Properties and preparation of olefin block copolymer/thermoplastic polyurethane blends

The properties of olefin block copolymer (OBC)/thermoplastic polyurethane (TPU) blends with or without maleic anhydride (MA) modification were characterized and compared. Compared with the OBC/TPU blends, OBC‐g‐MA/TPU blends displayed finer morphology and reduced domain size in the dispersed phase. The crystallization temperatures of TPU decreased significantly from 155.9 °C (OBC/TPU) to 117.5 °C (OBC‐g‐MA/TPU) at low TPU composition in the blends, indicating the inhibition of crystallization through the sufficient interaction of modified OBC with TPU composition. The modified systems showed higher thermal stability than the unmodified systems over the investigated temperature range due to the enhanced interaction through inter‐bonding. The highest improvement in tensile strength was more than fivefold for OBC‐g‐MA/TPU (50/50) in comparison with its unmodified blend via the enhanced interfacial interaction between OBC‐g‐MA and TPU. This also led to the highest Young's modulus of 77.8 ± 3.9 MPa, about twofold increase, among the investigated blend systems. A corresponding improvement on the ductility was also observed for modified blends. The modification did not vary the glass transition temperature and crystalline structure much, thus the improvement in the mechanical properties was mainly attributed to the improved compatibility and interaction from the compatibilization effect as well as increased viscosity from the crosslinking effect for modified blends. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43703.     

Blends of thermoplastic polyurethane (TPU) and polydimethyl siloxane rubber (PDMS), part-I: assessment of compatibility from torque rheometry and mechanical properties

Thermoplastic polyurethane (TPU) and polydimethyl siloxane rubber (PDMS) are two major polymers used extensively for biomedical applications. Blending of these polymers combines the superior mechanical properties, abrasion resistance, solvent resistance and aging resistance of TPU with chemical stability, inertness, flexibility and biocompatibility of PDMS. In the present investigation, an 80:20 blend of TPU and PDMS was selected for the preparation of an in situ compatibilized blend using ethylene methyl acrylate copolymer (EMA) as the compatibilizer. Effect of EMA on blends of ester type and ether type TPU with PDMS was studied. From the results obtained from torque rheometry, mechanical property evaluation, fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM) and scanning electron microscopy (SEM), it was concluded that 5 wt% of compatibilizer effectively compatibilized an 80:20 blend of ester type TPU and PDMS, whereas similar blend of ether type TPU required only 2 wt% compatibilizer.     

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     

Synthesis, characterization, and properties of a novel acrylic terpolymer with pendant perfluoropolyether segments

A novel acrylic terpolymer with pendant perfluoropolyether (PFPE) segments has been synthesized and fully characterized. By hexamethylene diisocyanate functional groups PFPE monofunctional macromonomers have been grafted on a poly(butyl methacrylate-co-hydroxyethyl acrylate-co-ethyl acrylate) random terpolymer. Such grafted copolymer behaves like an interface-active material, since the perfluoropolyether segments in solvent cast films rearrange themselves at the air-polymer interface by surface segregation. In addition, blends of the above graft copolymer with acrylic base polymers (either the terpolymer itself or a commercial copolymer) have been examined in terms of surface segregation and fluorine enrichment of the external layers.The critical surface tension, γ_c, of solid films made of the neat graft copolymer as well as of the polymer blend has been evaluated by contact angle measurements and Zisman plots. Even a small addition (5 wt%) of the fluorinated copolymer to the acrylic component has been found very effective in lowering the surface tension. The outermost surface composition has been investigated by XPS technique, confirming the strong fluorine enrichment. Furthermore, SEM and EDX analyses have been performed on cross-sectioned films, showing that in the above polymer blends macrophase surface segregation has originated a thick layer made of fluorinated copolymer close to the air-polymer interface.     

High-pressure solution blending of poly(?-caprolactone) with poly(methyl methacrylate) in acetone + carbon dioxide

The miscibility of blends of poly(?-caprolactone) (PCL, M_w = 14,300) with poly(methyl methacrylate) (PMMA, M_w = 15K or 540K) in acetone + CO₂ mixed solvent has been explored. The liquid-liquid phase boundaries at different temperatures have been determined for mixtures containing 10 wt% total polymer blend, 50 wt% acetone and 40 wt% CO₂. The PCL and PMMA contents of the blends were varied while holding the total polymer concentration at 10 wt%. The polymer blend solutions all displayed LCST-type behavior and required higher pressures than individual polymer components for complete miscibility. Complete miscibilities were achieved at pressures within 40 MPa. The DSC scans show that the blends are microphase-separated. The blends display the melting transition of PCL and the glass transition temperature of the PMMA phases. The presence of PMMA is found to influence the crystallization and melting behavior of PCL in the blends. The DSC results on heat of melting and the FTIR spectra, specifically the changes at 1295 cm⁻¹ band show the changes (decrease) in overall crystallinity of the blend upon addition of PMMA.     

Triple-shape memory properties of thermoplastic polyurethane/olefin block copolymer/polycaprolactone blends

Thermoplastic polyurethane (TPU)/olefin block copolymer (OBC)/polycaprolactone (PCL) blends (70/20/10 and 50/30/20) were melt-blended to form the first environmental OBC-based triple-shape memory polymer blends. In this work, PCL with low crystalline temperature (switching phase), OBC with medium crystalline temperature (switching phase), and TPU with high crystalline temperature (fixed phase) could form an alternative triple-shape memory polymer (TSMP). Two compatibilizers, OBC-g-glycidyl methacrylate (OBC-g-GMA) and dicumyl peroxide, were confirmed to show a synergistic effect in enhancing the compatibility further through the morphological observation. Crystallinity of both OBC and PCL in the blends with or without modification decreased in comparison with that of pure resin. For dual-shape behaviors, the shape fixing ratio (R_f) and shape recovery ratio (R_r) were up to 96.3% and 91.2% for the GMA and peroxide-modified blends (50/30/20). The higher amount of TPU didn’t give higher recovery ratio, but instead slightly lower R_r due to the morphology difference. For triple-shape behaviors, both TPU/OBC/PCL blend compositions with or without GMA or peroxide modifications gave high R_f(C→B) values in the first fixing stage, but slightly lower values R_f(B→A) in the second fixing stage, especially for (70/20/10) case. On the other hand, a reverse trend was observed for two recovery stages. To enhance the R_f(B→A) in the second fixing stage, higher deformation temperatures were considered, and a measurable increment on R_f(B→A) was attained. Through this subtle adjustment on the temperature difference between high and low deformation temperatures, the theoretical multi-shape memory shape could be readily tailored to meet different applications.     

Hot melt adhesive properties of PA/TPU blends compatibilized by EVA-g-MAH

A new copolyamide (PA52) with good adhesion to aluminum (Al) sheets was synthesized from caprolactam, nylon 66 salt, nylon 1010 salt, and stearic acid, and a series of PA52/TPU blends compatibilized by maleic anhydride-grafted ethylene vinyl acetate (EVA-g-MAH) were prepared for use as hot melt adhesives. In the ternary blends (PA52/EVA-g-MAH/TPU), the weight ratio of PA52 to TPU was kept constant at 50/50 and the amount of EVA-g-MAH was varied at 0, 2, 4, 6, and 8 wt% over the total weight of the blend, respectively. The solubility parameters were taken into account to describe the partial compatibility of PA52/TPU blends. The effects of EVA-g-MAH content on the melt viscosity, morphology, mechanical and thermal properties of ternary blends were systematically investigated, and the adhesion strength of hot melt adhesives based on the ternary blends were determined in terms of 90° peeling strength tests of Al/adhesive/ABS stacks. The results showed that the melt viscosity of ternary blends were greater than that of PA52/TPU blend, and the blend containing 6 wt% EVA-g-MAH exhibited an optimal miscibility behavior and excellent mechanical properties, at the same time, its peeling strength reached the maximum (120 N/25 mm).     

Polyethylene/starch blends with enhanced oxygen barrier and mechanical properties: Effect of granule morphology damage by solid-state shear pulverization

A mechanical process called solid-state shear pulverization (SSSP) was used to create blends or composites of polyethylene (PE) and starch that resulted in damaged granular structures. Because starch granules are unchanged when polymer/starch blends are made by melt mixing, this is the first time that damage (surface roughening, cracking, and clustering) to starch granule morphology has been reported in polymer/starch blends or composites. These morphological changes result in a 29% reduction in oxygen permeability for a 70/30 wt% PE/starch blend made by SSSP relative to neat PE; this compares with a 21% reduction in oxygen permeability when a similar blend is made by melt processing. In addition, relative to neat PE, the tensile modulus of a 70/30 wt% PE/starch blend is increased by 20% in the damaged starch case (vs. 10% in the blend made by melt mixing) while the reduction in tensile strength is significantly smaller than that found in melt-mixed blends.     

Miscibility, free volume behavior and properties of blends from cellulose acetate and castor oil-based polyurethane

A series of blend films from cellulose acetate (CA) and castor oil-based polyurethane (PU) were prepared. Morphology, miscibility, free volume behavior and properties of such blend films were investigated by wide-angle X-ray diffraction (WXRD), infrared, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), positron annihilation lifetime spectroscopy (PALS), thermogravimetric analysis and tensile test. The results indicated that lager free volume cavities did not form at the interface of two polymers although a certain degree of phase separation was found by the studies of SEM and DSC. Strong intermolecular hydrogen bonding interactions at the interface, which was proved by Fourier transform infrared spectroscopy, favors even better molecular packing, that is, PU dispersed in CA continuous phase to form fine microphase separation domain in the CA-rich blends. Due to such special interactions in the fine microphase separation domain structure, optimized properties of tensile strength, breaking elongation and cold-resistivity were obtained in the blend film with 75 wt% CA. The toughness of all the blend films was significantly higher than that of the film CA, owing to the plasticizing of PU elastomer in the blends.     

Supercritical CO2–assisted synthesis and characterization of a polystyrene/thermal polyurethane blend

A blend of polystyrene and thermal polyurethane (PS/TPU) was prepared using supercritical (SC) CO₂ as a substrate‐swelling agent and monomer/initiator carrier. The SC CO₂/styrene/TPU ternary system was studied. Virgin TPU and synthesized blends were characterized through differential scanning calorimetry, infrared spectroscopy, rheometric measurements, and SEM. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2016–2020, 2005     

Compatibilizing effects of block copolymer mixed with immiscible polymer blends by solid-state shear pulverization: stabilizing the dispersed phase to static coarsening

A continuous, industrially scalable process called solid-state shear pulverization (SSSP) leads to compatibilization of polystyrene (PS)/high-density polyethylene (HDPE) blends by addition of a commercially available styrene/ethylene-butylene/styrene (SEBS) triblock copolymer. Partial or full compatibilization is characterized by a reduction or elimination of coarsening of the dispersed-phase domains during high-temperature (190 °C), static annealing. In the case of a 90/10 wt% PS/HDPE blend, processing with 3.5 wt% SEBS block copolymer by SSSP yields a coarsening rate that is reduced by a factor of 10 (six) relative to a melt-mixed blend without copolymer (with 3.5 wt% SEBS block copolymer). Addition of 5.0 wt% SEBS block copolymer to the 90/10 wt% PS/HDPE blend during SSSP yields a reduction in coarsening rate by a factor of thirty relative to a melt-mixed blend without copolymer. With an 80/20 wt% PS/HDPE blend, pulverization with 10 wt% SEBS block copolymer yields cessation of coarsening when the average dispersed-phase domain diameter reaches 1.6-1.7 μm. The implications of these results for developing a new, technologically attractive method for achieving compatibilization of immiscible polymer blends are discussed.     

TPU/PLA nanocomposites with improved mechanical and shape memory properties fabricated via phase morphology control and incorporation of multi-walled carbon nanotubes nanofillers

Shape memory polymer nanocomposites based on thermoplastic polyurethane (TPU)/polylactic acid (PLA) blends filled with pristine multi-walled carbon nanotubes (MWCNTs) and modified MWCNTs─COOH were fabricated by direct melt blending technique and investigated for its morphology, mechanical, thermal, electrical, and shape memory properties. Morphological characterizations by using transmission electron microscope (TEM) and field emission scanning electron microscope (FESEM) revealed better dispersion of MWCNTs─COOH in the polymer blend, which is attributed to the improved interfacial interactions between the polymer blends and MWCNTs-COOH. Loading of the MWCNTs-COOH in the TPU/PLA blends resulted in the significant improvements in the mechanical properties such as tensile strength and elastic modulus and these effects are more pronounced on increasing the MWCNTs─COOH loading amount, when compared to the pristine MWCNTs filled system. Thermal analysis showed that the glass transition temperature of the blends increases slightly with increasing loading of both pristine and modified MWCNTs in the system. The resistance of nanocomposites decreased from 2 × 10¹² Ω to 3.2 × 10¹⁰ Ω after adding 3% MWCNTs─COOH. The shape memory performance tests showed that the enhancement of shape recovery by 252% could be achieved at 3% MWCNTs loading, when compared to that of TPU/PLA blends.     

Compatibilizing effect of EPM-g-MA in EPDM/poly(trimethylene terephthalate) incompatible blends

The morphology of immiscible and highly incompatible blends of Sorona^® polymer [Poly(trimethylene terephthalate), PTT] and ethylene propylene diene rubber (EPDM) blends has been studied with and without the addition of a compatibilizer precursor EPM-g-MA. These incompatible blends are characterized by a two-phase morphology, narrow interphase, and poor physical and chemical interactions across the phase boundaries. Therefore, a reactive route was employed to compatibilize these blends by the addition of maleic anhydride grafted ethylene propylene rubber (EPM-g-MA). The blends were prepared in an internal mixer. The morphology was examined by scanning electron microscopy (SEM) after preferential extraction of the minor phase. The SEM micrographs were quantitatively analyzed for domain size measurements. The morphology of the blends indicated that the EPDM phase was preferentially dispersed as domains in the continuous Sorona^® matrix up to 30% of its concentration. A co-continuous morphology was observed above 30 wt% of EPDM content followed by a phase inversion beyond 60 wt% of EPDM. The influence of EPM-g-MA on the phase morphology of blends was studied quantitatively by SEM. It was found that the addition of EPM-g-MA reduces the domain size of the dispersed phase followed by a leveling off at higher concentrations of the compatibilizer. This is an indication of interfacial saturation. The experimental compatibilization results were compared with theoretical predictions. The conformation of the compatibilizer at the interface was analyzed based on the area occupied by the compatibilizer at the blend interface. Free volume measurements using positron annihilation lifetime spectroscopy (PALS) were done to analyze the interaction of blends. In the case of uncompatibilized blends the free volume values tend to increase by the addition of EPDM phase showing high level of incompatibility. Addition of EPM-g-MA to the blends tends to decrease the free volume showing its compatibilizing effect.     

Reverse exfoliation in a polymer nanocomposite by blending with a miscible polymer

An investigation of the permeability to methanol of blends of a PA-6 nanocomposite and ethylene-vinyl alcohol copolymers (EVOH), containing approximately 32 mol% ethylene, has been conducted. Blends were prepared by melt compounding and permeation measurements were performed by gravimetric uptake methods. The nanocomposite polyamide exhibited significantly reduced permeability compared to the unmodified polymer. The blends exhibited permeability that was non-linear with blend composition. The nanoscale filler in a blend containing up to 50 wt% EVOH remained fully exfoliated, however, in a blend containing 75 wt% of EVOH there was little or no exfoliation and the blend had a measured permeability lower than that of either of the pure components. Electron microscopy and X-ray analysis has indicated a reversal of exfoliation of the nanocomposite filler particles to be responsible.     

Effect of tie-layer thickness on the adhesion of ethylene-octene copolymers to polypropylene

The adhesion of some ethylene-octene copolymers to polypropylene (PP) and high density polyethylene (HDPE) was studied in order to evaluate their suitability as compatibilizers for PP/HDPE blends. A one-dimensional model of the compatibilized blend was fabricated by layer-multiplying coextrusion. The microlayered tapes consisted of many alternating layers of PP and HDPE with a thin tie-layer inserted at each interface. The thickness of the tie-layer varied from 0.1 to 15 μm, which included thicknesses comparable to those of the interfacial layer in a compatibilized blend. The delamination toughness was measured in the T-peel test. Generally, delamination toughness decreased as the tie-layer became thinner with a stronger dependence for tie layers thinner than 2 μm. Inspection of the crack-tip damage zone revealed a change from a continuous yielded zone in thicker tie layers to a highly fibrillated zone in thinner tie layers. By treating the damage zone as an Irwin plastic zone, it was demonstrated that a critical stress controlled the delamination toughness. The temperature dependence of the delamination toughness was also measured. A blocky copolymer (OBC) consistently exhibited better adhesion to PP than statistical copolymers (EO). A one-to-one correlation between the delamination toughness and the reported performance of the copolymers as compatibilizers for PP/HDPE blends confirmed the key role of interfacial adhesion in blend compatibilization.     

Adhesion of CPO onto high modulus TPO: Lap-shear tests in conjunction with microscopy studies of the fracture surface structure

A lap-shear test was employed to investigate the failure mechanism of a chlorinated polyolefin (CPO) coating on a high-modulus thermoplastic olefin (TPO) substrate fabricated as a blend of a highly crystalline Ziegler-Natta isotactic polypropylene (iPP) and a crystalline metallocene poly(ethylene-butene) (9 wt% butene, EB9) impact modifier. The CPO was a chlorinated polypropylene containing 20 wt% Cl. The results showed that the fracture strength increased with increasing EB9 content in TPO blends. They also showed that the presence of xylene vapor during the bake step improved the adhesion between CPO and iPP itself (by 40%), but had a much smaller effect for the TPOs. Optical and transmission electronic microscopy images revealed a well-defined skin layer approximately 230 μm thick at the mold surface of the injection molded substrates. For the 25 wt% EB9 blend (TPO₂₅), this skin layer consists of thin fibers of EB trapped in a transcrystalline iPP matrix, with crystalline lamellae propagating from the matrix across the EB9 domains. Laser scanning confocal fluorescence microscopy (LCFM) and scanning electron microscopy images of iPP/CPO/iPP samples indicate that failure occurred close to the interface between the CPO and the iPP substrate, and, during fracture, the CPO layer maintained its original thickness. For the TPO/CPO/TPO sandwich samples, the fracture surfaces themselves were much rougher than that between CPO and iPP. Substantial deformation of the CPO layer was seen in the fractured samples, and failure was due primarily to cohesive fracture of the CPO in the region adjacent to the TPO substrate. From the perspective of newly introduced environmental regulations restricting aromatic hydrocarbons in automotive coatings, the most important result was the strong adhesion between CPO and TPO₂₅, with little difference between the samples exposed to xylene vapor and those not exposed to xylene.     

Polyoxymethylene/thermoplastic polyurethane blends compatibilized with multifunctional chain extender

Novel compatibilized polyoxymethylene/thermoplastic polyurethane (POM/TPU) blends are successfully developed using multifunctional chain extender, Joncryl ADR‐4368, as the compatibilizer. The outstanding compatibilization efficiency of Joncryl on POM/TPU blend was demonstrated by its even higher mechanical properties with only 0.5 wt % of Joncryl than those with 5 wt % of three commonly used compatibilizers. Addition of only 0.5 wt % Joncryl can double the impact strength and significantly improve its tensile strength and flexural strength for POM/TPU (75/25) blend. SEM images show that Joncryl can reduce TPU particle size and enhance the interfacial interactions between POM and TPU. The interparticle distance of TPU in POM/TPU/Joncryl blends was calculated as 0.2 μm, quite close to the critical matrix ligament thickness of POM/TPU blends (0.18 μm). The impact force profile vividly shows that the addition of Joncyl in POM/TPU blends can dramatically increase the total impact energy absorbed by this blend system and enhance the interfacial interactions between POM and TPU. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Characterizing interfacial structure of TPO/CPO/TPO adhesive joints by PFM-AFM and SEM

The influence of annealing and EBR component in injection-molded thermoplastic polyolefin (TPO) plaques on adhesion strength of CPO to TPO was investigated by a lap shear test. The TPO was fabricated as a blend of highly crystalline isotactic polypropylene (iPP) and low crystalline poly(ethylene-butene) impact modifier (EBR28). The CPO was a maleated chlorinated polypropylene containing 21.8 wt% Cl. High resolution pulsed force mode-atomic force microscopy (PFM-AFM) combined with the image analysis was used to characterize the interfacial properties of the lap shear joints. Based on PFM-AFM stiffness images, a “transition zone” with a width on the order of 600-1500 nm was observed between CPO and the TPO substrate that may play an important role in affecting the adhesion strength. This zone exhibits enhanced stiffness after annealing at 120 °C. The PFM-AFM images further show that the interface between iPP and CPO without annealing is very sharp and the interface between TPO and CPO without annealing is wider than the interface between iPP and CPO. Annealing (120 °C/20 min) leads to broadening of the interface between TPO and CPO. The thickness of the interface in lap shear joints was obtained from the z-directional line profiles of the stiffness maps. The fracture surface morphology was revealed by scanning electronic microscope (SEM), which showed that the fracture structure varied with both the addition of EBR28 in TPO plaques and the annealing condition. Finally, a correlation of interfacial properties to adhesion was obtained: higher stiffness in the transition zone coupled with a thicker interface resulted in stronger adhesion and cohesive failure within the CPO and TPO. In the case of CPO/iPP, the narrow interface and absence of a clearly defined transition zone correlated with interfacial failure between these components.     

Effect of loading-rate on fracture micromechanism of methylmethacrylate-butadiene-styrene polymer blend

Methylmethacrylate-butadiene-styrene (MBS) polymer blends having two different types of rubber particle distribution, monomodal and bimodal, were prepared, and their fracture properties and fracture mechanisms were investigated under quasi-static and impact loading. A fracture property, maximum J-integral J_max, was evaluated at both loading-rates, and it was shown that J_max values of the bimodal MBSs are much greater than that of the monomodal with small particles, and slightly better than that of the monomodal with large particles. Thick damage zones were observed in the crack-tip regions in the bimodal and monomodal with large particles, indicating larger energy dissipation during fracture initiation than in the monomodal with small particles in which damage zone is much thinner. TEM micrographs exhibit that extensive plastic deformation under quasi-static rate and multiple craze formation under impact loading rate are the primary toughening mechanisms in the bimodal MBS blends. By assessing both fracture properties and transparency, the bimodal blend with blend ratio: 2.5/7.5 (=140 nm/2.35 μm; total rubber particle content is 10 wt%) was proved to show the best performance as MBS polymer blend with satisfiable transparency and high fracture resistance.     

Secondary effects of antioxidant on PS/PVME blends

Interactions between the antioxidant Santonox (4,4′-thiobis(6-tert-butyl-m-cresol)) and the LCST polymer blend of polystyrene (PS) and polyvinylmethylether (PVME) were examined. The presence of the antioxidant caused inhomogeneities in blend films cast from toluene solutions at antioxidant compositions greater than 0.25 wt% of the PVME. Also, the cloud-point of the blend decreased linearly with antioxidant content with a slope of 21 °C/wt%. As expected, the ability of the antioxidant to prevent degradation of the PVME within the blend was found to increase with increasing Santonox composition. Based on these results, an antioxidant composition of no more than 0.10 wt% is recommended in the studies of PS/PVME blends.