Preparation and Rheology of Isocyanate Functionalized Graphene Oxide/Thermoplastic Polyurethane Elastomer Nanocomposites

Using monomer-functionalized nanofiller to prepare polymeric nanocomposites is a promising strategy toward achieving enhanced performance. In this study toluene-2,4-diisocyanate (TDI), one of the monomers used for synthesizing polyurethane, was covalently functionalized on graphene oxide (GO) and then the functionalized GO (TDI-GO) was polymerized with polycaprolactone diol (PCL) via in-situ polymerization, leading to chemically linked polyurethane nanocomposites through the covalent bonds between the isocyanate groups on GO and the hydroxyl-terminated PCL. Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and dispersion experiments of the nanofillers demonstrated that the TDI was successfully grafted onto the GO. The rheological properties were investigated to establish the structure-property relationships of the nanocomposites. The storage moduli (G’), loss moduli (G”) and complex viscosity (η*) of the samples increased monotonically with TDI-GO content, which is attributed to the strong polymer-filler interactions and the effective dispersion of the nanofillers. Additionally, the tan δ variation with frequency, the intersection of G’ and G”, Han plots, van Gurp-Palmen plots and Cole-Cole plots all showed that the incorporation of TDI-GO decreased the degree of microphase separation and improved the elastic properties of the nanocomposites. We suggest this is related to the enhanced interactions between the polymer and nanofillers, which strongly restricted the mobility and relaxation of the polymer chains.     

Morphology,Rheology, and Mechanical Properties of Polylactide/Poly(Ethylene-co-octene) Blends

Polylactide (PLA)/poly(ethylene-co-octene) (POE) blends containing ethylene-glycidyl methacrylate copolymer (EGMA) as a compatibilizer were prepared by melt blending. An immiscible, two-phase structure with POE dispersed in the PLA matrix was observed by scanning electron microscopy. It was found that the POE particle size was significantly decreased by the addition of EGMA, and the POE particle size and distribution decreased with the increase of the compatibilizer content up to 2% EGMA, beyond which the POE particle size and distribution remained unchanged. The reactions between the epoxy groups of EGMA and carboxylic or hydroxyl groups of PLA were elucidated by the Fourier transform infrared spectroscopy. Rheological results showed that the G′(ω), G″(ω), and complex viscosity of PLA/POE blends significantly increased at low frequencies with the addition of EGMA. The failure mode changed from brittle fracture of the neat PLA to ductile fracture of the PLA/POE blends.     

Properties and Structure of Dynamically Vulcanized TPU/EVM Blends

The preparation of dynamically vulcanized TPU (thermoplastic polyurethane)/EVM (ethylene-vinyl acetate copolymer rubber) blends and the effect of two peroxide curing agents, DCP (dicumyl peroxide) and BIPB (bis(tert-butyl peroxy isopropyl)benzene) on the mechanical properties, hot air aging, and oil resistance were investigated. Fourier transform infrared spectroscopy (FTIR), phase-contrast microscopy (PCM), and magnetic resonance crosslink density spectroscopy (MR-CDS) were used to analyze the curing reaction, phase structure, and crosslink density of dynamic vulcanizates. The results showed that the optimum parameters for dynamically vulcanized TPU/EVM by peroxide-DCP or BIPB in a HAAKE rheometer were: mixing temperature 140–150°C and rotor speed 30 rpm. The mechanical properties and oil resistance of these blends were improved by dynamic vulcanization. It was found that BIPB is a better curing agent than DCP for the dynamic vulcanization of TPU/EVM and its optimum content was 0.8 phr in the blend. FTIR spectra showed EVM and TPU could both be cured by peroxide in the blend and the curing reaction occurred at -CH₂- groups that were linked with -C- instead of -O- and -CH₃ groups in the blend. PCM photographs showed that dynamically vulcanized TPU/EVM blends had “sea-island” phase structure when the curing agent content was low and it had “interlocked/co-continuous” phase structure as the curing agent content was increased. The spin-lattice relaxation constant, T_21, measured with MR-CDS proved that the crosslink density of the cured blends increased with increasing curing agent content.     

The Thermal Stability and Flammability of Expandable Graphite-Filled Polypropylene/Thermoplastic Polyurethane Blends

Polypropylene/thermoplastic polyurethane (PP/TPU) blends filled with two different particle sizes (45 and 150 μm) of expandable graphite (EG) were prepared by melt blending. Thermogravimetric analysis (TGA) was carried out to explain the effect of EG on the thermal stability of PP/TPU blends. In addition, the fire behavior of PP/TPU and PP/TPU/EG was investigated by a cone calorimeter. The char morphology and carbonation of the above systems were also characterized. The experimental results indicated that intumescent EG significantly enhanced the thermal stability and fire resistance of these blends. With the smaller particle size of EG, the thermal stability and flame retardancy were improved. The results from TGA and cone calorimeter demonstrated that the addition of EG could retard the degradation of the polymer materials above the temperature of 500°C by promoting the formation of a compact char layer. This char layer prevented further degradation of the polymer matrix and protected it effectively from heat penetrating inside, resulting in lower weight loss rate and better flame-retarded performances.     

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

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

Preparation,Morphology and Properties of Poly(Trimethylene Terephthalate)/Thermoplastic Polyester Elastomer Blends

Poly(trimethylene terephthalate)(PTT)/thermoplastic polyester elastomer (TPEE) blends were prepared and their miscibility, crystallization and melting behaviors, phase morphology, dynamic mechanical behavior, rheology behavior, spherulites morphology, and mechanical properties were investigated by differential scanning calorimetry (DSC), scanning electron microscopy (SEM), dynamic mechanical analysis (DMA), parallel-plate rotational rheometry, polarized optical microscopy (POM), wide angle X-ray diffraction (WAXD), universal tensile tester and impact tester, respectively. The results suggested that PTT and TPEE were partially miscible in the amorphous state, the TPEE rich phase was dispersed uniformly in the solid matrix with a size smaller than 2 μm, and the glass transition temperatures of the blends decreased with increasing TPEE content. The TPEE component had a good effect on toughening the PTT without depressing the tensile strength. The blends had improved melt viscosities for processing. When the blends crystallized from the melt state, the onset crystallization temperature decreased, but they had a faster crystallization rate at low temperatures. All the blends’ melts exhibited a predominantly viscous behavior rather than an elastic behavior, but the melt elasticity increased with increasing TPEE content. When the blends crystallized from the melt, the PTT component could form spherulites but their morphology was imperfect with a small size. The blends had larger storage moduli at low temperatures than that of pure PTT.     

Effect of Phase Arrangement on Solid State Mechanical and Thermal Properties of Polyamide 6/Polylactide Based Co-polyester Blends

The main goal of this work is to correlate morphological parameters of the binary blend of polyamide 6 (PA6) and a polylactide (PLA) based biodegradable co-polyester blend (BioFlex) (scanning electron microscopy, solvent extraction method) with the solid-state mechanical properties (stress strain analysis) as well as thermal (differential scanning calorimetry) and selected physico-chemical characteristics (Fourier transform infrared spectroscopy and water uptake analysis). The blends of PA6/BioFlex were prepared in ratios of 100/0, 90/10, 75/25, 60/40, 50/50, 40/60, 25/75, 10/90 and 0/100 in wt.%. The occurrence of co-continuous morphology was observed within the range of 40 to 60 wt.% of BioFlex. Furthermore, the results show that the co-continuous morphology of PA6/BioFlex blends significantly affected both tensile (E modulus) and thermal properties (melting enthalpy) of the blends. In the case of the tensile properties, the effect of the morphological arrangement was strongly dependent on the deformation range. The presence of BioFlex in the blends reduced the crystallizability of PA6 noticeably. Co-continuous structure formation was observed to have a significant effect on the melting enthalpy of the blend. Composition morphology dependent responses were observed in the case of the FTIR and water uptake studies.     

Thermal Properties of Fe-octacarboxyl Acid Phthalocyanine/Polyurethane Blends

The thermal stability of PU has been a critical factor to influence its applications as engineering materials. In this paper, the thermal properties of Fe-octacarboxyl acid phthalocyanine (Fe-OCAP)/polyurethane (PU) blends were investigated. The glass transition temperatures (T_g) of Fe-OCAP/PU blends were analyzed by differential scanning calorimetry (DSC). The results showed that with increasing Fe-OCAP content up to 10% T_g of the samples decreased. Thermal stability of the samples was studied by thermogravimetric analysis (TGA). The decrease of the degradation rate of the samples with increasing Fe-OCAP content indicated an improvement of thermal stability for the modified samples. The activation energy of thermal degradation was calculated by the Freeman and Carroll method. The results showed that the activation energy increased with increasing Fe-OCAP content, which also indicated the improved thermal stability obtained in the modified samples. The thermal properties of the samples were influenced by the incorporation of Fe-OCAP.     

Mechanical and Thermal Properties of Polyurethane Elastomers Synthesized with Toluene Diisocyanate Trimer

A series of polyurethane elastomers (PUE) incorporating TDI (toluene diisocyanate) trimer were synthesized via an in-situ polymerization and prepolymer process. It was found that for the sample with 10 wt% or less TDI trimer, the stress–strain curves of PUE exhibited the characteristics of a ductile failure with relatively high tensile strength and elongation at break. However, with incorporation 20～30 wt% of TDI trimer, the samples changed to brittle fracture. All PUE samples exhibited a loss peak corresponding to the glass transition temperature (T_g ) of the soft-segments, which shifted to higher temperature and decreased in peak height by incorporation of the three-functional isocyanurate rings. Although the TDI trimer modified PUE showed only slightly higher onset and peak degradation values than that of PUE in the absence of TDI trimer, there were still big differences in the end temperatures of the second stage. The value of activation energy and frequency factor fluctuated for varying samples, indicating that the thermal stability of PUE can be improved to a certain degree by incorporation of TDI trimer, but not so remarkably.     

The Structure and Properties of Polyamide/Liquid Crystal Polymer Blends

Melt blended polyamide (PA)/liquid crystal polymer (LCP) blends were prepared and their structures and properties were studied. The tensile strength and impact strength of the PA/LCP blends increased with increasing small amount of LCP content. Compared with a pure PA sample, there was a 17.7% increase in the tensile strength and a 45.5% increase in the impact strength when the LCP content was less than 10%. On the other hand, the Vicat softening temperature decreased with increasing the LCP content. Differential scanning calorimetry (DSC) showed that small addition of LCP was beneficial to increase the crystallinity of PA component for PA/LCP blends and the melting peak for the PA component of PA/LCP blends shifted to lower temperature with increasing LCP content. Scanning electron microscopy (SEM) displayed a layered structure existing in the injection moldings of PA/LCP blends with the LCP crystals having a preferred orientation along the melt flow direction in the sub-skin, shearing layer, and core region. The increased crystallinity of PA component and preferred orientation structure of LCP phase were beneficial to increase the mechanical properties of the PA/LCP blends.     

Critical Value and Control of Complexation of Polylactide Blends Using Optical Purity

On the basis of the stereocomplex formation between poly(L-lactide) (PLLA) and poly(D-lactide) (PDLA), the stereocomplexation-induced surface properties of enantimeric polylactide blends were inverstigated by electron spectrometer for chemical analysis (ESCA) and contact angle measurements as a function of a degree of complexation. The complexation of blends was controlled by using the stereochemical polylactides (stPLAs) with percent D repeat unit contents (optical purity) of 100, 98, 95, 90, and 85%. The PLLA-b-poly(dimethyl siloxane) (PDMS)-b-PLLA triblock copolymer, instead of PLLA was used as a surface probe material because of the high surface segregation of PDMS blocks. From ESCA measurements, the surface segregation of PDMS of PLLA-b-PDMS-b-PLLA/stPLA blends with ≤10% optical impurity was rapidly decreased with a degree of complexation. However, the uncomplexed blends >10% optical impurity showed that the surface segregation of PDMS was nearly that of PLLA-b-PDMS-b-PLLA. Similar behaviors were observed in the contact angle measurements. These results indicate that 10% optical impurity is a critical value at which the complex formation and the surface properties of the PLLA-b-PDMS-b-PLLA/stPLA blends can be controlled.     

Oxygen Barrier Properties of Waterborne Polyurethane/Silica Hybrids

The oxygen barrier properties of films obtained from waterborne polyurethane/silica hybrid dispersions were analyzed. Two different types of polyurethanes were used, based on poly(propylene glycol) and poly(1,4-butylene adipate). Three different strategies were followed in the preparation of the hybrid dispersions. In the first type of materials (series 1), the inorganic part came exclusively from the covalent incorporation of trifunctional silane groups into the polymeric chains. The other two series contained, in addition to the trifunctional silane groups, tetrafunctional silane groups either physically blended (series 2) or “in situ” generated (series 3). Materials of series 1 showed an increase of the oxygen permeability coefficient with the silane content. However, the other two types of materials presented just the opposite dependence. In this latter case, the systems containing “in situ” generated silica (series 3) presented higher permeability coefficient values, probably because of the steric hindrance imposed by the polyurethane that gave rise to silica networks containing silanol groups and free volume holes. Moreover, lower permeability coefficient values were obtained when larger size particles were added. This fact could mean that the polyurethane/silica interface effects were not totally hindered even when the organic/inorganic phases were covalently bonded.     

Preparation and Properties of Polylactide/Poly(ethylene-co-octene)/nano-SiO2 Ternary Composites

Polylactide (PLA)/poly(ethylene-co-octene)(POE) blends with various contents of nano-SiO₂ were prepared via melt mixing. The structure and properties of the PLA/POE/nano-SiO₂ ternary composites were studied by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), rheometry, and tensile testing. The particle size of the dispersed POE phase first decreased with increasing nano-SiO₂ content and then remained constant. Nano-SiO₂ played an important role in the heterogeneous nucleation of PLA, which resulted in an increase of the crystallinity of PLA. The synergistic effect of both POE and nano-SiO₂ can significantly improve the toughness, strength, and modulus of PLA. When the ratio of PLA/POE/nano-SiO₂ was 90/10/0.5, PLA/POE/nano-SiO₂ composite had the best comprehensive properties.     

Studies on compatibilization of polypropylene/thermoplastic polyurethane blends and mechanism of compatibilization

This paper reports a study of compatibilization and the mechanism of compatibilization of polypropylene (PP)/thermoplastic polyurethane (TPU) blends with maleated polypropylene (PP-MA) and its graft copolymer with polyethylene oxide (PEO), (PP-MA)-g-PEO. The results of scanning electron microscope (SEM) and dynamic mechanical analysis showed that (PP-MA)-g-PEO was a very good compatibilizer for PP/TPU blends, while PP-MA also produced some compatibilization. The cocrystallization between bulk PP and PP segments of the compatibilizers was evidenced by differential scanning calorimetry studies. The specific interaction between TPU and polar parts of the compatibilizers was studied with Fourier transform infrared spectroscopy.     

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.     

Miscibility, Crystallization, and Rheological Behavior of Solution Casting Poly(3-hydroxybutyrate)/poly(ethylene succinate) Blends Probed by Differential Scanning Calorimetry, Rheology, and Optical Microscope Techniques

应用差示扫描量热、流变及偏光显微镜等方法研究了聚3-羟基丁酸酯/聚丁二酸乙二醇酯(PHB/PES)共混体系的相容性、结晶和流变行为．相图显示该共混体系有两个玻璃化转变,但PHB的熔点随其含量的减少而降低,这个结果证明该共混体系是部分相容的,同时应用偏光显微镜观察体系结晶形态的发展证实了这个结论．依赖于结晶温度和组成,PHB和PES能同时结晶,也能分步结晶,且PHB的球晶生长速率随PES含量的增加而增大．对于部分相容的聚合物共混体系,共混组成对球晶生长速率的影响也做了详细地讨论．     

Phase Structure of Compatibilized Poly(Lactic Acid)/Linear Low-Density Polyethylene Blends

Blends of PLA and linear low-density polyethylene (LLDPE) were compatibilized with glycidyl methacrylate (GMA)–grafted poly(ethylene-octene) copolymer (mPOE). Effects of compatilizer on phase structure of compatibilized PLA/LLDPE were studied by spreading coefficient calculation prediction, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and wide-angle X-ray diffraction (WAXD) analysis. The spreading coefficient calculations, based on experimental and calculated surface tension data, show that mPOE spreads on LLDPE extensively to encapsulate LLDPE completely, which is in good agreement with the results of DSC, SEM, and WAXD analysis. The chemical reaction between the end carboxyl groups or end hydroxyl groups of PLA and epoxy groups of mPOE, which is suggested as the driving force leading to an ideal interfacial adhesion between PLA and the dispersed phase, was confirmed by Fourier transform infrared ray (FT-IR) spectroscopy analysis.     

Properties of acrylonitrile butadiene rubber (NBR)/poly(lactic acid) (PLA) blends and their foams

Abstract

Thermoplastic elastomers and their foams were prepared by blending elastomeric acrylonitrile butadiene rubber (NBR) and rigid poly(lactic acid) (PLA) with various PLA compositions ranging between 0 and 40%. The thermal and mechanical properties and the morphologies of the blends with various PLA contents were investigated through universal testing machine, differential scanning calorimetry, thermogravimetric analysis, and scanning electron microscope analysis. The rheological properties during gel formation were in situ monitored through the evolution of torque with curing time. Furthermore, the microcellular structures and physical properties of the NBR/PLA foams prepared using organic blowing agents were studied. The NBR/PLA blends showed a two-phase morphology made of a continuous NBR matrix and micron or submicron nodules and the tensile strength and modulus; also, hardness of the NBR/PLA blends increased with the increase of the added PLA content. While the foamed samples exhibited a similar cell structure and foaming ratio to that of the pure NBR, the cell formation was considerably reduced as the added PLA content exceeded 30%. We conclude that the mechanical properties of NBR thermoplastic elastomer as well as its foams can be controlled by a judicious introduction of rigid and biodegradable PLA.     

Morphological,Thermal and Mechanical Properties of Compatibilized Nylon 6/ABS Blends

Super‐tough nylon 6/ABS blends were prepared by using styrene/acrylonitrile/maleic anhydride co‐polymer (SAM) as a compatibilizer. The variations in morphology, mechanical behavior, and crystallinity associated with the reaction of the SAM with the nylon were characterized. The results showed that the addition of SAM to nylon 6/ABS blends enhanced the interfacial adhesion between nylon 6 and ABS, and this led to the decrease of ABS domain size and the improvement of mechanical properties of their blends. Moreover, it could be found that the crystallinity and phase morphology changed with the variation of SAM.     

Structure and Properties of Polypropylene/Polyolefin Elastomer/Organic Montmorillonite Nanocomposites

The crystallinity, mechanical properties, and thermal stability of polypropylene (PP)/organic montmorillonite (OMMT) and PP/polyolefin elastomer (POE)/OMMT composites, with polypropylene-g-maleic anhydride/styrene (PPMS) as a compatibilizer for both, were compared. The results showed that the strong interaction between the clay platelets and compatibilizer, which were generated by the maleic anhydride (MAH), improved the compatibility of the polymer matrices with the OMMT. A unique lamellar, flocculated structure of OMMT was formed after introduction of the POE. The highly dispersed clay layers could act as nucleating agents, resulting in smaller spherulites and higher crystallization temperatures. Compared with pure PP, the PP/OMMT nanocomposite showed enhanced mechanical properties and thermal stability; however, the PP/POE/OMMT had the best impact toughness.