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1.
Phase continuity development and co-continuous morphologies are highly influenced by the nature of the interface in immiscible polymer blends. Blends of ethylene-propylene-diene terpolymer (EPDM) and polypropylene (PP) possess an interfacial tension of about 0.3 mN/m and provide an interesting model system to study the detailed morphology development in a very low interfacial tension binary system. A variety of blends with viscosity ratios of 0.2-5.0 and shear stresses of 11.7-231.4 kPa were considered. Using a variety of sophisticated morphology protocols it is shown that at low blend compositions, the dispersed phase actually exists as stable fibers of extremely small diameter of 50-200 nm and the continuity develops by fiber-fiber coalescence. An analysis using break-up times from Tomotika theory also supports the notion of highly stable dispersed fiber formation. These results challenge the current view of the dispersed phase as small spherical droplets. It is shown, under these conditions, that a seven-fold variation in the viscosity ratio has virtually no influence on % continuity or morphology, while a large change in the matrix shear stress from 11.7 to 90.9 kPa has an important effect on pore diameter. Both sides of the continuity diagram are studied and highly symmetrical continuity behavior is observed with composition. In fact a single master continuity curve is observed for these blends varying in viscosity ratio from 0.7-5.0 and with shear stresses from 11.7-90.9 kPa. Although the glass transition temperatures indicate that these materials are completely immiscible after melt mixing and cooling, it is shown that the blends demonstrate the morphological features of a partially miscible system. These results support a concept that the blend was partially miscible during melt blending, at which time the gross morphological features of the blend were developed, but becomes fully phase separated upon cooling. It appears that the quenching of the EPDM/PP blend from the melt is rapid enough to preserve the imprint of that partial miscibility on the gross blend morphology.  相似文献   

2.
In this paper, the compatibilization of polypropylene (PP)/high-density polyethylene (HDPE) blend was studied through morphological and interfacial tension analysis. Three types of compatibilizers were tested: ethylene-propylene-diene copolymer (EPDM), ethylene-vinylacetate copolymer (EVA) and styrene-ethylene/butylene-styrene triblock copolymer (SEBS). The morphology of the blends was studied by scanning electron microscopy. The interfacial tension between the components of the blends was evaluated using small amplitude oscillatory shear analysis. Emulsion curves relating the average radius of the dispersed phase and the interfacial tension to the compatibilizer concentration added to the blend were obtained. It was shown that EPDM was more efficient as an emulsifier for PP/HDPE blend than EVA or SEBS. The relative role of interfacial tension reduction and coalescence reduction to particle size reduction was also addressed. It was observed that the role of coalescence reduction is small, mainly for PP/HDPE (90/10) blends compatibilized by EPDM, EVA or SEBS. The results indicated that the role of coalescence reduction to particle size reduction is lower for blends for which interfacial tension between its components is low at compatibilizer saturation.  相似文献   

3.
Patrícia S. Calvão 《Polymer》2005,46(8):2610-2620
Here, the effect of concentration on the morphology and dynamic behavior of polymethylmethacrylate/polystyrene (PMMA/PS), for PS with two different molecular weight, and polymethylmethacrylate/polypropylene (PMMA/PP) blends was studied. The blends concentrations ranged from 5% to 30% of the dispersed phase (PS or PP). The dynamic data were analyzed to study the possibility of inferring the interfacial tension between the components of the blend from their rheological behavior using Palierne [Palierne JF. Rheol Acta 1990;29:204-14] [1] and Bousmina [Bousmina M. Acta 1999;38:73-83] [2] emulsion models. The relaxation spectrum of the blends was also studied. The dynamic behavior of 85/15 PS/PMMA blend were studied as a function of temperature. It was possible to fit both Palierne and Bousmina's emulsion models to the dynamic data of PMMA/PS blends, to obtain the interfacial tension of the blend. This was not the case for PMMA/PP. The relaxation spectrum of both blends was used to obtain the interfacial tension between the components of the blends. The values of interfacial tension calculated were shown to decrease when the concentration of the blends increased. It was shown using morphological analysis that this phenomenon can be attributed to the coalescence of the dispersed phase during dynamic measurements that occurs for large dispersed phase concentration. When the ‘coalesced’ morphology is taken into account in the calculations the interfacial tension inferred from rheological measurement did not depend on the concentration of the blend used. The values of interfacial tension found analyzing the dynamic behavior of one of the PMMA/PS blend were shown to decrease with temperature.  相似文献   

4.
A.R. Kamdar  B.C. Poon  A. Hiltner  E. Baer 《Polymer》2009,50(14):3319-2012
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.  相似文献   

5.
Morphology and mechanical properties of polypropylene (PP)/high density polyethylene (HDPE) blends modified by ethylene-propylene copolymers (EPC) with residual PE crystallinity were investigated. The EPC showed different interfacial behavior in PP/HDPE blends of different compositions. A 25/75 blend of PP/HDPE (weight ratio) showed improved tensile strength and elongation at break at low EPC content (5 wt %). For the PP/HDPE = 50/50 blend, the presence of the EPC component tended to make the PP dispresed phase structure transform into a cocontinuous one, probably caused by improved viscosity matching of the two components. Both tensile strength and elongation at break were improved at EPC content of 5 wt %. For PP/HDPE 75/25 blends, the much smaller dispersed HDPE phase and significantly improved elongation at break resulted from compatibilization by EPC copolymers. © 1995 John Wiley & Sons, Inc.  相似文献   

6.
In this study, sessile drops are imaged in a high-pressure and high-temperature view chamber to determine the density and interfacial tension of linear polypropylene (LPP) and branched polypropylene (BPP) melts in supercritical carbon dioxide (CO2). The pressure-volume-temperature (PVT) data of polyprophylene (PP)-CO2 is investigated by monitoring the swelling changes of the polymer melt in supercritical CO2. The density difference between the polymer/CO2 mixture and the CO2 is determined by combining the swelling results with the CO2 solubility information in the polymer melt. Both the Sanchez-Lacombe (SL) and the Simha-Somcynsky (SS) equations-of-state (EOS) are applied to predict the density of the PP-CO2 mixture, which is then compared to the density data obtained experimentally. The dependence of interfacial tension on the temperature and pressure of PP in supercritical CO2 is investigated at temperatures from 180 °C to 220 °C and pressures up to 31 MPa. Effects of long-chain branching on the density and interfacial tension of PP-CO2 mixtures are discussed.  相似文献   

7.
In this work, the linear viscoelastic behavior of PP/PS and PP/HDPE blends modified with SEBS and EPDM, respectively, was studied. Small amplitude oscillatory shear measurements were carried out at different temperatures, ranging from 190°C to 240°C. The storage (G') and loss (G") moduli curves obtained were horizontally shifted and curves of angle delta (δ) (δ = atan (G"/G')) as a function of complex shear modulus (G*), known as van Gurp plots, were obtained at several temperatures, to test the applicability of time‐temperature superposition principle (TTS) to these blends. The results showed that successful application of TTS depends on the flow energy of activation and horizontal shift factors of the individual components of the blend, on the interfacial properties of the blend and on the concentration of compatibilizer added to the blend. TTS application failed for PP/PS blend, but held for PP/HDPE blend. Addition of SEBS to PP/PS blends promoted successful TTS application at specific concentrations that corresponded to interfacial saturation of the dispersed phase. Addition of EPDM did not imply sensitive change on TTS application for the PP/HDPE blends.  相似文献   

8.
We have investigated melt blending approaches to interfacial localization of few-layer graphene in cocontinuous polymer blends with polyethylene as one of the components. When linear low-density polyethylene (LLDPE)/polypropylene (PP) or high-density polyethylene (HDPE)/polylactic acid (PLA) and graphene were mixed all together, graphene preferred polyethylene over PP or PLA. When PP and graphene were premixed and blended with polyethylene, some graphene was trapped at the blend interface but not enough to cover the large interfacial area. In contrast, an ultralow electrical percolation was achieved (< 0.1 vol%) in HDPE/PLA blend due to smaller interfacial area. In another approach, polystyrene was added as a tertiary minor component to HDPE/PLA blends. This continuous interfacial layer containing graphene led to a low electrical percolation threshold (< 0.2 vol%). From these investigations, we suggest general ways to reduce a percolation threshold by kinetic control of the morphology of cocontinuous polymer blends.  相似文献   

9.
In this work, the morphologies of polypropylene (PP)/ethylene‐propylene‐diene (EPDM) rubber/high density polyethylene (HDPE) 70/20/10 blends were studied and compared with the predictions of the spreading coefficient and minimum free energy models. The interfacial tension of PP/HDPE, PP/EPDM, and HDPE/EPDM blends were obtained by fitting the experimental dynamic storage modulus data to Palierne's theory. The prediction results showed core‐shell morphology (core of HDPE and shell of EPDM) in PP matrix. The PP/EPDM/HDPE blends were respectively prepared by direct extrusion and lateral injection method. Core‐shell morphology (core of HDPE and shell of EPDM) could be obtained with direct extrusion corresponding to the predicted morphology. The morphology of PP/EPDM/HDPE blends could be effectively controlled by lateral injection method. For PP/EPDM/HDPE blend prepared by lateral injection method, HDPE and EPDM phase were dispersed independently in PP matrix. It was found that the different morphology of PP/EPDM/HDPE blends prepared by two methods showed different rheological behavior. When the core‐shell morphology (core of HDPE and shell of EPDM) appeared, the EPDM shell could confine the deformation of HDPE core significantly, so the interfacial energy contribution of dispersed phase on the storage modulus of blends would be weaken in the low frequency region. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers  相似文献   

10.
Jianxiong Li  Qiang Wang  Jingshen Wu 《Polymer》2004,45(16):5719-5727
A high-density polyethylene (HDPE)/isotactic polypropylene (PP) (75/25) blend containing 25 wt% of PP was fibrillated by roller drawing at 138 °C. The fibrillated blend was processed again at temperatures ranging from 155 to 200 °C by compression molding or extrusion. The effects of molding temperature on the morphology and mechanical properties of the blend were investigated. Wide angle X-ray scattering (WAXS) and transmission electron microscopy (TEM) were used to study the morphology of the samples. The roller-drawn blend exhibited a fibrous structure with the chain direction aligned parallel to the drawing direction. After molding at 155 °C, the HDPE formed parallel-stacked lamellae retaining the parallel orientation after the melting of the PE crystals. As the molding temperature increased the parallel orientation gradually vanished and some of the parallel-stacked lamellae changed into twisted lamellae. The PP phase existed as fibrils in the PE matrix and the crystals stayed with their molecular chain aligned parallel to the fibrillation direction even when the molding temperature was far above the melting temperature of PP. Nevertheless, the orientation of the crystals did not change as the molding temperature increased from 155 to 165 °C. The internal structure of the PP fibrils changed from a needle structure to a parallel-stacked one. The PP fibrils induced the crystallization of the PE melt, leading to the formation of a trans-crystalline layer at their surface. As the molding temperature increased, more PE lamellae protruded into the PP fibrils and the interface between the PP fibrils and the PE matrix became diffuse.  相似文献   

11.
Ying Tao  John M. Torkelson 《Polymer》2005,46(13):4753-4761
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.  相似文献   

12.
Bing Na 《Polymer》2005,46(3):819-825
Epitaxial growth of high-density polyethylene (HDPE) onto lamellae of isotactic polypropylene (iPP), with HDPE chains inclined about 50° to that of iPP, has been achieved for the first time in their blends via dynamic packing injection molding. Even more, the epitaxial growth was found to be dependent on composition of the blends. The sequence of crystallization is not the dominant factor, but the fact that iPP crystallizes before HDPE is prerequisite for epitaxial growth of PE. Various lamellar orientations with composition can be explained by the competition between bulk crystallization and epitaxy at interfaces (i.e. iPP lamellae). In 20PP (20 wt% iPP by weight in blends), HDPE can readily crystallize in the bulk as a result of shear, and no epitaxial growth of PE is observed. For 80PP, however, bulk crystallization of HDPE can be depressed due to lack of nuclei in its bulk, resulting from a much finer droplets dispersed in the iPP matrix, and then epitaxial growth prevails.  相似文献   

13.
D.B. Hess  S.J. Muller 《Polymer》2002,43(4):1567-1570
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.  相似文献   

14.
Three triblock copolymers of poly[styrene-b-(ethylene-co-butylene)-b-styrene] (SEBS) of different molecular weights and one diblock copolymer of poly[styrene-b-(ethylene-co-butylene)] (SEB) were used to compatibilize high density polyethylene/syndiotactic polystyrene (HDPE/sPS, 80/20) blend. Morphology observation showed that phase size of the dispersed sPS particles was significantly reduced on addition of all the four copolymers and the interfacial adhesion between the two phases was dramatically enhanced. Tensile strength of the blends increased at lower copolymer content but decreased with increasing copolymer content. The elongation at break of the blends improved and sharply increased with increments of the copolymers. Drop in modulus of the blend was observed on addition of the rubbery copolymers. The mechanical performance of the modified blends is strikingly dependent not only on the interfacial activity of the copolymers but also on the mechanical properties of the copolymers, particularly at the high copolymer concentration. Addition of compatibilizers to HDPE/sPS blend resulted in a significant reduction in crystallinity of both HDPE and sPS. Measurements of Vicat softening temperature of the HDPE/sPS blends show that heat resistance of HDPE is greatly improved upon incorporation of 20 wt% sPS.  相似文献   

15.
A series of polyethylene (PE) blends consisting of a linear high density polyethylene (HDPE) and a linear low density polyethylene (LLDPE) with an octane-chain branch density of 120/1000 carbon was prepared at different concentrations. The two components of this set of blends possessed isorefractive indices, thus, making it difficult to detect their liquid-liquid phase separation via scattering techniques. Above the experimentally observed melting temperature of HDPE, Tm = 133 °C, this series of blends can be considered to be in the liquid state. The LLDPE crystallization temperature was below 50 °C; therefore, above 80 °C and below the melting temperature of HDPE, a series of crystalline-amorphous PE blends could be created. A specifically designed two-step isothermal experimental procedure was utilized to monitor the liquid-liquid phase separation of this set of blends. The first step was to quench the system from temperatures of known miscibility and isothermally anneal them at a temperature higher than the equilibrium melting temperature of the HDPE for the purpose of allowing the phase morphology to develop from liquid-liquid phase separation. The second step was to quench the system to a temperature at which the HDPE could rapidly crystallize. The time for developing 50% of the total crystallinity (t1/2) was used to monitor the crystallization kinetics. Because phase separation results in HDPE-rich domains where the crystallization rates are increased, this technique provided an experimental measure to identify the binodal curve of the liquid-liquid phase separation for the system indicated by faster t1/2. The annealing temperature in the first step that exhibits an onset of the decrease in t1/2 is the temperature of the binodal point for that blend composition. In addition, the HDPE-rich domains crystallized to form spherulites which decorate the phase-separated morphology. Therefore, the crystal dispersion indicates whether the phase separation followed a nucleation-and-growth process or a spinodal decomposition process. These crystal-decorated morphologies enabled the spinodal curve to be experimentally determined for the first time in this set of blends.  相似文献   

16.
We have systematically studied the crystallization and liquid-liquid phase separation (LLPS) kinetics in statistical copolymer blends of poly(ethylene-co-hexene) (PEH) and poly(ethylene-co-butene) (PEB) using primarily optical microscopy. The PEH/PEB blends exhibit upper critical solution temperature (UCST) in the melt and crystallization temperature below the UCST. The time evolution of the characteristic morphology for both crystallization and LLPS is recorded for blends at various compositions and following a quench from initial homogenous melts at high temperature to various lower temperatures. The crystallization kinetics is measured as the linear growth rate of the super structural crystals, whereas the LLPS kinetics is measured as the linear growth rate of the characteristic length of the late-stage spinodal decomposition. The composition dependence crystallization kinetics, G, shows very different characteristics at low and high isothermal crystallization temperature. Below 116 °C, G decreases with increasing PEB content in the blend, implying primarily the composition effect on materials transport; whereas at above 116 °C, G shows a minimum at about the critical composition for LLPS, implying the influence of the LLPS. On the other hand, LLPS kinetics at 130 °C is relatively invariant at different compositions in the two-phase regime. The length scale at which domains are kinetically pinned, however, depends strongly on the composition. In a blend near critical composition, a kinetics crossover is shown to separate the crystallization dominant and phase separation dominant morphology as isothermal temperature increases.  相似文献   

17.
Pierre Sarazin 《Polymer》2005,46(16):5966-5978
This paper demonstrates that temperature-induced coalescence effects during melt mixing have a major influence on the concentration range of dual-phase continuity and an order of magnitude effect on the co-continuous microstructure phase size. A detailed study on the effect of temperature of blending on the morphology of immiscible poly(ε-caprolactone)/polystyrene blends is presented. Polycaprolactone (PCL) and polystyrene (PS) are blended in a batch mixer at 50 and 5 min for various temperatures. The continuity of the phases is obtained by selective extraction of each phase and the microstructure is analyzed using image analysis on SEM micrographs and mercury intrusion porosimetry. It is observed that the blending temperature has only a small effect on the morphology up to a PS or PCL composition of about 20 or 30%. However, beyond that composition the effect is dramatic. The microstructure of the 50/50 blend demonstrates a phase size (dv) of 8.5 μm at 230 °C and 1.1 μm at 155 °C. Furthermore, the concentration range of co-continuity is broadened from 50-65%PS at 230 °C to 30-70%PS at 155 °C. The results at lower concentrations indicate that the temperature has little effect on the overall deformation/disintegration process, which appears to be due to compensating effects. For example, for PS in PCL, shear stress increases significantly at lower temperatures, but is counterbalanced by an increase in the viscosity ratio, elasticity of the phases and an increase in interfacial tension. Beyond a volume fraction of 0.30, the effect of temperature on coalescence plays a dominant role on the final morphology. It is shown in this paper that the observed morphology effects are controlled by the merging stage of coalescence. The data indicate the significant potential of mixing temperature as a tool for the morphology control of co-continuous polymer blends.  相似文献   

18.
In an attempt to provide superior products for the structural applications, this study aimed at preparing isotropic compatible high density polyethylene (HDPE)/ polypropylene (PP) blends without the use of the expensive compatibilization technique. Morphological and structural characterizations of the homopolymers and blends were carried out. In addition, some of the structurally important mechanical and thermal properties were characterized. Such characterizations were performed to investigate whether or not the blends are compatible and therefore acceptable for the structural applications. Scanning electron microscope (SEM) micrographs of the blend samples indicate that the interfacial adhesion between HDPE and PP phases is intimate in the 5/95 HDPE‐PP, good in the 85/15 HDPE‐PP and 95/5 HDPE‐PP, fair in the 30/70 HDPE‐PP and very poor in the 50/50 HDPE‐PP. Similarly, mechanical and thermal responses of the first three blends are remarkable. The 30/70 HDPE‐PP blend displays a fairly good performance. Whereas, the properties of the 50/50 HDPE‐PP blend are very poor. This decides that the first three blends are compatible and, therefore, structurally attractive materials. The fourth is partially compatible and, as a consequence, can be rather acceptable for the structural applications. However, the fifth is incompatible and, of course, is not acceptable for such applications. On the other hand, SEM micrographs and differential scanning calorimetry results indicate that the crystalline structures of individual polymers are appreciably affected by blending. Additionally, the study reveals that the end use performance of blends is strongly dependent on the crystalline structure changes occurring in each component due to blending as well as the compatibility between the blend components. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

19.
Biaxially oriented films of blends of high-density polyethylene (HDPE) with polypropylene (PP) homopolymer and PP copolymers prepared by twin-screw extrusion and lab-stretcher have been investigated by scanning electron microscopy (SEM), polarized microscopy, differential-scanning calorimeter, and universal testing machine. Three different kinds of PP copolymers were used: (i) ethylene–propylene (EP) random copolymer; (ii) ethylene–propylene (EP) block copolymer; (iii) ethylene–propylene–buttylene (EPB) terpolymer. In the SEM study of the morphology of films of HDPE with various PP blends, phase separation is observed between the PP phase and the HDPE phase for all blends and compositions. In all blends, HDPE serves to reduce the average spherulites size, probably acting as a nucleating agent for PP. The reduction of spherulite size appeared most significantly in the blend of EPB terpolymer and HDPE. A large increase of crystallization temperature was found in the blend of EPB terpolymer and HDPE compared with the unblended EPB terpolymer. For the blend of EPB terpolymer and HDPE, the improvement of tensile strength and modulus is observed with an increase of HDPE content, and this can be considered as a result of the role of HDPE in reducing average spherulite size. © 1994 John Wiley & Sons, Inc.  相似文献   

20.
The effect of high‐density polyethylene (HDPE)/polypropylene (PP) blending on the crystallinity as a function of the HDPE melt index was studied. The melting temperature and total amount of crystallinity in the HDPE/PP blends were lower than those of the pure polymers, regardless of the blend composition and melt index. The effects of the melt index, blending, and foaming conditions (foaming temperature and foaming time) on the void fractions of HDPEs of various melt indices and HDPE/PP blends were also investigated. The void fraction was strongly dependent on the foaming time, foaming temperature, and blend composition as well as the melt index of HDPE. The void fraction of the foamed 30:70 HDPE/PP blend was always higher than that of the foamed 50:50 HDPE/PP blend, regardless of the melt index. The microcellular structure could be greatly improved with a suitable ratio of HDPE to PP and with foaming above the melting temperature for long enough; however, using high‐melt‐index HDPE in the HDPE/PP blends had a deleterious effect on both the void fraction and cell morphology of the blends. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 364–371, 2004  相似文献   

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