Study on morphology of ternary polymer blends. II. Effect of composition

The composition effect on morphology of polypropylene/ethylene–propylene–diene terpolymer/polyethylene (PP/EPDM/PE) and polypropylene/ethylene–propylene–diene terpolymer/polystyrene (PP/EPDM/PS) ternary blends has been investigated. In all of the blends, polypropylene as the major phase was blended with two minor phases, that is, EPDM and PE or PS. From morphological studies using the SEM technique a core–shell morphology for PP/EPDM/PE and separated dispersed morphology for PP/EPDM/PS were observed. These results were found to be in agreement with the theoretical predictions. The composition of components affected only the size of dispersed phases and had no appreciable effect on the type of morphology. The size of each dispersed phase, whether it forms core or shell or disperses separately in matrix, can be related directly to its composition in the blend. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1138–1146, 2001     

Tuning gradient microstructures in immiscible polymer blends by viscosity ratio

Bioinspired gradient microstructures provide an attractive template for functional materials with tailored properties. In this study, filaments with gradient microstructures are developed by melt-spinning of immiscible polymer blends. The distribution of the gradient morphology is shown to be controlled by the viscosity ratio of polymers as well as the geometry of the capillary die. Distinct microstructure gradients with long thin fibrils near the surface region and short large droplets near the center region of the filament, as well as the inverse pattern, are formed in systems with different viscosity ratios. The shear flow field in the capillary can elucidate the formation mechanisms of gradient morphologies during processing. The results demonstrate how the features of a gradient microstructure can be tailored by the design of capillary geometry and processing conditions. The viscosity ratio is then introduced as an adjusting tool to control the gradient morphology in a given processing setup. In consequence, this study provides novel design routes for achieving gradient morphologies in immiscible polymers. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48165.     

Relationship between interfacial tension and dispersed‐phase particle size in polymer blends. I. PP/EPDM

Simple blends with different viscosity ratios of the components as well as compatibilized blends varying both in type and content of compatibilizers were used to study the relation between interfacial tension and dispersed‐phase particle size for PP/EPDM (80/20 wt %) blends in this work. Four compatibilizing systems, poly(ethylene‐co‐methacrylic acid) ionomers (EMA–I), dicumyl peroxide (DCP), DCP combined with EMA–I, and DCP in combination with trimethylol propane triacrylate (TMPTMA), were used. For blends prepared in an internal mixer, a power law relation was found between capillary number and torque ratio of the blends' components. This relation was used to estimate the interfacial tension for the compatibilized blends. The relation between steady‐state torque of the blends as a measure of viscosity and the estimated values of interfacial tension were also investigated. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3148–3159, 2002     

Elongational viscosity for miscible and immiscible polymer blends. I. PMMA and AS with similar elongational viscosity

The effects of miscibility and blend ratio on uniaxial elongational viscosity of polymer blends were studied by preparing miscible and immiscible samples at the same composition by using poly(methyl methacrylate) (PMMA) and poly(acrylonitrile-co-styrene) (AS). Miscible polymer blend samples for the elongational viscosity measurement were prepared by using three steps: solvent blends, cast film, and hot press. A phase diagram of blend samples was made by visual observation of cloudiness. Immiscible blend samples were prepared by maintaining the prepared miscible samples at 200°C, which is higher than cloud points using a LCST (lower critical solution temperature) phase diagram. The phase structure of immiscible blends was observed by an optical microscope. The elongational viscosity of all samples was measured at 145°C, which is lower than the cloud-point temperature at all blend ratios. The elongational viscosity of PMMA and AS was similar to each other. The strain-hardening property of miscible blends in the elongational viscosity was only slightly influenced by the blend ratio, and this was also the case with immiscible blends. The strain-hardening property was only slightly influenced, whether it was miscible or immiscible at each blend ratio. Polydispersity in molecular weight for blend samples was not changed by GPC (gel permeation chromatography) analysis. Almost no change in the polydispersity of the molecular weight for blends and the similarity of elongational viscosity between PMMA and AS resulted in little influence of the blend ratio and miscibility on the strain-hardening property. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 757–766, 1999     

Study on compatibilization of polypropylene-liquid crystalline polymer blends

The mechanical properties, melt rheology, and morphology of binary blends comprised of two polypropylene (PP) grades and two liquid crystalline polymers (LCP) have been studied. Compatibilization with polypropylene grafted with maleic anhydride (PP-g-MAH) has been attempted. A moderate increase in the tensile moduli and no enhancements in tensile strength have been revealed. Those findings have been attributed to the morphology of the blends, which is predominantly of the disperse mode. LCP fibers responsible for mechanical reinforcement were only exceptionally evidenced. Discussion of PP-LCP interfacial characteristics with respect to mechanical properties-morphology interrelations allowed evaluation of the compatibilizing efficiency of PP-g-MAH. Factors important for successful reinforcement of PP with LCP have been specified. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 969–980, 1997     

Study of the partial wetting morphology in polylactide/poly[(butylene adipate)‐co‐terephthalate]/polyamide ternary blends: case of composite droplets

The prediction of the morphology of ternary polymer blends requires a good knowledge of the values of the three interfacial tensions. We selected three polymers, either biobased or biodegradable, polyamide (PA), poly[(butylene adipate)‐co‐terephthalate] (PBAT) and polylactide (PLA), and we accurately measured their interfacial tensions using the retraction method, varying the molar mass or inverting the phases. The following values of interfacial tension were obtained: γ_PBAT/PLA = 3.3 ± 0.7 mN m^?1, γ_PA/PLA = 5.6 ± 0.3 mN m^?1 and γ_PBAT/PA = 3.0 ± 0.4 mN m^?1. These values were used to calculate the spreading coefficients giving rise to two negative coefficients and one coefficient close to zero. Ternary blends with various compositions, two different levels of viscosity for PBAT and different processing conditions were prepared. There was a very good agreement between the predictions of the spreading theory, when using the values of interfacial tension of the right order of magnitude, and the observed morphologies, whatever the polymer serving as a matrix. When PLA or PBAT was chosen as the matrix, the ternary blend morphology was composed of composite droplets, presenting a partial wetting morphology, dispersed in the polymer matrix. This morphology was observed whatever the composition, the viscosity of the PBAT phase and the processing conditions. A further calculation of the free energy confirmed this morphology. The formation process of this semi‐encapsulated morphology was observed during blending. © 2018 Society of Chemical Industry     

Compatibilized iPP/aPS blends: The effect of the viscosity ratio of the components on the blends morphology

More than 25 PP/PS/SEP blends, where PP is isotactic polypropylene, PS is atactic polystyrene, and SEP is poly(styrene‐block‐ethylene‐co‐propylene), were prepared. The main objective of this study was to investigate the influence of PP/PS viscosity ratio, λ_TM, on the blends' morphology. It was shown that λ_TM strongly influenced not only the overall morphology of the blends, but also the morphology of SEP, which exhibited as many as five different types of structure when blended with PP and/or PS. SEP was found an efficient compatibilizer of PP/PS blends as it decreased the average particle size in all studied systems. An interesting “by‐product” of this work was the discovery of a brand‐new type of polymer morphology, which was called morel structure. The characteristic feature of the morel structure was PS matrix compartmentalized by SEP. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2236–2249, 2006     

三元高分子共混体系Spinodal方程的理论推导

将经过改进的Flory状态方程(EOS)理论，引入到三元均聚高分子共混体系，得到三元体系的Flory状态方程。通过对高聚物共混自由能(△G^m)的热力学判据的讨论，得出三元均聚高分子共混体系相容性的临界条件，从而推导出三元均聚高分子共混体系的Spinodal方程。     

The viscosity of immiscible polymer blends: influences of the interphase and deformability

The viscosity of immiscible polymer blends has been studied via application of certain aspects of rheology. A symmetric mixture rule was derived, and the deviations from the ‘additivity rule’ have been associated, essentially, with the properties of the interphase, with its influence on the effective volumes of the two polymers constituting the blend and with the deformability of both the interphase and the disperse phase. The rule predicts a positive deviation for a mixture with a disperse-phase viscosity (η_d) greater than that (η_m) of the continuous medium, and a much higher-viscosity interphase, i.e. η_i å η_d ≥ η_m. Negative deviation is to be expected when the interphase has a much lower viscosity than those of the two pure polymers (η_d, η_m å η_i) in the blend. The viscosity and strength of the interphase depend mostly on the specific thermodynamic interactions that led to its creation.     

Effects of the viscosity ratio on polyolefin ternary blends

Polyolefin binary and ternary blends were prepared from polypropylene (PP), an ethylene–α‐olefin copolymer (mPE), and high‐density polyethylene (HDPE) on the basis of the viscosity ratio of the dispersed phase to the continuous phase. In PP/mPE/HDPE blends, fibrils were observed when the dispersed‐phase (mPE/HDPE) viscosity was less than that of PP, or when the viscosity of mPE was less than that of PP, although the viscosity of mPE/HDPE was greater than that of PP. The notched impact strength and mechanical properties such as the yield strength, flexural modulus, and hardness of PP/mPE binary blends further increased with the addition of HDPE according to the type of HDPE. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 4027–4036, 2004     

Phase behavior of ternary polymer blends with hydrogen bonding

Atactic poly (methyl methacrylate) (aPMMA) was found to be almost completely immiscible with poly(vinyl acetate) (PVAc). Both aPMMA and PVAc are known to be miscible with poly(vinyl phenol) (PVPh) according to literature. Adding of PVPh into immiscible aPMMA/PVAc mixtures is likely to improve their miscibility. Therefore, PVPh can be used as cosolvent to cosolubilize aPMMA and PVAc. A ternary blend consisting of aPMMA, PVAc, and PVPh was prepared and determined calorimetrically in this article. According to the calorimetry data, the ternary blend was determined to be miscible. The reason for the observed miscibility is because the interactions between PVAc and PVPh are similar to those between aPMMA and PVPh. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2797–2802, 2004     

Phase behavior of ternary polymer blends with favorable interactions

Atactic poly(methyl methacrylate) (aPMMA) and poly(vinyl pyrrolidone) (PVP) with a weight‐average molecular weight of 360,000 g/mol were found to be immiscible on the basis of preliminary studies. Poly(styrene‐co‐vinyl phenol) (MPS) with a certain concentration of vinyl phenol groups is known to be miscible with both aPMMA and PVP. Is it possible to homogenize an immiscible aPMMA/PVP pair by the addition of MPS? For this question to be answered, a ternary blend consisting of aPMMA, PVP, and MPS was prepared and measured calorimetrically. The role of MPS between aPMMA and PVP and the effects of different concentrations of vinyl phenol groups on the miscibility of the ternary blends were investigated. According to experimental results, increasing the vinyl phenol contents of MPS has an adverse effect on the miscibility of the ternary blends. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2064–2070, 2005     

PP/EHDPET共混体系熔体粘度对相转变的影响

以聚丙烯 (PP) /易水解聚酯 (EH DPET)共混体系为研究对象 ,测试了共混组分在不同加工温度与不同剪切速率下的熔体粘度。结果表明 ,加工温度与剪切速率的改变均会导致 PP与 EHDPET熔体粘度比的变化 ,进而影响到两组分的海 -岛结构构成。选择较高的加工温度及较低的剪切速率 ,可以使共混物 PP在高组成比时成为分散相。     

A study on the effects of SEBS‐g‐MAH on the phase morphology and mechanical properties of polypropylene/polycarbonate/SEBS ternary polymer blends

In this work, five ternary blends based on 70% by weight (wt %) of polypropylene (PP) with 30% wt of polycarbonate (PC)/poly(styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene)(SEBS) dispersed phase consists of 15 wt % PC and 15 wt % reactive (maleic anhydride grafted) and nonreactive SEBS mixtures at various ratios were prepared in a co‐rotating twin screw extruder. scanning electron microscopy (SEM) micrographs showed that the blends containing only nonreactive SEBS exhibited a fine dispersion of core‐shell particles. With decreasing the SEBS/SEBS‐g‐Maleic Anhydride (MAH) weight ratio, the morphology changed from the core‐shell particles to a mixed of core‐shell, rod‐like and individual particles. This variation in phase morphology affected the thermal and mechanical properties of the blends. DSC results showed that the blends containing only nonreactive SEBS exhibited a minimum in degree of crystallinity due to the homogeneous nucleation of core‐shell particles. Mechanical testing showed that in the SEBS/SEBS‐g‐MAH weight ratio of 50/50, the modulus and impact strength increased compared with the PP matrix while the yield stress had minimum difference with that of PP matrix. These effects could be attributed to the formation of those especial microstructures revealed by the SEM studies. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Evaluation of mechanical properties of polypropylene/polycarbonate/SEBS ternary polymer blends using Taguchi experimental analysis

In this work, ternary polymer blends based on polypropylene (PP)/polycarbonate (PC)/poly(styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene) (SEBS) triblock copolymer and a reactive maleic anhydride grafted SEBS (SEBS‐g‐MAH) at fixed compositions are prepared using twin‐screw extruder at different levels of die temperature (235‐245‐255°C), screw speed (70‐100‐130 rpm), and blending sequence (M1‐M2‐M3). In M₁ procedure, all of the components are dry blended and extruded simultaneously using Brabender twin‐screw extruder, whereas in M₂ procedure, PC, SEBS, and SEBS‐g‐MAH minor phases are first preblended in twin‐screw extruder and after granulating are added to PP continuous phase in twin‐screw extruder. Consequently, in M₃ procedure, PP and SEBS‐g‐MAH are first preblended and then are extruded with other components. The influence of these parameters as processing conditions on mechanical properties of PP/PC/SEBS ternary blends is investigated using L9 Taguchi experimental design. The responding variables are impact strength and tensile properties (Young's modulus and yield stress), which are influenced by the morphology of ternary blend, and the results are used to perform the analysis of mean effect as well. It is shown that the resulted morphology, tensile properties, and impact strength are influenced by extrusion variables. Additionally, the optimum processing conditions of ternary PP/PC/SEBS blends were achieved via Taguchi analysis. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Ultrasonic,refractometric, and viscosity studies of some polymer blends in solution

Miscibility studies of poly(vinyl pyrrolidone)–polystyrene and poly(vinyl pyrrolidone)–poly(methyl methacrylate) in mixed common solvent (dimethyl formamide + cyclohexanone) have been carried out in different percentages of the blend components. The ultrasonic velocity, viscosity, density, and refractive index have been measured at 30°C. The interaction parameters have been obtained using the viscosity data to probe the miscibility. The obtained results have been confirmed by the ultrasonic velocity, density, and refractive index. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1823–1827, 1998     

Synergetic toughness and morphology of poly(propylene)/nylon 11/maleated ethylene‐propylene diene copolymer blends

Polypropylene (PP)/nylon 11/maleated ethylene‐propylene‐diene rubber (EPDM‐g‐MAH) ternary polymer blends were prepared via melt blending in a corotating twin‐screw extruder. The effect of nylon 11 and EPDM‐g‐MAH on the phase morphology and mechanical properties was investigated. Scanning electron microscopy observation revealed that there was apparent phase separation for PP/EPDM‐g‐MAH binary blends at the level of 10 wt % maleated elastomer. For the PP/nylon 11/EPDM‐g‐MAH ternary blends, the dispersed phase morphology of the maleated elastomer was hardly affected by the addition of nylon 11, whereas the reduced dispersed phase domains of nylon 11 were observed with the increasing maleated elastomer loading. Furthermore, a core‐shell structure, in which nylon 11 as a rigid core was surrounded by a soft EPDM‐g‐MAH shell, was formed in the case of 10 wt % nylon 11 and higher EPDM‐g‐MAH concentration. In general, the results of mechanical property measurement showed that the ternary blends exhibited inferior tensile strength in comparison with the PP matrix, but superior toughness. Especially low‐temperature impact strength was obtained. The toughening mechanism was discussed with reference to the phase morphology. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Compatibilization and morphology development of immiscible ternary polymer blends

We report a novel and effective strategy that compatibilizes three immiscible polymers, polyolefins, styrene polymers, and engineering plastics, achieved by using a polyolefin-based multi-phase compatibilizer. Compatibilizing effect and morphology development are investigated in a model ternary immiscible polymer blends consisting of polypropylene (PP)/polystyrene(PS)/polyamide(PA6) and a multi-phase compatibilizer (PP-g-(MAH-co-St) as prepared by maleic anhydride (MAH) and styrene (St) dual monomers melt grafting PP. Scanning electron microscopy (SEM) results indicate that, as a multi-phase compatibilizer, PP-g-(MAH-co-St) shows effective compatibilization in the PP/PS/PA6 blends. The particle size of both PS and PA6 is greatly decreased due to the addition of multi-phase compatibilizer, while the interfacial adhesion in immiscible pairs is increased. This good compatibilizing effect is promising for developing a new, technologically attractive method for achieving compatibilization of immiscible multi-component polymer blends as well as for recycling and reusing of such blends. For phase morphology development, the morphology of PP/PS/PA6 (70/15/15) uncompatibilized blend reveals that the blend is constituted from PP matrix in which are dispersed composite droplets of PA6 core encapsulated by PS phase. Whereas, the compatibilized blend shows the three components strongly interact with each other, i.e. multi-phase compatibilizer has good compatibilization between the various immiscible pairs. For the 40/30/30 blend, the morphology changed from a three-phase co-continuous morphology (uncompatibilized) to the dispersed droplets of PA6 and PS in the PP matrix (compatibilized).     

Modified interfacial tensions measured in situ in ternary polymer blends demonstrating partial wetting

An in situ Neumann triangle-focused ion beam-atomic force microscopy (NT-FIB-AFM) method has been used to measure modified PS/HDPE interfacial tensions in ternary PS/PP/HDPE blends prepared by melt mixing and demonstrating partial wetting. The ternary blend was modified with SEB, SB and SEBS copolymers. Results related to the position of the PS droplet at the interface show that a symmetrical diblock copolymer is somewhat more efficient in decreasing the interfacial tension compared to an asymmetrical one of similar molecular weight, while the SEBS triblock copolymer appears to have no effect at all. Using the NT-FIB-AFM method, the lowest modified PS/HDPE interfacial tension is 3.0 ± 0.4 mN/m for the symmetric diblock, compared to 4.2 ± 0.6 mN/m (N = 34) for the unmodified interface. This corresponds to an apparent areal density in SEB copolymer equal to 0.16 ± 0.03 molecules/nm², which is near reported saturation values. By varying the concentration of the copolymer, an emulsification curve reporting the value of the PS/HDPE modified interfacial tension as a function of the apparent areal density of the copolymer at the PS/HDPE interface has been obtained. The interfacial tension values obtained by the NT-FIB-AFM approach are significantly higher than the 0.5 ± 0.2 mN/m (N = 3) result obtained by using the classical breaking thread method with the same materials. This discrepancy does not appear to be due to a poor migration of the copolymer to the PS/HDPE interface, but could instead be attributed to the interfacial elasticity of the compatibilized interface, a phenomena that has not been accounted for so far in experimental studies on the morphology of compatibilized multicomponent polymer blends.     

聚合物-表面活性剂对油/水界面剪切粘度的影响

利用正交实验设计研究了聚合物A、石油磺酸盐B、表面活性剂C三种因素共存时对原油模拟油/水界面剪切粘度的影响。单因素实验表明,表面活性剂C使原油模拟油/水界面粘度降低,而聚合物A的存在则使油/水界面剪切粘度上升。而三种因素共存时,在实验条件下,表面活性剂C对油/水界面剪切粘度有一定的影响,聚合物A和石油磺酸盐B看不出有较大影响。因此,在聚合物-表面活性剂复合驱体系中,界面剪切粘度的变化主要取决于体系中表面活性剂的变化。