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.     

Thermoplastic Vulcanizate Based on Poly(lactic acid) and Acrylic Rubber Blended with Ethylene Ionomer

A new thermoplastic vulcanizate (TPV) was developed by meltblending of poly(lactic acid) (PLA), acrylic rubber (ACM), and ethylene-methacrylic acid with sodium ions (EMAA-Na). The PLA/ACM/EMAA-Na blend showed low-yield strength, low modulus, and excellent strain recovery. It also demonstrated an increase in complex viscosity and decrease in melting temperature due to the interfacial reaction between the PLA and the ACM phases. The Fourier transform infrared spectroscopy results indicate that EMAA-Na can interact with both PLA and ACM, and that the Na⁺ ions act as a catalyst for the interfacial reaction between PLA and ACM, while PLA does not react with ACM without EMAA-Na. Moreover, the tensile strength at break of the PLA/ACM/EMAA-Na blend was observed to be extremely improved by the addition of hexamethylenediaminecarbamate (HMDC) due to the increasing of the cross-link density inside the rubber phase. The morphology of the PLA/ACM/EMAA-Na blend with HMDC was finer than that of PLA/ACM/EMAA-Na without HMDC. From the results, it is suggested that the interfacial reaction between the PLA and the ACM phases, the cross-linking in the ACM phase, and the finer morphology improved the mechanical properties of the blend.     

Preparation and Compatibility of EVM/TPU Blend

The preparation of EVM (ethylene‐vinyl acetate copolymer rubber)/TPU (thermoplastic polyurethane) blends with various ratios and their compatibility were investigated. The influence of mixing technology, filler type and content, the VA content in EVM (40 and 70 wt.%) and the addition of compatibilizers on the mechanical properties and the compatibility of the EVM/TPU blends were systematically studied.

The test results showed that in preparation of the blend, fillers should be added to the blend to improve the processability and that among the fillers used, silica showed the best reinforcing effect on the blends. The best parameters for blending EVM and TPU in a HAAKE rheometer was: mixing temperature 160°C, rotor speed 45 rpm and mixing time 15 min. The test results also showed that the compatibility of EVM 700 (VA=70%) with TPU was better than that of EVM400 (VA=40%). The addition of a compatibilizer EVM‐g‐MAH and EVM‐g‐FME improved the processability of the blends. The addition of EVM‐g‐MAH also improved the compatibility of EVM 700/TPU blend; both the mechanical properties and hot‐air aging properties of the blends were improved. However, the addition of EVM‐g‐FME did not improve the compatibility of EVM/TPU blends.     

Polyvinylidene Fluoride/Acrylonitrile Butadiene Rubber Blends Prepared Via Dynamic Vulcanization

Dynamically vulcanized blends based on polyvinylidene fluoride (PVDF)/acrylonitrile butadiene rubber (NBR) were prepared and characterized. The mixing torque and dynamic rheology analyses showed that the NBR phase increased the viscosity of the blends. Scanning electron microscopy (SEM) results showed that the NBR phase was in the form of spherical particles dispersed in the PVDF phase during dynamic vulcanization. Comparing PVDF-rich and NBR-rich blends, the size of the rubber particles in the NBR-rich blends were larger than those in PVDF-rich blends. Differential scanning calorimetry (DSC) results showed that the addition of the NBR phase reduced the PVDF crystallinity and T_m. Thermal gravimetric analysis (TGA) results showed that the dynamically vulcanized PVDF/NBR blends had a higher residual char mass than the neat PVDF and NBR. For PVDF-rich blends, the PVDF can be highly toughened by NBR; the Izod impact strength of the PVDF/NBR (70/30) blend was 77.5 kJ/m², which was about six times higher than that of pure PVDF. For rubber-rich blends, the PVDF component was beneficial to the mechanical properties of the blends, which can be used as thermoplastic elastomers.     

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.     

Tearing and Rheological Properties of Fully Biodegradable Poly(Lactic Acid)/Poly(Ethylene Glutaric-Co-Terephthalate) Copolyester Blends

The tearing and rheological properties of poly(lactic acid) (PLA)/poly(ethylene glutaric-co-terephthalate) copolyester (FP) blends were investigated using a wide range of blending ratios. The tearing strength values of PLA/FP were always significantly higher than that of the PLA specimen. The melt flow indexer and capillary rheometer analyses indicated that the viscous flow became difficult and the melt strength of PLA was improved after the addition of FP. The interactions between the molecular chains of PLA and FP adds FP branching and lengthens the macromolecular chains and the degree of macromolecular entanglement increases. The blends with 5 wt% FP reached the maximum melt strength and minimum flow index n, while the tearing strength approached the maximum level. At higher FP contents, the melt flow properties PLA/FP blends increased and the melt strength decreased, the tearing strength of PLA/FP blends also decreased.     

Reactive Compatibilization of Poly(trimethylene terephthalate)/Polypropylene Blends by Polypropylene‐graft‐Maleic Anhydride. Part 1. Rheology,Morphology, Melting,and Mechanical Properties

Poly(trimethylene terephthalate)/polypropylene (PTT/PP) blends were prepared by melt blending. The rheology, morphology, melting, and mechanical properties of PTT/PP blends were investigated with and without the addition of polypropylene‐graft‐maleic anhydride (PP‐g‐MAH). The melt viscosity results showed that the fluid behavior of PTT/PP blends exhibited great disparity to that of PTT but similar to that of PP; the dispersed flexible PP phase in the blends served as a “ball bearing effect” under shear stress, which made the fluid resistance markedly reduced; by contrast, the relatively rigid PTT dispersed phase made only a small contribution to the viscosity. With 5 wt.% PP‐g‐MAH addition during melt processing, both the shear viscosity and the non‐Newtonian index of 70/30 PTT/PP blend were increased over that of the corresponding uncompatibilized one, whereas the shear viscosity of the 30/70 PTT/PP melt decreased slightly indicating that a considerable amount of PP‐g‐MAH did not act as compatibilizer but probably served as plasticizer.

With the increasing of the other component, the melting temperature of the PTT phase showed a slight decrease while the melting temperature of the PP phase showed a slight increase. 5 wt.% PP‐g‐MAH addition had little influence on the melting temperatures of the two components. When PP≤20 wt.%, the cold crystallization temperature of the PTT phase (T_cc (PTT‐phase)) showed little change with the composition; however, it shifted to higher temperature when PP≥30 wt.%. The variations of the T_cc (PTT‐phase), with and without PP‐g‐MAH, suggested that, when PTT was a minor component, the excess PP‐g‐MAH which did not act as compatibilizer might serve as a plasticizer that made the PTT's cold crystallization process to be easier. The SEM results indicated that, for the uncompatibilized blends, the interfaces from particles pulling‐out are clear and smooth, while, for compatibilized blends, the reactive products are at the interfaces. The mechanical properties suggested that PP‐g‐MAH did not result in significant improvement of the toughness of the blend, but the tensile strength increased markedly.     

Correlation of the Morphological and Mechanical Properties of a Biodegradable Blend Based on Polylactic Acid

A series of binary and ternary blends composed of polylactic acid (PLA), low-density polyethylene (LDPE), and chitosan (CS) were prepared and characterized in terms of their morphological and mechanical properties. The mechanical properties of the prepared blends, including tensile properties and impact strength, were compared with neat PLA. In addition, the effect of incorporation of maleic anhydride-grafted linear low-density polyethylene (LLDPE-g-MA) as a compatibilizing agent, and the order of mixing on the mechanical and morphological properties of the ternary blends were also studied. It was observed that addition of CS enhanced the stiffness of PLA/LDPE blends while it decreased the toughness and tensile strength. It was demonstrated that addition of LLDPE-g-MA, up to 10 wt%, had no significant compatibilizing effect. However, the mechanical results indicated that when 15 wt% of LLDPE-g-MA was loaded, it started to play a compatibilizing role and caused an improvement in the toughness properties of ternary blend.     

Preparation and characterization of poly(lactic acid)/poly(methyl methacrylate) blend tablets for application in quantitative analysis by micro Raman spectroscopy

Poly(lactic acid) (PLA) is a biodegradable polymer that has a variety of applications, one of which is as biomaterial in surgery or as functional layers on implants, due to its compatibility with living tissue. This paper reports the possibilities of quantification of poly(lactic acid) (PLA) in a polymer matrix such as poly(methyl methacrylate) (PMMA) by micro Raman spectroscopy (MRS). Blends of amorphous poly(DL‐lactic acid) with poly(methyl methacrylate) were prepared by the procedure of dissolution/precipitation. Thermal properties of the blends such as the glass transition temperature (Tg) were characterized by differential scanning calorimetry (DSC). The PLA/PMMA blends exhibited only a single glass transition region, indicating that this system is miscible. The PLA/PMMA system obeys the Gordon–Taylor equation (Tg versus PLA content). Various concentration ratios of PLA blends were prepared to use as a basis for quantitative analysis by MRS. Intensities of the characteristic bands at 813 cm⁻¹ (νCOC of PMMA) and 873 cm⁻¹ (νC―COO of PLA) were used for the calculation. The calibration graph showed a good linear correlation with an R² value of 0.9985. On the basis of the calibration curve obtained, the determined content of several PLA/PMMA blends was in good agreement when compared with nominal contents. The limit of detection (LOD) and quantification (LOQ) were calculated by the calibration data set as signal‐to‐noise method. The relative standard deviation of this method was lower than 10% and the accuracy better than 4%. This study demonstrated that Raman spectroscopy provides an alternative non destructive method for quantitative analysis of PLA in a PMMA matrix. Copyright © 2015 John Wiley & Sons, Ltd.     

Effect of Unplasticized Poly Vinyl Chloride (UPVC) Molecular Weight and Graft-Acrylonitrile-Butadiene-Styrene (g-ABS) Content on Compatibility and Izod Impact Strength of UPVC/g-ABS Blends

In this study three grades of rigid poly vinyl chloride (PVC) having different molar masses were melt blended with graft-acrylonitrile-butadiene-styrene (g-ABS) in different compositions. The effect of PVC molecular weight and g-ABS composition on the compatibility and Izod impact strength of the blends were investigated. Differential scanning calorimetry (DSC) results showed a single glass transition temperature (T_g) for all the blends, representative of miscibility between the PVC phase and the styrene-acrylonitrile copolymer (SAN) phase of g-ABS which, in turn, led to compatibility of the PVC/g-ABS blends. It was observed that in all the PVC grades the blends Izod impact strength increased with increasing g-ABS content. Also, at a given composition of g-ABS, by increasing the molecular weight of the PVC phase the impact strength of the blends increased. The morphology of the fracture surfaces from the impact tests were analyzed using scanning electron microscopy (SEM) micrographs and the results showed that with increasing g-ABS content in the blend, cloudy regions increased and eventually begin to overlap each other, and the deformed material on the fracture surfaces increased. This was attributed to the blend compatibility causing greater energy dissipation in the fracture process.     

Single/Double Soft-Templates Involved Synthesis of Polyaniline Blends: Interfacial Polymerization and Characterization by AC Impedance Analysis

Polyaniline (PANI) blends with single and double soft-templates (polyvinylpyrrolidone – PVP and/or sodium dodecylbenzenesulfonate – SDBS) were synthesized using interfacial polymerization. Fourier transform infrared (FTIR) spectral study confirmed blend formation. Polyaniline-polyvinylpyrrolidone (PANI-PVP) blend had submicron aggregates of 50–150 nm nanoparticles while PANI-SDBS blend had extensively agglomerated large size flakes/grains. Polyaniline-polyvinylpyrrolidone-sodium dodecylbenzenesulfonate (PANI-PVP-SDBS) blend had larger aggregates, besides significant number of smaller grains. Alternating current (AC) impedance analysis was performed to determine their electrical properties. At room temperature the AC conductivity of the blend materials was in the increasing order, PANI < PANI-PVP < PANI-SDBS < PANI-PVP-SDBS. But other parameters, like critical frequency and power law index s, exhibited a decreasing trend in the blend materials. With regard to frequency-dependence, all the materials showed constant AC conductivity at low frequencies, but at higher frequencies and at higher temperatures conductivity increased gradually. The obeyance of a universal power law and the range of s values (0.12 < s < 0.78) suggested a correlated barrier hopping (CBH) mechanism for AC conductivity of all the materials. The trends in electrical properties that were characteristic of the role of single/double soft-templates were explained in terms of improved π-electron delocalization and hopping mechanism.     

Unusual Phase Separation Kinetics in Poly(Methyl Methacrylate)/Poly(Styrene-co-Acrylonitrile) (PMMA/SAN) Blends with PMMA of Different Molecular Weights

The influence of molecular weight of poly (methyl methacrylate) (PMMA) on the thermodynamics and dynamics of phase separation in PMMA/poly (styrene-co-acrylonitrile) (SAN) blends was investigated via optical microscopy, time-resolved small-angle light scattering (SALS), and dynamic rheological measurements. It was found that the cloud point temperature of the blends decreased with an increase in the molecular weight of the PMMA. The phase separation rates of PMMA 48K/SAN and PMMA 85K/SAN blends with the near-critical composition were almost the same at small quench depths due to the limited mobility of molecular chains at low temperatures. However, an unexpected phase separation dynamics was observed at larger quench depths. Not only the morphology evolution but also the apparent diffusion coefficient D_app calculated from SALS revealed that the phase separation rate was faster in the PMMA 85K/SAN blend than in the PMMA 48K/SAN blend. The possible reasons for this unusual rapid kinetics of phase separation observed in the higher molecular weight blend were discussed in terms of molecular mobility and viscoelasticity.     

Rheological,thermal, and mechanical properties of poly(ethylene naphthalate)/poly(ethylene terephthalate) blends

Structural, Theological, thermal, and mechanical properties of blends of poly(ethylene naphthalate) (PEN) and poly(ethylene terephthalate) (PET) obtained by melt blending were investigated using capillary rheometry, differential scanning calorimetry (DSC), scanning electron microscopic (SEM) observation, tensile testing. X-ray diffraction, and ¹H nuclear magnetic resonance (NMR) measurements. The melt Theological behavior of the PEN/PET blends was very similar to that of the two parent polymers. The melt viscosity of the blends was between that of PEN and that of PET. Thermal properties and NMR measurement of the blends revealed that PEN is partially miscible with PET in the as molded blends, indicating that an interchange reaction occurs to some extent on melt processing. The blend of 50/50 PEN/PET was more difficult to crystallize compared with blends of other PEN/PET ratios. The blends, once melted during DSC measurements, almost never showed cold crystallization and subsequent melting and definitely exhibited a single glass transition temperature between those of PEN and PET during a reheating run. Improvement of the miscibility between PEN and PET with melting is mostly due to an increase in transesterification. The tensile modulus of the PEN/PET blend strands had a low value, reflecting amorphous structures of the blends, while tensile strength at the yield point increased linearly with increasing PEN content.     

The Effect of Poly(Ethylene Succinate) on Mechanical Properties of PLLA/PES Blend Prepared by Melt-Blending

Fully biodegradable poly(L-lactide) and poly(ethylene succinate) (PLLA/PES) blends were prepared via melt-blending using PLLA and PES as reactants in a stainless steel chamber. The prepared PLLA/PES blend, as well as neat PLLA and PES, was characterized by Fourier transform infrared spectra (FTIR) and X-ray diffraction (XRD) to confirm the structure and the crystallization of PLLA in the blend. The mechanical properties of PLLA/PES blends were determined by bending and tensile tests and the effects of PES content on the mechanical properties of PLLA/PES blends were investigated. It was found that blending some amount of PES could significantly improve the elongation at break while still keeping considerably high strength and modulus. With increasing PES content, both strength and modulus gradually decreased; however the elongation at break significantly increased. SEM was used to examine the morphology of fracture surfaces of PLLA/PES blends.     

Improving the Barrier Properties of Poly(Lactic Acid) by Blending with Poly(Ethylene-Co-Vinyl Alcohol)

Poly(lactic acid) (PLA)/poly(ethylene-co-vinyl alcohol) (EVOH) blends were prepared via melt blending to improve the barrier properties of PLA. The phase morphologies and final properties (rheological behavior, thermal and dynamical-mechanical features, barrier properties, and mechanical behaviors) of the blends were investigated as a function of the EVOH content. The results indicated that hydroxyl groups of EVOH promoted the degradation of PLA, and thus affected the viscosities and morphologies of the resulting blends. The intrinsic viscosities of PLA in the blends decreased with the content of EVOH. The PLA and EVOH presented typical phase-separated morphologies, with a relatively small domain size of the EVOH phase. The EVOH enhanced the cold-crystallization behavior of PLA. The barrier properties to water vapor and oxygen increased linearly with increasing EVOH content.     

Preparation and Evaluation of the Morphology,Flammability, and Mechanical Properties of the Acrylonitrile‐Butadiene‐Styrene/Poly (vinyl chloride) Blends

Blends of two grades of acrylonitrile‐butadiene‐styrene (ABS) with three different compounds of poly (vinyl chloride) (PVC) were prepared via melt processing and their morphology, flammability, and physical and mechanical properties were investigated. SEM results showed that the ABS/PVC blend is a compatible system. Also, it can be inferred from fracture surface images that ABS/PVC blends are tough, even at low temperatures. It was found that properties of these blends significantly depend on blend composition and PVC compound type; however, the ABS types have only a small effect on blend properties. On blending of ABS with a soft PVC compound, impact strength, and melt flow index (MFI) increased, but tensile and flexural strength decreased. In contrast, blending of ABS with a rigid PVC compound improved fire retardancy and some mechanical properties and decreased MFI and impact strength.     

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．     

A Study on Compatibility and Properties of POE/PS/SEBS Ternary Blends

Ethylene‐α‐olefin copolymer (POE)/polystyrene (PS)/poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene) (SEBS) blends were prepared via melt blending in a co‐rotating twin‐screw extruder. The effects of SEBS copolymer on the morphology and rheological and mechanical properties of the blends were studied. Scanning electron microscopy (SEM) photos showed that the addition of SEBS copolymer resulted in finer dispersion of PS particles in the POE matrix and better interfacial adhesion between POE and PS compared with POE/PS blends, which exhibited a very coarse morphology due to the immiscibility between them. Interestingly, the tensile strength increased from 12.5 MPa for neat POE to 23.5 MPa for the POE/PS/SEBS (60/10/30) blend, whereas the tensile strengths of POE/PS (85.7/14.3) blend and POE/SEBS (66.7/33.3) blend were only 10.5 and 16.5 MPa, respectively. This indicates that both SEBS copolymer and PS have a synergistic reinforcing effect on POE. Dynamic mechanical thermal analysis (DMTA) and dynamic rheological property measurement also revealed that there existed some interactions between POE and SEBS as well as between SEBS and PS. DMTA results also showed that the storage modulus of POE increased when PS and SEBS were incorporated, especially at high temperature, which means that the service temperature of POE was improved.     

Mechanical Properties and Morphology of LDPE/PP Blends

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

Phase Morphology and Mechanical Properties of Polyamide-6/Polyolefin Elastomer-g-Maleic Anhydride Blends

The effects of addition of varying amounts of polyolefin elastomers (POE) (with and/or without grafted maleic anhydride) on the morphology and mechanical properties of polyamide-6 (PA6)-based blends were studied. Scanning electron microscopy (SEM) was employed to obtain some detailed quantitative analyses of the morphology of the fracture behavior for the blends containing 80 wt% PA6 and 20 wt% total elastomer. Impact strength, tensile strength, and flexural strength were also measured for these blends. The results showed that POE and PA6 were an incompatible system, but the POE-g-MAH was compatible and had a toughening effect on PA6. PA6-g-POE was formed through the reaction between POE-g-MAH and PA6 during the melt extrusion process, which reduced the size of the dispersed phase and improved the impact and tensile strength of the blends. The impact strength was improved by nine times compared with the pure PA6 or the binary blend PA6/POE when the blend ratio of the ternary blend PA6/POE/POE-g-MAH was 80/16/4.