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1.
The proposed predictive format for the tensile compliance, Db(t), of polymer blends is based on (1) a two‐parameter equivalent box model (EBM) and (2) calculations of the phase continuity of components in blends by using modified equations of the percolation theory. The input data encompass (1) selected parameters characterizing the creep of parent polymers and (2) critical volume fractions v1cr and v2cr of constituents in blends (delimiting the interval of phase cocontinuity). To describe the effects of time and stress on tensile compliance, a routinely used empirical equation was found suitable. Parameters characterizing the creep of parent polymers and their blends were extracted from generalized dependencies obtained through the superposition of time dependencies of tensile compliance assessed for a series of applied stresses and reconstructed with regard to the strain‐induced free‐volume expansion. Reconstructed dependencies can be approximated by a straight line, which simplifies the predictive format. The comparison of experimental and calculated compliance dependencies shows that the proposed format plausibly predicts the blend creep behavior over the studied interval of 0.1–10,000 min. The upswing in blend compliance after a long period of creeping is attributed to the redistribution of stresses acting on the constituents in the course of the creep under a constant load. This format is believed to have allowed the researchers in this study to anticipate (at least semiquantitatively) the creep behavior of intended blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 641–651, 2003  相似文献   

2.
Polymers commonly undergo deformation under an applied stress over their lifetime; some deformations are irrecoverable once the source of stress is removed. Therefore an understanding of the response of a polymer can be achieved by investigating the viscoelastic properties using creep experiments, where the behaviour can be monitored under small deformational loads. Poly(propylene) (PP) was blended with a polar elastic, thermoplastic, poly[ethylene‐co‐(methyl acrylate)] (EMA), to toughen the matrix. EMA formed a dispersed phase in PP that maintained its strength through its crystallinity rather than crosslinking. EMA can form a compatible interface with PP through inclusion of maleated‐PP as a compatibiliser. The viscoelasticity of the PP–EMA blends, particularly the creep behaviour is an important factor if the properties of PP are to be maintained. The creep and recovery of PP–EMA blends with varying compositions were investigated under different loads and number of cycles. High EMA content provided an alternative deformation pathway due to its elastomeric properties. The experimental creep behaviour has been evaluated using the 4‐element model with some limitations evident in the viscoelastic transitional region.

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3.
The effect of nanosilica addition on the morphology and mechanical properties of blends of isotactic PP and an ethylene/octene copolymer (EOC) is studied. TEM reveals that the well‐dispersed nanoparticles are localized exclusively in the PP phase. In the presence of a maleated PP compatibilizer addition of nanosilica leads to more finely dispersed EOC domains and a finer co‐continuous morphology. The nanoparticles reduce the rate of coalescence of the dispersed phase domains. The mechanical properties depend on the EOC and PP‐g‐MA content. Tensile and flexural properties are significantly enhanced in the presence of the silica nanoparticles, whereas impact properties are not affected. These enhancements are attributed to the favorable microstructure of the blends.

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4.
TPVs are prepared by dynamic vulcanization in which crosslinking of an elastomeric polymer takes place during its melt mixing with a thermoplastic polymer under high‐shear conditions. 30:70 wt% blends of PP and ethylene–octene copolymer are vulcanized using electron‐induced reactive processing (EIReP) employing a range of absorbed doses (25, 50, and 100 kGy) while keeping the electron energy and treatment time fixed. The structure/property relationships of the prepared samples are studied using various characterization techniques such as DMA, DSC, SEM, and melt rheology. The results suggest that EIReP offers a novel route to prepare TPVs without any chemical crosslinking and coupling agents.

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5.
In this work, the predictive control of a three‐phase catalytic reactor is considered. A predictive control algorithm, which has a non‐linear internal model represented by functional link networks, is proposed. This network structure has been shown to have a good non‐linear approximation capability, with the advantage that the estimation of its weight is a linear optimization problem. The results show the potential of the proposed procedure when it is applied to the 2‐methyl‐cyclohexanol production process, which is a non‐linear, distributed parameter and time‐varying process, typical of many important industrial systems.  相似文献   

6.
The effect of organically modified clay on the morphology and properties of poly(propylene) (PP) and poly[(butylene succinate)‐co‐adipate] (PBSA) blends is studied. Virgin and organoclay modified blends were prepared by melt‐mixing of PP, PBSA and organoclay in a batch‐mixer at 190 °C. Scanning electron microscopy studies revealed a significant change in morphology of PP/PBSA blend in the presence of organoclay. The state of dispersion of silicate layers in the blend matrix was characterized by X‐ray diffraction and transmission electron microscopic observations. Dynamic mechanical analysis showed substantial improvement in flexural storage modulus of organoclay‐modified blends with respect to the neat polymer matrices or unmodified blends. Tensile properties of virgin blends also improved in the presence of organoclay. Thermal stability of virgin blends in air atmosphere dramatically improved after modification with organoclay. The effect of organoclay on the melt‐state liner viscoelastic properties of virgin blends was also studied. The non‐isothermal crystallization behavior of homopolymers, virgin, and organoclay‐modified blends were studied by differential scanning calorimeter. The effect of incorporation of organoclay on the cold crystallization behavior of PP/PBSA blends is also reported.

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7.
Summary: The crystallization of the PBT minor phase in an EEA continuous matrix has been studied by DSC and SEM. When PBT is the minor phase, PBT crystallizes at a lower temperature, as expected, near Tc,f1 = 105 °C. Introducing different CB nanoparticles into the EEA continuous phase at contents increasing from 0.02 to 5 wt.‐% leads to important modifications of the PBT crystallization. A new PBT exotherm appears at Tc,f2 = 144 °C on the addition of CB, becoming really visible at Tc,f3 = 158 °C and finally moving to Tc,n = 185 °C at high content. The areas corresponding to these new peaks were found to increase to the detriment of that of the fractionated crystallization at Tc,f1 = 105 °C. Morphological studies and interfacial tension measurements were made to understand the surprising activity of the CB. Moreover, the substitution of the EEA phase with the less polar LLDPE confirmed the importance of the strong interactions developed by EEA with CB aggregates.

Melting and recrystallization DSC curves for the PBT/EEA 60/40 blend.  相似文献   


8.
It is still not clear why the long‐term properties of plastic weld seams can only be differentiated by the very expensive medium tensile creep tests. One hypothesis for justifying this is based on the change in the structure of the weld seam surroundings, another cites the consumption of antioxidants and the following ageing in the weld seam area to be responsible for this. Butt‐welded weld seams made of poly(propylene) were systematically produced under different process parameters. Corresponding to the particular hypothesis, these weld seams were then analyzed in various ways to find correlations or to prove one of the hypotheses. Regarding their short‐term weld seam quality, the analyzed weld seams could not be differentiated through short‐term tensile or short‐term bend test. However, the medium tensile creep tests showed significant differences in both time until failure and long‐term weld seam quality. Under long‐term loading, the start of the brittle crack could be detected in most weld seams in the fine spherulite‐zone or between this zone and the area of the flow lines. This demonstrated again that only long‐term tests are suitable for examining different weld seam qualities. Depending on the welding parameters, times until failure decline with increasing heated‐tool temperature and heating time. Though these parameters lead to a higher consumption of antioxidants in the weld seam, a degradation was not detected in the breaking area. In fact, increasing heated‐tool temperatures and heating times, as well as higher joining pressures lead to a change in the internal structure of the material. This can be seen in morphological structure analyses in the larger bend of the entire weld seam area. A larger bend, however, correlates with higher residual stresses in the weld seam. In the medium tensile creep tests, these residual stresses as well as the tensile stress in the border region and the compressive stress in the middle are superimposed by the tensile stress resulting from the test stress. Thus a greater bend of the weld seam area and higher residual stresses in the weld seam itself lead to shorter times until failure in medium tensile creep tests.

Schematic representation of the formation of residual stresses in a weld seam and residual stresses in the different bended weld seam areas.  相似文献   


9.
Summary: Propylene was copolymerized with 10‐undecen‐1‐ol using dimethylsilanylbis(2‐methyl‐4‐phenyl‐1‐indenyl)zirconium dichloride as catalyst and MAO and TIBA as cocatalysts. Comonomer incorporations from 0.1 to 0.9 mol‐% (0.5 to 3.6 wt.‐%) were obtained. These hydroxyl functionalized copolymers were applied as compatibilizers to PP/PA6 blend with a composition of 70/30. For comparison, hydroxyl functionalized polyethylene prepared with metallocene catalyst and commercial MAH grafted ethylene butyl acrylate (E/BA/MAH) and poly(propylene) (PP‐g‐MAH) were also used as compatibilizers. Effects of the compatibilizers on morphology and mechanical and thermal properties of the blends were studied. Enhanced adhesion between the blend components was observed in morphology and dynamic mechanical studies. Although improvement in toughness was not as pronounced as expected, there were indications that the hydroxyl functionalized propylene copolymers prepared with metallocene catalysts could serve as a new type of compatibilizer in polymer blends.

SEM micrograph (5 000×) of an PP/PA6/PP‐co‐OH4 blend.  相似文献   


10.
The effect of hydrophilic and hydrophobic nanosilica on the morphological, mechanical and thermal properties of polyamide 6 (PA) and poly(propylene) (PP) blends is investigated by extrusion compounding. Depending on the difference between the polymer/nanoparticle interfacial tensions, different morphologies are obtained as highlighted by TEM and SEM. Hydrophobic nanosilica migrates mainly at the PA/PP interface, which leads to a clear refinement of PP droplet size. The macroscopic properties of the hybrid blends are discussed and interpreted in relation with the blend morphology and melt‐mixing procedure. The control over coalescence allows a morphology refinement of the blends and improves mechanical properties.

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11.
This paper presents a simulation‐based approach for designing a non‐linear override control scheme to improve the performance of a local linear controller. The higher‐level non‐linear controller monitors the dynamic state of the system and calculates an override control action whenever the system is predicted to move outside an acceptable operating regime under the local controller. The design of the non‐linear override controller is based on a cost‐to‐go function, which is constructed by using simulation or operation data. The cost‐to‐go function delineates the admissible region of state space within which the local controller is effective, thereby yielding a switching rule.  相似文献   

12.
An overview of non‐linear model predictive control (NMPC) is presented, with an extreme bias towards the author's experiences and published results. Challenges include multiple solutions (from non‐convex optimization problems), and divergence of the model and plant outputs when the constant additive output disturbance (the approach of dynamic matrix control, DMC) is used. Experiences with the use of fundamental models, multiple linear models (MMPC), and neural networks are reviewed. Ongoing work in unmeasured disturbance estimation, prediction and rejection is also discussed.  相似文献   

13.
14.
The long‐term viscoelastic behavior of reinforced all‐poly(propylene) composites was studied by flexural creep tests. Both unidirectional and cross‐ply laminates were prepared from PURE® coextruded tapes by vacuum bag molding in an autoclave. The specimens were subjected to isothermal creep tests at different temperatures ranging from 20 to 80 °C under an applied load. The time‐temperature superposition principle was verified for the creep data. An Arrhenius type relationship was found to better describe the shift data obtained from the creep tests. The activation energies relating to the different reinforcement architecture and different relaxation process were calculated.

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15.
A composite of boehmite alumina nanoparticles and a PP/PA12 blend is prepared. WAXD and SEM suggest that a low filler loading enhances the coalescence of PA12, whereas a higher loading reverses the situation. DSC, DMA and TGA reveal that the final properties of the blend composites such as crystallization temperatures, flexural storage moduli, or thermal degradation temperatures improve with increasing nanoparticle loading. The data are compared with the neat polymers and the compatibilized blend, and the results show that the compatibility increases only at high nanoparticle loading, and most of the thermal properties improve with increasing nanoparticle content in the blends. The presence of interfacial interactions between the polymer matrices and the filler was confirmed via FTIR.

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16.
Summary: Blends of poly(acrylonitrile‐butadiene‐styrene) (ABS) and poly(ether ether ketone) (PEEK), in which PEEK has been used as a reinforcing medium for the ABS matrix in ratios up to 20 wt.‐% of the blend, were prepared by melt mixing using a laboratory mixer. All the blend compositions were processed at the ABS processing temperature so that the PEEK was dispersed in the ABS matrix without actually melting. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) studies revealed that the glass transition temperature (Tg) of the ABS phase in the blend did not show any appreciable change with composition. The dynamic storage modulus measured by DMA was found to be higher for the blend as compared to pure ABS due to reinforcement of the matrix by PEEK. The tensile strength and modulus behavior of these blends were found to follow the curves predicted using models proposed for composite systems having perfect adhesion, which shows the presence of some physical interaction between the blend components. The good tensile properties of the blend have been correlated with the observed morphology. The disperse phase in the blend has been found to be present in extremely small (sub‐micron) dimensions, which not only provides more surface area for possible interactions between the blend components but also result in efficient stress transfer between the matrix and the dispersed phase during the tensile tests. The thermal stability of the blends was investigated using thermogravimetric analysis (TGA). TGA further revealed that the constituents degraded at their respective decomposition temperatures.

SEM micrograph of tensile fractured surface of an ABS/PEEK 90/10 blend.  相似文献   


17.
In this study, isotactic poly(propylene) (PP)/poly(oxymethylene) (POM) blend films, including of POM as minor phase in the range of 10–30 wt%, are prepared in a twin screw extruder equipped with a slit‐die and cast film haul‐off unit. It is found that the blend films show characteristic immiscible matrix‐droplet morphology. Short‐term uniaxial tensile creep behaviors of films imply that the introducing of POM significantly improves the elastic modulus and decreases the total creep strain of PP/POM blends. Creep tests are also performed at various temperatures and long‐term deformations of samples are predicted by applying of time‐temperature superposition principle and the Findley model. It is found that the presence of POM domains into PP matrix enhances the creep resistance of PP especially at high temperatures. It is concluded that the PP‐rich PP/POM blend films show much lower short and long‐term creep strains compared to PP.

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18.
Polypropylene (PP)/nylon 11/maleated ethylene‐propylene‐diene rubber (EPDM‐g‐MAH) ternary polymer blends were prepared via melt blending in a corotating twin‐screw extruder. The effect of nylon 11 and EPDM‐g‐MAH on the phase morphology and mechanical properties was investigated. Scanning electron microscopy observation revealed that there was apparent phase separation for PP/EPDM‐g‐MAH binary blends at the level of 10 wt % maleated elastomer. For the PP/nylon 11/EPDM‐g‐MAH ternary blends, the dispersed phase morphology of the maleated elastomer was hardly affected by the addition of nylon 11, whereas the reduced dispersed phase domains of nylon 11 were observed with the increasing maleated elastomer loading. Furthermore, a core‐shell structure, in which nylon 11 as a rigid core was surrounded by a soft EPDM‐g‐MAH shell, was formed in the case of 10 wt % nylon 11 and higher EPDM‐g‐MAH concentration. In general, the results of mechanical property measurement showed that the ternary blends exhibited inferior tensile strength in comparison with the PP matrix, but superior toughness. Especially low‐temperature impact strength was obtained. The toughening mechanism was discussed with reference to the phase morphology. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

19.
Summary: A thermoplastic poly(hydroxyl‐amino ether) polymer (BLOX) was blended with a diglycidyl ether of bisphenol A monomer (DGEBA). This system may be used as a crosslinkable thermoplastic. It means that it may be processed in an extruder like a classic thermoplastic, and cured by etherification reactions initiated by tertiary amine groups of the BLOX in a second step, to produce a material with good mechanical properties. In order to understand and quantify the etherification reactions occurring at high temperature (135 °C), between epoxy groups of the diepoxy and hydroxyl groups of the thermoplastic, a model system was studied based on DGEBA in excess and ethanolamine. In the model system the rate of the etherification reaction was well described by a second‐order kinetic equation. The specific rate constants and the epoxy conversion at the gel were related to the polarity of the reactive medium. The polyetherification occurring in the DGEBA‐BLOX system could also be fitted with a second‐order kinetics. A significant increase in the reaction rate was observed when using high BLOX concentrations.

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20.
The reactive compatibilization effect of a small molecule, bismaleimide (BMI), on poly(butylene terephthalate) (PBT)/low‐density polyethylene (LDPE) and PBT/ethylene propylene diene (EPDM) rubber blends were investigated. All the blends were prepared by melt blending in the mixing chamber of a Haake Rheocord. The particle size of dispersed phase was reduced by >ten times by adding 1.2 wt % of BMI as observed with scanning electron microscopy. The torque‐time curve recorded during mixing showed that the addition of BMI leads to a significant increase in the viscosity of PBT, LDPE, EPDM, and the blends. This indicates that a chemical reaction has taken place. It was confirmed that free radicals are involved in the reactions because the addition of a stabilizer to the blends has removed all the compatibilizing effect, and the torque‐time curve does not show any increase in viscosity. A possible mechanism of compatibilization is proposed. The shear forces during melt mixing cause the rupture of chemical bond in the polymers, which form macroradicals of PBT, LDPE, or EPDM. These macroradicals react with BMI to form PBT‐BMI‐LDPE or PBT‐BMI‐EPDM copolymers. These in situ‐formed copolymers act as compatibilizers to give a significant refinement of the blend morphology. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2049–2057, 1999  相似文献   

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