Crystallization,melting behavior,and morphology of BPP/HDPE blend

The crystallization, melting behavior, and morphology of a low ethylene content block propylene–ethylene copolymer (BPP) and a high-density polyethylene (HDPE) blend were studied. It was found that the existence of ethylene–propylene rubber (EPR) in BPP has more influence on the crystallization of HDPE than on that of PP. This leads to the decreasing of the melting temperature of the HDPE component in the blends. It is suggested that the EPR component in BPP shifted to the HDPE component during the blending process. The crystallinity of the HDPE phase in the blends decreased with increasing BPP content. The morphology of these blends was studied by polarized light microscopy (PLM) and SEM. For a BPP-rich blend, it was observed that the HDPE phase formed particles dispersed in the PP matrix. The amorphous EPR chains may penetrate into HDPE particles to form a transition layer. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 69: 2469–2475, 1998     

Comparison of olefin copolymers as compatibilizers for polypropylene and high‐density polyethylene

Some polyolefin elastomers were compared as compatibilizers for blends of polypropylene (PP) with 30 wt % high‐density polyethylene (HDPE). The compatibilizers included a multiblock ethylene–octene copolymer (OBC), two statistical ethylene–octene copolymers (EO), two propylene–ethylene copolymers (P/E), and a styrenic block copolymer (SBC). Examination of the blend morphology by AFM showed that the compatibilizer was preferentially located at the interface between the PP matrix and the dispersed HDPE particles. The brittle‐to‐ductile (BD) transition was determined from the temperature dependence of the blend toughness, which was taken as the area under the stress–strain curve. All the compatibilized blends had lower BD temperature than PP. However, the blend compatibilized with OBC had the best combination of low BD temperature and high toughness. Examination of the deformed blends by scanning electron microscopy revealed that in the best blends, the compatibilizer provided sufficient interfacial adhesion so that the HDPE domains were able to yield and draw along with the PP matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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.     

Blends of poly(propylene) and polyacetal compatibilized by ethylene vinyl alcohol copolymers

Polymer blends of poly(propylene) (PP) and polyacetal (polyoxymethylene, POM) with ethylene vinyl alcohol (EVOH) copolymers were investigated by differential scanning calorimetry (DSC), rheological, tensile, and impact measurements, Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). The PP–POM–EVOH blends were extruded with a co‐rotating twin‐screw extruder. The ethylene group in the EVOH is partially miscible with PP, whereas the hydroxyl group in the EVOH can form hydrogen bonding with POM. The EVOH tends to reside along the interface, acting as a surfactant to reduce the interfacial tension and to increase the interfacial adhesion between the blends. Results from SEM and mechanical tests indicate that a small quantity of the EVOH copolymer or a smaller vinyl alcohol content in the EVOH copolymer results in a better compatibilized blend in terms of finer phase domains and better mechanical properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1471–1477, 2003     

乙丙嵌段共聚物相对分子质量及链结构对PP/EPR共混体系结构与性能的影响

设计合成了一系列不同相对分子质量和乙烯平均序列长度的乙丙嵌段共聚物（EP）,并将其作为聚丙烯（PP）/二元乙丙橡胶（EPR）共混体系的增容剂,考察了EP用量、相对分子质量及乙烯平均序列长度对共混体系性能及分散相形态演变的影响。结果表明,EP增容PP/EPR体系时存在最佳添加量,少量EP的加入可有效提高PP/EPR共混体系的抗冲击性能,并对分散相尺寸及形态起到良好的调控作用;同时,EP的相对分子质量越大对共混体系的冲击性能提高越明显,EP的组成与EPR越接近,对共混体系的增容效果越明显。     

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     

Study on morphology of ternary polymer blends. I. Effects of melt viscosity and interfacial interaction

The morphology of some ternary blends was investigated. In all of the blends polypropylene, as the major phase, was blended with two different minor phases, ethylene–propylene–diene terpolymer (EPDM) or ethylene–propylene–rubber (EPR) as the first minor phase and high‐density polyethylene (HDPE) or polystyrene (PS) as the second minor phase. All the blends were investigated in a constant composition of 70/15/15 wt %. Theoretical models predict that the dispersed phase of a multiphase polymer blend will either form an encapsulation‐type phase morphology or phases will remain separately dispersed, depending on which morphology has the lower free energy or positive spreading coefficient. Interfacial interaction between phases was found to play a significant role in determining the type of morphology of these blend systems. A core–shell‐type morphology for HDPE encapsulated by rubber was obtained for PP/rubber/PE ternary blends, whereas PP/rubber/PS blends showed a separately dispersed type of morphology. These results were found to be in good agreement with the theoretical predictions. Steady‐state torque for each component was used to study the effect of melt viscosity ratio on the morphology of the blends. It was found that the torque ratios affect only the size of the dispersed phases and have no appreciable influence on the type of morphology. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1129–1137, 2001     

Morphologies of blends of isotactic polypropylene and ethylene copolymer by rapid expansion of supercritical solution and isobaric crystallization from supercritical solution

Isotactic polypropylene (iPP) and ethylene‐butene (EB) copolymers were dissolved in supercritical propane and precipitated by rapid expansion of supercritical solution (RESS) and isobaric crystallization from SS (ICSS). The cloud‐point pressures of the ternary solutions were found to increase as the immiscibility of PP and EB copolymer increased (i.e., as the number of ethyl branches in the EB copolymers decreased). The RESS process resulted in microfibers and a trace of microparticles, and the EB copolymer domains in the blends decreased in size as the ethyl branch content in the EB copolymers increased. The thermal stability of the copolymer domains was improved by synthesizing thermoplastic vulcanizate (TPV) from PP and ethylene‐propylene‐diene terpolymer in a supercritical propane solution followed by RESS. The ICSS process produced microcellular polymeric foamlike materials, but the two polymers were precipitated independently by thermally induced phase separation. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1478–1487, 2000     

Blends of propylene-ethylene and propylene-1-butene random copolymers: I. Morphology and structure

Samples of propylene-ethylene (EP) and propylene-(1-butene) (BP) random copolymers with various comonomer content (2-3.1 wt% ethylene, 9.9 wt% 1-butene), were melt-mixed in Brabender internal mixer at various compositions (25/75, 50/50, 75/25). Films of copolymers and blends, as well as of a homopolymer sample (iPP), obtained by compression moulding and with different thermal history were characterized by optical and scanning electron microscopy (OM, SEM), small-angle light scattering (SALS), small- and wide angle X-ray scattering (SAXS, WAXS) and differential scanning calorimetry (DSC). It was found that all copolymers and blends studied crystallized exclusively in monoclinic α-modification forming spherulitic structure in a very broad undercooling range. The average size of spherulites is smaller in the copolymer containing 1-butene as compared to those containing ethylene or to iPP homopolymer, due to enhanced heterogeneous nucleation in BP copolymer. SEM microscopic observations demonstrated that EP and BP copolymers were miscible at all examined compositions and form homogeneous blends. Structural and morphological analysis indicated that the comonomer units are incorporated into growing crystallites in both EP and BP copolymers, while the non-crystallizing material is rejected out of the crystallites. For small concentrations of comonomer some of non-crystallizing species are pushed ahead of the front of growing spherulite into interspherulitic regions. For higher comonomer concentration these species are mostly trapped in intraspherulitic regions. Melting behavior of copolymers reflects the incorporation of comonomer into crystalline phase: melting temperature and crystallinity degree decrease in copolymers and blends as compared to plain iPP.     

An investigation on recycled PET/PP and recycled PET/PP‐EP compatibilized blends: Rheological,morphological, and mechanical properties

The effectiveness of P(E‐co‐MA‐co‐GMA) as a compatibilizer for recycled PET/PP and recycled PET/PP‐EP (polypropylene (ethylene‐propylene) heterophase copolymer) blends was investigated by means of morphological (scanning electron microscopy), rheological (small amplitude oscillatory shear), mechanical (tensile, flexural and impact tests), and thermal (differential scanning calorimetry) properties. Compatibilizer concentration ranged from 1 to 5 wt % with respect to the whole blend. All blends were obtained in a 90/10 composition using a twin screw extruder. Compatibilization effects for PETr/PP‐EP were more pronounced due to ethylene segments present in both PP‐EP and P(E‐co‐EA‐co‐GMA). PETr/PP‐EP has shown greater dispersed phase size reduction, a more solid‐like complex viscosity behavior and larger storage modulus at low frequencies in relation to PETr/PP blend. For both investigated blends, mechanical properties indicated an improvement in both elongation at break and impact strength with increasing compatibilizer content. PETr/PP‐EP blends showed improved performance for the same level of compatibilizer content. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41892.     

Effect of ultrasound on extrusion of polypropylene/ethylene–propylene–diene terpolymer blend: Processing and mechanical properties

The effects of ultrasonic irradiation on extrusion processing and mechanical properties of polypropylene (PP)/ethylene–propylene–diene terpolymer (EPDM) blends are examined. Results show that appropriate irradiation intensity can prominently decrease die pressure and apparent viscosity of the melt, increase output, as well as increase toughness of PP/EPDM blends without harming rigidity. In case the blends are extruded with ultrasonic irradiation twice, the impact strength of the blend rises sharply at 50–100 W ultrasonic intensity, and amounts to more than 900 J/m, 1.5 times as high as that of blend without ultrasonic irradiation. Scanning electron microscopy observation shows that with ultrasonic irradiation, morphology of uniform dispersed EPDM phase and good adhesion between EPDM and PP matrix was formed in PP/EPDM blend. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3519–3525, 2003     

Evaluation of olefinic block copolymer blends with amorphous polyolefins—effect of different unsaturated and saturated hydrocarbon tackifier resins on blend miscibility

Blends of ethylene–octene based olefinic block copolymer (OBC) with two amorphous polyolefin (APO) polymers [atactic propylene homopolymer (PP) and ethylene–propylene copolymer (PE–PP)] were evaluated at three different ratios. Dynamic mechanical analysis (DMA) and transmission electron microscopy (TEM) evaluations were performed to determine the blend miscibility characteristics. Viscoelastic properties of both OBC blends with PP polymer, and OBC blends with PE–PP copolymer showed incompatibility. Analysis revealed that both blends formed two phase morphologies. The effect of three unsaturated aliphatic hydrocarbon resins with varying aromatic content and two saturated hydrocarbon resins with different chemistries were evaluated as compatibilizing agent for OBC/PP and OBC/PE–PP blends. A 1 : 1 polymer blend ratio of OBC/PP and OBC/PE–PP was selected to better understand the influence of resin addition at three different levels 20, 30, and 40 wt %. The fully aliphatic unsaturated resin seems to improve the miscibility of the OBC/PP blends at higher resin addition levels, but reduced the miscibility as the aromatic content of the resin increases. However, OBC/PE–PP blends showed improved miscibility with increasing aromatic content. A ternary phase morphology was particularly observed for both OBC/PP and OBC/PE–PP blends with highly aromatic (14%) unsaturated hydrocarbon resin, in which OBC formed the continuous phase, and PP, PE–PP, and unsaturated hydrocarbon resins formed the dispersed phase. Interestingly, we did not observe much difference in miscibility characteristics between the two saturated resin chemistries in both blend systems (OBC/PP and OBC/PE–PP). The Harkins spreading coefficient concept was used to better understand the ternary blend dispersed phase morphology. Spreading coefficients indicate that the free hydrocarbon resins (both unsaturated and saturated) were encapsulated by the amorphous PP or amorphous PE–PP polymer in the dispersed phase for the respective blend compositions. Overall OBC–PP and OBC/PE–PP blends showed better miscibility characteristics with both saturated aliphatic hydrocarbon resins, irrespective of the difference in resin chemistries. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2624–2644, 2013     

Compatibilization of PP/EPDM blends by grafting acrylic acid to polypropylene and epoxidizing the diene in EPDM

In this article, ethylene–propylene–diene‐rubber (EPDM) was epoxidized with an in situ formed performic acid to prepare epoxided EPDM (eEPDM). The eEPDM together with the introduction of PP‐g‐AA was used to compatibilize PP/EPDM blends in a Haake mixer. FTIR results showed that the EPDM had been epoxidized. The reaction between epoxy groups in the eEPDM and carboxylic acid groups in PP‐g‐AA had taken place, and PP‐g‐EPDM copolymers were formed in situ. Torque test results showed that the actual temperature and torque values for the compatibilized blends were higher than that of the uncompatibilized blends. Scanning electron microscopy (SEM) observation showed that the dispersed phase domain size of compatibilized blends and the uncompatibilized blends were 0.5 and 1.5 μm, respectively. The eEPDM together with the introduction of PP‐g‐AA could compatibilize PP/EPDM blends effectively. Notched Izod impact tests showed that the formation of PP‐g‐EPDM copolymer improved the impact strength and yielded a tougher PP blend. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3949–3954, 2006     

Multilayered core–shell structure of the dispersed phase in high‐impact polypropylene

The multiphase morphology of high impact polypropylene (hiPP), which is a reactor blend of polypropylene (PP) with ethylene–propylene copolymer, was investigated by transmission electron microscopy, selected area electron diffraction, atomic force microscopy, and field‐emission scanning electron microscopy techniques in conjunction with an analysis of the hiPP composition and chain structure based on solvent fractionation, ¹³C‐NMR, and differential scanning calorimetry measurements. A multilayered core–shell structure of the dispersed phase of hiPP in solution‐cast films and the bulk was observed. The inner core was mainly composed of polyethylene (including its long blocks) together with part of PP, the intermediate layer was ethylene–propylene random copolymer, and the outer shell consisted of ethylene–propylene multiblock copolymers. The formation process and controlling factors of the multilayered core–shell structure are discussed. This kind of multiphase morphology of hiPP caused the material to possess both a high rigidity and high toughness. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermal properties and crystallization behavior of polyolefin ternary blends

Crystallization behaviors, spherulite growth and structure, and the crystallization kinetics of polypropylene (PP)/ethylene‐α‐olefln copolymer (mPE)/high‐density polyethylene (HDPE) ternary blends and of mPE/HDPE binary blends have been studied using polarizing optical micrography (POM) and differential scanning calorimetry (DSC). In mPE/HDPE blends, large pendant groups of mPE disturbed spherulite growth of HDPE, leading to a different crystallite morphology and isothermal kinetics. Non‐isothermal properties, morphology, and isothermal crystallization kinetics of PP in ternary blends were significantly influenced by the composition and crystallization behavior of the mPE/HDPE binary blends as well as the crystallization condition. Polym. Eng. Sci. 44:1858–1865, 2004. © 2004 Society of Plastics Engineers.     

Mechanical properties and morphology of polyethylene–polypropylene blends with controlled thermal history

The effect of time–temperature treatment on the mechanical properties and morphology of polyethylene–polypropylene (PE–PP) blends was studied to establish a relationship among the thermal treatment, morphology, and mechanical properties. The experimental techniques used were polarized optical microscopy with hot‐stage, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and tensile testing. A PP homopolymer was used to blend with various PEs, including high‐density polyethylene (HDPE), low‐density polyethylene (LDPE), linear low‐density polyethylene (LLDPE), and very low density polyethylene (VLDPE). All the blends were made at a ratio of PE:PP = 80:20. Thermal treatment was carried out at temperatures between the crystallization temperatures of PP and PEs to allow PP to crystallize first from the blends. A very diffuse PP spherulite morphology in the PE matrix was formed in partially miscible blends of LLDPE–PP even though PP was present at only 20% by mass. Droplet‐matrix structures were developed in other blends with PP as dispersed domains in a continuous PE matrix. The SEM images displayed a fibrillar structure of PP spherulite in the LLDPE–PP blends and large droplets of PP in the HDPE–PP blend. The DSC results showed that the crystallinity of PP was increased in thermally treated samples. This special time–temperature treatment improved tensile properties for all PE–PP blends by improving the adhesion between PP and PE and increasing the overall crystallinity. In particular, in the LLDPE–PP blends, tensile properties were improved enormously because of a greater increase in the interfacial adhesion induced by the diffuse spherulite and fibrillar structure. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1151–1164, 2000     

Compatibilization of poly(vinyl chloride) with polyamide and with polyolefin by using poly(lauryllactam‐random‐caprolactam‐block‐caprolactone)

The compatibilization of various poly(vinyl chloride) (PVC) blends was investigated. The blend systems were PVC‐polyamide 12 (PA12), PVC‐polypropylene (PP), and PVC‐ethylene‐propylene‐diene rubber (EPDM) with a new compatibilizing agent, random‐block terpolymer poly(ω‐lauryllactam‐random‐?‐caprolactam‐block‐?‐caprolactone) or systems containing these copolymers. The results were compared to those obtained in previous studies using poly(ω‐lauryllactam‐block‐?‐caprolactone) copolymer. The new block copolymer was specially synthesized by reactive extrusion. Observation by scanning electron microscopy (SEM) revealed that compatibilized blends had a finer morphology than the noncompatibilized blends. Addition of 10 weight percent (wt%) of block copolymer proved to be sufficient to give a significant improvement of the mechanical properties of the immiscible PVC blends at room temperature and at high temperatures that were above the glass transition temperature of PVC. For polyolefins, a three‐component compatibilizing system including maleated polypropylene, polyamide 12, and block copolymer was used. It was found that poly(ω‐lauryllactam‐random‐?‐caprolactam‐block‐?‐caprolactone) was the more efficient compatibilizing agent for the modification of PVC‐polyamide 12, PVC‐polypropylene, and PVC‐ethylene‐propylene‐diene rubber blends. J. VINYL. ADDIT. TECHNOL., 11:95–110, 2005. © 2005 Society of Plastics Engineers     

Effects of dispersed phase composition on thermoplastic polyolefins

Ternary blends of polypropylene (PP), ethylene–octene copolymer (mPE), and high‐density polyethylene (HDPE) were prepared based on the phase behavior and physical properties of mPE/HDPE binary blends, and the results were interpreted in terms of morphology and both rheological and mechanical properties of the ternary blends as well as the binary blends. It was found that when mPE encapsulates HDPE in the PP matrix, compared to the encapsulation of mPE by HDPE, better blend properties were obtained, presumably because of the compatibilizing effect of mPE between PP and HDPE. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 179–188, 2004     

Effect of ultrasound on extrusion of PP/EPDM blends: Structure and mechanical properties

The effects of ultrasonic irradiation on the mechanical properties, morphology, and crystal structure of polypropylene (PP)/ethylene‐propylene‐diene terpolymer (EPDM) blends were examined. Results show that appropriate irradiation intensity can noticeably increase the toughness of the PP/EPDM blends without reducing rigidity. Scanning electron microscopic (SEM) observation shows that with ultrasonic irradiation, the morphology of a well‐dispersed EPDM phase is formed in the PP/EPDM blend. The glass transition temperatures of PP and EPDM phase approach each other as a result of ultrasonic irradiation. Differential Scanning Calorimetric (DSC) analysis indicates that the crystallinities of the PP and EPDM phases increase with ultrasonic irradiation, and β crystals of PP form in the PP/EPDM blend with ultrasonic irradiation, which is proven by wide angle X‐ray diffraction (WAXD) analysis. Polym. Eng. Sci. 44:1509–1513, 2004. © 2004 Society of Plastics Engineers.     

The effect of addition of different elastomers upon the crystalline nature of PP

Thermal and morphological studies have been performed on polymer blends based on ethylene–octene copolymer (PEE)/PP and ethylene–propylene–diene copolymer (EPDM)/PP. The thermal and morphological behavior of PEE, EPDM, PEE/PP, and EPDM/PP systems were analyzed by differential scanning calorimetry (DSC) and polarizing light microscopy, respectively. It was observed that the behaviors of crystallization kinetics of PEE/PP and EPDM/PP blends were similar. It was also observed that addition up to 10–20% (w/w) of elastomers resulted in increasing of spherulite size. The heat of fusion (ΔH_f) and crystallinity degree of PEE/PP and EPDM/PP systems decreased when the elastomer contents were increased. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3530–3537, 2001