Blends of thermoplastic polyurethane and polypropylene. II. Thermal and morphological behavior

Neat thermoplastic polyurethane (TPU), polypropylene (PP), and TPU/PP blends with different weight ratios that were prepared in a twin‐screw extruder were investigated with differential scanning calorimetry and light and scanning electron microscopy. The results confirmed PP matrix to TPU matrix phase inversion in the concentration region between 60/40 and 80/20 TPU/PP blends. The total degree of crystallinity of the blends and the crystallization temperature of PP decreased with increasing TPU content. On the other hand, the addition of elastomeric TPU to PP significantly increased the spherulite size of PP. The TPU melt islands in the PP matrix prolonged the crystallization of PP during solidification, and this enhanced the growth of spherulites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

The influence of filler treatment on the properties of TPU/PP blends: I. Thermal properties and stability

Commercially available organosilane (3‐glycidoxypropyltrimethoxysilane (GPTMS)) coupling agent was used to treat talc in order to improve the affinity relative between the filler and the polymer in composites as well as filler and polymer in the thermoplastic polyurethane/polypropylene (TPU/PP) blends (talc content was 5 wt%). The talc particles were first modified with GPTMS and then introduced into TPU, PP as well as TPU/PP blends with different weight ratios of polymers using blending method and subsequently injection molded in a hydraulic press. The aim was to report the effect of silane coupling agent on the thermal and morphological properties of talc filled composites and blends. The results showed that the thermal properties of the TPU, PP composites and TPU/PP blends were improved with the addition of silane treated talc (higher melting (T_m), crystallization (T_c) temperatures and degree of crystallinity (χ_c)). The glass transition temperature (T_g) obtained by dynamic mechanical analysis (DMA) of the TPU soft segments in TPU/PP blends increased with the addition of untreated and silane treated talc due to lower mobility of the soft segments in TPU and better miscibility of TPU and PP. TPU/PP blends with the silane treated talc show better thermal stability than the TPU/PP blends with untreated talc. POLYM. ENG. SCI., 55:1920–1930, 2015. © 2014 Society of Plastics Engineers     

The morphology,properties, and shape memory behavior of polylactic acid/thermoplastic polyurethane blends

Biodegradable polylactic acid (PLA) was compounded with thermoplastic polyurethane (TPU) by twin‐screw extrusion at weight ratios of 90/10, 80/20, 70/30, and 60/40. The blends were investigated based on their phase morphology, thermal and mechanical properties, and shape memory properties. The tensile results showed that PLA was successfully toughened by TPU. When the TPU content was 40%, the elongation‐at‐break increased to 400%. The SEM morphology showed that TPU was dispersed uniformly in the PLA matrix; DMA and DSC results indicated that the two polymers were immiscible. Most interestingly, it was found that the blends exhibited a shape memory behavior and, unlike most of the existing shape memory polymers (SMPs), the PLA/TPU blends could be deformed at room temperature without an extra heating and cooling step. During the deformation process, TPU acted as a toughening agent that prevented the PLA/TPU blends from breaking; thus, the temporary shape could be kept and internal stress was stored in the blends. Upon heating to above the glass transition temperature of PLA (about 60°C), the deformed parts regained their original shapes quickly along with the release of the stress. POLYM. ENG. SCI., 55:70–80, 2015. © 2014 Society of Plastics Engineers     

Thermoplastic polyurethane/polypropylene blends based on novel vane extruder: A study of morphology and mechanical properties

Thermoplastic polyurethane (TPU) polypropylene (PP) blends of different weight ratios were prepared with a self‐made vane extruder (VE), which generates global dynamic elongational flow, and a traditional twin‐screw extruder (TSE), which generates shear flow. The mechanical properties, phase morphology, thermal behavior, and spherulite size of the blends were investigated to compare the different processing techniques. Samples prepared with a VE had superior mechanical properties than the samples prepared with a TSE. Scanning emission micrographs show that the fiber morphology of the TPU/PP blends (<60 wt% TPU) was improved by elongational flow in VE. Differential scanning calorimetry curves indicate that a dynamical elongational flow could improve the miscibility of the TPU/PP blends. The U‐shaped spherulite size curve indicates the changes in the spherulite size, as observed from a polarization microscope. Interlocked spherulites also reveal the apparent partial miscibility of the TPU/PP blends under elongational flow. POLYM. ENG. SCI., 54:716–724, 2014. © 2013 Society of Plastics Engineers     

Interaction of thermoplastic polyurethane with polyamide 1212 and its influence on the thermal and mechanical properties of TPU/PA1212 blends

To improve the heat resistance of polyester‐based thermoplastic polyurethane (TPU), in the present work, polyamide 1212 (PA1212) was chosen as a modifier and a series of TPU/PA1212 blends with different compositions were prepared using a twin screw extruder. The solubility parameters, characteristic of chemical structures, hydrogen‐bonding interaction, as well as interfacial tension of the single component and blends were taken into account to describe the good compatibility of TPU/PA1212 blends. The effect of PA1212 content on the rheological behaviors, morphology, mechanical, and thermal properties of TPU/PA1212 blends were systematically investigated with scanning electron microscope, tensile strength measurement, thermal gravimetry analysis, differential scanning calorimetry, and Vicat softening temperature (VST). The results showed that PA1212 formed submicron dispersion domains in the TPU matrix, indicating good compatibility between TPU and PA1212. A slight increase of the tensile strength was achieved as PA1212 content is relatively low. Because of the strong hydrogen‐bonding interaction between TPU and PA1212, the thermal stability of the blends is improved, and VST values rise up from about 80 (pure TPU) to 100°C, showing attractive potential application. POLYM. ENG. SCI., 2008. © 2007 Society of Plastics Engineers     

Morphologies and mechanical properties of polylactide/thermoplastic polyurethane elastomer blends

To explore a potential method for improving the toughness of a polylactide (PLA), we used a thermoplastic polyurethane (TPU) elastomer with a high strength and toughness and biocompatibility to prepare PLA/TPU blends suitable for a wide range of applications of PLA as general‐purpose plastics. The structure and properties of the PLA/TPU blends were studied in terms of the mechanical and morphological properties. The results indicate that an obvious yield and neck formation was observed for the PLA/TPU blends; this indicated the transition of PLA from brittle fracture to ductile fracture. The elongation at break and notched impact strength for the PLA/20 wt %TPU blend reached 350% and 25 KJ/m², respectively, without an obvious drop in the tensile strength. The blends were partially miscible systems because of the hydrogen bonding between the molecules of PLA and TPU. Spherical particles of TPU dispersed homogeneously in the PLA matrix, and the fracture surface presented much roughness. With increasing TPU content, the blends exhibited increasing tough failure. The J‐integral value of the PLA/TPU blend was much higher than that of the neat PLA; this indicated that the toughened blends had increasing crack initiation resistance and crack propagation resistance. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

含异氰酸酯基的低聚物和聚醚增容改性POM/TPU共混物

利用双螺杆挤出机制备了聚甲醛(POM)/热塑性聚氨酯弹性体(TPU)、POM/TPU/含异氰酸酯基的低聚物(Z)以及POM/TPU/Z/聚醚3种共混物。采用力学性能测试、差示扫描量热分析(DSC)、偏光显微镜(PLM)、傅里叶转换红外线光谱 (FTIR)、扫描电子显微镜(SEM)、动态力学性能分析(DMA)等,研究了3种共混物的力学性能、结晶行为及形态结构。结果表明：共混物的缺口冲击强度和断裂伸长率随TPU含量的增加而提高;异氰酸酯基低聚物（Z）和聚醚在促进分散相分散、增强两相间的相容性方面发挥重要作用,降低了聚甲醛的结晶度,能够有效地提高共混物的缺口冲击强度和断裂伸长率。     

Morphology and mechanical properties of blends of thermoplastic polyurethane and polyolefins

Polyolefins (PO) were melt mixed with thermoplastic polyurethane (TPU) in a 20 : 80 weight ratio with or without compatibilizer containing 0.5 wt % of maleic anhydride. Effects of component viscosities on morphology and on mechanical properties of the blend were studied by scanning electron microscope (SEM), tensile property analysis, and dynamic mechanical analysis (DMA). It was found that the disperse particle size of compatibilizer‐free blends decreased with the decreasing viscosity ratio of the disperse phase to TPU. The efficiency of the compatibilizer in reducing the particle size varied with viscosity ratios of the disperse phase to compatibilizer. However, the particle size did not decrease with the decreasing viscosity ratio monotonically. With lower viscosity ratio, addition of 5 wt % compatibilizer resulted in a greater reduction of particle size and less loss in the tensile properties as compared to the TPU matrix. For the polyethene (PE) that has the lowest viscosity value among all the POs, its size in the blend was stabilized with the addition of compatibilizer and no compatibilization was detected by DMA and by tensile property analysis. The mobility of the disperse phase and compatibilizer and the dispersion competition between them seemed important. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 875–883, 2006     

Interfacial reaction and its influence on phase morphology and impact properties of modified‐polyacetal/thermoplastic polyurethane blends

The cationic polymerization of 1,3,5‐trioxane, 1,3‐dioxolane and a small amount of 2‐hydroxyacetic acid (HAA) was carried out, and the resulting modified‐polyacetal (POM) was blended with thermoplastic polyurethane (TPU) in melt. The results of ¹H NMR analysis indicated that HAA was almost incorporated in the modified‐POM, and that the resulting carboxyl end‐group and hydroxyl end‐group in the modified‐POM reacted with TPU during the melt blending. There were many boundary layers between the cavities and matrix in the modified‐POM/TPU (82/18 by weight) blend that was etched with tetrahydrofuran (THF), and the diameter of the cavities became ～0.3–1 μm long when the blending time reached 10 min. The results of scanning electron microscopic (SEM) observation and dynamic mechanical analysis (DMA) indicated that the modified‐POM/TPU blend had a good compatibility because of the interfacial reaction between the modified‐POM and TPU phase in the blend. The modified‐POM/TPU blend exhibited higher Charpy impact strength when compared with a normal‐POM/TPU blend; the toughness of the modified‐POM/TPU blend attributed to the good compatibility between the two phases. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4375–4382, 2006     

Preparation and characterization of nanoclay‐filled polyurethane/polypropylene blends

Ester‐based thermoplastic polyurethane (TPU) nanocomposites were prepared by melt blending at 190°C, using 3 wt% Cloisite 10A (organically modified montmorillonite clay) as the nanoscale reinforcement [TPU(C10A)]. The nanocomposites were subsequently melt‐blended with polypropylene (PP) using maleic anhydride–grafted polypropylene (MA‐g‐PP) as a compatibilizer [in the ratio of 70/30‐TPU/PP, 70/25/5‐TPU/PP/MA‐g‐PP, 70/25/5‐TPU (C10A)/PP/MA‐g‐PP]. Besides giving substantial increase in modulus, tensile strength, and other properties, organoclay reinforcement functions as a surface modifier for TPU hard segment resulting in improved dispersion. The morphology and other characteristics of the nanocomposite blends were investigated in terms of X‐ray diffraction, fourier transform infrared spectroscopy, differential scanning calorimetry, dynamic mechanical analysis, tensile properties, scanning electron microscopy, and atomic force microscopy. The results indicate that the ester‐TPU(C10A)/PP/MA‐g‐PP exhibited better dispersion than other blend systems; abrasion resistance and water absorption resistance were also better for this system. POLYM. ENG. SCI., 50:1878–1886, 2010. © 2010 Society of Plastics Engineers     

Effects of polyoxyethylene nonylphenol on dynamic mechanical properties and crystallization of polypropylene

Polypropylene (PP) was blended with polyoxyethylene nonylphenol (PN) in a twin-screw extruder and injection moulded. The dynamic mechanical properties of PP/PN blends were characterized by dynamic mechanical analyser (DMA). The glass transition temperature (T_g) of PP showed a slight decrease with incorporation of PN. Differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD) and polarized optical microscopy (POM) were employed to investigate the effects of PN on crystallization of PP. In a study of nonisothermal crystallization of PP and PP/PN blends, crystallization parameter analysis showed the addition of PN reduced the peak temperature of crystallization. β-form crystals of PP coexisted with α-form crystals in PP/PN blends, and oriented on the surface layer of injection moulded bar as revealed by WAXD. The degree of orientation was determined using Hermans orientation function. The thermal stability of β-form crystals was evaluated using high temperature WAXD and POM.     

Super‐Tough and Highly‐Ductile Poly(l‐lactic acid)/Thermoplastic Polyurethane/Epoxide‐Containing Ethylene Copolymer Blends Prepared by Reactive Blending

Ethylene‐methyl acrylate‐glycidyl methacrylate copolymer (E‐MA‐GMA) is employed to improve the impact toughness of poly(l ‐lactic acid) (PLLA)/thermoplastic polyurethane (TPU) blends by reactive melt‐blending. The reaction and miscibility between the components are confirmed by Fourier transform infrared spectroscopy, dynamic mechanical analysis, and differential scanning calorimetry. A super‐tough PLLA/TPU/E‐MA‐GMA multiphase blend (75/10/15) exhibits a significantly improved impact strength of 77.77 kJ m^?2, which is more than 17 times higher than that of PLLA/TPU (90/10) blend. A co‐continuous‐like TPU phase structure involving E‐MA‐GMA phase at the etched cryo‐fractured surface and the high‐orientated matrix deformation at the impact‐fractured surface are observed by scanning electron microscopy. The high‐orientated matrix deformation induced by the co‐continuous TPU phase structure is responsible for the super toughness of PLLA/TPU/E‐MA‐GMA blends.     

Miscibility,Mechanical and Thermal Properties of Melt-Mixed Poly(trimethylene terephthalate)/Polypropylene Blends

This study examined the miscibility, mechanical and thermal properties of melt-mixed blends of PTT(poly(trimethylene terephthalate)) with PP(isotatic polypropylene). DMA and SEM results indicated that the PTT/PP blends are immiscible. Revealed from TGA analyses, the blends with a higher PP content showed a higher degradation temperature. A complex melting behavior was observed for the blends. The isothermal crystallization kinetics of the blends was analyzed from 200°C to 210°C using the Avrami equation. The WAXD results showed that the crystal structure of PTT remained unchanged in the blends. Nevertheless, the PP rich blends possessed lower tensile strength and higher elongation at break.     

The study of morphology,thermal and thermo‐mechanical properties of compatibilized TPU/SAN blends

The compatibilizing efficiency of three different compatibilizers in thermoplastic polyurethane/styrene‐co‐acrylonitrile (TPU/SAN) blends was investigated after their incorporation via melt‐mixing. The compatibilizers studied were poly‐ε‐caprolactone (PCL), a mixture of polystyrene‐block‐polycaprolactone (PS‐b‐PCL) and polystyrene‐block‐poly(methyl methacrylate) (PS‐b‐PMMA), and a mixture of polyisoprene‐block‐polycaprolactone (PI‐b‐PCL) and polybutadiene‐block‐poly(methyl methacrylate) (PB‐b‐PMMA). All compatibilizers were synthesized by living anionic polymerization. Investigations of thermal and thermo‐mechanical properties performed by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DTMA), respectively, were systematically classified into two groups, i.e. blends of TPU or SAN with 20 wt% of different compatibilizers (so‐called limit conditions) and TPU/SAN 25/75 blends with 5 wt% of different compatibilizers. In order to determine the compatibilizer's location, morphology of TPU/SAN 25/75 blends was studied with transmission electron microscopy (TEM). Different compatibilization activity was found for different systems. Blends compatibilized with PCL showed superior properties over the other blends. Polym. Eng. Sci. 44:838–852, 2004. © 2004 Society of Plastics Engineers.     

Study on thermoplastic polyurethane/polypropylene (TPU/PP) blend as a blood bag material

Blends with different ratios of thermoplastic polyurethane/polypropylene (TPU/PP) were prepared by melt mixing using an internal Haake mixer. Properties of the blends were investigated using SEM micrographs of cryofractures and measurement of the mechanical strength, water absorption, cell culture, and platelet adhesion in vitro tests, which were compared with those of PVC blood bags. The effect of the addition of the ethylene–vinyl acetate (EVA) copolymer on the TPU/PP blend properties was investigated. The results indicated that a TPU/PP/EVA = 80/20/5 blend can be used as a new blood bag material. It was observed that the blend is homogeneous with higher mechanical strength than that of the commercial PVC blood bag. This blend also showed a compatible cell response in contact with L929 fibroblast cells and fewer tendencies to interaction with platelets compared to the PVC blood bag. Although the blends were immissible and no chemical reaction at the interface could be found, the blood compatibility of the blends were improved. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2496–2501, 2003     

Mechanical properties and structural characteristics of dynamically photocrosslinked PP/EPDM blends

The mechanical properties and crystal morphological structures of dynamically photocrosslinked polypropylene (PP)/ethylene‐propylene‐diene terpolymer (EPDM) blends have been studied by mechanical tests, wide‐angle X‐ray diffraction (WAXD), scanning electron microscopy (SEM), and differential scanning calorimetry (DSC). Dynamically photocrosslinking of PP/EPDM blends can improve the mechanical propertiess considerably, especially the notched Izod impact strength at low temperature. Data obtained from mechanical tests show that the notched Izod impact strength of a dynamically photocrosslinked sample with 30% EPDM at ?20°C is about six times that of an uncrosslinked sample with the same EPDM component. The results from the WAXD, SEM, and DSC measurements reveal the enhanced mechanism of impact strength for the dynamically photocrosslinked PP/EPDM blends as follows: (i) the β‐type crystal structure of PP is formed and the interplanar distance of β‐type crystal increases slightly with an increase in the EPDM component; (ii) the droplet size of the EPDM phase in the photocrosslinked PP/EPDM blends is obviously reduced and the droplet number is increased with an increase in the EPDM component during the dynamical photocrosslinking process; (iii) the graft copolymer of PP‐g‐EPDM is formed at the interface between PP and EPDM components. All the above changes from the crystal morphological structures are favorable for increasing the compatibility and enhancing the toughness of PP/EPDM blends at low temperatures.     

Effect of alkali‐resistant glass fiber on polypropylene/polystyrene blends: Modeling and characterization

Alkali‐resistant glass fiber (GF) reinforced polypropylene (PP)/polystyrene (PS) blends were prepared by melt mixing in a Thermo Haake Rheochord mixer. Variation in thermal and mechanical properties with the addition of glass fibers into the polypropylene/polystyrene blends was investigated. The characterization of PP/PS/GF composites was done by dynamic mechanical analysis (DMA), thermogravimetric analysis, scanning electron microscope, and transmission electron microscope. The experimentally observed tensile properties of glass fiber reinforced PP/PS blends were compared with various published models. It was found that the experimental results agree well with Hui‐ Shia and series models. DMA tests revealed an increase in storage modulus with fiber loading confirms the greater degree of stress transfer from the matrix to the fiber. TEM micrographs reveal that the glass fibers are located at the interface between the blend components. POLYM. COMPOS., 37:398–406, 2016. © 2014 Society of Plastics Engineers     

Dynamic‐mechanical and thermal characterization of polypropylene/ethylene–octene copolymer blend

Polypropylene/Ethylene–Octene copolymer (PP/EOC) blends were prepared by melt blending technique followed by compression molding. The effect of addition of EOC on the mechanical behavior of the PP matrix was investigated. Tensile and flexural strengths decreased with the incorporation of EOC. However, the impact strength of the matrix polymer increased in all the blend systems. The blends prepared at 30% EOC content showed an increase in the impact strength to the tune of 380% as compared with polypropylene (PP) matrix. The morphology of the fractured surfaces was investigated employing Scanning Electron Microscopy. SEM micrographs depicted the formation of biphase structure, wherein the EOC phases were homogeneously dispersed as small droplets within the PP matrix. WAXD patterns revealed that the α monoclinic form of isotactic PP does not show any significant change with the incorporation of EOC up to 70 wt %. DSC thermograms revealed a decrease in the melting temperature of the virgin matrix with the addition of EOC. The blend system at 50% EOC exhibited a broad crystallization exotherm at 75°C thus indicating multiple crystallization behavior primarily attributed to the difference in the nucleation process. Further DMA analysis showed presence of two different relaxation peaks corresponding to the T_g of EOC and PP matrix respectively, confirming the formation of a biphase structure. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Oriented distribution structure,interaction, and performance of thermoplastic polyurethane/selective hindered amine hybrids

By employing the melt blending method, selective hindered amines were oriented to disperse in the hard phase of thermoplastic polyurethane (TPU). The microstructure and performance of organic hybrids consisting of TPU and poly‐[(1‐hydroxyethyl ‐2,2,6,6‐ tetramethyl‐ 4‐hydroxyl piperidine)]‐glycolsuccinate (GW‐622) and poly‐{[6‐(1,1,3,3‐tetramethylbutyl) ‐imino]‐[1,3,5‐triazine‐2,4‐ dimethyl] [2‐(2,2,6,6‐ tetramethyl piperidinyl)‐ imino]‐cyclohexane‐[4‐(2,2,6,6‐tetramethyl piperidinyl)‐imino]} (GW‐944) were investigated by dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), scanning electric microscopy (SEM), and tensile measurement. The neat TPU matrix displayed only one glass transition peak in the DMA curve, whereas the TPU/GW‐622 hybrids exhibited two overlapping loss peaks, and the TPU/GW‐944 hybrids demonstrated two separated relaxation peaks. The second excited relaxation peak of the hybrids was attributed to the oriented distribution of hindered amine in TPU and strong intermolecular interactions between the hindered amine and the hard segments of TPU. The complex and interesting evolution in structure and properties of the hybrids with hindered amine incorporation was interpreted. The loss peak areas (TA) of the hybrids increased greatly, and the high temperature damping properties was expected to improve. This kind of novel hybrid presented a promising future as high performance damping material. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Scrutinizing the influence of peroxide crosslinking of dynamically vulcanized EVA/TPU blends with special reference to cable sheathing applications

A novel thermoplastic vulcanizate (TPV) based on the blends of ethylene vinyl acetate/thermoplastic polyurethane (EVA/TPU) at various blend ratios has been developed via dynamic vulcanization at 180 °C using di‐(2‐tert‐butyl peroxy isopropyl) benzene (DTBPIB) peroxide as the cross‐linking agent. Modification of the EVA/TPU blends via dynamic crosslinking significantly improves the tensile strength and modulus of the system and the improvement is more significant for EVA/TPU 50/50 and 60/40 blends. AFM study shows that crosslinked EVA particles are dispersed in the continuous TPU matrix and the dispersed EVA domain sizes are relatively smaller in EVA/TPU 50/50 and 60/40 blends leading to good mechanical properties. FTIR spectroscopy has been used to characterize the specific chemical changes occurring due to dynamic vulcanization. This TPV has excellent retention of physico‐mechanical properties even after reprocessing twice and the blends also have very good thermal resistance as indicated by aging study. The samples were found to exhibit remarkable improvement in oil resistance property as compared to their uncrosslinked counterpart. The creep behavior of the blends significantly improves after dynamic crosslinking and blends with higher TPU content show better creep resistance. Volume resistivity of all the peroxide vulcanized blends is in the range of 10¹³ ohm cm, which is suitable for cable sheathing application. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43706.