Epitaxial Crystallization of Linear Polyethylene in Blends with Isotactic Polypropylene

The structure and morphology of extrusion-oriented ribbons of polypropylene/polyethylene blends is described. The blends with 20%, 30%, and 40% of oriented isotactic polypropylene fibrils show homo- and heteroepitaxial structures. Partial mutual solubility of the blend components influenced the melting and crystallization behavior.     

Isothermal Crystallization and Miscibility of Isotactic Polypropylene/Poly(cis-butadiene) Rubber Blends

Isotactic polypropylene/poly(cis-butadiene) rubber (iPP/PcBR) blends were prepared by melt mixing. Isothermal crystallization and miscibility for neat iPP and blends of iPP/PcBR were investigated by differential scanning calorimetry. The presence of PcBR remarkably affected isothermal crystalline behaviors of iPP. An addition of PcBR caused shorter crystallization time and a faster overall crystallization rate, meaning a heterogeneous nucleation effect of PcBR upon crystallization of iPP. For the same sample, the crystallization peak was broader and the supercooling decreased as the crystallization temperature increased. The Avrami equation was suitable to describe the primary isothermal crystallization process of iPP and blends. The addition of PcBR led to an increase of values of the Avrami exponent n, which we suggest was because the blends had a stronger trend of instantaneous three-dimensional growth than neat iPP. The equilibrium melting point depression of the blends was observed, indicating that the blends were partly miscible in the melt.     

Properties and Crystallization Behaviors of Isotactic Polypropylene Under Action of an Effective Nucleating Agent

The calcium salt of hexahydrophthalic acid (Hyperform HPN-20E) is an effective nucleating agent for polyethylene which was developed by Milliken Chemical Co., (USA) in recent years. In this paper, the properties and crystallization behaviors of isotactic polypropylene (iPP) in the presence of Hyperform HPN-20E were investigated by using differential scanning calorimetry and polarized optical microscopy. Addition of Hyperform HPN-20E improved the tensile, flexural and optical properties of iPP significantly and increased the crystallization rate of iPP greatly. The nucleation effects were comparable to the nucleation efficiency of a highly effective commercial iPP nucleating agent Hyperform HPN-68. When the addition amount of Hyperform HPN-20E in iPP was 0.2 wt.%, the tensile strength, tensile modulus, flexural strength, and flexural modulus of iPP were increased by 10.81%, 8.65%, 16.67%, and 11.96%, respectively, compared to those of pure iPP; the haze value was decreased by 42.44% and the crystallization peak temperature was increased by 11.2°C. In addition, incorporation of Hyperform HPN-20E in iPP greatly reduced the spherulite size of iPP.     

Crystalline Morphology and Nonisothermal Crystallization Behaviors of iPP/PcBR Blends

Isotactic polypropylene/poly(cis‐butadiene) rubber (iPP/PcBR) blends were prepared by melt mixing. The influence of PcBR content on crystalline morphology and nonisothermal crystallization behaviors of iPP was investigated by polarized optical microscopy (POM), small angle light scattering (SALS), and differential scanning calorimetry (DSC). The POM showed that an increase of PcBR ranging from 10 vol% to 40 vol% led to less perfection of spherulites, vaguer boundaries between spherulites, and smaller spherulite size, which was quantitatively validated by SALS. The presence of PcBR also remarkably affected the nonisothermal crystallization behaviors of iPP. An addition of PcBR caused higher crystallization peak temperature and a faster crystallization rate, meaning a heterogeneous nucleation effect of PcBR upon crystallization of iPP. For the same sample, the crystallization peak temperature moved to lower temperature and the crystallization rate increased as the cooling rate increased. The Ozawa and combined Avrami and Ozawa equations were used to describe the nonisothermal crystallization process of iPP and blends. The combined Avrami and Ozawa equation was more appropriate for the crystallization of the blends. Crystallization activation energy of iPP and blends was calculated by the Kissinger equation; the result showed that crystallization activation energy decreased as the content of PcBR increased from 30 vol% to 40 vol%.     

Mechanical Properties and Crystallization Behavior of Polycarbonate/Polypropylene Blends

The mechanical properties, morphology, and crystallization behavior of polycarbonate (PC)/polypropylene (PP) blends, with and without compatibilizer, were studied by tensile and impact tests, scanning electron microscopy (SEM), X-ray diffraction (XRD), and differential scanning calorimetry (DSC). The tensile and impact strengths of PC/PP blends decreased with increasing the PP content due to poor compatibility between the two phases. But the addition of compatibilizer improved the mechanical properties of the PC/PP blends, and the maximum value of the mechanical properties, such as tensile and impact strengths of PC/PP (80/20 wt%) blends, were obtained when the compatibilizer was used at the amount of 4 phr. The SEM indicated that the compatibility and interfacial adhesion between PC and PP phases were enhanced. DSC results that showed the crystallization and melting peak temperatures of PP increased with the increase of the PP content, which indicated that the amorphous PC affected the crystallization behavior. However, both the PC and compatibilizer had little effect on the crystallinity of PP in PC/PP blends based on both the DSC and XRD patterns.     

The Crystallization and Morphology of Isotactic Polypropylene Nucleated by Magnesium Sulfate Whiskers Surface Modified by Pimelic Acid

Pimelic acid (PA) was used to modify the surface of magnesium sulfate whiskers (M-HOS). The treated M-HOS and its effects as a function of concentration on the crystallization and morphology of isotactic polypropylene (iPP) were investigated. Scanning electron microscopy (SEM), wide-angle X-ray diffraction (WAXD), thermogravimetic analysis (TGA), and Fourier transform infrared spectroscopy (FTIR) revealed that PA reacted with M-HOS and formed magnesium pimelate on the surface after the reaction. The results of differential scanning calorimetry (DSC) and polarized light microscopy (PLM) showed that the treated M-HOS had the ability to induce β-spherulites, increase the crystallization temperature and decrease the size of spherulites in iPP. It was the most effective to form β-spherulites when the content of PA treated M-HOS was 5 wt%.     

Confined Crystallization in Polymer Blends: DSC Studies of the Behavior and Kinetics of Isothermal Crystallization of Polypropylene in Poly(cis-butadiene) Rubber Blends

Thermal properties of polypropylene with poly(cis-butadiene) rubber (iPP/PcBR) blends have been measured by differential scanning calorimetry (DSC), and the melting point T_m, crystallization temperature T_c, enthalpy Δ H (melting enthalpies and crystalline enthalpies), and equilibrium melting point T⁰ _m have been measured and calculated. The variation of T_m, T_c, Δ H and T⁰ _m with composition in the blends was discussed, showing that an interaction between phases is present in iPP/PcBR blends. The degree of supercooling characterizing the interaction between two phases in the blends and the crystallizability of the blends which bears a relationship to the composition of the blends was discussed. The kinetics of isothermal crystallization of the crystalline phase in iPP/PcBR blends was studied in terms of the Avrami equation, and the Avrami exponent n and velocity constant K were obtained. The Avrami exponent n is between 3 and 2, meaning that iPP has a thermal nucleation with two dimensional growths. The variation of the Avrami exponent n, velocity constant K, and crystallization rate G bear a relation to the composition of the blends, n increases with increasing content ofPcBR. K also increased with increasing content of PcBR. All of the K for the blends are greater than for pure iPP. The crystallization rate G (t_1/2) depends on the compositions in the blends; all G of the blends are greater than for iPP.     

Influence of Mixing Technique on Microstructure and Impact Properties of Isotactic Polypropylene/ Poly(Cis-Butadiene) Rubber Blends

Isotactic polypropylene/poly(cis-butadiene) rubber (iPP/PcBR vol%: 80/20) blends were prepared by melt mixing with various mixing rotation speeds. The effect of mixing technique on microstructure and impact property of blends was studied. Phase structure of the blends was analyzed by scanning electron microscopy (SEM). All of the blends had a heterogeneous morphology. The spherical particles attributed to the PcBR-rich phase were uniformly dispersed in the continuous iPP matrix. With increase of the mixing rotation speed, the dispersed phase particle's diameter distribution became broader and the average diameter of the separated particles increased. The spherulitic morphology of the blends was observed by small angle light scattering (SALS). Higher mixing rotation speed led to a more imperfect spherulitic morphology and smaller spherulites. Crystalline structure of the blends was measured by wide angle X-ray diffraction (WAXD) and small angle X-ray scattering (SAXS). The introduction of 20 vol% PcBR induced the formation of iPPβ crystals. Higher rotation speed led to a decrease in microcrystal dimensions. However, the addition of PcBR and the increase of mixing rotation speed did not affect the interplanar distance. The long period values were the same within experimental error as PcBR was added or the mixing rotation speed quickened. The normalized relative degree of crystallinity of the blends slightly increased under lower rotation speeds (30 and 45 rpm) and decreased under higher rotation speeds. The notched Izod impact strength of the blends was enhanced as a result of the increase of mixing rotation speed.     

Crystallization of α and γ Phases in Isotactic Polypropylene with Low Ethylene Content: Isothermal Crystallization and Secondary Crystallization

Crystallization and melting behaviors of isotactic polypropylene (iPP) with low ethylene content during an isothermal process and on heating just after it are investigated by means of in situ x-ray diffraction. At every isothermal temperature investigated here, the formations of α and γ phases are confirmed. The ratio of γ to α increases with an increase in isothermal temperature. On heating just after the isothermal process, the γ starts melting at a lower temperature than the α. This may be due to the small crystallite size of the γ crystallization during the isothermal process. On cooling after the completion of the isothermal crystallization, the secondary crystallization accelerates, and the γ phase crystallizes predominantly. The fractionation is considered to occur in the primary crystallization during the isothermal process. The low-molecular-weight portion of the materials, which remained in amorphous regions of the spherulite during the isothermal process, crystallizes into the γ phase in the secondary crystallization. Furthermore, the fractionation behavior seems to be enhanced at higher temperatures.     

Effect of β-Nucleating Agent on the Crystallization,Mechanical Properties,and Heat Resistance of Injection-Molded Isotactic Polypropylene

Injection-molded β-isotactic polypropylene (β-iPP) was prepared with a commercial β-nucleating agent (NT-A). The effect of NT-A on the crystallization, mechanical properties, and heat resistance of β-iPP was investigated by differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), polarized light microscopy (PLM), and mechanical and heat deflection tests. DSC and WAXD analysis showed that the content of β-crystals in the nucleated iPP was higher than that of pure iPP, and the content of β-crystals of the core was higher than that of the skin. PLM observations showed that injection-molded iPP had an obvious skin-core structure. NT-A induced abundant β-crystals and resulted in small spherulites which improved the Izod notched impact strength. When the content of NT-A was 0.075wt%, the Izod notched impact strength reached a maximum, 2.6 times more than that of pure iPP. The heat distortion temperature was also improved by NT-A.     

The Effect of Microwave Irradiation on the Crystallization Behavior of PET/PEN Blends

The crystallization behavior of poly(ethylene terephthalate) (PET)/poly(ethylene‐ 2,6‐naphthalate) (PEN) blends before and after microwave irradiation for different time intervals has been investigated by means of wide angle X‐ray diffraction (WAXD) and differential scanning calorimetry (DSC) techniques. It was found that microwave irradiation could greatly affect the crystallization behavior of PET/PEN blends and significantly enhance their degree of crystallinity. For the PET/PEN (90/10) blends, the degree of crystallinity increased from 15 to 45%; for the PET/PEN (60/40) blends, the degree of crystallinity significantly increased, from 1 to 36%. However, with increasing irradiation time, the degree of crystallinity didn't continually increase. It reached a maximum at certain time point. The cold crystallization enthalpy △Hcc gradually decreased as microwave irradiation time increased and the melting enthalpy △Hm vis‐à‐vis the long time interval of such irradiation was decreased. In addition, the mechanism for microwave irradiation affecting the crystallization behavior of polymers is discussed.     

Mechanical,Thermal, and Surface Properties of Ultrahigh Molecular Weight Polyethylene/Polypropylene Blends

Various compositions of ultrahigh molecular weight polyethylene/polypropylene (UHMWPE/PP) blends were prepared in decalin, with the rheological, mechanical, thermal, and surface properties of the blends being determined using the solution cast film. Viscosity and mechanical properties of the blends decreased below the additivity value with increasing PP content implying that PP molecules disturb the entanglement of UHMWPE. Contact angle of the blend films with a water drop increased with increasing content of PP. The atomic force microscope (AFM) images showed that the surface of cast UHMWPE was very smooth whereas that of cast PP was very uneven. For blends, the surface became rough and uneven with increasing content of PP. The melting temperature of PP (T _mP) decreased in the blends with increasing UHMWPE content while that of UHMWPE (T _mU) remained almost constant in blends.     

Nanofilled Polypropylene/Poly(trimethylene terephthalate) Blends: A Morphological and Mechanical Properties Study

Polypropylene (PP) /poly(trimethylene terephthalate), (PTT), binary blends in the presence of two interfacial modifier as well as two organically modified nanoclay additives were studied in terms of mechanical and morphological characteristics. Scanning electron microscopy confirmed the incompatibility of the system which was solved to some extent through incorporating the nanoclay as well as functional compatibilizers. An evaluation of the specimens via static mechanical tests in tensile mode gave credence to the assumption that the higher the PTT content, the higher the mechanical performance would be. Furthermore, the compatibilizer-containing blends not only exhibited higher toughness, but also possessed enhanced stiffness when a maleated compatibilizer was added. The tensile modulus was promoted further in the presence of clay nanoparticles; however, toughness was somewhat sacrificed. The Barentsen as well as Halpin-Tsai models were found to describe the binary blends modulus. The reinforcing impact of the nanoclay was exploited to a greater degree in the presence of the compatibilizer.     

Thermoplastic Elastomers Based on Natural Rubber/Polypropylene Blends: Effect of Blend Ratios and Dynamic Vulcanization on Rheological,Thermal, Mechanical,and Morphological Properties

Thermoplastic elastomers (TPEs) based on natural rubber (NR)/polypropylene (PP) with different blend ratios were prepared and studied. The TPEs were obtained by dynamic vulcanization of NR/PP using a sulfur (S)/N-tert-butyl-2-benzothiazolesulphenamide (TBBS) and tetramethylthiuram disulphide (TMTD) curative system during processing in the melt state in an internal mixer equipped with cam rotors. Rheological, thermal, mechanical, dynamic, and morphological properties of the TPEs prepared were investigated. Based on this study a mechanism for the NR crosslinking was proposed where the sulfur vulcanization occurs through radical substitution in the forms of polysulfide bridges. The dynamic vulcanization process increases the stiffness of the NR phase in the TPEs and modifies the rheological and thermal behavior of the system compared to the behavior of the basic material PP. The crosslinked NR particles restrict the spherulitic growth and the regular arrangement of the spherulites of PP phase, decreasing the crystallinity degree. On the other hand, a reduction of mobility of the chain segments was also observed and, consequently, an increase of the T_g values. NR/PP TPEs with high content of NR showed superior mechanical performance compared to the uncrosslinked NR/PP blends in terms of tensile strength, Young's modulus and hardness. An increase of approximately 320% in Young's modulus values was obtained for the NR70/PP30 TPE compared to NR70/PP30. Morphological studies revealed the formation of large aggregates of NR domains in NR/PP TPEs which increased in size with an increase of the rubber content.     

Assessment of Compatibility in Polypropylene/Poly(lactic acid)/Ethylene Vinyl Alcohol Ternary Blends: Relating Experiments and Molecular Dynamics Simulation Results

Two systems of polypropylene (PP), poly(lactic acid) (PLA) and ethylene vinyl alcohol copolymer (EVOH) ternary blends having different compositions were extruded in a co-rotating twin screw extruder. The first system was PP/PLA (75/25) with various EVOH contents, the second one was PP/EVOH (75/25) having various PLA contents. The effects of composition on the morphology and the tensile and impact properties of the blends were investigated. There were increases in the tensile modulus and tensile strength with an increase in the EVOH and PLA contents in the first and second systems, respectively. A molecular dynamics (MD) simulation was used to investigate the compatibility between the components. Prediction of the miscibility of the blends was carried out by determining the interaction parameters (χ), mixing energies (ΔH_mix), phase diagrams and Gibbs free energies. The MD simulation showed a UCST behavior for the components. Moreover, the simulation results showed a compatibilizer effect for the EVOH component. The experimental values of the dynamic mechanical thermal analysis (DMTA) and mechanical properties were correlated to the MD results. There was a good correlation between the MD and DMTA results. The modulus values using the parallel and Davis models were near to the experimental ones. A good fitting to the mixture law with addition of EVOH confirmed a good compatibilzing effect of it between the PP and PLA components.     

Synthesis of a Novel Flame Retardant and Its Synergistic Effect With a Phosphapheanthrene Flame Retardant in Polypropylene/Polyethylene Vinyl Acetate Blends

A novel flame retardant (NSiB) containing nitrogen, silicon and boron was synthesized through reacting of N-(β-aminoethyl)-γ-aminopropyl trimethoxy-silane (KH-792) and boric acid. The structure of NSiB was characterized by Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy with energy dispersive spectrometry (SEM-EDS). The effects of NSiB on the flame retardancy and thermal behaviors of polypropylene (PP)/polyethylene vinyl acetate (EVA) blends were investigated by limiting oxygen index value (LOI), vertical burning tests (UL-94) and thermal gravimetric analysis tests (TGA). The results showed that the flame retardancy and thermal stability of PP/EVA blends were improved with the addition of NSiB. When 7.5 wt% DOPO (phosphaphenanthrene) and 0.5 wt% NSiB were incorporated, the LOI value of the PP/EVA blends was 26.9%, and the class V-0 of UL-94 test was passed, as compared to the LOI value of 22.4% and class V-2 of UL-94 test for 8.0 wt% DOPO only and 16.7% and fail, respectively, for the PP/EVA blends alone. The char structure observed by SEM indicated that the surface of the char for the PP/EVA/7.5 wt% DOPO/0.5 wt% NSiB blends had a denser and continuous char structure when compared with that of the PP/EVA blends and PP/EVA/8.0 wt% DOPO blends. These results indicated that there was a good synergistic effect for NSiB and DOPO.