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1.
Aiming at further investigating the combination effect of concentration of β‐nucleating agent (β‐NA) and stereo‐defect distribution on the crystallization behavior of β‐nucleated isotactic polypropylene (β‐iPP), in this study, the crystallization behavior and polymorphic morphology of twoβ‐iPP resins with nearly same average isotacticity (PP‐A and PP‐B) but different uniformities of stereo‐defect distribution were investigated by differential scanning calorimetry (DSC), wide angle X‐ray diffraction (WAXD) and polarized optical microscopy (POM). The results of DSC and WAXD showed that the addition of TMB‐5 increases the crystallization temperature and decreases the spherulite sizes of both PP‐A and PP‐B, and reduces their crystallization energy barriers as well; however, the polymorphic behaviors of PP‐A and PP‐B exhibit different dependence on the TMB‐5 concentration. For PP‐A with less uniform distribution of stereo‐defects, β‐phase can be observed only when the TMB‐5 concentration is no less than 0.1 wt.%, while for PP‐B with more uniform stereo‐defect distribution, addition of 0.01 wt.% TMB‐5 can induce the formation of β‐phase. Moreover, the analysis of POM indicated that the crystalline morphologies of both PP‐A and PP‐B change greatly with the TMB‐5 concentration, and the variation features of PP‐A and PP‐B are quite different from each other. PP‐B with more uniform stereo‐defect distribution was more favorable for the formation of large amount of β‐phase in the presence of wide concentration range of TMB‐5. The different polymorphic behaviors and their different dependences on the β‐NA concentration were related to the different uniformities of stereo‐defect distribution of the samples, since the distribution of stereo‐defects could restrain the regular insertion of molecular chains during crystallization and thus determine the tendency the α‐phase crystallization of the sample. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

2.
Nucleation characteristics of isotactic polypropylene (iPP) nucleated by the α/β compounded nucleating agents (NAs) were investigated by wide‐angle X‐ray scattering, differential scanning calorimetry and mechanical testing. The results showed that the nucleation effect of the α/β compounded NAs depends on not only nucleation efficiency (NE) of individual β and α NAs and their ratios but also the processing conditions, especially the cooling rates. The nucleating characteristics of the α/β compounded NAs can be illustrated by competitive nucleation. The NA with high NE played a leading role during iPP crystallization even at a low weight ratio and at different cooling rates. The stiffness and toughness of iPP can be simultaneously improved by using suitable compositions at the appropriate ratios. Finally, the nonisothermal crystallization kinetics of iPP nucleated with the α/β compounded NAs was described by Caze method and the crystallization activation energy of nucleated iPP was calculated by Kissinger equation. The result indicated that the crystal growth pattern of nucleated iPP was heterogeneous nucleation followed by three‐dimension spherical growth. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 653–665, 2010  相似文献   

3.
The effects of nucleating agents (NAs) on fracture toughness of injection‐molded isotactic poly(propylene)/ethylene‐propylene‐diene terpolymer (PP/EPDM) were studied in this work. Compared with PP/EPDM blends without any NA, PP/EPDM/NA blends show very small and homogeneous PP spherulites. As we expected, PP/EPDM blends nucleated with β‐phase NA aryl amides compound (TMB‐5) present not only a significant enhancement in toughness but also a promotion of brittle‐ductile transition. However, the addition of α‐phase NA 1,3:2,4‐bis(3,4‐dimethylbenzylidene) sorbitol (DMDBS) has no apparent effect on the toughness of the blends. The impact‐fractured surface morphologies of such samples were analyzed via scanning electronic microscope (SEM). More detail work about the toughening mechanisms of elastomer and NA based on elastomer particles size and matrix crystal structures were carried out. Our results suggest that, besides the crystal structures of matrix, the elastomer particles size and size distribution plays an important role in controlling the toughening effect of nucleated PP/elastomer blends. The smaller the elastomer particles size and lower the polydispersity, the more apparent the synergistic toughening effect of NA and elastomer is. This investigation provides a fresh insight into the understanding of toughening mechanism of elastomers in PP blends and facilitates to the design of super toughened PP materials. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 46–59, 2009  相似文献   

4.
Previous work showed that there was a synergistic effect of nucleating agent (NA) and elastomer in improving the fracture resistance of isotactic polypropylene (PP), relating to the formation of large amounts of β‐PP (β‐NA nucleated system) or the decrease of the spherulites diameters of α‐PP (α‐NA nucleated system). To find the direct relation between the synergistic efficiency of NA/elastomer and the microstructures of the materials, in this work, the ethylene‐propylene‐diene terpolymer (EPDM) modified PP blends with compounded NAs (β/α) were adopted and the changes of the microstructure and mechanical properties were investigated comparatively. The results showed that, with the adjustment of the mass fraction of compounded NAs, the microstructures of PP matrix including supermolecular structure and the relative fraction of β‐PP (Kβ) change accordingly. Specifically, the Kβ of β‐PP was successfully adjusted in the wide range of 0–78.9%. Consequently, the stiffness and the fracture resistance of the PP/EPDM blends were easily controlled in different degrees. It is believed that this work could provide a guide map for the design and preparation of certain polymer blends satisfying certain requirement. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011  相似文献   

5.
Sodium benzoate (SB), a conventional nucleating agent of α‐phase isotactic polypropylene (iPP) was discovered to induce the creation of β‐phase iPP under certain crystalline conditions. Polarized optical microscopy (POM) and wide angle X‐ray diffraction (WAXD) were carried out to verify the versatile nucleating activity of SB and investigate the influences of SB's content, isothermal crystallization temperature, and crystallization time on the formation of β‐phase iPP. The current experimental results indicated that, under isothermal crystallization conditions, SB showed peculiar nucleating characteristics on inducing iPP crystallization which were different from those of the commercial β form nucleating agent (TMB‐5). The content of β crystal form of iPP nucleated with SB (PP/SB) increased initially with the increase of crystallization temperature, nucleating agent (SB) percentage or crystallization time, reached a maximum value, and then decreased as the crystallization temperature, nucleating agent percentage or crystallization time further increased. While the content of β crystal form of iPP nucleated with TMB‐5 (PP/TMB‐5) showed a completely different changing pattern with the crystallization conditions. The obvious difference of the two kinds of nucleating agents on inducing iPP crystallization can be explained by the versatile nucleating ability of SB. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1183–1192, 2008  相似文献   

6.
Crystallization and melting behaviors of isotactic polypropylene (iPP) nucleated with compound nucleating agents of sodium 2,2′‐methylene‐bis (4,6‐di‐tert‐butylphenyl) phosphate (hereinafter called as NA40)/dicyclohexylterephthalamide (hereinafter called as NABW) (weight ratio of NA40 to NABW is 1:1) were studied by differential scanning calorimetry and wide‐angle X‐ray diffraction (WAXD), the relative β‐amount of iPP nucleated with these compound nucleating agents was also calculated in Turner‐Jones equation by using wide‐angle X‐ray diffraction data. Under isothermal crystallization, there exists a temperature range favorable for formation of β‐iPP. When the concentration of compound nucleating agents is 0.2 wt %, the temperature range is from 100 to 140 °C. While in nonisothermal crystallization, lower cooling rate is favorable for form of β‐iPP and the relative β‐amount of iPP increases with the decreasing of cooling rate in crystallization process. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 911–916, 2008  相似文献   

7.
In the present work, α‐form nucleating agent 1,3:2,4‐bis (3,4‐dimethylbenzylidene) sorbitol (DMDBS, Millad 3988) is introduced into the blends of polypropylene/ethylene–octene copolymer (PP/POE) blends to study the effect of the nucleating agent on the toughness of PP/POE blends through affecting the crystallization behavior of PP matrix. Compared with the PP/POE blends, in which the toughness of the blends increases gradually with the increasing content of POE and only a weak transition in toughness is observed, addition of 0.2 wt % DMDBS induces not only the definitely brittle‐ductile transition at low POE content but also the enhancement of toughness and tensile strength of the blends simultaneously. Study on the morphologies of impact‐fractured surfaces suggests that the addition of a few amounts of DMDBS increases the degree of plastic deformation of sample during the fracture process. WAXD results suggest that POE induces the formation of the β‐form crystalline of PP; however, DMDBS prevents the formation of it. SEM results show that the addition of DMDBS does not affect the dispersion and phase morphologies of POE particles in PP matrix. DSC and POM results show that, although POE acts as a nucleating agent for PP crystallization and which enhances the crystallization temperature of PP and decreases the spherulites size of PP slightly, DMDBS induces the enhancement of the crystallization temperature of PP and the decrease of spherulites size of PP more greatly. It is concluded that the definitely brittle–ductile transition behavior during the impact process and the great improvement of toughness of the blends are attributed to the sharp decrease of PP spherulites size and their homogeneous distribution obtained by the addition of nucleating agent. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 577–588, 2008  相似文献   

8.
Sodium 2,2′‐methylene‐bis(4,6‐di‐tert‐butylphenyl) phosphate (NA40) and N,N‐dicyclohexylterephthalamide (NABW) are high effective nucleating agents for inducing the formation of α‐isotactic polypropylene (α‐iPP) and β‐iPP, respectively. The isothermal crystallization kinetics of iPP nucleated with nucleating agents NABW, NA40/NABW (weight ratio of NA40 to NABW is 1:1) and NA40 were investigated by differential scanning calorimetry (DSC) and Avrami equation was adopted to analyze the experimental data. The results show that the addition of NABW, NA40/NABW and NA40 can shorten crystallization half‐time (t1/2) and increase crystallization rate of iPP greatly. In these three nucleating agents, the α nucleating agent NA40 can shorten t1/2 of iPP by the largest extent, which indicates that it has the best nucleation effect. While iPP nucleated with NA40/NABW compounding nucleating agents has shorter t1/2 than iPP nucleated with NABW. The Avrami exponents of iPP and nucleated iPP are close to 3.0, which indicates that the addition of nucleating agents doesn't change the crystallization growth patterns of iPP under isothermal conditions and the crystal growth is heterogeneous three‐dimensional spherulitic growth. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 590–596, 2007  相似文献   

9.
Previous work showed that annealing induced the great improvement of fracture resistance of β‐iPP, relating to the decreased number of chain segments in the amorphous region. To further prove the rationality of this observation, in this work, the ethylene‐octene copolymer (POE) toughened isotactic polypropylene (iPP) blends with or without β‐phase nucleating agent (β‐NA) were adopted and the changes of microstructure and fracture resistance during the annealing process were further investigated comparatively. The results showed that, whether for the α‐phase crystalline structure (non‐nucleated) or for the β‐phase crystalline structure (β‐NA nucleated) in iPP matrix, annealing can induce the dramatic improvement of fracture resistance at a certain annealing temperature (120–140 °C for β‐NA nucleated blends whereas 120–150 °C for non‐nucleated blends). Especially, non‐nucleated blends exhibit more apparent variations in fracture resistance compared with β‐NA nucleated blends during the annealing process. The phase morphology of elastomer, supermolecular structure of matrix, the crystalline structure including the degree of crystallinity and the relative content of β‐phase, and the relaxation of chain segments were investigated to explore the toughening mechanism of the samples after being annealed. It was proposed that, even if the content of elastomer is very few, the excellent fracture resistance can be easily achieved through adjusting the numbers of chain segments in the amorphous phase by annealing. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010  相似文献   

10.
In this study, α-phase nucleating agent (NA) 1,3:2,4-bis(3,4-dimethylbenzylidene) sorbitol (DMDBS), β-phase rare earth NA (WBG), and their compound NAs were introduced into isotactic polypropylene (iPP) matrix, respectively. Crystallization kinetics and subsequent melting behavior of the nucleated iPPs were comparatively studied by differential scanning calorimetry (DSC) under both isothermal and nonisothermal conditions. For the isothermal crystallization process, it is found that the Avrami model successfully described the crystallization kinetics. The active energy of nonisothermal crystallization of iPP was determined by the Kissinger method and showed that the addition of nucleating agents increased the activation energy. Melting behavior and crystalline structure of the nucleated iPPs are dependent on the nature of NAs and crystallization conditions. Higher proportion of β-phase can be obtained at higher content of β-nucleating agent and lower crystallization temperature or lower cooling rate.  相似文献   

11.
A layer multiplying coextrusion process was used to produce multilayered polypropylene/polystyrene (PP/PS) films with various nucleating agents. When heated into the melt, the thin PP layers broke up into submicron PP droplets that exhibited fractionated crystallization. If the initial PP layers were 20 nm or less, the resulting droplets exhibited exclusively homogeneous nucleation. If a nucleating agent was added, the systematic departure from homogeneous nucleation provided insight into the nature of the heterogeneous nucleation. In this study, we used thermal analysis, atomic force microscopy (AFM), and wide angle X‐Ray scattering (WAXS) to examine the effect of two nucleating agents. We confirmed with WAXS and AFM that a soluble sorbitol nucleating agent for the PP α‐form operates in three concentration regimes as proposed in a previous study. Morphologically, homogeneous nucleation of the submicron droplets produced a granular texture. The correlation length from small‐angle X‐Ray scattering (SAXS) suggested that the grains contained 1–3 mesophase domains. Drawing on classical nucleation theory, the critical size nucleus of an individual mesophase domain was estimated to be about 2 nm3, which was considerably smaller than the mesophase domain. This pointed to mesophase crystallization that included the processes of nucleation and growth. Additional experiments were performed with nucleating agents for the PP β‐form. However, they were not effective in nucleating crystallization of the droplets, presumably because they were essentially insoluble in PP and the nucleating particles were too large to be accommodated in the PP droplets. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011  相似文献   

12.
This article reports crystallization behaviors of isotactic polypropylene (iPP) with an aryl amide derivative (TMB‐5) as β‐form nucleating agent. The effects of nucleating agent concentration, thermal history and assemble morphology of nucleating agent on the crystallization behaviors of iPP were studied by differential scanning calorimetry, X‐ray diffraction, and polarized optical microscopy. The results indicated that the TMB‐5 concentration should surpass a threshold value to get products rich in β‐iPP. The diverse morphologies of TMB‐5 are determined by nucleating agent concentration and crystallization condition. At higher concentrations, the recrystallized TMB‐5 aggregates into needle‐like structure, which induces mixed polymorphic phases on the lateral surface and large amount of β modification around the tip. High β nucleation efficiency was obtained at the lowest studied crystallization temperature, which is desirable for real molding process. TMB‐5 prefers to recrystallize from the melt at higher concentration and lower crystallization temperature. The difference in solubility, pertinent to concentration and crystallization temperature, determined the distinct crystallization behaviors of iPP. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1725–1733, 2008  相似文献   

13.
The orientation behavior of isotactic polypropylene (iPP) in α‐ and β‐crystal form was investigated by rheo‐optical Fourier transformed infrared (FTIR) spectroscopy. This method enabled quantification of the degree of orientation as a feature of structural changes during uniaxial elongation in not only the crystalline phase but also the amorphous one. Molecular orientation mechanisms can be successfully derived from experimental results. Generally, three mechanisms were detected for iPP: (1) interlamellar separation in the amorphous phase, (2) interlamellar slip and lamellar twisting at small elongations, and (3) intralamellar slip at high elongations. The third mechanism was favored by α‐PP, whereas β‐PP favored the second mechanism, which, in fact, was responsible for the different mechanical properties of both materials at the macroscopic level. On the other hand, crystallization conditions may have significantly affected the amorphous orientation. Nevertheless, for both iPP types the chains in the amorphous phase always oriented less than did those in the crystalline phase. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4478–4488, 2004  相似文献   

14.
By using a commercial β‐nucleating agent (TMB‐5) for polypropylene (PP), it was observed that high β‐crystal content in a compatibilized blend of polypropylene/polyamide‐6 (labeled as Blend‐03 in this work) can be achieved for samples prepared by compression moulding. As β‐PP possesses more superior impact strength then α‐PP, and the β to α transformation is an important mechanism of energy absorption for β‐PP, it is of obvious interest to understand the possibilities of β to α transformation in β‐polypropylene/polyamide‐6 blends. Tensile tests were performed at temperatures of 20, 30, 40, and 50 °C, and the occurrence of β to α transformation was monitored by differential scanning calorimeter and wide angle X‐ray diffraction measurements. It was observed that the β to α transformation in Blend‐03 could only be activated at elevated tensile testing temperatures. This was related to the increase in tensile elongation at break with the increase in tensile testing temperature. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2674–2681, 2007  相似文献   

15.
The selectivities of different β‐nucleating agents might be quite different from each other, which is important in determining the crystallization and properties of the obtained β‐isotactic polypropylene (β‐iPP). However, the relationship between molecular structure and dynamic crystallization behavior of β‐iPP nucleated by dual‐selective β‐nucleating agent (DS‐β‐NA) is still not clear. In this study, the dynamic crystallization and melting behavior of two β‐iPP with nearly same average isotacticity but different stereo‐defect distribution, nucleated by a DS‐β‐NA (N,N′‐dicyclohexyl‐2,6‐naphthalenedicarboxamide; trade name TMB‐5), were studied by differential scanning calorimetry, wide‐angle X‐ray diffraction, and scanning electronic microscopy. The results indicated that in the presence of TMB‐5, the dynamic crystallization and melting behavior of the samples are quite different because the joint effects of the dual selectivity of TMB‐5 and stereo‐defect distribution of the iPP under different cooling rates. Two important roles were observed: (i) slow cooling rate favors the formation of high β‐fraction; and (ii) high crystallization temperature favors the crystallization of α‐phase accelerated by TMB‐5. Generally, the dual selectivity of the DS‐β‐NA, the stereo‐defect distribution of iPP, and the cooling rate were important factors in determining the formation of β‐crystal. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

16.
The nonisothermal crystallization behaviors of isotactic polypropylene (iPP) with an aryl amide derivative TMB‐5 as β‐form nucleating agent has been investigated by differential scanning calorimetry, X‐ray diffraction, and polarized optical microscopy. The feature of crystallite morphology depends on concentration and thermal conditions. At low concentrations, TMB‐5 molecules aggregate into fibril structures and presented blunt exothermic peak with a shoulder at high temperature. The surface of these fibrils host active sites tailored for the nucleation of β‐iPP, represented by clusters of microcrystallites. With increasing concentration, αβ‐transcrystalline layer develops on the lateral surface of needle‐shaped TMB‐5. Enhanced multiple endotherms indicate the ensuing crystals are less perfect and easily transformed into more stable forms. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 314–325, 2009  相似文献   

17.
Isotactic polypropylene (i‐PP) can crystallize in different crystal modifications. In this article, the effect of sepiolite (one‐dimensional) and carbon black (three‐dimensional) fillers on the solid‐state drawability of i‐PP is discussed. The cross‐hatched structure of thermodynamically most stable α‐crystal phase in i‐PP does not allow for perfect chain alignment during solid‐state drawing. The β‐phase i‐PP, obtained by addition of specific nucleating agents, crystallizes in a non‐cross‐hatched spherulitic structure and allows more easy drawing. Depending on the filler type, β–α transformation takes place at different draw ratios, as was observed by in situ wide‐angle X‐ray diffraction measurements. It was observed that β‐nucleated i‐PP has a lower yield stress and can be drawn further than i‐PP crystallized in the α‐crystal phase. If added in the right amount, both carbon black and sepiolite have a reinforcing effect on PP tapes. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1071–1082  相似文献   

18.
The structural transformation of homogeneously nucleated metastable mesophase of polypropylene (PP) particles was investigated in this study. We demonstrated the formation of heterogeneity‐free mesophase by slow cooling of the droplets unlike mesophase formation by quenching of the PP melt, which contained large number of bulk nuclei. Submicron size PP droplets were produced by thermal break up of PP and polystyrene layered film assembly. When cooled from melt, the PP droplets crystallized into mesophase at 44 °C revealing granular morphology. Subsequent heating thermogram of the PP particles showed a broad exotherm, which was attributed to the transformation of mesophase into α‐phase. This transformation was investigated during heating by annealing the PP particles at different temperatures. Annealed PP particles were analyzed by means of thermal, morphological and structural properties measurements. Results revealed a two step process for the transformation process. In the first step, the internal rearrangement of PP chains, as against melting and recrystallization of the mesophase, was observed. Since granular morphology was not affected significantly up to 120 °C, it was suggested that translational and rotational motions of PP helices produced ordered α‐phase. In the second step, increment in grain size distribution was observed, when the droplets were annealed at 140 °C. The results were attributed to enhanced chain mobility and merging of the grain boundaries. Annealing at 160 °C revealed the formation of short lamellar structures. Crystal thickening, melting and recrystallization of α‐phase were suggested at high temperature annealing. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011  相似文献   

19.
The effect of different concentrations of single‐walled carbon nanotubes (SWNTs) on the nonisothermal crystallization kinetics, morphology, and mechanical properties of polypropylene (PP) matrix composites obtained by melt compounding was investigated by means of X‐ray diffraction, differential scanning calorimetry, optical and scanning electron microscopy, and dynamic mechanical thermal analysis. Microscopy showed well‐dispersed nanotube ropes together with small and large aggregates. The modulus was found to increase by about 75% at a level of 0.5 wt % nanotubes. The SWNTs displayed a clear nucleating effect on the PP crystallization, favoring the α crystalline form rather than the β form. The crystallization kinetics analysis showed a significant increase in activation energy on incorporating nanotubes. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2445–2453, 2005  相似文献   

20.
The effects of preparation method, composition, and thermal condition on formation of β‐iPP in isotactic polypropylene/ethylene–propylene rubber (iPP/EPR) blends were studied using modulated differential scanning calorimeter (MDSC), wide angle X‐ray diffraction (WAXD), and phase contrast microscopy (PCM). It was found that the α‐iPP and β‐iPP can simultaneity form in the melt‐blended samples, whereas only α‐iPP exists in the solution‐blended samples. The results show that the formation of β‐iPP in the melt‐blended samples is related to the crystallization temperature and the β‐iPP generally diminishes and finally vanishes when the crystallization temperature moves far from 125 °C. The phenomena that the lower critical temperature of β‐iPP in iPP/EPR obviously increases to 114 °C and the upper critical temperature decreases to 134 °C indicate the narrowing of temperature interval, facilitating the formation of β‐iPP in iPP/EPR. Furthermore, it was found that the amount of β‐iPP in melt‐blended iPP/EPR samples is dependent on the composition and the maximum amount of β‐iPP formed when the composition of iPP/EPR blends is 85:15 in weight. The results through examining the effect of annealing for iPP/EPR samples at melt state indicate that this annealing may eliminate the susceptibility to β‐crystallization of iPP. However, only α‐iPP can be observed in solution‐blended samples subjected to annealing for different time. The PCM images demonstrate that an obvious phase‐separation happens in both melt‐blended and solution‐blended iPP/EPR samples, implying that compared with the disperse degree of EPR in iPP, the preparation method plays a dominant role in formation of β‐iPP. It is suggested that the origin of formation of β‐iPP results from the thermomechanical history of the EPR component in iPP/EPR. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1704–1712, 2007  相似文献   

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