Study on poly(ethylene terephthalate)/polypropylene microfibrillar composites. II. Solid‐state drawing behavior

A (20/80) blend of poly(ethylene terephthalate)/polypropylene (PET/PP) was solid‐state drawn to enhance the molecular orientation of the PET microfibers. Effects of drawing temperature (23–140°C) and drawing speed (max. 1000 mm/min) on the morphology and draw ratio of the blend were studied and discussed based on the drawing behaviors of the pure polymers. In cold drawing, there seemed to be a critical drawing speed below which the natural draw ratios of the polymers remained constant, but above which the draw ratios first decreased slightly because of suppression of molecular relaxation and then increased because of breakage of highly strained molecules and disintegration of lamellar crystals into finer mosaic blocks. Macroscopically, the pure PP and the PET/PP composite extrudates gave similar draw ratios at the same speeds. SEM showed that the PET microfibers suffered a smaller elongation than the PP matrix and severe voiding occurred at the PET/PP interface. Furthermore, substantial fiber breakage occurred during cold drawing at speeds above 200 mm/min. In comparison, drawing at 100°C caused no obvious interfacial voiding and fiber breakage. Furthermore, the natural draw ratio of the blend was lower than that of the pure PP extrudate, indicating that the PET microfibers had constrained the deformation of the PP matrix. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1989–2000, 2004     

In situ fibrillar reinforced PET/PA‐6/PA‐66 blend

Ternary fibrillar reinforced blends are obtained by melt‐blending of poly(ethylene terephthalate) (PET), polyamide 6 (PA‐6) and polyamide 66 (PA‐66) (20/60/20 by weight) in the presence of a catalyst, followed by cold drawing of the extruded bristles to a draw ratio of about 3.4 and additional annealing of the drawn blend at 220 or 240°C for 4 or 8 h. The blend samples are studied by DSC, X‐ray diffraction, SEM, and static and dynamic mechanical testing (DMA). SEM and DMA show that PA‐6 and PA‐66 form a homogeneous, continuous matrix in which PET regions are dispersed. X‐ray and DSC measurements of the drawn and annealed at 220°C samples suggest mixed crystallization (solid solubility) of PA‐6 and PA‐66, and cooperative crystallization of PET with the two polyamides. After annealing at 240°C (above the melting point of PA‐6 and below that of PET), the polyamide matrix becomes partially disoriented, while the oriented, fibrillar PET is preserved and plays the role of a reinforcing element. The DSC results for the same samples suggest in situ generation of an additional amount of copolymer. This additional copolymerization, together with that generated during blend mixing in the extruder, improves the compatibility of the blend components (mostly at the PET‐polyamide interface) and alters the chemical composition of the blend.     

Effect of pimelic acid treatment on the crystallization,morphology, and mechanical properties of isotactic polypropylene/mica composites

Pimelic acid (PA) is used as a new surface modifier for mica (MC). The effects of PA treatment on the crystallization, morphology, and mechanical properties of isotactic polypropylene (iPP)/MC composites have been investigated. FTIR analysis reveals that PA reacted with phlogopite MC, and pimelates are formed during the treatment. The results of wide angle X‐ray diffraction, differential scanning calorimetry, and polarized light microscopy prove that PA‐treated MC induces a large amount of β‐iPP and decreases the spherulite size of iPP. The results of SEM show that PA treatment improves the orientation and dispersion of MC plates in the matrix. The notched impact strength of the composites is improved dramatically by PA‐treated MC. The superior toughness is ascribed to the more ductile β spherulites, preferential orientation of MC plates, small spherulite size, and improved dispersion of MC plates in the matrix. POLYM. COMPOS., 31:1572–1584, 2010. © 2009 Society of Plastics Engineers     

Physical properties of polyamide 6/metallocene isotactic polypropylene conjugated filaments

Polyamide 6 (PA 6) and metallocene isotactic polypropylene (m‐iPP) polymers were extruded (in proportions of 75/25, 50/50, and 25/75) from two melt twin‐screw extruders to prepare three PA 6/m‐iPP conjugated filaments. This study investigated the physical properties of PA 6/m‐iPP conjugated filaments with gel permeation chromatography, differential scanning calorimetry, thermogravimetric analysis, potentiometry, rheometry, density‐gradient measurements, wide‐angle X‐ray diffraction, extension stress–strain measurements, and scanning electron microscopy. The flow behavior of PA 6/m‐iPP polyblended polymers exhibited negative‐deviation blends, and a 50/50 PA 6/m‐iPP blend showed the minimum value of the melt viscosity. The experimental results from differential scanning calorimetry indicated that PA 6 and m‐iPP molecules formed an immiscible system. The tenacity of the PA 6/m‐iPP conjugated filaments decreased initially and then increased as the m‐iPP content increased. The crystallinities and densities of the PA 6/m‐iPP conjugated filaments had a linear relationship with the blend ratio. Morphological observations revealed that the blends had a dispersed‐phase structure. A pore/fiber morphology of a larger size (from 0.5 to 3 μm in diameter) was observed after a formic acid (PA 6 was moved)/xylene (m‐iPP was moved) treatment on the cross section of a PA 6/m‐iPP conjugated filament. PA 6 and m‐iPP polymers were proved to be an incompatible system. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1471–1476, 2006     

Molecular structures and physical properties of heat‐drawn conjugate fibers

As‐spun poly(trimethylene terephthalate) (PTT)/poly(ethylene terephthalate) (PET) side‐by‐side conjugate fibers were drawn to investigate the effects of drawing conditions on structure development and physical properties. Effects of draw ratio and heat‐set temperature were observed. In the state of an as‐spun fiber, the molecular orientation of PTT was higher than PET, whereas PET molecular orientation increased remarkably over PTT with increasing draw ratio. Crimp contraction increased sharply at a draw ratio over 2.0, where the crystalline structure of the PET developed sufficiently. A heat‐set temperature of at least 140°C was required to develop sufficient crimp contraction. The crystallinity and orientation of the PET were attributed mainly to the crimp contraction of the drawn fiber. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers     

In situ studies on the temperature‐related deformation behavior of isotactic polypropylene spherulites with uniaxial stretching: The effect of crystallization conditions

The deformation behavior of isotactic polypropylene (iPP) spherulites with uniaxial stretching was investigated at different drawing temperatures via in situ polarized optical microscope (POM) observation. The iPP spherulites were prepared by two procedures: cooled to the room temperature from melt and annealed at 135, 140, and 145°C for 3 h. It was found that the crystallization conditions dominate the crystalline morphology and even the tensile properties of iPP. For iPP which crystallized during cooling progress, the spherulites were imperfect and the boundaries of the spherulites were diffuse, displaying good toughness at various drawing temperatures. For iPP annealed at high temperatures displayed the brittle fracture‐modes and the crack happened between spherulites, which due to the large and perfective spherulites have thick lamellas and weak connection at interspherulitic boundary. The shape and size of the iPP spherulites formed at 140 and 145°C are affected with uniaxial stretching till to the fracture of the samples at different drawing temperatures. The spherulites obtained at 135°C are deformed along the drawing direction at 100°C but not affected at low drawing temperatures, indicating the toughness increased with the increase of the drawing temperatures. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Transport and mechanical properties of iPP–sPP fibers

The drawing behavior of a blend of syndiotactic and isotactic polypropylene (iPP–sPP 50:50 w/w) was investigated at different temperatures and compared to that of pure polymers. The film of pure sPP showed that the presence of iPP allowed the blend to reach a much higher draw ratio. Fibers were obtained by drawing the blend at 110°C. The axial elastic modulus of the fibers was measured as a function of draw ratio up the highest λ = 10. The sorption and diffusion of dichloromethane vapors in the undrawn and drawn samples were studied in order to provide information about the structural organization of the amorphous phase. The elastic modulus of the fibers displayed a more‐than‐linear increase with the draw ratio, suggesting a good interconnection of the amorphous phases. The orientation of the chains with increasing λ determined a decrease of entropy and fractional free volume (FFV) and a tighter packing of the chains along the drawing direction, explaining the strong increase of the elastic modulus. The transport properties, which confirmed the mechanical properties, showed a stiffening of the amorphous phase after λ = 6, evidenced by a dual‐type sorption isotherm for the fibers and a sharp drop in the zero‐concentration diffusion coefficient. As a consequence, the permeability of the fibers was much lower than that of the unoriented sample. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 539–545, 2001     

Structure,processing, morphology,and property relationships of biaxially drawn Ziegler–Natta/metallocene isotactic polypropylene film

The structure, processing, morphology, and property relationships of biaxially drawn isotactic polypropylene (BOPP) film of mixed metallocene isotactic PP (m‐iPP) and Ziegler–Natta iPP (ZN‐iPP) homopolymer compositions are developed. The DSC and film drawing behavior show cocrystallization of the ZN‐iPP and m‐iPP components. The structure, processing, morphology, and property relations of ZN‐iPP/m‐iPP blends are compared with ZN‐iPP of varying isotacticities. The ZN‐iPP/m‐iPP blends exhibit reduced biaxial yield stress [σ_y(T)]. A fractional crystallinity model collapses the σ_y(T) data into a common normalized form over a range of draw temperatures, ZN‐iPP tacticities, and blend compositions. The simplified model is extended to define the interrelationships of yield activation and strain hardening behavior into regimes differentiated by characteristic draw stress (crystallinity) levels. Structure–property models are developed to explain the effect of draw temperature and resin–blend microstructure on the draw behavior, film stiffness, barrier, elongation, and synergies of the BOPP film processing–property balance. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2400–2415, 2001     

Processing and characterization of injection moldable polymer–particle composites applicable in brazing processes

A novel method has been developed to process highly filled polymer–particle composites to test samples as braze metal preforms. Polypropylene (PP), low‐density polyethylene (LD‐PE) and high‐density polyethylene (HD‐PE) were used as polymer matrices. Two types of nickel‐based braze metal microparticles (Ni 102 and EXP 152) were compounded to the polymer matrices at filler contents up to 65 vol %. With enhancing filler content, torque at kneading rotors, and injection molding parameter were significantly affected by increasing viscosity. Injection molded composites show well‐distributed spherical microparticles and particle–particle interactions. Polymers decompose residue‐free at temperatures above 550°C, even for their composites. Adding particles reduces polymer crystallinity, whereas defined cooling at 5°C/min significantly increases the crystallinity and melt peak temperature of polymers compared to undefined cooling prior injection molding. Storage modulus of polymers increases significantly by adding filler particles. LD‐PE + 65 vol % EXP 152 show the most suitable composite performance. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Drawing and ultimate tensile properties of modified polyamide 6 fibers

The drawing and ultimate tensile properties of the modified PA 6 (MPA) fiber specimens prepared at varying drawing temperature were systematically investigated, wherein the MPA resins were prepared by reactive extrusion of PA 6 with the compatibilizer precursor (CP). At any fixed drawing temperature, the achievable draw ratio (D_ra) values of MPA as‐spun fiber specimens increase initially with increasing CP contents, and then approach a maximum value, as their CP contents are close to the 5 wt% optimum value. The maximum D_ra values obtained for MPA as‐spun fiber specimens prepared at the optimum CP content reach another maximum as their drawing temperatures approach the optimum drawing temperature at 120°C. The tensile and birefringence values of PA 6 and MPA fiber specimens improve consistently as their draw ratios increase. Similar to those found for their achievable drawing properties, the ultimate tensile and birefringence values of MPA fiber specimens approach a maximum value, as their CP contents and drawing temperatures approach the 5 wt% and 120°C optimum values, respectively. Investigations including Fourier transform infrared, melt shear viscosity, gel content, thermal and wide angle X‐ray diffraction experiments were performed on the MPA resin and/or fiber specimens to clarify the optimum CP content and possible deformation mechanisms accounting for the interesting drawing, birefringence, and ultimate tensile properties found for the MPA fiber specimens prepared in this study. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

The use of master curves to describe the simultaneous effect of cooling rate and pressure on polymer crystallization

In a previous work a master‐curve approach was applied to experimental density data to explain isotactic polypropylene (iPP) behaviour under pressure and high cooling rates. Suitable samples were prepared by solidification from the melt under various cooling rate and pressure conditions with the help of a special apparatus based on a modified injection moulding machine. The approach here reported is more general than the case study previously shown, and is suitable to be applied to several materials and for different measures related to crystalline content. The proposed simple model is able to predict successfully the final polymer properties (density, micro‐hardness, crystallinity) by superposition of the effect of cooling rate and the effect of pressure in a wide range of experimental conditions. For this purpose three semi‐crystalline polymers were studied [iPP, polyamide‐6 (PA6) and poly(ethyleneterephthalate) (PET)], which exhibited remarkably different behaviour when crystallized under pressure and high cooling rates Copyright © 2003 Society of Chemical Industry     

In situ microfibrillar‐reinforced composites of isotactic polypropylene/recycled poly(ethylene terephthalate) system and effect of compatibilizer

Recycled poly(ethylene terephthalate) from waste bottles (hereafter, rPET) was used as an reinforcing material for isotactic polypropylene (iPP) based on the concept of in situ microfibrillar‐reinforced composites (iMFCs). Microfibers of rPET were successfully generated during melt‐extrusion and subsequent drawing and preserved in the final injection‐molded specimens. The effects of draw ratio, initial size of ground rPET flakes, and rPET content on morphological appearance of the extrudates and the as‐formed rPET fibers and mechanical properties of the as‐prepared iMFCs were investigated. The results showed that diameters of the as‐formed rPET fibers decreased with increasing draw ratio, and the initial size of ground rPET flakes did not affect the final diameters of the as‐formed rPET fibers nor the mechanical properties of the as‐prepared iMFCs. Flexural modulus, tensile modulus, and tensile strength of iPP/rPET iMFCs were improved by the presence of rPET microfibers and further improvement could be achieved by the addition of maleic anhydride‐grafted iPP (PP‐g‐MA), which was used as the compatibilizer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:1173–1181, 2006     

聚酯——聚乙烯共混纤维研究

探讨了PET与不同分子量的高密度聚乙烯和低密度聚乙烯共混体的流变性能、可纺性以及共混纤维的形态结构与性能。结果表明,[η]=0.65的PET与[MI]=6.9的HDPE的共混体的可纺性较好,纺成的纤维具有以PE为海、PET为岛的海—岛型形态结构,经90℃拉伸5倍和100℃热处理后,PE高度结晶,而其中的PET仍处于非晶态。这样的纤维具有较好的力学性能,制成的非织布试样在140℃进行处理,PE皮层发生熔融粘接,PET微纤发生结晶,控制收缩,保持纤维形态。     

Effects of zone drawing on the structure of metallocene polyethylene

The influence of zone drawing on bulk properties and structure of metallocene polyethylene (m‐PE) is reported. Two different m‐PE materials were subjected to tensile stresses above the yield point by zone drawing in the temperature range from 50 to 100°C. Drawn materials were characterized by using small‐ and wide‐angle X‐ray scattering (SAXS, WAXS), molecular retraction, and small‐angle light scattering (SALS). Structural changes were studied as a function of drawing temperature, engineering stress, and draw ratio. WAXS showed strong crystalline orientation in drawn samples, and only the orthorhombic crystal modification was observed. SAXS showed lamellar orientation in drawn samples. At low drawing temperatures of 50 or 60°C, draw ratio increased as a step function of stress. There is a stress barrier, which must be exceeded before high‐draw ratios can be achieved at these temperatures. At drawing temperatures of 70°C or above, the barrier stress is low enough that draw ratio increases nearly linearly as a function of stress. Below the stress barrier, spherulitic structure is observed by small‐angle light scattering (SALS). Elongation occurs via deformation of the interspherulitic amorphous phase. Molecular retraction was low for these samples, indicating mostly plastic deformation of the amorphous material. Above the stress barrier, SALS showed that spherulites are destroyed. Elongation occurs via deformation of the intraspherulitic amorphous phase. Molecular retraction for these samples was high, indicating elastic deformation of the amorphous material. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3492–3504, 2001     

Thermal behavior and morphological characteristics of cationic dyeable poly(ethylene terephthalate) (CD‐PET)/metallocene isotactic polypropylene (m‐iPP) conjugated fibers

Cationic dyeable poly(ethylene terephthalate) (CD‐PET) and metallocene isotactic polypropylene (m‐iPP) polymers were extruded (in the proportions of 75/25, 50/50, 25/75) from two melt twin‐screw extruders to prepare CD‐PET/m‐iPP (and m‐iPP/CD‐PET)‐conjugated fibers of the island‐in‐sea type. This study investigated the thermal behavior and mechanical and morphological characteristics of the conjugated fibers using DSC, TGA, WAXD, melting viscosity rheometer, density indicator, tenacity measurement, and a polarizing microscope. Melting behavior of CD‐PET/m‐iPP polyblended polymers exhibited negative‐deviation blends (NDB) and the 50/50 blend showed a minimum value of the melt viscosity. Experimental results of the DSC indicated CD‐PET and m‐iPP molecules formed a partial miscible system. The tenacity of CD‐PET/m‐iPP‐conjugated fibers decreased initially and then increased as the m‐iPP content increased. Crystallinities and densities of CD‐PET/m‐iPP‐conjugated fibers presented a linear relation with the blend ratio. On the morphological observation, it was revealed that the blends were in a dispersed phase structure. In this study, the CD‐PET microfibers were successfully produced with enhanced diameters (from 2.2 to 2.5 μm). Additionally, m‐iPP colored fibers (m‐iPP fibers covered with CD‐PET polymer) were also successfully prepared. Meanwhile, the presence of PP‐graft‐MA compatibilizer improved the tenacity considerably. Blends with 10 wt % compatibilizer exhibited maximum improvement in the tenacity for m‐iPP colored fibers. The dye exhaustions of various fabrics followed the order: m‐iPP colored fibers > conventional CD‐PET fibers > CD‐PET microfibers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5396–5405, 2006     

PBT/PET conjugated fibers: Melt spinning,fiber properties,and thermal bonding

This work examines the PBT/PET sheath/core conjugated fiber, with reference to melt spinning, fiber properties and thermal bonding. Regarding the rheological behaviors in the conjugated spinning, PET and PBT show the smallest difference between their melt‐viscosity at temperatures of 290°C and 260°C respectively, which has been thought to represent optimal spinning conditions. The effect of processing parameters on the crystallinity of core material‐PET was observed and listed. In order of importance, these factors are the draw ratio, the heat‐set temperature, and the drawing temperature. The crystallinity of sheath material‐PBT, however, can be considered to be constant, independent of any processing parameters. The bulk orientation, rather than the crystallinity of PET core, dominates the tenacity of PBT/PET sheath/core fiber. Moreover, heat‐set treatment after drawing is recommended to yield a highly oriented conjugated fiber. With respect to thermal bonding, PBT/PET conjugated fibers processed via high draw ratio but low‐temperature heat setting can form optimal thermal bonds at a constant bonding temperature of 10°C above the T_m of PBT.     

Reinforced thermal conductivity and mechanical properties of in situ microfibrillar composites through multistage stretching extrusion

To surmount difficulty of the melt processing and deterioration of mechanical properties of polymer composites induced by high fraction of the reinforced fibers and thermal conductive fillers, polyethylene (PE)/boron nitride (BN)/polyamide 6 (PA6) and PE/BN/poly(‐hydroxybenzate‐co‐DOPO‐benzenediol dihydrodiphenyl ether terephthalate) (PHDDT) in situ microfibrillar composites were prepared through multistage stretching extrusion. The experimental results showed that both the tensile and impact strength of the PE/BN/PA6 and PE/BN/PHDDT composites were improved. Meanwhile, the thermal conductivities of the PE/BN, PE/BN/PA6, and PE/BN/PHDDT composites were also reinforced. Based on the equation proposed by Y. Agari, the new modified equations can well predict the thermal conductivity of the composites prepared through multistage stretching extrusion with different number of laminating‐multiplying elements. In addition, it was found that PHDDT can act as a “processing aid” to reduce the viscosity of the PE/BN composites. POLYM. COMPOS., 38:2663–2669, 2017. © 2015 Society of Plastics Engineers     

Recrystallization behavior of β‐isotactic polypropylene in homogeneous and heterogeneous matrix–fiber composites

β‐isotactic polypropylene (β‐iPP) cylindritic crystals were produced in homogeneous iPP fiber–matrix composites and heterogeneous polyamide (PA)–iPP fiber–matrix composites under different sample preparation conditions. The melt recrystallization behaviors of the β‐iPP crystals obtained in the homogeneous and heterogeneous composites were studied by optical microscopy. The experimental results show that, by heating the sample to 180 °C, the birefringence contributed by the iPP crystals in both α‐ and β‐forms disappears completely. During the cooling process, the β‐iPP crystals in the homogeneous composite appear again, while the iPP in the heterogeneous composite crystallizes in its α‐form. This demonstrates the different origins of the β‐iPP cylindrites in the homogeneous and heterogeneous composites. While the β‐iPP cylindrites in the heterogeneous composite are associated with the sample preparation procedure, the β‐iPP cylindrites in the homogeneous composite are produced by recrystallization of the molten but incompletely relaxed iPP fibers. In situ observation of the melt recrystallization process shows that the molten iPP oriented fibers crystallize first during the cooling process at relatively higher temperature in the α‐form. Abundant randomly dispersed β‐iPP nuclei formed at the surface of the recrystallized iPP fibers, which generate the β‐iPP cylindrites. Copyright © 2012 Society of Chemical Industry     

Enhanced thermal conductivity of PE/BN composites through controlling crystallization behavior of PE matrix

In this article, in order to enhance the thermal conductivity of the polyethylene (PE)/boron nitride (BN) composites through controlling the crystallization behavior of the PE matrix, the crystallization and melting behavior of the PE in the PE/BN composites was investigated. When the BN content was more than 10 wt%, an extra weak exothermic peak (T _h) at 130°C was observed. Moreover, after the annealing of the PE/BN composites at 130°C, the extra weak melting peaks (T _mh) of the PE in the PE/BN composites were also observed and shifted to the high temperature with increasing annealing time, which proved that the T _h was induced by PE crystallization. Meanwhile, the results of temperature‐dependent absorbance IR spectra of the PE/BN composites showed that the crystallization peak (729 cm⁻¹) remarkably appeared at 130.2°C, indicating that the crystallization of the PE in the PE/BN composites can occur at 130.2°C. When the annealing time and temperature were 20 min and 130°C, the thermal conductivity of the PE/BN composite was 16% higher than that of the unannealed PE/BN composites. In addition, the results of the wide angle X‐ray diffraction (WAXD) showed that the BN particles had no influence on the PE crystalline form in the PE/BN composites. POLYM. COMPOS., 38:2806–2813, 2017. © 2015 Society of Plastics Engineers