties. The results show that the interfacial behaviors of the PCL/PLA blends highly depend on the interface‐located copolymers. The presence of copolymers reduces the interfacial tension and emulsified the phase interface, leading to stabilization of the interface and retarding both the shape relaxation and the elastic interface relaxation. As a result, besides the relaxation of matrices (τ_m) and the shape relaxation of the dispersed PLA phase (τ_F), a new relaxation behavior (τ_β), which is attribute to the relaxation of Marangoni stresses tangential to the interface between dispersed PLA phase and matrix PCL, is observed on the compatibilized blends. In contrast to that of the diblock copolymers, the triblock copolymers show higher emulsifying level. However, both can improve the overall interfacial properties and enhance the mechanical strength of the PCL/PLA blends as a result. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 756–765, 2010     

Effect of styrene-4-vinyl pyridine diblock copolymer on morphological,thermal, and mechanical properties of poly(2,6-dimethyl-1,4-phenylene ether)/polyethylene ionomer blends

The compatibilizing effects of a styrene-4-vinyl pyridine diblock copolymer on the properties of immiscible poly(2,6-dimethyl-1,4-phenylene ether) (PPE)/polyethylene ionomer (Surlyn) blends are investigated by examining the phase morphology and the thermal and mechanical properties. The block copolymer is synthesized by sequential anionic polymerization at ?78°C and melt-mixed with PPE and Surlyn at 290°C. When a small amount of block copolymer is present, the domain size of the dispersed phase becomes smaller. The tensile strength and elongation at break increase with addition of the block copolymer for PPE-rich matrix blends, whereas the tensile strength increases but the elongation at break decreases for Surlyn-rich matrix blends. These effects are interpreted in terms of the interfacial activity and the reinforcing effect of the block copolymer. From the experimental results, it is concluded that the block copolymer plays a role as an effective compatibilizer for PPE/Surlyn blends. © 1994 John Wiley & Sons, Inc.     

Monte Carlo simulation of phase separation of A/B/A‐B ternary mixtures

Monte Carlo simulations were used to model A/B/A‐B ternary mixtures with different AB diblock copolymer volume fractions for which both the dispersed and continuous phase volume fractions were kept constant. For concentrations of the diblock copolymer below a critical value, the domain size increment of the dispersed phase decreases linearly with the copolymer concentration. This is in agreement with the predictions of Noolandi and Hong. The dependence of the domain size as a function of the copolymer volume fraction can also be fitted by the equation of Tang and Huang. Our simulations indicate, for the first time, that the micelles form before saturation of the interface occurs. This means that the formation of the micelles is not a result of the saturation of the interface.     

对称两嵌段共聚物/均聚物共混体系受限在球形纳米孔内的自组装行为

采用模拟退火方法系统研究了对称两嵌段共聚物AB/均聚物A或C混合体系受限在球形纳米孔内的自组装行为.结果表明,体系的自组装结构受均聚物含量、均聚物链长、受限尺度以及A-C间相互作用强度的影响.随着均聚物含量的变化,体系可形成多种自组装结构,包括类洋葱层、笼状、类拱顶状、螺旋状、堆叠圆盘和圆环、平层、及球状结构.当A-C...     

The influence of partial emulsification on coalescence suppression and interfacial tension reduction in PP/PET blends

This study examines how the relative role of coalescence suppression and interfacial tension reduction influence the particle size at various levels of in situ compatibilization. The polymers studied are polyethylene terephthalate (PET) as matrix and a polypropylene (PP) as dispersed phase compatibilized by a triblock copolymer of poly(styrene–hydrogenated butadiene–styrene) (SEBS) grafted with maleic anhydride. The interfacial tension was studied by the breaking‐thread method, and it was used along with the morphology to characterize the emulsification efficacy of the copolymers. By modifying the concentration of MA grafted on the SEBS, different levels of emulsification of the blends were obtained. A comparison of 1/99 and 10/90 PP/PET blends compatibilized by SEBS‐g‐MA allows one to distinguish the relative role of interfacial tension and coalescence suppression in diminishing particle size. It is shown that varying degrees of residual coalescence remain, depending on the level of %MA in the copolymer. A detailed study of the 2%MA system below interfacial saturation was carried out to shed further light on the dependence of coalescence suppression on emulsification level and interfacial coverage. After separating out the contribution of interfacial tension on particle size reduction, it is shown that coalescence suppression for this system increases gradually with areal density of modifier at the interface right up to the region of interfacial saturation. Finally, the interfacial and morphological data were used to test the ability of the Lee and Park model to describe coalescence in polymer blends. Reasonable agreement was found between the parameter c₁, describing the coalescence in that model, and the trends related to residual coalescence from this study. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 939–951, 1999     

The relative role of coalescence and interfacial tension in controlling dispersed phase size reduction during the compatibilization of polyethylene terephthalate/polypropylene blends

The breaking thread and the sessile drop methods have been used to evaluate the interfacial tension between a polypropylene (PP) and a polyethylene-terephthalate (PET). An excellent correlation was found between the two. The breaking thread technique was then used to evaluate the interfacial tension of these blends at various levels of a styrene-ethylene butylene-styrene grafted with maleic anhydride (SEBS-g-MA) compatibilizer. In order to evaluate the relative roles of coalescence and interfacial tension in controlling dispersed phase size reduction during compatibilization, the morphology of PP/PET 1/99 and 10/90 blends compatibilized by a SEBS-g-MA were studied and compared. The samples were prepared in a Brabender mixer. For the 10/90 blend, the addition of the compatibilizer leads to a typical emulsification curve, and a decrease in dispersed phase size of 3.4 times is observed. For the 1/99 blend, a 1.7 times reduction in particle size is observed. In the latter case, this decrease can only be attributed to the decrease of the interfacial tension. It is evident from these results that the drop in particle size for the 10/90 PP/PET blend after compatibilization is almost equally due to diminished coalescence and interfacial tension reduction. These results were corroborated with the interfacial tension data in the presence of the copolymer. A direct relationship between the drop in dispersed phase size for the 1/99 PP/PET blend and the interfacial tension reduction was found for this predominantly shear mixing device. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 2271–2280, 1997     

PAmXD,6/PP-g-MA blends. III. Microstructure,blend melt viscosity,and copolymer concentration relationship

This work deals with the relationship between microstructure, melt viscosity, and copolymer concentration of PAmXD,6/PP-g-MA blends [poly(m-xylylene adipamide)/maleic anhydride functionalized polypropylene]. The blends were processed in a Brabender plastograph at a temperature of 265 ± 5°C and at 45 rpm. The characterization of the microstructure was carried out through SEM analysis after microtome leveling and chemical etching. The melt viscosity of the components and of the blends was measured by the Brabender torque. It was found that the copolymers concentration controls the dimension of the dispersed phase. The composition of the blend (dispersed phase weight percent) has a more limited influence. Variations of the components viscosity ratio during the mixing time have little, if any influence on the dimension of the dispersed phase. A linear relation between the Brabender torque and the specific interfacial area was found. The determination of the copolymer weight fraction leads to the establishment of a close relation between the copolymer concentration and the specific interfacial area. For blends containing from 0 to 7.5 wt % of copolymer, this relation is linear and consequently the concentration of copolymer at the interface is constant at about one copolymer macromolecule per 16 nm². © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1313–1327, 1997     

Morphology of reactive PP/PS blends with hyperbranched polymers

To study the efficiency of different mechanism for reactive compatibilization of polypropylene/polystyrene (PP/PS) blends main chain or terminal functionalized PP and terminal functionalized PS have been synthesized by different methods. While the in-situ block and graft copolymer formation results in finer phase morphologies compared to the corresponding non-reactive blends, the morphology development in the ternary blend system PP/PS + HBP (hyperbranched polymer) is a very complex process. HBP with carboxylic acid endgroups reacts preferably with the reactive sites of the oxazoline functionalized PS (PS-Ox) and locates mainly within the dispersed PS-Ox phase. A bimodal size distribution of the PS-Ox particles within the oxazoline modified PP (PP-Ox) matrix phase is observed with big PS-Ox particles (containing the HBP as dispersed phase) and small PS-Ox particles similar in size like the unimodal distributed particles in the non-reactive PP-Ox/PS-Ox blends. Factors influencing the morphology are discussed.