Surface‐directed morphology evolution in ternary blends of polyethylene,polypropylene, and ethylene–propylene copolymer: A study by laser scanning confocal fluorescence microscopy

With laser scanning confocal fluorescence microscopy, we demonstrate a novel type of morphology evolution in moderately thick films (70–100 μm) of ternary blends of polypropylene (PP), polyethylene (PE), and ethylene–propylene rubber (EPR), in which EPR is labeled with a benzothioxanthene dye (HY‐EPR). The blends are prepared by solution blending, and the phase morphology evolves during the annealing of the blend films in a stainless steel mold. Our results indicate that wetting of the mold surface is a driving force in morphology evolution for the two blend compositions investigated. For 81/14/5 PP/PE/HY‐EPR, phase evolution within the mold results in a laminar structure and hydrodynamic channels, features which have previously been found in thin films of polymer blends as a result of surface‐directed spinodal decomposition. In a blend with a lower weight fraction of the dispersed phase (92/7/1 PP/PE/HY‐EPR), we find that the PE/HY‐EPR domains are larger and more polydisperse closer to the surface because of wetting of the mold wall. We also show that the phase morphology in these films can be controlled by the nature of one or both of the surfaces being varied. When one of the mold surfaces is replaced with a thin film of PP homopolymer, we observe draining of PE/HY‐EPR from the PP to the mold surface, which results in a bilayer structure. A trilayer morphology is likewise obtained by the replacement of both mold surfaces with PP. We also carry out three‐dimensional image reconstruction on a single PE/HY‐EPR particle within the 81/14/5 PP/PE/HY‐EPR blend to obtain detailed information on the interphase structure. We find that HY‐EPR of this composition (30/70 ethylene/propylene) fully coats the PE dispersed phase and partially penetrates the PE droplets. This result falls between the interphase structures found for previously investigated EPR compositions (40/60 and 80/20 ethylene/propylene). © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 637–654, 2003     

Maleic Anhydride Polyethylene Octene Elastomer Toughened Polyamide 6/Polypropylene Nanocomposites: Mechanical and Morphological Properties

A series of polyamide 6/polypropylene (PA6/PP) blends and nanocomposites containing 4 wt% of organophilic modified montmorillonite (MMT) were designed and prepared by melt compounding followed by injection molding. Maleic anhydride polyethylene octene elastomer (POEgMAH) was used as impact modifier as well as compatibilizer in the blend system. Three weight ratios of PA6/PP blends were prepared i.e. 80:20, 70:30, and 60:40. The mechanical properties of PA6/PP blends and nanocomposite were studied through flexural and impact properties. Scanning electron microscopy (SEM) was used to study the microstructure. The incorporation of 10 wt% POEgMAH into PA6/PP blends significantly increased the toughness with a corresponding reduction in strength and stiffness. However, on further addition of 4 wt% organoclay, the strength and modulus increased but with a sacrifice in impact strength. It was also found that the mechanical properties are a function of blend ratio with 70:30 PA6/PP having the highest impact strength, both for blends and nanocomposites. The morphological study revealed that within the blend ratio studied, the higher the PA6 content, the finer were the POEgMAH particles.     

Synthesis and characterization of polyethylene‐g‐polystyrene as the compatibilizer for polypropylene/ Polystyrene blends

Polyethylene‐g‐polystyrene (PE‐g‐PS) was synthesized as a compatibilizer for polypropylene/polystyrene­(PP/PS) blends by the living radical polymerization of styrene with polyethylene‐co‐glycidylmethacrylate (PE‐co‐GMA). The compatibilizer effect of PE‐g‐PS on the morphology and thermal properties of PP/PS blends was investigated. The crystalline temperature of PP in PP/PS blends decreased with increasing PE‐g‐PS contents. Morphologies of PP/PE‐g‐PS/PS blends showed much better dispersion of each domain for higher PE‐g‐PS contents. The molecular weight of PS segment in PP/PE‐g‐PS/PS blend was increased by addition of styrene monomer during the post melt blending process where post living radical polymerization reaction proceeded. Copyright © 2003 John Wiley & Sons, Ltd.     

Morphology evolution and location of ethylene–propylene copolymer in annealed polyethylene/polypropylene blends

Binary blends of linear low density polyethylene (PE) and polypropylene (PP), and ternary blends of PE, PP, and EP copolymer (EPR) were prepared in a finely mixed state. In all blends the ratio of PP to PE was 85/15. In some of the blends, the PE component was labeled with a fluorescent dye; in other blends, the EPR component was labeled. These blends were investigated by laser scanning confocal fluorescence microscopy [LCFM] as a function of annealing time as well as EPR compatibilizer content. In this way we were able to follow the evolution of sample morphology and the location of the EPR in the blends. The presence of EPR in the blends retards the growth of droplets of the dispersed PE phase. When EPR was added in amounts up to 5 wt %, it tended to cover the PE droplets in patches rather than form a true core-shell structure. In the LCFM images, the EPR/PP interface appeared sharper than the EPR/PE interface. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 979–991, 1997     

Crystallization behavior of polypropylene/polycarbonate blends

Crystallization behavior and morphology of polypropylene (PP)/polycarbonate (PC) blends have been studied by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). In the study of non-isothermal crystallization of the blends, the phenomenon of multiple crystallization peaks of PP/PC blends was related to the blend morphology in which PP was the dispersed phase as small droplets in the PC matrix. The phenomenon of a single crystallization peak of the PP/PC blends was related to the blend morphology in which PP was a continuous phase; in that case the crystallization peak temperatures of the blends were higher than that of the PP. The isothermal crystallization kinetics of the PP and PP/PC (80/20) blend were described by the Avrami equation. The results showed that the Avrami exponent of the PP/PC (80/20) blend was higher than that of the PP, and the crystallization rate of the PP/PC (80/20) blend was faster than that of the PP. The crystallization rate of the PP and PP/PC (80/20) blend were calculated according to the Hoffmann theory. Both the PP and PP/PC (80/20) blend had maximum crystallization rates. The temperature at the maximum crystallization rate for the PP/PC (80/20) blend was higher than that of the PP.     

Capillary extrusion of polypropylene/high-density polyethylene immiscible blends as studied by rheo-particle image velocimetry

The capillary extrusion of polypropylene (PP) and high-density polyethylene (HDPE) immiscible blends was studied in this work by rheo-particle image velocimetry (Rheo-PIV). The PP/HDPE blends were prepared by single screw extrusion and extruded through a transparent capillary die at a temperature of 200 °C and concentrations of 80/20, 60/40, 40/60 and 20/80 wt%, respectively. PIV measurements described accurately the flow behavior of PP/HDPE blends and revealed continuous velocity profiles in the die, without macroscopic phase separation, for all the blends in the resolution range of the PIV technique. The flow behavior of all the blends was shear-thinning (power-law) type and their viscosities laid in between the values corresponding to the neat polymers and increased in an exponential way along with the concentration of the highest viscosity component in the blend (HDPE). Also, it was found that the extruded blends acquired a stratified morphology and that HDPE mitigates extrudate distortions in PP, meanwhile PP eliminates slip and flow instabilities in HDPE by migrating to the region of highest shear stresses in the die. Migration of PP to the capillary wall was corroborated by Raman spectroscopy measurements on the periphery of solid extrudates. Finally, via calculations of the density of the molten blends under flow using the velocity profiles in the die, we show that the homopolymers are compatible in the molten state and follow a simple inverse relation for their density, and an exponential one for their viscosity.     

Preparation of microcellular polypropylene/polystyrene blend foams with tunable cell structure

By using supercritical carbon dioxide (sc‐CO₂) as the physical foaming agent, microcellular foaming was carried out in a batch process from a wide range of immiscible polypropylene/polystyrene (PP/PS) blends with 10–70 wt% PS. The blends were prepared via melt processing in a twin‐screw extruder. The cell structure, cell size, and cell density of foamed PP/PS blends were investigated and explained by combining the blend phase morphology and morphological parameters with the foaming principle. It was demonstrated that all PP/PS blends exhibit much dramatically improved foamability than the PP, and significantly decreased cell size and obviously increased cell density than the PS. Moreover, the cell structure can be tunable via changing the blend composition. Foamed PP/PS blends with up to 30 wt% PS exhibit a closed‐cell structure. Among them, foamed PP/PS 90:10 and 80:20 blends have very small mean cell diameter (0.4 and 0.7 µm) and high cell density (8.3 × 10¹¹ and 6.4 × 10¹¹ cells/cm³). Both of blends exhibit nonuniform cell structure, in which most of small cells spread as “a string of beads.” Foamed PP/PS 70:30 blend shows the most uniform cell structure. Increase in the PS content to 50 wt% and especially 70 wt% transforms it to an irregular open‐cell structure. The cell structure of foamed PP/PS blends is strongly related to the blend phase morphology and the solubility of CO₂ in PP more than that in PS, which makes the PP serve as a CO₂ reservoir. Copyright © 2009 John Wiley & Sons, Ltd.     

Phase morphology, crystallisation behaviour and mechanical properties of isotactic polypropylene/high density polyethylene blends

The phase morphology, crystallisation behaviour and mechanical properties of isotactic polypropylene (iPP)/high density polyethylene (HDPE) blends were investigated. It was found that the properties are intimately related to each other. The morphology of the blends showed a two phase structure in which the minor phase was dispersed as domains in the major continuous matrix phase. The domain size of the dispersed phase increased with increasing concentration of that phase due to coalescence. It was also found that the domain size of the dispersed phase depends on the viscosity difference between the two phases. For a given HDPE/iPP blend, where HDPE is the matrix and iPP is the dispersed phase, the iPP domains were smaller than HDPE domains of the corresponding iPP/HDPE blend where iPP is the matrix and HDPE is the dispersed phase. A co-continuous morphology was observed at 50/50 PP/HDPE composition. Crystallinity studies revealed that blending has not much effect on the crystalline melting point of polypropylene and high density polyethylene. The crystallisation enthalpy and heat of fusion values of HDPE and PP in the blend were decreased as the amount of the other component increased. The variation in percent crystallinity of HDPE and PP in the blend was found to depend on the morphology of the blend. All the mechanical properties except Young's modulus and hardness showed negative deviation from the additivity line. This is due to the incompatibility of these blends.     

Mutual influence of LDPE and PP in their blends during crystallization

An indication for the mutual influence of LDPE and PP was the change of the morphology parameters of PE and PP at different ratios of the polymers in blends. That influence depends on the blend composition and is different for PE and PP. It is especially interesting in the blend PE75/PP25 where the influence between PE and PP shows dependence also on the sample geometry. Melting parameters, non-isothermal crystallization parameters - crystallization peak temperature T_c, crystallization begin temperature T_onset, half-width w_1/2 of the crystallization peak, degree of crystallinity α and crystallization rate coefficient CRC, as well as the isothermal kinetics parameters showed dependence on the blend composition. It was established that PE is more stable then PP concerning the mutual influence of both polymers on their crystallization. It was established that PE affects the crystal nucleation of PP and causes a decreasing of PP spherulite size.     

HDPE/PP共混物在振动剪切作用下的力学性能与形态控制

采用高剪切引起的相容与振动剪切保压方式控制共混物的形态,结果表明,当共混体系中HDPE/PP为92/8时的试样拉伸强度为97.1MPa,而80/20试样的缺口冲击强度为45.5kJ/m₂,较静态试样分别提高4.3倍和9.5倍.采用振动剪切注射技术可以针对某一组分获得高强度、高韧性的HDPE/PP共混制件.     

A novel method for the pore size control of the battery separator using the phase instability of the ternary mixtures

The battery separator plays a key role in determining the capacity of the battery. Since separator performance mainly depends on the pore size of membrane, development of a technique for the fabrication of the membrane having controlled pore size is essential in producing a highly functional battery separator. In this study, microporous membranes having the desired pore size were produced via thermally‐induced phase separation (TIPS) process. Control of the phase boundaries of polymer‐diluent blends is the main concern in manipulating pore size in TIPS process, because pore size mainly depends on the temperature gap between phase separation temperature of the blend and the crystallization temperature of polymer. Microporous membranes having controlled pore size were produced from polyethylene (PE)/dioctyl phthalate (DOP) blends, PE/isoparaffin blends, and polymer/diluent‐mixture ternary blends, that is, PE/(DOP/isoparaffin) blends. PE/DOP binary blends and PE/(DOP/isoparaffin) ternary blends exhibited typical upper critical solution temperature (UCST) type phase behavior, while PE formed a homogeneous mixture with isoparaffin above the crystallization temperature of PE. When the mixing ratio of polymer and diluent‐mixture was fixed, the phase separation temperature of PE/diluent‐mixture blend first increased with increasing DOP content in the diluent‐mixture, went through a maximum centered at about 80 wt % DOP and then decreased. Furthermore, the phase separation temperatures of the PE/diluent‐mixture blends were always higher than that of the PE/DOP blend when diluent‐mixture contained more than or equal to 20 wt % of DOP. Average pore size of microporous membrane prepared from PE/DOP blend and that prepared from PE/isoparaffin blend were 0.17 and 0.07 μm, respectively. However, average pore size of microporous membrane prepared from ternary blends was varied from 0.07 to 0.5 μm by controlling diluent mixing ratio. To understand the phase behavior of ternary blend, phase instability of the ternary mixture was also explored. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2025–2034, 2006     

iPP/HDPE/EPDM三元共混体系的组分分布、相容性和结晶行为

用DSC、~(13)C-NMR、SEM和WAXD等方法研究了IPP/HDPE/EPDM三元共混体系的组分分布、相容性和结晶行为。实验结果表明,EPDM与PE组分的相容性优于与PP组分的相容性,多数EPDM分子链段能够分布在PE组分中;EPDM含量为15％时,共混物相容性最好,SEM照片呈现晶体微区的互连或网络状结构;随EPDM含量增加,总结晶度X_c减小,其中PE组分结晶度X_(cE)有较大幅度地降低,PP组分结晶度X_(cp)基本没有变化,这可以根据EPDM和PE、PP之间相容性的差异以及PE、PP两组分在冷却过程中不同的结晶行为来解释。     

Properties of immiscible and ethylene-butyl acrylate-glycidyl methacrylate terpolymer compatibilized poly (lactic acid) and polypropylene blends

Poly(lactic acid) (PLA) and polypropylene (PP) blends of various proportions were prepared by melt-compounding. The miscibility, phase morphology, thermal behavior, and mechanical and rheological properties of the blends were investigated. The blends were immiscible systems with two typical morphologies, spherical droplet and co-continuous, and could be obtained at various compositions. Complex viscosity, storage modulus and loss modulus depend on the PP content. Thermal degradation of all blends led to two weight losses, for PLA and PP. The incorporation of PP improved the thermal stability of the blend. The effect of compatibilizer (ethylene-butyl acrylate-glycidyl methacrylate terpolymer, EBA-GMA) on the morphology and mechanical properties of 70/30 w/w PLA/PP blends was investigated. The tensile strength of these blends reached a maximum for 2.5 wt% EBA-GMA, and impact strength increased with increasing EBA-GMA content, suggesting that EBA-GMA is an effective compatibilizer for PLA/PP blends.     

Probing Liquid-Liquid Phase Separation of a Polyethylene Blend with Thermal Analysis

Summary: A series of polyethylene (PE) blends consisting of a high density polyethylene (HDPE) and a linear low density polyethylene (LLDPE) with a butene-chain branch density of 77/1000 carbon was prepared at different concentrations. The LLDPE only crystallized below 50 °C, therefore, above 80 °C and below the melting temperature of HDPE, only HDPE crystallized in the PE blends. A specifically designed multi-step experimental procedure based on thermal analysis technique was utilized to monitor the liquid–liquid phase separation (LLPS) of this set of PE blends. The main step was first to quench the system from the homogeneous temperatures and isothermally anneal them at a prescribed temperature higher than the equilibrium melting temperature of the HDPE for the purpose of allowing the phase morphology to develop from LLPS, and then cool the system at constant rate to record the non-isothermal crystallization. The crystallization peak temperature (T_p) was used to character the crystallization rate. Because LLPS results in HDPE-rich domains where the crystallization rates are increased, this technique provided an experimental measure to identify the binodal curve of the LLPS for the system indicated by increased T_p. The result showed that the LLPS boundary of the blend measured by this method was close to that obtained by phase contrast optical microscopy method. Therefore, we considered that the thermal analysis technique based on the non-isothermal crystallization could be effective to investigate the LLPS of PE blends.     

Physico-mechanical properties and biodegradation of oxo-degradable HDPE/PLA blends

Blends of high density polyethylene/poly(lactic acid) with/without compatibilizer and pro-oxidant (cobalt stearate) were prepared by melt blending technique. In ratio 80/20, the blend revealed a good combination of tensile properties and optimum poly(lactic acid) content. The improvement in mechanical properties of this blend was achieved by addition of 4 phr compatibilizer. Cobalt stearate (CoSt) was added to 80/20 blends in 0.1% and 0.2% (w/w) ratios. The obtained blends were characterized by DSC, SEM, FTIR spectroscopy, rheological study, etc. All the prepared blends were able to biodegrade in composting environment and the blend containing pro-oxidant was maximum degraded.     

iPP/HDPE/EPDM三元共混体系的组分分布、相容性和结晶行为

 用DSC、¹³C-NMR、SEM和WAXD等方法研究了IPP/HDPE/EPDM三元共混体系的组分分布、相容性和结晶行为。实验结果表明,EPDM与PE组分的相容性优于与PP组分的相容性,多数EPDM分子链段能够分布在PE组分中;EPDM含量为15％时,共混物相容性最好,SEM照片呈现晶体微区的互连或网络状结构;随EPDM含量增加,总结晶度X_c减小,其中PE组分结晶度X_cE有较大幅度地降低,PP组分结晶度X_cp基本没有变化,这可以根据EPDM和PE、PP之间相容性的差异以及PE、PP两组分在冷却过程中不同的结晶行为来解释。     

Effect of compatibilizer on morphology and properties of HDPE/Nylon 6 blends

The compatibilization effect of linear low‐density polyethylene‐grafted maleic anhydride (LLDPEgMA) and high‐density polyethylene‐grafted maleic anhydride (HDPEgMA) on high‐density polyethylene (HDPE)/polyamide 6 (Nylon 6) blend system is investigated. The morphology of 45 wt %/55 wt % polyethylene/Nylon 6 blends with three compatibilizer compositions (5 wt %, 10 wt %, and 15 wt %) are characterized by atomic force microscopic (AFM) phase imaging. The blend with 5 wt % LLDPEgMA demonstrates a Nylon 6 continuous, HDPE dispersed morphology. Increased amount of LLDPEgMA leads to sharp transition in morphology to HDPE continuous, Nylon 6 dispersed morphology. Whereas, increasing HDPEgMA concentration in the same blends results in gradual morphology transition from Nylon 6 continuous to co‐continuous morphology. The mechanical properties, oxygen permeability, and water vapor permeability are measured on the blends which confirm the morphology and indicate that HDPEgMA is a better compatibilizer than LLDPEgMA for the HDPE/Nylon 6 blend system. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 281–290     

Morphology and mechanical properties of immiscible polyethylene/polyamide12 blends prepared by high shear processing

In this work,completely immiscible polyethylene/polyamidel2 (PE/PA12) blends were prepared by high shear extruder.The morphology and mechanical properties of the blends were investigated as a function of rotation speed.It wasfound that the high shear processing is an effective method to improve the dispersion of the PAl2 phase in PE matrix whenPAl2 contents are 5 wt％ and 10 wt％,and the dispersed phase particle size is reduced with the increase of rotation speed from 100 r/min to 500 r/min.However,with further increase of PAl2 content to 20 wt％,high shear processing has no effect on the phase morphology of the blends.Accordingly,a largely increased elongation at break and impact strength are observed for PE/PA12/95/5 and PE/PA12/90/10 blends obtained at high rotation speeds but no effect on the property of PE/PA12/80/20.Annealing experiment demonstrated that the obtained phase morphology is not stable thus compatibilizer should be introduced in the future work.This work could provide a guideline for the application of high shear processing in the preparation of polymer blends with huge polarity difference.     

纳米刚性微粒与橡胶弹性微粒同时增强增韧聚丙烯的研究

通过力学性能测试、动态力学试验、ＤＳＣ 分析以及材料断面形貌与结构分析等手段,对以纳米二氧化硅（ＳｉＯ２） 为刚性微粒、以三元乙丙橡胶（ＥＰＤＭ） 为弹性微粒组成的聚丙烯（ＰＰ）／ 纳米ＳｉＯ２／ＥＰＤＭ 的同时增强增韧效果进行了研究．结果显示,上述两种微粒可同时大幅度提高ＰＰ 的韧性、强度和模量,当ＰＰ／ 纳米ＳｉＯ２／ＥＰＤＭ 为８０／３／２０ 时,两种微粒体现较明显的协同增韧效应．纳米ＳｉＯ２ 可提高ＰＰ 的结晶温度和结晶速度,并使球晶细化．纳米ＳｉＯ２ 刚性微粒在ＰＰ连续相中以微粒团聚体形态分布,构成团聚体的平均微粒数约为６ ～７ ,其与ＰＰ基体表现出较强的结合牢度．ＰＰ／ 纳米ＳｉＯ２／ＥＰＤＭ 的综合性能已接近或达到工程塑料的性能．     

Evaluation of the SEBS copolymer in the compatibility of PP/ABS blends through mechanical,thermal, thermomechanical properties,and morphology

Polypropylene (PP) blends with acrylonitrile-butadiene-styrene (ABS) were prepared using the styrene-ethylene-butylene-styrene copolymer (SEBS) as a compatibilizing agent. The blends were prepared in a co-rotational twin-screw extruder and injection molded. Torque rheometry, Izod impact strength, tensile strength, heat deflection temperature (HDT), differential scanning calorimetry, thermogravimetry, and scanning electron microscopy properties were investigated. The results showed that there was an increase in the torque of PA6/ABS blends with SEBS addition. The PP/ABS/SEBS (60/25/15%) blend showed significant improvement in impact strength, elongation at break, thermal stability, and HDT compared with neat PP. The elastic modulus and tensile strength have not been significantly reduced. The degree of crystallinity and the crystalline melting temperature increased, indicating a nucleating effect of ABS. The PP/ABS blends compatibilized with 12.5% and 15% SEBS presented morphology with well-distributed fine ABS particles with good interfacial adhesion. As a result, thermal stability has been improved over pure PP and the mechanical properties have been increased, especially impact strength. In general, the addition of the SEBS copolymer as the PP/ABS blend compatibilizer has the advantage of refining the blend's morphology, increasing its toughness and thermal stability, without jeopardizing other PP properties.