Dual lamellar crystal structure in poly(vinylidene fluoride)/acrylic rubber blends and its biaxial orientation behavior

The miscibility for melt-mixed poly(vinylidene fluoride) (PVDF)/acrylic rubber (ACM) blends and the crystal morphology of PVDF in the blends were investigated over the whole composition ranges by dynamic mechanical analysis (DMA), wide-angle X-ray diffraction (WAXD), small-angle X-ray scattering (SAXS), and transmission electron microscopy (TEM). DMA measurements revealed that PVDF is miscible with ACM in ACM-rich system, and partially miscible in PVDF-rich system. Two kinds of PVDF lamellar structures with different long periods were detected by SAXS and TEM for the partially miscible blends. In the miscible system, only one kind of crystal lamellae with enlarged long period is found. The two kinds of lamellar structures in the blend show different orientation behavior during the uniaxial stretching to result in a biaxial orientation. The lamellae with short long period are oriented vertical to the stretching direction, while those with large long period were found to be oriented parallel to the stretching direction.     

Thermoplastic Acrylic Rubber Physically Crosslinked by Tiny Poly(vinylidene fluoride) Crystals

Summary: Acrylic rubber showed greatly improved mechanical properties and very nice elasticity when blended with small amount of PVDF. PVDF crystallized into very sparse and loose spherulites in the blends with ACM molecular chains incorporated into the PVDF lamellae. These micro‐crystals were precisely dispersed in the ACM matrix and acted as the physical crosslink points for the matrix upon stretching. Therefore, the ACM/PVDF blends containing small amounts of PVDF display the typical properties of thermoplastic elastomers with large elongation at break, high tensile strength, and excellent strain recovery from the highly deformed state.

Schematic diagram of physically crosslinked ACM by the tiny PVDF crystals in ACM‐rich PVDF/ACM blends.     

Crystallization behavior and hydrophilicity of poly(vinylidene fluoride)/poly(methyl methacrylate)/poly(vinyl pyrrolidone) ternary blends

Ternary blends composed of matrix polymer poly(vinylidene fluoride) (PVDF) with different proportions of poly(methyl methacrylate) (PMMA)/poly(vinyl pyrrolidone) (PVP) blends were prepared by melt mixing. The miscibility, crystallization behavior, mechanical properties and hydrophilicity of the ternary blends have been investigated. The high compatibility of PVDF/PMMA/PVP ternary blends is induced by strong interactions between the carbonyl groups of the PMMA/PVP blend and the CF₂ or CH₂ group of PVDF. According to the Fourier transform infrared and wide‐angle X‐ray difffraction analyses, the introduction of PMMA does not change the crystalline state (i.e. α phase) of PVDF. By contrast, the addition of PVP in the blends favors the transformation of the crystalline state of PVDF from non‐polar α to polar β phase. Moreover, the crystallinity of the PVDF/PMMA/PVP ternary blends also decreases compared with neat PVDF. Through mechanical analysis, the elongation at break of the blends significantly increases to more than six times that of neat PVDF. This confirms that the addition of the PMMA/PVP blend enhances the toughness of PVDF. Besides, the hydrophilicity of PVDF is remarkably improved by blending with PMMA/PVP; in particular when the content of PVP reaches 30 wt%, the water contact angle displays its lowest value which decreased from 91.4° to 51.0°. Copyright © 2011 Society of Chemical Industry     

Understanding of intermolecular interaction in PVDF/PTW blends: Crystallization behavior,thermal, and dynamic mechanical properties

Poly(vinylidene fluoride) (PVDF)/ poly(ethylene–butylacrylate–glycidyl methacrylate) (PTW) blends were directly prepared by melt blending and the interaction and properties of PVDF/PTW blends were explored systematically. The crystallization behavior, thermal stability, dynamic mechanical property, and morphological features of PVDF/PTW blends with different ratios have been studied by XRD, attenuated total reflection Fourier transform infrared spectroscopy, differential scanning calorimeter analysis (DSC), thermal gravimetric analysis (TGA), dynamic mechanical analysis, and polarized optical microscopy (POM). The results showed that the crystalline structure of neat PVDF was dominantly α‐phase crystalline and the incorporation of PTW had no effect on the crystalline structure of PVDF in the PVDF/PTW blends. And T_g of PVDF in PVDF/PTW blends shifted to higher temperature compared with that of neat PVDF, indicating the weak interaction between PVDF and PTW, which was corresponding to DSC and TGA results. An increase in the coarseness and ring‐band spacing observed from POM further substantiated the weak interaction between PVDF and PTW. This work provided a way for preparing improved properties of PVDF/PTW blends for the coating material. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43908.     

Influence of fluorine interface to the crystallization of poly (vinylidene fluoride)/silicone rubber/fluororubber elastomeric tertiary blends via dynamical curing

ABSTRACT

We demonstrate the influence of fluorine interface to the crystallization of poly(vinylidene fluoride) (PVDF)/silicone rubber (SR)/fluororubber (FKM) tertiary dynamic curing blends. In contrast to PVDF/SR binary blend, the average size of PVDF spherulites turns smaller and the crystallization rate is lower in PVDF/SR/FKM tertiary blend when more fluororubber component was added into the blends at the same crystallization temperature. Incorporation of FKM does not change the crystalline form of PVDF in the blends. The resulting mechanical properties of tensile strength, flexural strength, Izod impact strength and elongation at break for PVDF/SR/FKM tertiary blends are enhanced compared with PVDF/SR binary blend.     

Influence of compatibilizers on mechanical properties,crystallization, and morphology of polypropylene/scrap rubber dust blends

Polypropylene blends containing a dispersed phase of scrap rubber dusts obtained from sport shoes manufacture; midsole (M, vulcanized EVA foam) and outsole (O, vulcanized rubber blend of NR, SBR, and BR) were studied. The influence of various compatibilizers on the mechanical properties of these blends were investigated. Significant development of impact strength was attained by using 6 and 10 phr of styrene–ethylene–butylene–styrene (SEBS) and maleic anhydride‐grafted styrene–ethylene–butylene–styrene (SEBS‐g‐MA) as compatibilizers for both compounds filled with midsole and outsole dusts. The tensile strength of each compound was slightly decreased when the compatibilizer loading increased, whereas the elongation at break was significantly increased. The enhancements of the impact strength and the elongation at break are believed to arise from reduction of interfacial tension between two phases of the rubber and the PP, which results in some reduction of the particle size of the fillers. Scanning electron microscopy (SEM) confirmed the evidence of the reduction of scrap rubber dust into small rubber particle sizes in the compound, and also showed the occurrence of some fibrils. Optical microscopy (crossed polars) observations suggested that the addition of the rubber dust resulted in a less regular spherulite texture and less sharp spherulite boundaries. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 148–159, 2002     

PLA/chain‐extended PEG blends with improved ductility

Melt blending of polylactic acid (PLA) and a chain‐extended polyethylene glycol (CE‐PEG) have been performed in an effort to toughen the PLA without significant loss of modulus and ultimate tensile strength. The chain‐extended PEG was prepared with melt condensation of a low molecular weight PEG and 4,4′‐methylenebis(phenylisocyanate) (MDI) for enhancement of the molecular weight of PEG. The thermal and mechanical properties, miscibility and phase morphologies of blends were investigated. By using thermal and fracture surface analysis, the blends were found to be a partially miscible system with shifted glass transition temperatures. The addition of CE‐PEG leads to slight decrease in tensile strength and modulus, while the elongation at break is characterized by an important increase (540%), compared with neat PLA and PLA/PEG (low molecular weight PEG, M_n = 35,000). The relative ductility of PLA/CE‐PEG is 40 times higher than that of neat PLA. The brittle fracture of neat PLA was transformed into a ductile fracture by the addition of CE‐PEG. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

PLA/PPA共混材料的相容性和热力学性能

采用熔融共混的方法制备了聚己二酸丙二醇酯(PPA)增塑改性聚乳酸(PLA)材料,采用动态力学热分析(DMA)测试仪、差示扫描量热仪(DSC)、扫描电子显微镜(SEM)等手段研究了聚乳酸/聚己二酸丙二醇酯(PLA/PPA)共混材料的相容性、热性能和力学性能。结果表明,在PPA组分质量分数低(5%)的时候,共混物是完全相容体系;随着PPA组分含量的增加,共混物的玻璃化转变温度及冷结晶温度降低,断裂伸长率大幅度增加,当PPA质量分数为20%时,共混材料的断裂伸长率达到248%,获得了良好的增塑聚乳酸的效果。     

Miscible blends of poly(4‐vinyl phenol)/poly (trimethylene terephthalate)

A new miscible blend of all compositions comprising poly(4‐vinyl phenol) (PVPh) and poly(trimethylene terephthalate) (PTT) was discovered and reported. The blends exhibit a single composition‐dependent glass transition and homogeneous phase morphology, with no lower critical solution temperature (LCST) behavior upon heating to high temperatures. Interactions and spherulite growth kinetics in the blends were also investigated. The Flory–Huggins interaction parameter (χ₁₂) and interaction energy density (B) obtained from analysis of melting point depression are negative (χ₁₂ = ?0.74 and B = ?32.49 J cm^?3), proving that the PVPh/PTT blends are miscible over a wide temperature range from ambient up to high temperatures in the melt state. FTIR studies showed evidence of hydrogen‐bonding interactions between the two polymers. The miscibility of PVPh with PTT also resulted in a reduction in spherulite growth rate of PTT in the miscible blend. The Lauritzen–Hoffman model was used to analyze the spherulite growth kinetics, which showed a lower fold‐surface free energy (σ_e) of the blends than that of the neat PTT. The decrease in the fold‐surface free energy has been attributed to disruption of the PTT lamellae exerted by PVPh in an intimately interacted miscible state. Copyright © 2004 Society of Chemical Industry     

Effect of crystallization on microstructure and mechanical properties of poly[(ethylene oxide)‐block‐(amide‐12)]‐toughened poly(lactic acid) blend

The effect of crystallization on the microstructure and mechanical properties of a poly[(ethylene oxide)‐block‐(amide‐12)] (PEBA)‐toughened poly(lactic acid) (PLA) blend was investigated. Annealing was used to govern the crystallization microstructure and hence the mechanical properties of the blend. Crystallization resulted in the morphology of the PLA component altering from a continuous amorphous phase to continuous crystalline phase. Moreover, as the crystallization of PLA proceeded, the degree of crystallinity, spherulite size and lamellar thickness increased, and the interlamellar and interspherulitic connections became weaker. These led to the large plastic deformation in the matrix during tension being suppressed, and cracks appeared easily under tensile load, which was favorable to fracture for the blend during tension and so a small elongation at break was obtained. However, the elongation at break for all the annealed specimens was higher than that for neat amorphous PLA, suggesting that PEBA still showed a toughening effect for PLA under annealing. © 2012 Society of Chemical Industry     

Thermoplastic polyurethane and nitrile butadiene rubber blends with layered double hydroxide nanocomposites by solution blending

Polymer blending coupled with nanofillers has been widely accepted as one of the cheaper methods to develop high‐performance polymeric materials for various applications. In the present work, dodecyl sulfate intercalated Mg? Al‐based layered double hydroxide (DS‐LDH) was used as nanofiller in the synthesis of polyurethane blended with nitrile butadiene rubber (PU/NBR; 1:1 w/w) nanocomposites, which were subsequently characterized. X‐ray diffraction (XRD) and transmission electron microscopy (TEM) confirmed the partial dispersion of Mg? Al layers in PU/NBR blends at lower filler content followed by aggregation at higher filler loading. In comparison to the neat PU/NBR blend, the tensile strength (156%) and elongation at break (21%) show maximum improvement for 1 wt% filler loading. The storage and loss moduli, thermal stability and limiting oxygen index of the nanocomposites are higher compared to the neat PU/NBR blend. Glass transition temperature and swelling measurements increase up to 3 wt% DS‐LDH loading in PU/NBR compared to either neat PU/NBR or its other corresponding nanocomposites. XRD and TEM analyses indicate the partial distribution of DS‐LDH in PU/NBR blends suggesting the formation of partially exfoliated nanocomposites. The improvements in mechanical, thermal and flame retardancy properties are much greater compared to the neat blend confirming the formation of high‐performance polymer nanocomposites. Copyright © 2009 Society of Chemical Industry     

Rheology, phase morphology, mechanical, impact and thermal properties of polypropylene/metallocene catalysed ethylene 1-octene copolymer blends

Blends of a polypropylene (PP) and a metallocene catalysed ethylene-octene copolymer (EOC) were prepared using a single screw extruder fitted with a barrier screw design. The EOC used had 25 wt% 1-octene content and the weight fraction of EOC in the blends covered the range 1-30 wt.% Viscosity values for the blends determined experimentally from dual capillary rheological studies were similar to those calculated theoretically using the log additivity principle described by Ferry. This result together with scanning electron microscopy (SEM) observations and evidence from tan δ curves from dynamic mechanical thermal analysis showed PP and EOC to be partially miscible for blends having 10 wt% EOC or less. The tensile modulus, break strength and flexural modulus of the blends decreased with respect to virgin PP as the weight fraction of EOC was increased to 30 wt.% The diminution in mechanical properties was concomitant with an initial increase in elongation at break from 40% for neat PP to 140% for the blend with 15 wt% EOC before decreasing to 65% when 30 wt% EOC was blended. The optimum impact modification of the PP used in this study, in the temperature range −40 to 23 °C, was achieved by blending with between 20 and 30 wt% EOC.     

Mechanical and thermal characteristics and morphology of polyamide 6/isotactic polypropylene blends in the presence of a β‐nucleating agent

The mechanical and thermal characteristics and morphology of polyamide 6 (PA6)/isotactic polypropylene (iPP) blends (10/90 w/w) prepared with different processing procedures and incorporated with an aryl amide nucleating agent, a kind of β‐nucleating agent (β‐NA) for iPP, were investigated. The yield strength and flexural modulus of the blends decreased as β‐NA was introduced into the blends, whereas the impact strength and elongation at break improved. The crystalline structures of the blends closely depended on (1) the processing conditions and (2) competition between the β‐nucleating effect of β‐NA and the α‐nucleating effect of PA6 for iPP. Scanning electron microscopy, differential scanning calorimetry, and X‐ray diffraction were adopted to reveal the microstructures of the blends. At a low β‐NA content (<0.1 wt %), the α‐phase iPP dominated the blends, whereas the relative content of the β‐phase iPP increased remarkably when the β‐NA content was not less than 0.1 wt %. The processing conditions also showed profound influences on the supermolecular structures of iPP; this resulted in different mechanical properties of the blends. As for PA6, the crystallization behavior and crystalline structure did not exhibit obvious changes, but PA6 did play an important role in the epitaxial crystallization of iPP on PA6. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation of thermoplastic vulcanizates based on waste crosslinked polyethylene and ground tire rubber through dynamic vulcanization

An environmental‐friendly approach called high‐shear mechanical milling was developed to de‐crosslink ground tire rubber (GTR) and waste crosslinked polyethylene (XLPE). The realization of partial devulcanization of GTR and de‐crosslinking of XLPE were confirmed by gel fraction measurements. Fourier transform infrared spectral studies revealed that a new peak at 1723.3 cm^?1 corresponds to the carbonyl group (? C?O) absorption was appeared after milling. The rheological properties showed that the XLPE/GTR blends represent lower apparent viscosity after mechanical milling, which means that the milled blends are easy to process. Thermoplastic vulcanizates (TPVs) could be prepared with these partially de‐crosslinked XLPE/GTR composite powders through dynamic vulcanization. The mechanical properties of the XLPE/GTR composites increased with increasing cycles of milling. The raw XLPE/GTR blends could not be processed to a continuous sheet. After 20 cycles of milling, the tensile strength and elongation at break of XLPE/GTR (50/50) composites increased to 6.0 MPa and 185.3%, respectively. The tensile strength and elongation at break of the composites have been further improved to 9.1 MPa and 201.2% after dynamic vulcanization, respectively. Re‐processability study confirmed the good thermoplastic processability of the TPVs prepared. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Melt blending of polylactide and poly(methyl methacrylate): Thermal and mechanical properties and phase morphology characterization

Blends of polylactide with poly(methyl methacrylate), PLA/PMMA, were prepared by a semi‐industrial twin screw extruder and afterwards were injection molded. Blends were studied using different techniques as Fourier Transform Infrared Spectroscopy (FTIR), Dynamic Mechanical Analysis (DMA), Differential Scanning Calorimetry (DSC), Scanning Electron Microscopy (SEM), and mechanical properties by means of tensile and impact tests, were also studied. This work helped better understanding of apparently contradictory results reported in the literature for PLA/PMMA blends prepared by melt compounding. DSC first heating scan and DMA results showed partially miscible blends, whereas the second DSC heating scan showed miscible blends. For miscible blends, T_g values were predicted using Gordon‐Taylor equation. On the other hand, Small and Van Krevelen approaches were used to estimate the solubility parameters of neat PLA and neat PMMA, and Flory‐Huggins interaction parameter was calculated from solubility parameters. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42677.     

Phase separation,cure kinetics,and morphology of epoxy/poly(vinyl acetate) blends

Epoxy based on diglycidyl ether of bisphenol A + 4,4′diaminodiphenylsulfone blended with poly(vinyl acetate) (PVAc) was investigated through differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA) and environmental scanning electron microscopy (ESEM). The influence of PVAc content on reaction induced phase separation, cure kinetics, morphology and dynamic‐mechanical properties of cured blends at 180°C is reported. Epoxy/PVAc blends (5, 10 and 15 wt % of PVAc content) are initially miscible but phase separate upon curing. DMTA α‐relaxations of cured blends agree with T_g results by DSC. The conversion‐time data revealed the cure reaction was slower in the blends than in the neat system, although the autocatalytic cure mechanism was not affected by the addition of PVAc. ESEM showed the cured epoxy/PVAc blends had different morphologies as a function of PVAc content: an inversion in morphology took place for blends containing 15 wt % PVAc. The changes in the blend morphology with PVAc content had a clear effect on the DMTA behavior. Inverted morphology blends had low storage modulus values and a high capability to dissipate energy at temperatures higher than the PVAc glass‐transition temperature, in contrast to the behavior of neat epoxy and blends with a low PVAc content. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1507–1516, 2007     

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     

Study on the damping of EVM based blends

The mechanical and damping properties of blends of ethylene‐vinyl acetate rubber(VA content >40 wt %) (EVM)/nitrile butadiene rubber (NBR) and EVM/ethylene‐propylene‐diene copolymer (EPDM), both with 1.4 phr BIPB (bis (tert‐butyl peroxy isopropyl) benzene) as curing agent, were investigated by DMA. The effect of polyvinyl chloride (PVC), chlorinated polyvinyl chloride (CPVC), and dicumyl peroxide (DCP) on the damping and mechanical properties of both rubber blends were studied. The results showed that in EVM/EPDM/PVC blends, EPDM was immiscible with EVM and could not expand the damping range of EVM at low temperature. PVC was miscible with EVM and dramatically improved the damping property of EVM at high temperature while keeping good mechanical performance. In EVM/NBR/PVC blends, PVC was partially miscible with EVM/NBR blends and remarkably widened the effective damping temperature range from 41.1°C for EVM/NBR to 62.4°C, while CPVC mixed EVM/NBR blends had an expanded effective damping temperature range of 63.5°C with only one damping peak. Curing agents BIPB and DCP had a similar influence on EVM/EPDM blends. DCP, however, dramatically raised the height of tan δ peak of EVM/NBR = 80/20 and expanded its effective damping temperature range to 64.9°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Rheological,mechanical and morphological properties of thermoplastic vulcanizates based on high impact polystyrene and styrene‐butadiene rubber

Thermoplastic vulcanizates (TPVs) based on high impact polystyrene (HIPS)/styrene‐butadiene rubber (SBR) blends were prepared by dynamic vulcanization technique. The rheological, mechanical and morphological properties of the dynamically vulcanized blends were investigated systematically. As determined by capillary rheometer, the apparent viscosity of the blends decreases as the shear rate increases, indicating obvious pseudoplastic behavior. At low shear rate, the apparent viscosity of these blends is considerably higher than that of neat HIPS and decreases with the increase of HIPS concentration. The increase of HIPS content in the dynamically vulcanized blends contributes to the increase of tensile strength and hardness properties, while elongation at break and tensile set at break reach a maximum at 30 and 50 wt % of the HIPS content, respectively. The etched surfaces of the HIPS/SBR TPVs were investigated using field‐emission scanning electron microscopy, the morphological study reveals continuous HIPS phase and finely dispersed SBR elastomeric phase in the TPVs. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Mechanical properties and morphology of polyethylene–polypropylene blends with controlled thermal history

The effect of time–temperature treatment on the mechanical properties and morphology of polyethylene–polypropylene (PE–PP) blends was studied to establish a relationship among the thermal treatment, morphology, and mechanical properties. The experimental techniques used were polarized optical microscopy with hot‐stage, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and tensile testing. A PP homopolymer was used to blend with various PEs, including high‐density polyethylene (HDPE), low‐density polyethylene (LDPE), linear low‐density polyethylene (LLDPE), and very low density polyethylene (VLDPE). All the blends were made at a ratio of PE:PP = 80:20. Thermal treatment was carried out at temperatures between the crystallization temperatures of PP and PEs to allow PP to crystallize first from the blends. A very diffuse PP spherulite morphology in the PE matrix was formed in partially miscible blends of LLDPE–PP even though PP was present at only 20% by mass. Droplet‐matrix structures were developed in other blends with PP as dispersed domains in a continuous PE matrix. The SEM images displayed a fibrillar structure of PP spherulite in the LLDPE–PP blends and large droplets of PP in the HDPE–PP blend. The DSC results showed that the crystallinity of PP was increased in thermally treated samples. This special time–temperature treatment improved tensile properties for all PE–PP blends by improving the adhesion between PP and PE and increasing the overall crystallinity. In particular, in the LLDPE–PP blends, tensile properties were improved enormously because of a greater increase in the interfacial adhesion induced by the diffuse spherulite and fibrillar structure. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1151–1164, 2000