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1.
The stacked lamellar morphology commonly found in extruded semicrystalline materials has a strong influence on the flow direction, with respect to the loading direction, and on the stability and localization phenomena in tensile experiments. A multiscale numerical model was used to simulate the effect on the macroscopic behavior of a stacked lamellar microstructure. The model established a link between the microscopic, the mesoscopic, and the macroscopic levels. The constitutive properties of the material were identified for the crystallographic and amorphous domains. The average fields of an aggregate of individual phases, having preferential orientations, formed the constitutive behavior of the extruded material. The microscopic morphology of the extruded high‐density polyethylene is based on wide‐angle X‐ray diffraction experiments. The macrostructure was described by a finite element model. The microstructure‐induced deformation hardening in the extrusion direction was found to stabilize the macrostructure when it was loaded in the flow direction. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2983–2994, 2004  相似文献   

2.
Equilibrium sorption and uptake kinetics of n‐butane and n‐pentane in uniform, biaxially oriented, semicrystalline polyethylene terephthalate films were examined at 35 °C and for pressures ranging from 0 to approximately 76 cmHg. Sorption isotherms were well described by the dual‐mode sorption model. Sorption kinetics were described either by Fickian diffusion or a two‐stage model incorporating Fickian diffusion at short times and protracted polymer structural relaxation at long times. Diffusion coefficients increased with increasing penetrant concentration. n‐Butane solubility was lower than that of n‐pentane, consistent with the more condensable nature of n‐pentane. However, n‐butane diffusion coefficients were higher than those of n‐pentane. Infinite‐dilution, estimated amorphous phase diffusion and solubility coefficients were well correlated with penetrant critical volume and critical temperature, respectively. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 1160–1172, 2001  相似文献   

3.
Some manufacturing processes of polymeric materials, such as injection molding or film blowing, cause the final product to be highly anisotropic. In this study, the mechanical behavior of drawn polyethylene (PE) tapes is investigated via micromechanical modeling. An elasto‐viscoplastic micromechanical model, developed within the framework of the so‐called composite inclusion model, is presented to capture the anisotropic behavior of oriented semicrystalline PE. Two different phases, namely amorphous and crystalline (both described by elasto‐viscoplastic constitutive models), are considered at the microstructural level. The initial oriented crystallographic structure of the drawn tapes is taken into account. It was previously shown by Sedighiamiri et al. (Comp. Mater. Sci. 2014, 82, 415) that by only considering the oriented crystallographic structure, it is not possible to capture the macroscopic anisotropic behavior of drawn tapes. The main contribution of this study is the development of an anisotropic model for the amorphous phase within the micromechanical framework. An Eindhoven glassy polymer (EGP)‐based model including different sources of anisotropy, namely anisotropic elasticity, internal stress in the elastic network and anisotropic viscoplasticity, is developed for the amorphous phase and incorporated into the micromechanical model. Comparisons against experimental results reveal remarkable improvements of the model predictions (compared to micromechanical model predictions including isotropic amorphous domains) and thus the significance of the amorphous phase anisotropy on the overall behavior of drawn PE tapes. © 2019 The Authors. Journal of Polymer Science Part B: Polymer Physics published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 378–391  相似文献   

4.
《先进技术聚合物》2018,29(2):736-745
High density polyethylene (HDPE) nanocomposite reinforced with 2 weight percent carbon nanotube (CNT) was fabricated using mechanical milling method. Microscopic evaluations revealed appropriate dispersion of CNTs in the matrix, and tensile tests demonstrated that the tensile strength was increased by 17%. Thermal and mechanical properties of the composite samples were investigated after equal channel angular pressing (ECAP) for up to 3 passes via route A at temperature of 80°C. Density and differential scanning calorimetry (DSC) results represented decrement in crystallinity after ECAP which was led to drop in hardness and tensile yield strength of the deformed samples. Micro Vickers and Shore D hardness results also revealed clear anisotropy in mechanical properties caused by ECAP. Dilatometry results and observation of the impact fractured surfaces of deformed samples demonstrated that oriented structures formed in amorphous and crystalline regions of the composite. This microstructure evolution also caused increase in impact strength of ECAP deformed specimens. Dynamic mechanical behavior of the processed samples was modified following ECAP. The α and γ relaxation temperatures were decreased due to the reduction of thickness of crystalline lamella obtained from DSC results, in 1 pass ECAP deformed sample. Dynamic storage and loss modulus of 3 passes ECAP deformed samples were significantly decreased due to the sharp drop in their crystallinity.  相似文献   

5.
Recent developments in the area of polymerization reactor design and optimization have been highlighted using polyethylene terephthalate (PET) as an example. Both the DMT and the TPA routes for its manufacture have been discussed and it has been demonstrated that a good understanding of the various physical processes present in industrial reactors is required before good models can be developed. The simulations carried out have been tested on some industrial scale reactors as well as pilot plants and improvements have been suggested based on these studies. Presented at the Symposium on ‘Polymer Science and Engineering’ during the Annual Meeting of the Academy, Nainital, October 1982.  相似文献   

6.
To evaluate the compatibilizing effects of isocyanate (NCO) functional group on the polyethylene terephthalate/low density polyethylene (PET/LDPE) blends, LDPE grafted with 2-hydroxyethyl methacrylate-isophorone diisocyanate (LDPE-g-HI) was prepared and blended with PET. The chemical reaction occurred during the melt blending in the PET/LDPE-g-HI blends was confirmed by the result of IR spectra. In the light of the blend morphology, the dispersions of the PET/LDPE-g-HI blends were very fine over the PET/LDPE blends. DSC thermograms indicated that PET microdispersions produced by the slow cooling of the PET/LDPE-g-HI blends were largely amorphous, with low crystallinity, due to the chemical bonding. The tensile strengths of the PET/LDPE-g-HI blends were higher than those of the PET/LDPE blends having a poor adhesion. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 447–453, 1998  相似文献   

7.
The degradation of polyethylene terephthalate (PET) bottles has been successfully achieved by depolymerization through glycolysis with pentaerythritol. The reaction was performed at 250°C in the presence of an organotin catalyst. The glycolyzed products were characterized by 1D and 2D nuclear magnetic resonance (NMR) spectroscopy. The existence of the chemical bond between the polyol and the PET was detected through heteronuclear multiple bond correlation spectroscopy, and the NMR signals of different species were separated according to their diffusion coefficient by diffusion-ordered spectroscopy. This method offers a rapid quantification of glycolyzed products. Furthermore, it was found that the major product was the mono-pentaerythritol ester followed by the di-pentaerythritol ester, and lastly the tri-pentaerythritol ester.  相似文献   

8.
The oxygen‐barrier properties of amorphous copolyesters based on ethylene terephthalate with 10%, or less, of an acid comonomer were examined. Comonomer units were isophthalate, phthalate, 1,5‐naphthalate, 1,8‐naphthalate, 2,6‐naphthalate, 1,8‐anthracenate, 2,6‐anthracenate, and 2,7‐pyrenate. Even 2.5 mol % comonomer significantly affected the permeability. Linear comonomers decreased the permeability. In contrast, small amounts of a kinked comonomer increased the permeability. However, increasing the amount of kinked comonomer further (gradually) decreased permeability P below that of polyethylene terephthalate. Generally, comonomer affected solubility S less than diffusivity D; therefore, changes in P reflected primarily changes in D. The solubility and diffusivity depended on copolymer composition in accordance with static and dynamic free‐volume concepts of gas permeability in glassy polymers. The solubility correlated with the amount of free volume, as determined by the glass‐transition temperature. This study also explored the relationship of dynamic free volume, which determines D, to thermally accessible segmental motions of the polymer chain. The effect of comonomer on D correlated with the intensity of the gauche component of the subambient γ relaxation. Changes in the fraction of gauche‐glycol conformations resulting from copolymerization were confirmed by Fourier transform infrared spectroscopy. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1900–1910, 2001  相似文献   

9.
Publications on polyethylene terephthalate (PET) continue to increase including the number of publications on recycling. PET is a versatile material with the ability to be remade from its polymer state through mechanical recycling and even back to its original monomer through advanced recycling. The scale of PET's use affords continued research and applications in improved recycling. Publications on new uses of discarded PET and the ability to clean and convert it into many forms including alternative materials are expanding with an attempt to complete circular use or improve the end of life. As indicated in life cycle assessment studies, increases in recycling lower the energy required to manufacture products. The future for PET will reduce energy demands further with the largest breakthroughs in recycling technologies and bio-sourced resins trending toward zero energy and carbon negative solutions. Opportunities remain for improvement in the use of PET with light weighting. The testing of new resins, development of bio-feedstocks, improvements in engineering, processing, recycling, and design continue to provide benefits. This review provides context for these developments.  相似文献   

10.
《先进技术聚合物》2018,29(1):52-60
Polyethylene terephthalate (PET) was melt blended with linear low density polyethylene (LLDPE) and subsequently compounded with glass fibers (GF) as reinforcements at percentages ranging from 15 to 45 wt% of LLDPE and 5 to 30 wt% of GF. Thermal, morphological, and mechanical properties of the prepared composites were investigated. It was found that compounding PET/LLDPE blends with GF would be beneficial in producing composites that are thermally stable with good mechanical properties. For example, the impact strength of the composites containing 85/15 wt% (PET/LLDPE) at relatively high loading of GF, ie, from 15 to 30 wt%, was higher than that of the GF‐reinforced neat PET. When increasing the percentage of LLDPE in the composites, the impact strength increased with increasing GF content, and this was also better than that of GF‐reinforced PET whose impact strength drastically decreased upon increasing the GF%. The improvement in mechanical properties of the composite, we suggest, should be correlated with the morphologies of the composites where the visualized interface adhesion tended to be better at higher loadings of both LLDPE and GF.  相似文献   

11.
The interphase layer in semicrystalline polyethylene (PE) serves as the transition between the crystalline lamellae and the amorphous domains and is recognized as the third constituent of PE. When PE undergoes large deformations, this interphase layer together with the amorphous phase behaves hyperelastically. Because of the metastable nature and nanometric size of the interphase and its intimate mechanical coupling to the neighboring crystal and amorphous domains, detailed characterization of its hyperelastic properties have eluded detailed experimental evaluation. To extract these properties, a combined algorithm is proposed based on applying the constitutive relations of an isotropic, compressible, hyperelastic continuum to the molecular dynamics simulation results of a PE stack from Lee and Rutledge (Macromolecules 2011, 3096–3108). The simulation element is incrementally deformed to a large strain, during which the stress–strain information is recorded. Assuming a neo‐Hookean model, the tensorial constitutive equation is derived. The hyperelastic parameters for the central amorphous phase, the interphase layer, and the interlamellar domain are identified with the help of the optimization notion and a set of nonnegative objective functions. The identified hyperelastic parameters for the interlamellar domain are in good agreement with the ones estimated experimentally and frequently used in the literature for the noncrystalline phase. The specifically developed sensitivity analysis indicates that the shear modulus is identified with a higher degree of certainty, in contrast to the bulk modulus. It is also revealed that the presented continuum mechanics analysis is able to capture the melting/recrystallization and rotation of crystalline chains that take place during the deformation. The evolutions of the boundaries of the hyperelastic elements are also identified concurrently with the hyperelastic parameters as the by‐product of the presented methodology. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1692–1704  相似文献   

12.
Recycled poly(ethylene terephthalate) (R‐PET) was blended with four types of polyethylene (PE), linear low density polyethylene (LLDPE; LL0209AA, Fs150), low density polyethylene (LDPE; F101‐1), and metallocene‐LLDPE (m‐LLDPE; Fv203) by co‐rotating twin‐screw extruder. Maleic anhydride‐grafted poly(styrene‐ethylene/butyldiene‐styrene) (SEBS‐g‐MA) was added as compatibilizer. R‐PET/PE/SEBS‐g‐MA blends were examined by scanning electron microscopy (SEM), differential scanning calorimeter (DSC), dynamic mechanical analysis (DMA), and mechanical property testing. The results indicated that the morphology and properties of the blends depended to a great extent on the miscibility between the olefin segments of SEBS‐g‐MA and PE. Due to the proper interaction between SEBS‐g‐MA and LDPE (F101‐1), most SEBS‐g‐MA, located at the interface between two phases of PET and LDPE to increase the interfacial adhesion, lead to better mechanical properties of R‐PET/LDPE (F101‐1) blend. However, both the poor miscibility of SEBS‐g‐MA with LLDPE (LL0209AA) and the excessive miscibility of SEBS‐g‐MA with LLDPE (Fs150) and m‐LLDPE (Fv203) reduced the compatibilization effect of SEBS‐g‐MA. DSC results showed that the interaction between SEBS‐g‐MA and PE obviously affected the crystallization of PET and PE. DMA results indicated that PE had more influence on the movement of SEBS‐g‐MA than PE did. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

13.
Shrinkage and structural evolution of oriented high‐density polyethylene on heating were investigated by a combination of thermomechanical analysis (TMA) and synchrotron small angle X‐ray scattering (SAXS) techniques. Under varying load conditions, TMA study was performed to record the continuous length changes as a function of temperature. The value of shrinkage without any load could be evaluated by a linear extrapolation method, which eliminated the influence of the required tension by traditional TMA approach. In addition, the apparent modulus of network was used to describe the nature of entangled molecular network in detail during the shrinkage process. Importantly, it was found that the apparent modulus decreased gradually with increasing temperature. Furthermore, the SAXS data provided a direct evidence for the variation trend of shrinkage stress obtained by the tensile testing stage, and the results confirmed that the shrinkage force mainly originates from interfibrillar networks. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 368–376  相似文献   

14.
Tractable polysilanes were prepared by the copolymerization of a methyl‐n‐propylsilylene (MP) unit into poly(dimethylsilylene), which neither dissolves in common solvents nor melts before decomposition. Although poly(dimethylsilylene‐co‐methyl‐n‐propylsilylene) has poor solubility in the composition range of the dimethylsilylene (DM) unit to the MP unit (DM/MP = 7/3 ∼ 9/1), the copolymers form the columnar mesophase at elevated temperatures. Highly oriented rods were prepared via the extrusion of the copolymers with a circular tube die in a temperature range in which the transition to the columnar mesophase began to occur (70°C when DM/MP = 7/3 and 8/2 and 120°C when DM/MP = 9/1). The extruded rods were characterized in detail by dynamic viscoelasticity and wide‐angle X‐ray diffraction (WAXD) to clarify the structure–mechanical‐property relationship. The orientation functions of the extruded rods were determined by the azimuthal intensity distribution of the WAXD reflection. The orientation function and dynamic storage modulus increased with an increasing extrusion ratio. The dynamic storage modulus at −150°C was 8 ∼ 10 GPa at the highest extrusion ratio and correlated well with the crystal orientation function. The dynamic storage modulus at room temperature was lowered by the structural relaxations at −100 ∼ +30°C, which corresponded to the molecular motion of the rigid molecular chains of the copolymer and the local molecular motion of the MP unit. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 698–706, 2000  相似文献   

15.
In this article, we address in situ synthesis of polyethylene terephthalate (PET) nanocomposites using the bis (2‐hydroxyethyl) phthalate monomer and inorganic layered materials (sulfanilic acid salt‐modified magnesium aluminum‐layered double hydroxides [MgAl LDH‐SAS] and Dimethyloctadecyl [3‐(trimethoxysilyl) propyl] ammonium chloride [DTSACl] and tetraethyl orthosilicate [TEOS]‐ modified clay [CL120‐DT]). The dispersion morphology of the synthesized nanocomposites was evaluated using XRD and TEM, from these results, it was confirmed that 0.5 wt% loaded PET/MgAl LDH‐SAS and PET/CL120‐DT nanocomposites have flocculated and intercalated morphologies, respectively. Thermomechanical analyses were performed by thermogravimetric analysis, dynamic mechanical analysis, and differential scanning calorimetry, respectively. Moreover, the water vapor transmission rate (WVTR) values of a pure PET, PET/CL120‐DT 0.5 wt%, and PET/MgAl LDH‐SAS 0.5 wt% nanocomposites were found to be 49, 45, and 46 g·m?2·day?1, respectively. Furthermore, the gas barrier properties of PET composite films containing various amounts of inorganic nanoparticles were investigated using Gas permeability analysis (GPA).  相似文献   

16.
Dynamic mechanical properties and microstructure of an organic hybrid consisting of chlorinated polyethylene (CPE) and 3,9‐bis[1,1‐dimethyl‐2{β‐(3‐tert‐butyl4‐hydroxy‐5‐methylphenyl)propionyloxy}ethyl]‐2,4,8,10‐tetraoxaspiro[5,5]‐undecane (AO‐80) were investigated. The AO‐80 clearly exhibited two second‐order transitions at 6 and 69 °C in addition to the melting: the transition at lower temperature is assigned to the glass transition, and the transition at higher temperature is considered to be caused by the dissociation of hydrogen bond between the hydroxyl groups of AO‐80. When blending with CPE, part of AO‐80 molecules was dispersed into the CPE matrix, and most of them formed an AO‐80‐rich phase. As a result, a novel transition appeared above the glass‐transition temperature of the CPE matrix. It was assigned to the dissociation of the intermolecular hydrogen bond between the α‐hydrogen of CPE and the hydroxyl groups of AO‐80 within the AO‐80‐rich phase. Dynamic mechanical properties and microstructure of CPE/AO‐80 hybrid were controlled by the thermal treatment. It was found that the CPE/AO‐80 hybrid is a good damping material and shows a shape memory effect. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2285–2295, 2000  相似文献   

17.
The relaxation behavior of six fluorinated aromatic poly(ethers) was investigated using dynamic mechanical analysis. The glass transition temperature was found to increase as the size and rigidity of linking groups increased and varied between 168°C for a dimethyl linking group and 300°C for a bicyclic benzoate ether-linking group. For the α-relaxation the steepness of time/temperature plots and broadness of the loss curves could be qualitatively correlated with chemical structure in a manner predicted by the coupling model of relaxation. Well-separated sub-Tg transitions were also observed, as a shoulder on the low temperature side of the α-peak, and as a broad, low loss transition around −100°C. The higher temperature process was similar to the structural relaxation often found in quenched glassy polymers, while the position, intensity, and breadth of the subambient process was sensitive to chemical structure. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1963–1971, 1997  相似文献   

18.
A quantitative study was undertaken of the anisotropy of low‐strain mechanical behavior for specially oriented polyethylene with controlled crystalline and lamellar orientation. The samples were prepared by the die drawing of injection‐molded rods of polyethylene and annealing. This produced a parallel lamellar structure for which a simple, three‐dimensional composite laminate model could be used to calculate the expected anisotropy. Experimental data, including X‐ray strain measurements of the lateral crystalline elastic constants, showed good quantitative agreement with the model prediction. The X‐ray strain measurements confirmed that the amorphous regions exert large constraints on the crystalline phase in the lateral directions, where an order of magnitude difference was found between the measured apparent lateral crystalline compliances in the lamellar‐stack sample and the expected values for a perfect crystal. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 755–764, 2000  相似文献   

19.
Crystallization of polyethylene terephthalate and i-polypropylene in nonisothermal conditions is studied by means of differential scanning calorimetry. Measurements, carried out at several constant cooling rates, are interpreted in terms of a new theory1,2 that takes into account effects related to a transient, nonsteady-state course of the process as well as athermal nucleation, which may occur under such circumstances. This article gives preliminary results based on analysis of final crystallinity reached at the end of cooling. Results indicate that the classical isokinetic approach is not adequate to describe crystallization kinetics at high cooling rates. A parameter quantizing the magnitude of deviations from isokinetic law is evaluated. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2821–2827, 1999  相似文献   

20.
Dynamic mechanical experiments performed on a semicrystalline sample of poly(ethylene terephthalate) evidenced the relaxation processes (α and β) that occur in the polymer. Multifrequency experiments were used both in order to calculate the apparent activation energy of relaxation and to point out how the dynamic conditions alter not only the main relaxations, but the overlapping melting/recrystallization events that succeed after the glass transition. Heating rate seems to affect these phenomena in a way similar to frequency. Also, a consecutive heating step was carried out to support the statements.  相似文献   

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