Effect of composition on the linear viscoelastic behavior and morphology of PMMA/PS and PMMA/PP blends

Here, the effect of concentration on the morphology and dynamic behavior of polymethylmethacrylate/polystyrene (PMMA/PS), for PS with two different molecular weight, and polymethylmethacrylate/polypropylene (PMMA/PP) blends was studied. The blends concentrations ranged from 5% to 30% of the dispersed phase (PS or PP). The dynamic data were analyzed to study the possibility of inferring the interfacial tension between the components of the blend from their rheological behavior using Palierne [Palierne JF. Rheol Acta 1990;29:204-14] [1] and Bousmina [Bousmina M. Acta 1999;38:73-83] [2] emulsion models. The relaxation spectrum of the blends was also studied. The dynamic behavior of 85/15 PS/PMMA blend were studied as a function of temperature. It was possible to fit both Palierne and Bousmina's emulsion models to the dynamic data of PMMA/PS blends, to obtain the interfacial tension of the blend. This was not the case for PMMA/PP. The relaxation spectrum of both blends was used to obtain the interfacial tension between the components of the blends. The values of interfacial tension calculated were shown to decrease when the concentration of the blends increased. It was shown using morphological analysis that this phenomenon can be attributed to the coalescence of the dispersed phase during dynamic measurements that occurs for large dispersed phase concentration. When the ‘coalesced’ morphology is taken into account in the calculations the interfacial tension inferred from rheological measurement did not depend on the concentration of the blend used. The values of interfacial tension found analyzing the dynamic behavior of one of the PMMA/PS blend were shown to decrease with temperature.     

PP/PS共混熔纺中相结构沿纺程的梯度演变

将聚丙烯(PP)/聚苯乙烯(PS)按质量比92∶8进行共混纺丝,以自制的纺程取样器对PP/PS熔融纺丝进行纺程取样,利用冷冻超薄切片机获得纺程各点取样纤维的横截面和纵剖面,扫描电子显微镜观察纤维中PS分散相的形貌,研究了共混熔融纺丝中梯度结构沿纺程的演变及其梯度结构的形成机理。结果表明:PS分散相数目沿纤维径向呈现内密外疏的梯度分布,这一差异沿着纺程不断增大;PS分散相在纺程0~60 cm发生形变,纺丝速度为125~500 m/min下PS分散相直径逐渐减小,当纺丝速度达到1 000 m/min时,PS分散相直径在纺程0~20 cm减小,在纺程20~60 cm增加,PS分散相液滴在此区域发生了明显的聚并,在纤维表层各个纺丝速度下分散相都呈现不同程度的聚并现象;在PP/PS共混纤维中呈现中心层分散相液滴形变程度大表层形变程度小的梯度差异,但高速纺丝会弱化这一差异。     

Composition and compatibilization induced morphology alteration in PVDF/LLDPE blends: correlation between rheology and morphology

Correlation between the rheology and morphology of PVDF/LLDPE blends as well as the effect of LLDPE-g-MA compatibilizer on the microstructure and viscoelastic properties of these blends were studied in detail. Morphology development from matrix-dispersed to co-continuous and again to dispersed-matrix was well predicted using various linear viscoelastic analyses and confirmed via direct SEM experiments and continuity index analysis. Compatibilization induced alteration in the microstructure of the blends, particularly PVDF/PE 50/50 blend from co-continuous morphology to dispersed-matrix one, was also concluded from viscoelastic analysis and confirmed. It was shown that the feeding order had a distinct effect on morphology of the blends near the phase inversion composition. “Phase within a phase within a phase” morphology was observed near the phase inversion region, provided that the components are fed simultaneously. Different melting and crystallization temperature range of PVDF and PE phases was understood to be the main reason of this observation. It was also shown that compatibilization had higher impact on LLDPE-rich blends than PVDF-rich blends, while narrowed the co-continuity composition range.

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Melt rheology and morphology of PP/SEBS/PC ternary blend

Melt rheological properties of the ternary blend of isotactic polypropylene (PP), styreneethylene–butylene–styrene terpolymer (SEBS), and polycarbonate (PC), PP/SEBS/PC, are studied in a wide range of composition, such that PP is the matrix and SEBS and PC are the minor components, with the proportion of one varying from 0 to 30% at various fixed compositions of the other. The respective binary blends, PP/SEBS and PP/PC, studied as the reference systems for interpretation of results on the ternary blends yielded interesting new information about the morphology development and its correlation with melt rheological properties of these binary blends. The studies include the measurement of melt rheological properties on a capillary rheometer in the shear rate range 10¹–10⁴ s^?1 at a fixed temperature of 240°C. The data presented as conventional flow curves are analyzed for the effect of blend composition and shear rate on pseudoplasticity, melt viscosity, and melt elasticity, and role of each individual component is identified. Morphology of dispersed phases of these blends is studied through scanning electron microscopy of the cryogenically fractured and suitably etched surfaces. Variations of morphology with blend composition and shear rate showed interesting correlation with melt rheological properties, which are discussed in detail. An important finding of the morphological studies is that in the PP/SEBS/PC ternary blend the SEBS phase forms two types of morphologies depending on the blend composition and shear rate: (i) simple droplets and (ii) boundary layer at the surface of the PC droplets. © 1993 John Wiley & Sons, Inc.     

Characterization of phase morphology of polymer melts (PP/PE blends) via rheology

The viscoelastic behavior of high impact polypropylene (PP) melts, a multiphase system with an isotactic PP matrix and inclusions consisting of mainly amorphous ethylene–propylene copolymer (EP), is strongly influenced by the size of small inclusions. The dynamic moduli of such two‐phase systems (reactor products) are well described by Palierne's emulsion model. For this analysis the reactor product is separated into matrix and dispersed phase via the different solubility in xylene. This analysis also provides information on the ratio interfacial tension to particle size of the dispersed phase. With morphology data (particle size) of the solidified heterophasic samples (Transmission Electron Microscopy), we estimate the interfacial tension between PP and EP copolymer via the emulsion model of Palierne and from the relaxation time spectra according to Gramespacher and Meissner. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Composite droplets with core/shell morphologies prepared from HDPE/PS/PMMA ternary blends by twin‐screw extrusion

Ternary blends of PS and PMMA in a PE matrix were prepared by twin‐screw extrusion to investigate the core/shell encapsulation phenomenon in the composite droplet. The PS was found to encapsulate the PMMA to form composite droplets within the PE matrix as expected from the spreading coefficient theory. The effects of dispersed phase concentration, viscosity ratio, feeding sequence and twin‐screw operating conditions were investigated. The blend morphology was observed by scanning electron microscopy after selective extraction of either PS or PMMA, and average core and composite droplet diameters were determined by image analysis. Although it is known that the structure of composite droplet blends can be substantially altered through control of the volume fraction of the components in the dispersed phase, this study demonstrates that blends with a 1:1 composite droplet volume fraction are relatively stable to large variations in the minor phase viscosities and processing conditions. Twin‐screw extrusion thus provides a highly robust technique for the melt processing of blends possessing composite droplet morphologies. Polym. Eng. Sci. 44:749–759, 2004. © 2004 Society of Plastics Engineers.     

Development of fibrillar morphology in immiscible PP/PS blends under shear flow

The formation dynamics of fibrillar morphology in dilute immiscible polypropylene (PP)/polystyrene blends under simple shear flow is investigated using optical‐shear technique. Two strategies in generating fibrillar droplets under shear flow, namely temperature quench and shear jump, are studied. It is found that the shear‐induced deformation of PP droplets is closely related to the total shear strain and changes of rheological properties of components during the temperature quench or shear‐jump process. The shape evolution of fibrillar droplets under shear flow displays large deviation to the prediction of affine deformation theory based on Newtonian fluids and that of three deformation models, which consider the viscoelastic properties of components. The possible effect of droplet coalescence, breakup, and interfacial slip on the deviation between the experimental data and the prediction values for droplet deformation are discussed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Morphological and rheological detection of the phase inversion of PMMA/PS polymer blends

The phase inversion process was investigated from different points of view. First, a reliable on-line and off-line method of morphology detection using light microscopy is established. The method provides fast information that can be used to discriminate between different types of morphologies. Second, TEM images are modelled with Markov Random Fields. For characterization purposes image features are introduced and tested. A combination of features allows classification of different morphologies of PMMA/PS blends. In the third part we show that the rheological properties of blends allow also discrimination between different morphologies. Received: 6 November 1997/Revised version: 3 December 1997/Accepted: 3 December 1997     

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。     

PP接枝聚合物对PP/PS共混物相形态的影响

通过原子转移自由基反应合成了聚丙烯(PP)接枝聚苯乙烯(PS) (PP-g-PS),研究了PP-g-PS对PP/PS共混物相形态的影响.采用扫描电子显微镜、偏光显微镜观察了共混物的断面形貌和等温结晶形态.结果表明: 加入PP-g-PS对PP/PS共混物起到了良好的增容作用,表现在两相界面模糊,分散相尺寸减小.当PP-g-PS中x(PS)为5.10% 左右时即可起到增容改善相界面的作用.相容性的提高改善了PP/PS共混物的发泡性能.     

Effect of the mixing conditions on the phase structure of PP/PS blends

The effect of the rate and time of mixing in a batch mixer on the phase structure of polypropylene/polystyrene (PP/PS) blends with various rheological properties of the components was studied. Regions with substantially different average sizes of the dispersed particles were found in the studied blends. Differences between the average size of the particles in individual regions of the samples persist in all blends and mixing conditions under study. No dependence of the average particle size on the rate of mixing has been obtained for the PP/PS (75/25) blends. On the other hand, decrease of the average particle size with increasing rate of mixing has been found for the PP/PS (95/5) blend. These results are discussed as a consequence of the competition between the breakup and coalescence of the dispersed particles. © 1996 John Wiley & Sons, Inc.     

The morphology and mechanical properties of dynamic packing injection molded PP/PS blends

As a part of long-term project aimed at super polyolefin blends, in this work, we report the mechanical reinforcement and phase morphology of the immiscible blends of polypropylene (PP) and polystyrene (PS) achieved by dynamic packing injection molding (DPIM). The shear stress (achieved by DPIM) and interfacial interaction (obtained by using styrene-butadiene-styrene (SBS) as a compatibilizer) have a great effect on phase morphology thus mechanical properties. The shear-induced morphology with core in the center and oriented zone surrounding the core was observed in the cross-section areas of the samples. The phase inversion was also found to shift towards lower PS content under shear stress, at 70 wt% in the core and 30 wt% in the oriented zone, compared with 80 wt% for static samples (without shear). The tensile strength, tensile modules and impact strength were found largely increase by means of either shear stress or compatibilizer. The PS particle size is greatly reduced with adding of SBS, and the reduced particle size results in greater resistance to deformation, which causes the co-continuous structure at oriented zone change into droplet morphology. The morphology resulting from blending and processing was discussed based on effect of interfacial tension, shear rate, phase viscosity ratio and composition. The observed change of mechanical properties was explained based on the combined effect of phase morphology (droplet-matrix or co-continuous phase) and molecular orientation under shear stress.     

Tensile properties and morphology of the dynamically cured EPDM and PP/HDPE ternary blends

The tensile properties and morphology of the polyolefin ternary blends of ethylenepropylene–diene terpolymer (EPDM), polypropylene and high density polyethylene were studied. Blends were prepared in a laboratory internal mixer where EPDM was cured in the presence of PP and HDPE under shear with dicumyl peroxide (DCP). For comparison, blends were also prepared from EPDM which was dynamically cured alone and blended with PP and HDPE later (cure–blend). The effect of DCP concentration, intensity of the shear mixing, and rubber/plastics composition was studied. The tensile strength and modulus increased with increasing DCP concentration in the blends of EPDM-rich compositions but decreased with increasing DCP concentration in blends of PP-rich compositions. In the morphological analysis by scanning electron microscopy (SEM), the small amount of EPDM acted as a compatibilizer to HDPE and PP. It was also revealed that the dynamic curing process could reduce the domain size of the crosslinked EPDM phase. When the EPDM forms the matrix, the phase separation effect becomes dominant between the EPDM matrix and PP or HDPE domain due to the crosslinking in the matrix.     

Influences of component ratio of minor phases and charge sequence on the morphology and mechanical properties of PP/PS/PA6 ternary blends

In this study, influences of both component ratio of minor phases and charge sequence on the morphology and mechanical performance in typical ternary blends, polypropylene (PP)/polystyrene (PS)/polyamide-6 (PA6), have been studied. Reactive compatibilization of the blends has been carried out using multi-monomer melt grafted PP with anhydride groups and styrene segments. For uncompatibilized blends, scanning electron microscope (SEM) and selective solvent extraction showed that the blends presented a core–shell morphology with PS as shell and PA6 as core in the PP matrix, in spite of the component ratio and charge sequence. The shell thickened and droplet size decreased with increasing the PS/PA6 component ratio. While for compatibilized blends, the addition of compatibilizers resulted in a significant reduction of the dispersed droplet size and the phase structure of the dispersed phases was greatly dependent on the charge sequence. When the blending of PA6, g-PP, and PP are preceded, the encapsulation structure reversed into the structure of PS phase encapsulated by PA6 phase, which led to better tensile and flexural strength of the blends.     

Analysis of phase morphology and dynamics of immiscible PP/PA1010 blends and its partial-miscible blends during melt mixing from SEM patterns

The formation and evolution of the phase morphology of polypropylene (PP) with Nylon1010 (PA1010) blends before and after adding the compatibilizer, polypropylene grafted maleic anhydride (PP-g-MAH), during melt mixing are investigated by the pattern analysis of scanning electron microscope (SEM). The average particle diameter DP_AV, characteristic length Λ and the average characteristic length Λm are calculated to discuss the melt mixing process. It is proved, by the figure-estimation theory, that the distribution of Λ is log-normal distribution. Furthermore, the phase morphology during melt mixing is discussed in depth by the parameters of the log-normal distribution. The results demonstrate that the structure of the dispersed phase during melt mixing evolves with dynamical self-similarity through the competition of break-up and coalescence of dispersed phase. A fractal dimension, based on the probability density of the character length, is calculated in this study. The results show that the fractal dimension is an effective parameter to characterize the melt mixing process of polymer blends.     

Rheological properties,tensile properties,and morphology of PP/EPDM/lonomer ternary blends

The rheological and tensile properties and the morphology of polypropylene (PP)/ethylenepropylene-diene terpolymer(EPDM)/ionomer ternary blends were investigated, using a rheometric dynamic spectrometer (RDS), a dynamic mechanical thermal analyzer (DMTA), a tensile tester, and a scanning electron microscope (SEM). Two kinds of poly(ethylene-co-methacrylic acid) (EMA) ionomers, neutralized with different metal ions (Na⁺ and Zn⁺⁺), were used. Blends were melt-mixed, using a laboratory internal mixer at 190°C. The composition of PP and EPDM was fixed at 50/50 by wt % and the EMA ionomer contents were varied from 5 to 20 wt %, based on the total amount of PP and EPDM. It was found that the ternary blends, containing Na-neutralized ionomer, showed considerably different rheological properties and morphology as compared to the PP/EPDM binary blends, due to the compatibilizing effect of the ionomer for PP and EPDM, while the ternary blends, containing the Zn-neutralized ionomer, did not. The compatibilizing effect was most prominent at 5 wt % ionomer concentration. © 1994 John Wiley & Sons, Inc.     

Phase morphology and stability of co-continuous (PPE/PS)/PA6 and PS/PA6 blends: effect of rheology and reactive compatibilization

(PPE/PS)/PA6 and PS/PA6 blends were prepared by means of melt-extrusion. They were compatibilized using the reactive styrene-maleic anhydride copolymer with 2 wt% maleic anhydride (SMA2). The effect of compatibilization on the phase inversion and the stability of the resulting co-continuous blend structures were investigated using scanning electron microscopy, dissolution and extraction experiments. The onset of co-continuity shifted towards lower PA6 concentrations according to the change in blend viscosity ratio. The melting order of the components inside the extruder could result in a change in the observed co-continuity interval in slowly developing phase morphologies. The unmodified co-continuous blends were not stable and did break-up into a droplet/matrix type of morphology upon annealing in the melt depending on the blend composition. Although the stability of the threads during annealing improved upon compatibilization because of the lower resulting interfacial tension, the decreased possibility for recombination and coalescence during flow reduced the co-continuous region for the compatibilized blends. It is proposed that a dynamic equilibrium between break-up and recombination phenomena after the initial network formation is necessary to maintain the network structure.     

Rheology‐morphology correlation in PET/PP blends: Influence of type of compatibilizer

Rheological and morphological properties of melt processed poly(ethylene terephthalate) (PET)/polypropylene (PP) blends are presented. Two types of compatibilizer namely, PP‐g‐MA <MA= maleic anhydtide> and Elvaloy PTW, an n‐butyl acrylate glycidyl methacrylate ethylene terpolymers, were incorporated at different levels to the PET/PP blend system. Scanning electron microscopy revealed that the dispersed particle sizes were smaller in PET‐rich blends than PP‐rich blends. With increasing compatibilizer level, the refinement of morphology was observed in both the systems. However, the blends compatibilized with PTW showed a more refined (smaller) particle size, and at high PTW content (10 wt%), the morphology changed towards monophasic. The significant changes in morphology were attributed to the highly reactive nature of PTW. Investigation of rheological properties revealed that the viscosity of the PET/PP blends followed typical trends based on mixing rule, which calculates the properties of blends based on a linear average. Incorporation of PP‐g‐MA into the blends resulted in a negative deviation in the viscosity of the system with respect to that of the neat blend. With increasing PP‐g‐MA level, the deviation became more pronounced. Although incorporation of the compatibilizer into the PET/PP blends refined the morphology, it led to a drastic drop of viscosity, which could be attributed to inherently lower molecular weight of the compatibilizer. In the case of the blends compatibilized by PTW, a strong positive deviation in rheological properties was observed that confirmed the stronger interaction between the blend components due to reactive compatibilization process, which led to the more refined morphology in this series of blends. J. VINYL ADDIT. TECHNOL., 19:25–30, 2013. © 2013 Society of Plastics Engineers