The crystallization and transition behavior of poly(vinylidene fluoride)/copoly(chlorotriofluorethylene-vinylidene fluoride) blends

Thermal analysis of solution precipitated blends of two crystallizable polymers, poly(vinylidene fluoride) (PVDF) and copoly(chlorotrifluorethylene-vinylidene fluoride) (copoly(CTFE-VDF)), has been carried out to study the transition temperatures, crystallinity, and crystallization rates. PVDF crystallizes over the whole blend composition either during precipitation from solution or upon cooling from the melt. The high degree of crystallinity attained, higher than in PVDF by itself, suggests the occurrence of partial PVDF-copolymer cocrystallization. The melt crystallization temperature, decreasing with cooling rate, is lower in PVDF-rich blends than for lean blends. However, the heat of crystallization increases with cooling rate, suggesting that the crystal composition depends on crystallization rate. No significant melting temperature depression due to blending was observed. However, the blends glass transition (T_g) changes linearly with composition, but less than expected by any mixing rule applicable to compatible systems. Annealing of the blends above T_g results in an additional crystalline phase consisting mainly of the copolymer. The amount of these crystals increases with PVDF content, due to partial cocrystallization and kinetic effects. The addition of the copolymer to PVDF results in a volume-filling spherulitic structure consisting of spherulites which decrease in size with increasing copolymer content.     

Primary structure and physical properties of poly(ethylene terephthalate)/poly(ethylene naphthalate) resin blends

The morphology and properties of blends of poly(ethylene naphthalate) (PEN) and poly(ethylene terephthalate) (PET) that were injection molded under various conditions were studied. Under injection molding conditions that make it possible to secure transparency, blends did not show clear crystallinity at blending ratios of more than 20 mol% in spite of the fact that crystallinity can be observed in the range of PEN content up to 30 mol%. Because both transparency and crystallinity could be secured with a PEN 12 mol% blend, this material was used in injection molding experiments with various injection molding cycles. Whitening occurred with a cycle of 20 sec, and transparency was obtained at 30 sec or more. This was attributed to the fact that transesterification between PET and PEN exceeded 5 mol% and phase solubility (compatibility) between the PET and PEN increased when the injection molding time was 30 sec or longer. However, when the transesterification content exceeded 8 mol%, molecularly oriented crystallization did not occur, even under stretching, and consequently, it was not possible to increase the strength of the material by stretching. PET/PEN blend resins are more easily crystallized by stretch heat‐setting than are PET/PEN copolymer resins. It was understood that this is because residual PET, which has not undergone transesterification, contributes to crystallization. However, because transesterification reduces crystallinity, the heat‐set density of blends did not increase as significantly as that of pure PET, even in high temperature heat‐setting. Gas permeability showed the same tendency as density. Namely, pure PET showed a substantial decrease in oxygen transmission after high temperature heat‐setting, but the decrease in gas permeability in the blend material was small at heat‐set temperatures of 140°C and higher.     

Morphology and thermal properties of maleic anhydride grafted polypropylene/ethylene–vinyl acetate copolymer/wood powder blend composites

Maleic anhydride grafted polypropylene (MAPP) was blended with ethylene–vinyl acetate (EVA) copolymer to form MAPP/EVA polymer blends. Wood powder (WP) was mixed into these blends at different weight fractions to form MAPP/EVA/WP blend composites. Differential scanning calorimetry (DSC) analysis of the blends showed small melting peaks between those of EVA and MAPP, which indicated interaction and cocrystallization of fractions of EVA and MAPP. The presence of MAPP influenced the EVA crystallization behavior, whereas the MAPP crystallization was not affected by the presence of EVA. Scanning electron microscopy, Fourier transform infrared spectroscopy, and DSC results show that the WP particles in the MAPP/EVA blend were in contact with both the MAPP and EVA phases and that there seemed to be chemical interaction between the different functional groups. This influenced the crystallization behavior, especially of the MAPP phase. The thermogravimetric analysis results show that the MAPP/EVA blend had two degradation steps. An increase in the WP content in the blend composite led to an increase in the onset of the second degradation step but a decrease in onset of the first degradation step. The presence of WP in the blend led to an increase in the modulus but had almost no influence on the tensile strength of the blend. The dynamic mechanical analysis results confirm the interaction between EVA and MAPP and show that the presence of WP only slightly influenced the dynamic mechanical properties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Rheological and thermal properties of binary blends of polypropylene and poly(ethylene‐CO‐1‐octene)

Dynamic viscoelastic properties of binary blends consisting of an isotactic polypropylene (i‐PP) and ethylene‐1‐octene copolymer (PEE) were investigated to reveal the relation between miscibility in the molten state and the morphology in the solid state. In this study, PEE with 24 wt % of 1‐octene was employed. The PEE/PP blend with high PEE contents showed two separate glass‐relaxation processes associated with those of the pure components. These findings indicate that the blend presents a two‐phase morphology in the solid state as well as in the molten state. The PEE/PP blend with low PEE content showed a single glass‐relaxation process, indicating that PEE molecules were probably incorporated in the amorphous region of i‐PP in the solid state. The DMTA analysis showed that the blends with low PEE contents presented only one dispersion peak, indicating a certain degree of miscibility between the components of these blends. These results are in accordance with the results of the rheological analysis. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1634–1639, 2001     

Morphology and mechanical properties of biaxially oriented films of polypropylene and HDPE blends

Biaxially oriented films of blends of high-density polyethylene (HDPE) with polypropylene (PP) homopolymer and PP copolymers prepared by twin-screw extrusion and lab-stretcher have been investigated by scanning electron microscopy (SEM), polarized microscopy, differential-scanning calorimeter, and universal testing machine. Three different kinds of PP copolymers were used: (i) ethylene–propylene (EP) random copolymer; (ii) ethylene–propylene (EP) block copolymer; (iii) ethylene–propylene–buttylene (EPB) terpolymer. In the SEM study of the morphology of films of HDPE with various PP blends, phase separation is observed between the PP phase and the HDPE phase for all blends and compositions. In all blends, HDPE serves to reduce the average spherulites size, probably acting as a nucleating agent for PP. The reduction of spherulite size appeared most significantly in the blend of EPB terpolymer and HDPE. A large increase of crystallization temperature was found in the blend of EPB terpolymer and HDPE compared with the unblended EPB terpolymer. For the blend of EPB terpolymer and HDPE, the improvement of tensile strength and modulus is observed with an increase of HDPE content, and this can be considered as a result of the role of HDPE in reducing average spherulite size. © 1994 John Wiley & Sons, Inc.     

Fractionation and characterization of an ethylene–propylene copolymer produced with a MgCl2/SiO2/TiCl4/diester‐type ziegler–natta catalyst

An ethylene–propylene copolymer synthesized with a Ziegler–Natta catalyst was fractionated by a combination of dissolution/precipitation and temperature‐gradient extraction fractionation. The fractions were characterized with ¹³C‐NMR, differential scanning calorimetry, and wide‐angle X‐ray diffraction. The fractionation was carried out mainly with respect to the content of ethylene, but the crystallizable propylene sequences could also exert an influence on the fractionation. The copolymer contained a series of components with wide variations in the compositions. With an increase in the ethylene content, the structure of the fractions became blockier and blockier, and the fraction extracted at 111°C had the blockiest structure. A further increase in the ethylene content led to a decrease in the length and number of the propylene sequences. Differential scanning calorimetry results showed that the composition distribution in single fractions was not homogeneous, and multiple melting peaks were observed. Wide‐angle X‐ray diffraction results revealed both polyethylene and polypropylene crystals in most of the fractions. Short propylene sequences could be included in the polyethylene crystals, and short ethylene sequences could also be incorporated into the polypropylene crystals. The incorporation of propylene sequences into polyethylene crystals strongly depended on the sequence distribution and crystallization conditions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

High pressure crystallization of random propylene-ethylene copolymers: α-γ Phase diagram

Two random propylene copolymers with low ethylene content synthesized by Ziegler-Natta catalysts were used is this study to investigate the formation of γ-crystal phase during isothermal crystallization at high pressures. At atmospheric pressure these copolymers crystallize in a mixture of α- and γ-crystals. The content of the γ-phase in the copolymer crystals increased with increasing defect content, crystallization temperature and pressure. Wide-angle X-ray diffraction studies showed that crystallization of these copolymers at pressures above 88 MPa and temperature above 142 °C leads to formation of pure γ-phase. The equilibrium melting temperature of the γ-phase has been determined as a function of defect content and crystallization pressure. Temperature-pressure-composition α-γ phase diagram of isotactic polypropylene was constructed based on the Gibbs free energy approach. This diagram enabled the extrapolation of the equilibrium melting temperatures of both phases for defect free isotactic polypropylene. They were found to be 186.9°C for the α-phase and 189.9°C for the γ-phase.     

Crystallization of PP in PP/SEBS blends and its correlation with tensile properties

Crystallization of polypropylene (PP) in the blends of PP with styrene–ethylene butylene–styrene triblock copolymer (SEBS) is studied through differential thermal analysis (DTA) and X-ray diffraction measurements. Analysis of crystallization exotherm peaks in terms of crystallization nucleation and growth rates, crystallite size distribution, and crystallinity revealed differences in the morphology of PP component in the blend in the different regions of blend composition. Crystallinity determined by X-ray diffraction and DTA showed identical variations with blend composition. Variations in tensile properties of these blends with blend composition are also reported. Correlations of the various tensile properties with the crystallization parameters, viz., the crystallinity and crystallite size distribution, are presented, which confirm the influence of crystallization of PP component on the tensile properties of these blends.     

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     

聚丙烯/乙丙抗冲共聚物合金结晶行为研究

实验室聚合得到乙烯单元含量分别为0.94 %、1.67 %、3.00 %(摩尔分数,下同)的聚丙烯/乙丙抗冲共聚物（PP/EPR）合金样品,用差示扫描量热法研究了样品的等温结晶和非等温结晶行为。实验结果表明,各样品在不同温度下的等温结晶均符合Avrami方程;同一样品,等温结晶温度越高,结晶所需要的时间就越长,结晶速率越低,非等温结晶时随着降温速率的增加,结晶温度范围变宽并向低温移动;对于不同样品,等温结晶的结晶速率随乙烯单元含量增加而降低,但当乙烯单元含量为3.00 %时出现相反的情况,非等温结晶时的结晶温度也有同样的规律。     

Crystallization Behavior of the Blends of Isotactic Polypropylene and Ethylene-Propylene Blocky Copolymers

Two ethylene-propylene copolymer fractions (EP90 and EP120) were separated from a polypropylene in-reactor alloy by extraction with n-octane at different temperatures. ¹³C-NMR shows that these two fractions have a blocky structure and WAXD reveals that both ethylene and propylene sequences in these two fractions are crystallizable. However, EP90 has higher propylene content and the average length of propylene sequences is longer. These two fractions were blended with isotactic polypropylene (PP) at various proportions, respectively, and crystallization behavior and morphology of the blends were investigated. It is found that both EP90 and EP120 are partially compatible with PP. The phase-separated domains have a nucleation effect on crystallization of PP, leading to increase in crystallization temperature and crystallinity of PP in the blends. EP90 and EP120 also affect the relative content of β crystals in an irregular way. The number of EP90-rich domains in PP/EP90 blends is larger than that of EP120-rich domains in PP/EP120 blends, but the size of EP90-rich domains is smaller, indicating that EP90 has better compatibility with PP than EP120. Spherulites are formed in all the blends. The data were analyzed with Hoffman-Lauritzen theory of crystallization regime and the free energy of the folding surface (σ_e) was derived. Addition of EP90 and EP120 has little effect on the transition temperature from regime II to regime III. The value of σ_e for the PP/EP90 blends is similar to that of neat PP, but σ_e of the PP/EP120 blends is a little higher than that of neat PP.     

Crystallization behavior of PEO in blends of poly(ethylene oxide)/poly(2‐vinyl pyridine)‐b‐(ethylene oxide) block copolymer

The crystallization behavior of two molecular weight poly(ethylene oxide)s (PEO) and their blends with the block copolymer poly(2‐vinyl pyridine)‐b‐poly(ethylene oxide) (P2VP‐b‐PEO) was investigated by polarized optical microscopy, thermogravimetric analysis, differential scanning calorimetry, and atomic force microscopy (AFM). A sharp decreasing of the spherulite growth rate was observed with the increasing of the copolymer content in the blend. The addition of P2VP‐b‐PEO to PEO increases the degradation temperature becoming the thermal stability of the blend very similar to that of the block copolymer P2VP‐b‐PEO. Glass transition temperatures, T_g, for PEO/P2VP‐b‐PEO blends were intermediate between those of the pure components and the value increased as the content of PEO homopolymer decreased in the blend. AFM images showed spherulites with lamellar crystal morphology for the homopolymer PEO. Lamellar crystal morphology with sheaf‐like lamellar arrangement was observed for 80 wt% PEO(200M) and a lamellar crystal morphology with grain aggregation was observed for 50 and 20 wt% blends. The isothermal crystallization kinetics of PEO was progressively retarded as the copolymer content in the blend increased, since the copolymer hinders the molecular mobility in the miscible amorphous phase. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

The melt compatibility of blends of polypropylene and ethylene-propylene copolymers

Blends of polypropylene with ethylene-propylene copolymers of various compositions have been studied by small angle neutron scattering with regard to their compatibility at room temperature and in the melt. It has long been known that such blends separate into distinct phases at lower temperatures due to the crystallinity of the isotactic polypropylene, The work described herein has shown that these blends are also immiscible in the melt, even where the ethylene content of the copolymer is as low as 8 percent. Moreover, the separated phase domains grew rapidly at melt temperatures. Blends of atactic polypropylene with isotactic polypropylene did become miscible upon melting.     

LLDPE/LDPE blends. I. Rheological,thermal, and mechanical properties

Structure and mechanical properties were studied for the binary blends of a linear low density polyethylene (LLDPE) (ethylene‐1‐hexene copolymer; density = 900 kg m⁻³) with narrow short chain branching distribution and a low density polyethylene (LDPE) which is characterized by the long chain branches. It was found by the rheological measurements that the LLDPE and the LDPE are miscible in the molten state. The steady‐state rheological properties of the blends can be predicted using oscillatory shear moduli. Furthermore, the crystallization temperature of LDPE is higher than that of the LLDPE and is found to act as a nucleating agent for the crystallization of the LLDPE. Consequently, the melting temperature, degree of crystallinity, and hardness of the blend increase rapidly with increases in the LDPE content in the blend, even though the amount of the LDPE in the blend is small. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3153–3159, 1999     

Linear low-density polyethylene/poly(ethylene-ran-butene) elastomer blends: Miscibility and crystallization behavior

The phase and crystallization behavior of the blends consisting of LLDPE (0.7 mol% hexene copolymer) and PEB (26 mol% butene copolymer) have been investigated using optical microscopy (OM), differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD). The blends exhibited an upper critical solution temperature of 162°C. The solubility parameter analysis showed that the solubility parameter of LLDPE decreased more rapidly than that of PEB with temperature. However, due to the slow kinetics of phase separation, at lower crystallization temperatures, the crystallization and melting behavior of LLDPE mainly reflected the miscibility between LLDPE and PEB. Crystallization from the two-phase state could present two crystallization peaks. PEB didnt change the crystal cell unit and crystallinity of LLDPE, but changed its distribution of lamellar thickness or crystal perfection. The dilute effect of PEB also changed the overall nature of the nucleation and growth process of LLDPE. The equilibrium melting temperature in this blend could be obtained by the Hoffman-Weeks method, and comparing with that of the pure LLDPE, it was reduced and kept relatively constant in the bi-phase state. The phase diagram made up of the LLPS boundary, equilibrium melting temperatures and melting temperatures observed may be better to indicate the phase and crystallization behavior of LLDPE/PEB blends.     

Synthesis and characterization of macromolecular surface modifier PP--PEG for polypropylene

A novel macromolecular surface modifier, polypropylene-grafted-poly(ethylene glycol) copolymer (PP-g-PEG), was synthesized by coupling polypropylene containing maleic anhydride with monohydroxyl-terminated poly(ethylene glycol). The effects of the reaction condition on the graft reactions were studied. The copolymers were characterized by IR, ¹H NMR, thermogravimetry (TG) and differential scanning calorimetry (DSC). The results indicated that the graft reactions were hindered by increasing the molecular weight of PP or PEG. The graft copolymer was found to have a higher initial thermal degradation temperature and lower crystallization capacity as compared with pure PP, and the side chain of PEG hindered the PP chain from forming a perfect ? crystal. The thermal stability of PP-g-PEG decreased with the increasing content or molecular weight of PEG. The copolymers were blended with polypropylene to modify the surface hydrophilicity of the products. The results of attenuated total reflectance FTIR spectroscopy (ATR-FTIR) showed that PP-g-PEG could diffuse preferably onto the surface of the blends and be suitable as an effectual macromolecular surface modifier for PP.     

Cocrystallization and miscibility studies of blends of ultrahigh molecular weight polyethylene with conventional polyethylenes

Ultrahigh molecular weight polyethylene (UHMWPE) was mechanically mixed with conventional polyethylenes (LLDPE, HDPE, and LLDPE) using an internal mixer. Rheological studies of these blends suggest that UHMWPE seems to be miscible with LLDPE, HDPE, and LDPE in the melt state. Yield characteristics are observed in all blend systems, particularly in high UHMWPE blend compositions. Differential scanning calorimetry and small-angle light scattering studies show that cocrystallization takes place in the blends of UHMWPE/LLDPE and UHMWPE/HDPE blends. However, separate crystals are formed in UHMWPE/LDPE. The formation of separate crystals may be attributed to long chain branching of conventional low-density polyethylene. Tensile properties of the former two blends vary almost linearly with blend compositions, while deviations are seen in the latter UHMWPE/LDPE blends.     

Interfacial crystallization and its mechanism in in-situ dynamically vulcanized iPP/POE blends

The effect of in-situ crosslinking of poly (ethylene-co-octene) (POE) rubber phase on the interfacial crystallization of isotactic polypropylene (iPP) in dynamically vulcanized iPP/POE blends was studied. The results showed that in situ crosslinking of POE obviously increased the interfacial crystallization of iPP in the dynamically vulcanized blends, comparing with that of pure iPP and the unvulcanized blend. The interfacial crystallization of iPP was further increased with the increase in crosslink degree. After annealing, the obvious interfacial crystallization was still obtained in the blend with high crosslink degree. Based on the fluctuation assisted nucleation mechanism in solution blended iPP/polyolefin block copolymer (OBC) blends, we proposed for the first time the interfacial crystallization mechanism in dynamically vulcanized blends: the oriented chains of iPP formed by concentration fluctuation at the interface during phase separation or shearing stress during melt mixing can be maintained because of the in situ crosslinking of POE phase, resulting in the enhancement of nucleation density at the iPP/POE interface. Our study proposes a new interfacial crystallization mechanism, and provides guidance for the preparation of high performance thermoplastic vulcanizates (TPVs) product by tailoring the interfacial crystallization of TPVs.     

Uniaxial deformation of an elastomer nanocomposite containing modified carbon nanofibers by in situ synchrotron X-ray diffraction

Structure and property of a nanocomposite consisting of modified carbon nanofibers (MCNFs), homogenously dispersed in an elastomeric ethylene/propylene (EP) random copolymer (84.3 wt% P) matrix, were studied by in situ synchrotron X-ray diffraction during uniaxial deformation. The MCNF acted as a nucleating agent for crystallization of the α-form of isotactic polypropylene (iPP) in the matrix. During deformation at room temperature, strain-induced crystallization took place, while the transformation from the γ phase to α phase also occurred for both unfilled and 10 wt% MCNF-filled samples. The tensile strength of the filled material was consistently higher than that of pure copolymer. However, when compared with pure copolymer, the highly stretched nanocomposite exhibited a higher amount of unoriented crystals, a lower degree of crystal orientation and a higher amount of γ crystals. This behavior indicated that polymer crystals in the filled nanocomposite experienced a reduced load, suggesting an effective load transfer from the matrix to MCNFs. At elevated temperatures, the presence of MCNFs resulted in a thermally stable physically cross-linked network, which facilitated strain-induced crystallization and led to a remarkable improvement in the mechanical properties. For example, the toughness of the 10 wt% nanocomposite was found to increase by a factor of 150 times at 55 °C.     

Blends and thermoplastic interpenetrating polymer networks of polypropylene and polystyrene-block-poly(ethylene-stat-butylene)-block-polystyrene triblock copolymer. 1: Morphology and structure-related properties

Blends of polypropylene (PP), the triblock copolymer polystyrene-block-poly(ethylene-stat-butylene)-block-polystyrene (SEBS), and processing oil were found to form thermoplastic interpenetrating polymer network (IPN) structures in a composition range from about 10 to 55% by weight polypropylene. The IPN structure was confirmed by electron microscopy and by solvent extraction. At high elongations, the cocontinuous blends showed a stress-strain behavior similar to rubber and no signs of the typical necking phenomenon normally associated with polypropylene at large deformations. The processing oil used to improve the processing properties of SEBS was found to partly dissolve in the polypropylene phase, causing a marked lowering of the polypropylene glass-transition temperature. The distribution coefficient for oil between polypropylene and SEBS was estimated to be 0.35. While the degree of crystallinity of polypropylene did not vary with blend composition, the melting temperature decreased from 162.7°C in the pure polypropylene to 149.3°C in the blend with lowest polypropylene content. The large melting point depression suggests that polypropylene, the EB fraction of SEBS, and the oil may form a homogeneous melt phase. This probably explains the formation of an IPN structure on cooling.