Injection Molding Shrinkage and Mechanical Properties of Polypropylene Blends

Polypropylene (PP) blends based on isotactic polypropylene (iPP), propylene-ethylene block copolymer (bPP), and propylene–ethylene random copolymer (rPP) were prepared by melt blending and the effects of content of bPP and rPP on the shrinkage during solidification and storage and mechanical properties of the blends were studied. It was found that the addition of polypropylene copolymer could effectively reduce the processing shrinkage of iPP and the lowest shrinkage of the blends was achieved at a loading of 2 wt% bPP or rPP. The flexural modulus and tensile strength of the blends decreased a little while the impact strength and elongation at break were improved greatly compared with those of iPP.     

Mechanical Properties and Rheological Behavior of Dynamically Vulcanized Trans-Polyisoprene/Polypropylene Blends

The degree of dynamic vulcanization, mechanical properties, rheological behavior, and the ageing-resistant performance of thermoplastic vulcanizates (TPVs) based on Trans 1,4-polyisoprene/polypropylene (TPI/PP) blends with the blend ratios of 70/30, 60/40, and 50/50 were investigated. The results showed that TPI fully dynamically vulcanized in the Haake mixer chamber when mixed with PP, and the specimen with the blend ratio 70/30, for the same sulfur content in all samples, had the lowest cross-linking degree of the TPI phase. The shear viscosity of TPI/PP-TPVs dropped as the shear rate increased and the specimen with the blend ratio 70/30 had a relatively greater shear viscosity in the region of shear rates less than 1000 s^?1. With the antiageing agent Vulkanox 4020 NA (Bayer) added, all the TPI/PP-TPVs showed good ageing characteristics, and the specimen with the blend ratio 70/30 possessed the best mechanical properties.     

Crystallization Behavior of Poly(Trimethylene Terephthalate)/Polycarbonate Blends

The crystallization behavior of poly(trimethylene terephthalate (PTT) in compatibilized and uncompatibilized PTT/polycarbonate (PC) blends are investigated in the research reported in this paper. The differential scanning calorimetry (DSC) results showed that the crystallization behaviors of PTT/PC blends were very sensitive to PC content. The onset (T_ci) and the peak (T_c) crystallization temperatures shifted to lower temperatures whereas the area of the exotherm decreased quickly as the PC content was increased. The Avrami exponent, n, decreased from 4.32 to 3.61 as the PC content was increased from 0 to 20 wt %, and the growth rate constant, Z _c , decreased gradually as well. This suggests that the nucleation mechanism exhibits the tendency of changing gradually from a thermal nucleation to an athermal mode although the growth mechanism still remains three‐dimensional. When epoxy (2.7 phr) was added as a compatibilizer during melt blending, the T_ci and T_c shifted slightly to higher temperature (≤2°C), and the crystallization enthalpy, however, exhibited an increased crystallinity with the exception of the 90/10/2.7 phr PTT/PC/Epoxy. This suggests that the epoxy make a positive contribution to the PTT crystallization. Moreover, the influences of epoxy on the crystallization behaviors of PTT/PC blends are related to the epoxy content. By contrast, the compatibilizer of ethylene‐propylene‐diene copolymer graft glycidyl methacrylate (EPDM‐g‐GMA, ≤6.3 phr) had little effect on the crystallization behavior of PTT/PC blends. For PTT/PC/Epoxy (2.7 phr) blends, the Avrami exponent, n, decreased to near 3, while the growth rate constant, Z _c , increased slightly as PC content was increased from 0 to 20 wt %. It is suggested that epoxy accelerated the process of the nucleation mechanism changing from thermal nucleation to an athermal mode. The EPDM‐g‐GMA had little effect on the nucleation mode and spherical growth mechanism. The PTT spherulite morphologies in PTT/PC blends were very sensitive to blend composition. Completely different morphologies were observed in pure PTT, PTT/PC, PTT/PC/Epoxy, and PTT/PC/EPDM‐g‐GMA blends.     

Influence of Polycarbonate on the Crystallization Behavior of Poly(Trimethylene Terephthalate)/Polycarbonate Blends

To determine the factors influencing the retardation of the crystallization of poly(trimethylene terephthalate) (PTT) when PTT is blended with polycarbonate (PC), different PTT/PC blends were prepared via the melt mixing method. The relationships between the crystallization behavior and blend composition, as well as the phase morphology, were investigated. The results showed that the predominant reason for the retardation in crystallization is due to the PC content and phase morphology. The PC influences the crystallization of PTT via two methods. First, it retards PTT crystallization. Secondly, the PC exhibits a nucleation effect on the PTT crystallization which is, however, much weaker compared to the negative effect PC exerts with regards to PTT crystallization. When the processing temperature and shear rate remains unchanged, the two effects of PC determine the crystallization behavior of the blend. The phase morphology, which is strongly dependent on the mixing temperature and the shear rate, and which is also related to mixing time, had an appreciable impact on PTT crystallization. In the case of similar adhesion with the interface, a finer PC phase domain would show a slightly stronger nucleation effect on PTT crystallization.     

Mechanical Properties and Morphology of LDPE/PP Blends

Two types of polypropylene (PP) with different molecular structure, namely, homogeneous PP (PPH) and PP block‐copolymer (PPC), were blended with a long chain, branched, low density polyethylene (LDPE) in a twin screw extruder and then injection moulded into test specimens; the mechanical properties and morphology of the blends are reported. The tensile strength, elastic modulus, flexural strength, and flexural modulus of the blends increased monotonically with increasing PP content, although exhibiting a slightly negative deviation from the rules of mixtures due to the relatively poor compatibility of the components, which caused the blends to separate into individual phases. Comparatively, these mechanical properties of the LDPE/PPH blend were much higher than that of the LDPE/PPC blend, which was attributable mainly to the fact that the mechanical properties of neat PPH are stronger than that of neat PPC. With respect to the impact strength of the blends, a maximum value appeared in LDPE/PPH blends when PPH content was about 20% and also in LDPE/PPC blends when PPC content was about 40%.     

Micro and Macro Injection Molded Parts of Isotactic Polypropylene/Polyethylene Blends: Shear-Induced Crystallization Behaviors and Morphological Characteristics

The present study focused on the importance of scale effect (micro- and macro-injection molded parts) and iPP content to the formation of epitaxial crystallization and crystal structure formed in injection-molded bars of high-density polyethylene (HDPE)/isotactic polypropylene (iPP) blends. After making the blends with different iPP content via melt mixing, the injection-molded bars were prepared via both micro and conventional injection molding. Hot stage polarized light microscopy (HS-PLM), scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) were used to investigate their morphological and crystal features. The results indicated that an appropriate matching of micro-part and relative high iPP content was most favorable for epitaxial crystallization. The micro-parts had a large fraction of shear layer in comparison with macro-parts. The SEM observations showed that the shear layer of the former consisted of a highly oriented shish-kebab structure. The memory effect of the crystalline structure of the micro-parts and macro-parts at high temperature, investigated in detail through HS-PLM experiments, showed that micro-part had a relatively high memory effect of the preceding crystallization process.     

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.     

Crystallization Behavior and Crystal Morphology of PTT/PBT Blends

The crystallization behavior and crystal morphology of the poly(trimethyl terephthalate) (PTT)/poly(butylene terephthalate) (PBT) blends were investigated by means of differential scanning calorimetry (DSC), wide angle X‐ray diffraction (WAXD) and polarized light microscopy (PLM) techniques. It was found that the two components crystallized simultaneously in the crystalline regions. The degree of crystallinity changed with PTT content. Crystalline properties were worse when the ratio of PBT and PTT contents was close to 50:50, but were better when PBT content was greatly different from PTT content.     

Mechanical Properties,Rheology, and Crystallization of Epoxy-Resin-Compatibilized Polyamide 6/Polycarbonate Blends: Effect of Mixing Sequences

Blends of polyamide 6 (PA6)/polycarbonate (PC)/epoxy resin (EP) were melt blended with three different mixing sequences. Their mechanical properties, crystallization, and rheological behaviors, as well as the morphology, were investigated via mechanical testing, differential scanning calorimetry (DSC), dynamic rheometry, and scanning electron microscopy (SEM). It was noted that the mixing sequences affected the distribution of EP in the PA6 matrix, as well as the reactivity of EP with PA6 and PC. Mechanical testing showed that the blends prepared by the first (S₁, blending PA6, PC, and EP simultaneously) and second mixing sequences (S₂, blending PC with a premixture of PA6/EP) had higher notched Izod impact strengths due to the formation of PA6-EP-PC block copolymer (named as the AEC structure) during compounding, as evidenced by the results of dynamic rheology and SEM. Whereas for the third sequence (S₃, blending PA6 with a premixture of PC/EP), EP could barely react with PA6 and PC, leading to little formation of AEC structure, which resulted in a poor notched Izod impact strength of the blends. The incorporation of EP actually acted as a plasticizer to improve the elongation at break of the S₃ blends. In addition, the DSC results and SEM observations showed that there were distinct differences in the crystallization and morphology of the samples prepared by the different mixing sequences.     

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.     

Microstructure and Properties of Polypropylene/Clay Nanocomposites

Nanocomposites of polypropylene (PP) containing various contents of Cloisite 15A nanoclay particles were prepared by one-step melt compounding in a twin screw extruder. Tensile and impact properties of the nanocomposite systems were investigated and correlated with their microstructures. The tensile modulus increased with an increase in Cloisite 15A content but the tensile strength, elongation at break, and impact strength were decreased. WAXS and TEM studies showed almost exfoliated structures. There was a decrease in permeability values with an increase in nanoclay content up to 5 wt. %. Exceeding this content of nanoclay had no significant effect on permeation due to the aggregation phenomenon at high concentrations of the nanoparticles. Most of the examined micromechanical models for prediction of the tensile modulus of the nanocomposite were successful despite being based on fiber-shaped fillers. An exfoliated structure of clay within the nanocomposite was assumed for the modeling using a molecular dynamics simulations approach, employing Dreiding, Forcite, and COMPASS force fields, in order to investigate the best one for a successful estimation of elastic modulus. Relative to the experimental modulus values of the nanocomposites, which were around 1100–1200 MPa, the COMPASS force field had the best correlation with the values with a slight departure of about 10%.     

Morphology,Nonisothermal Crystallization Behavior and Mechanical Properties of Polypropylene Modified by Ionomers

The morphology and nonisothermal crystallization behavior of polypropylene modified by ionomers based on ethylene copolymers (Surlyn 8920 and 9320) were investigated by using scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). The crystallization rate of polypropylene was accelerated by the ionomers which initiated heterogeneous nucleation of the polypropylene. At low ionomers content (0.25 wt%), Surlyn 8920, neutralized by sodium, was more efficient to enhance the crystallization rate of polypropylene than Surlyn 9320 (neutralized by zinc). The crystallization process of polypropylene modified by the ionomers was analyzed by different kinetics models. The study showed that the Mo approach was applicable for this system, whereas the Avrami, Jeziorny, and Ozawa methods were not. Furthermore, the notched impact strength of polypropylene modified by the ionomers was increased without any reduction of tensile strength and flexural modulus.     

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.     

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.     

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.     

Effect of Interfacial Structure on Crystallization Behavior of Polypropylene/Polyolefin Elastomer/Barium Sulfate Ternary Composites

In this paper, interfacial structure induced development of crystallization behavior of polypropylene (PP)/polyolefin elastomer (POE)/barium sulfate (BaSO₄) ternary composites was studied by DSC. Two kinds of PP (copolymer and homopolymer) were used. The compatibility between PP and POE had a distinct influence on nucleation and crystal growth of PP in PP/POE binary composites. The crystallization rate of PP homopolymer increased because of the heterogeneous nucleation by POE, while the crystallinity of PP homopolymer decreased because of an inhibition effect of the hexane side chains in POE. BaSO₄ particles acted as heterogeneous nucleating agents of PP in ternary composites. The dispersion of BaSO₄, controlled by interfacial design, had a distinct influence on the nucleation activity of BaSO₄ in ternary composites. Interfacial structure had the same effect on nucleation activity of BaSO₄ particles and crystallization rate of PP matrix in PP copolymer ternary composites as those in PP homopolymer ternary composites.     

Study on the Non-isothermal Melt Crystallization Kinetics of PTT/PBT Blends

Macro-kinetic models, namely the modified Avrami, Ozawa, Mo, and Kissinger models, were applied to investigate the non-isothermal melt crystallization process of PTT/PBT blends by DSC measurements. It was found that the modified Avrami model can describe the non-isothermal melt crystallization processes of PTT/PBT blends fairly well. When the cooling rates range from 5 to 20°C/min, the Ozawa model could be used to satisfactorily describe the early stage of crystallization. However, the Ozawa model didn't fit the polymer blends in the late stage of crystallization, because it ignored the influence of secondary crystallization. Under the conditions of the non-isothermal melt crystallization, it was found that the cooling rates and the blend composition affect the crystallization for blends according to Kissinger crystallization kinetics parameters. The crystallization kinetics constant K_a increases with increasing cooling rate, indicating the crystallization rates of PTT, PBT, and PTT/PBT blends were improved. The crystallization kinetic activation energy parameters are good agreement with the results from isothermal crystallization processes of the polymer blends. The crystallization activation energy of PTT/PBT blends is higher than the activation energy of PTT and PBT.     

Oriented Crystallization of Polyethylene in Compatible Blends with Polyamide 11

The oriented crystallization of polyethylene (PE) in uniaxially oriented films of compatible blends with polyamide 11 (PA11) was studied. The PE sample used was a random copolymer of PE with methacrylic acid (MAA), poly(ethylene-co-methacrylic acid) (PEMAA), with 4wt% MAA units. Oriented films of PA11/PEMAA blends were prepared by uniaxial drawing of the melt-mixed blends. The drawn films with fixed lengths were heat-treated at 120°C for 3min to melt the PE component, followed by cooling the sample to room temperature at a rate of 2°C/min to recrystallize the PE (designated slowly crystallized sample). The PE component crystallized in elongated domains of PEMAA with diameters of 0.5–2 μ m and lengths of 5–10 μ m for the PA11/PEMAA = 80/20 blend, resulting in the oriented crystallization of PE crystals. The crystal b-axis of PE was highly oriented in the direction perpendicular to drawing, while the crystal a-axis was weakly oriented in the drawing direction in the slowly crystallized sample of the PA11/PEMAA = 80/20 blend. The a-axis orientation of PE crystals in the PA11/PEMAA = 80/20 blend contributes to the improvement of mechanical properties in the direction perpendicular to drawing.     

Rheology,Crystallization, Mechanical and Barrier Properties of Polyamide 6/66 Nanocomposites with Exfoliated Organoclays

Nylon copolymer/clay (NC) nanocomposites were prepared using PA6/66 as a matrix and organoclay as a nanofiller through a two-step melt-compounding method. It was shown that the organoclay flakes were well exfoliated and dispersed in the PA6/66 matrix. With increasing content of organoclay, the apparent shear viscosity and the entrance pressure drop of the NC nanocomposites decreased whereas the corresponding shear activation energy increased, suggesting that the NC nanocomposites were suitable to be used in shear-flow rather than extension-flow related processes. Investigations of the crystallization behaviors of the NC nanocomposites indicated that the organoclay addition was capable of facilitating the γ-form crystal formation, which is suggested to be due to the restriction effect of the organoclay on the PA6/66 chain motion during the crystallization. Compared to the neat PA6/66, the tensile strength and elongation at break of the NC nanocomposites were both enhanced at an appropriate content of the organoclay. In addition, the NC nanocomposites exhibited enhanced barrier properties due to the high specific surface area and the homogeneous dispersion of the organoclay.     

Effects of Carbon Nanotubes on the Morphology and Properties of Uncompatibilized and Maleic Anhydride-grafted Polypropylene-compatibilized Polyamide 6/Polypropylene Blends

The effects of carbon nanotubes (CNTs) on the morphology of uncompatibilized and maleic anhydride-grafted polypropylene (MAPP)-compatibilized polyamide 6 (PA6)/polypropylene (PP) (70/30 w/w) blends prepared using a torque rheometer were investigated. TEM observations showed that the CNTs were selectively located in the major PA6 phase and at the interface. Such localization of nanofillers in the literature usually leads to a refinement in a sea-island morphology. Unexpectedly, our results show that increasing amounts of CNTs in the samples prepared using a torque rheometer led to a transformation from typical sea-island morphology to co-continuous morphology for uncompatibilized PA6/PP blends and to partial fibrillization of the PP domains for MAPP-compatibilized PA6/PP blends. These unusual morphological changes are attributed to a retarded morphology evolution process caused by the CNTs. According to rheological measurements and theoretical analysis, this was achieved through the role of CNTs in enhancing the viscoelasticity of the PA6 phase and promoting interfacial slip. The electrical resistivites, crystallization, and melting behavior of all samples were also studied.