首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 646 毫秒
1.
The effect of propylene–ethylene copolymers (PEc) with different ethylene‐unit contents on melting and crystallization behaviors of isotactic‐polypropylene (iPP) were investigated by differential scanning calorimetry (DSC) and polarized light microscopy (PLM). The results show that the addition of PEc decreases significantly crystallization temperature (Tc) of iPP, but slightly affects melting temperature (Tm). With increasing the ethylene‐unit content of the propylene–ethylene copolymers, the decrease in crystallization temperature of iPP is smaller. The PLM results show that the spherulite growth rate decreases with increasing crystallization temperature for iPP and iPP/PEc blends. The higher the ethylene‐unit content of the copolymers is, the lower the spherulite growth rate (G) of iPP/PEc blends is. The influence of the PEc on nucleation rate constant (Kg) and fold surface energy (σe) of iPP was examined by nucleation theory of Hoffman and Lauritzen. The results show that both Kg and σe of iPP/PE20(80/20) and iPP/PE23(80/20) blends are higher than those of iPP, demonstrating that the overall crystallization rate of iPP/PEc blends decreased as compared to that of iPP, resulting from the decrease of the nucleation rate and the spherulite growth rate of iPP. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

2.
A novel highly active β‐nucleating agent, β‐cyclodextrin complex with lanthanum (β‐CD‐MAH‐La), was introduced to isotactic polypropylene (iPP). Its influence on isothermal crystallization and melting behavior of iPP was investigated by differential scanning calorimeter (DSC), wide‐angle X‐ray diffraction (WAXD), and polarized light microscopy (PLM). WAXD results demonstrated that β‐CD‐MAH‐La was an effective β‐nucleating agent, with β‐crystal content of iPP being strongly influenced by the content of β‐CD‐MAH‐La and the isothermal crystallization temperature. The isothermal crystallization kinetics of pure iPP and iPP/β‐CD‐MAH‐La was described appropriately by Avrami equation, and results revealed that β‐CD‐MAH‐La promoted heterogeneous nucleation and accelerated the crystallization of iPP. In addition, the equilibrium melting temperature (T) of samples was determined using linear and nonlinear Hoffman‐Weeks procedure. Finally, the Lauritzen‐Hoffman secondary nucleation theory was applied to calculate the nucleation parameter (Kg) and the fold surface energy (σe), the value of which verify that the addition of β‐CD‐MAH‐La reduced the creation of new surface for β‐crystal and then led to faster crystallization rate. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

3.
l ‐Isoleucine (l ‐Ile) was identified as an efficient anti‐nucleating agent for isotactic polypropylene (iPP). At 0.08 wt %, l ‐Ile could significantly decrease the peak crystallization temperature (Tcp) of iPP by up to 8 °C at a cooling rate of 20 °C/min. Furthermore, l ‐Ile exhibited both anti‐nucleation and pro‐nucleation abilities; i.e., a low content of l ‐Ile inhibited iPP crystallization, whereas a high content promoted iPP crystallization. The unique crystallization behavior of iPP in the presence of l ‐Ile was investigated by differential scanning calorimetry, polarized optical microscopy (POM), and rheological measurement. According to POM, a low content of l ‐Ile completely dissolved in the iPP melt, whereas a high content of l ‐Ile did not. Therefore, a mechanism by which l ‐Ile inhibits and promotes the nucleation of iPP was proposed. Dissolving l ‐Ile molecules in the iPP melt hindered the homogeneous nucleation of iPP as a “dilution effect”; however, as the content increases, l ‐Ile could not be completely dissolved in molten iPP, and the residual crystals of l ‐Ile thus provided heterogeneous nucleation sites for iPP and further promoted its crystallization. Experimental evidence from rheology and POM supported this mechanism. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45956.  相似文献   

4.
The crystallization and melting behavior of isotactic polypropylene (iPP) and polypropylene copolymer (co‐PP) containing silicon dioxide (SiO2) were investigated by differential scanning calorimeter (DSC). SiO2 had a heterogenous nucleating effect on iPP, leading to a moderate increase in the crystallization temperature and a decrease in the half crystallization time. However, SiO2 decreased the crystallization temperature and prolonged the half crystallization time of co‐PP. A modified Avrami theory was successfully used to well describe the early stages of nonisothermal crystallization of iPP, co‐PP, and their composites. SiO2 exhibited high nucleation activity for iPP, but showed little nucleation activity for co‐PP and even restrained nucleation. The iPP/SiO2 composite had higher activation energy of crystal growth than iPP, indicating the difficulty of crystal growth of the composite. The co‐PP/SiO2 composite had lower activation energy than co‐PP, indicating the ease of crystal growth of the composite. Crystallization rates of iPP, co‐PP, and their composites depended on the nucleation. Because of its high rate of nucleation, the iPP/SiO2 composite had higher crystallization rate than iPP. Because of its low rate of nucleation, the co‐PP/SiO2 composite had lower crystallization rate than co‐PP. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1889–1898, 2006  相似文献   

5.
In this study, the melt structure of isotactic polypropylene (iPP) nucleated with α/β compounded nucleating agents (α/β‐CNA, composed of the α‐NA of 0.15 wt % Millad 3988 and the β‐NA of 0.05 wt % WBG‐II) was tuned by changing the fusion temperature Tf. In this way, the role of melt structure on the crystallization behavior and polymorphic composition of iPP were investigated by differential scanning calorimetry (DSC), wide‐angle X‐ray scattering (WAXD) and scanning electron microscopy (SEM). The results showed that when Tf = 200°C (iPP was fully molten), the α/β‐CNA cannot encourage β‐phase crystallization since the nucleation efficiency (NE) of the α‐NA 3988 was obviously higher than that of the β‐NA WBG‐II. Surprisingly, when Tf was in 179–167°C, an amount of ordered structures survived in the melt, resulting in significant increase of the proportion of β‐phase (achieving 74.9% at maximum), indicating that the ordered structures of iPP played determining role in β‐phase crystallization of iPP nucleated with the α/β‐CNA. Further investigation on iPP respectively nucleated with individual 3988 and WBG‐II showed that as Tf decreased from 200°C to 167°C, the crystallization peak temperature Tc of iPP/3988 stayed almost constant, while Tc of iPP/WBG‐II increased gradually when Tf < 189°C and became higher than that of iPP/3988 when Tf decreased to 179°C and lower, which can be used to explain the influence of ordered structure and α/β‐CNA on iPP crystallization. Using this method, the selection of α‐NA for α/β‐CNA can be greatly expanded even if the inherent NE of β‐NA is lower than that of the α‐NA. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41355.  相似文献   

6.
Melt nucleation and crystallization behavior of homo‐isotatic polypropylene (homo‐iPP), maleic anhydride (MAH)‐grafted‐iPP, and MAH‐modified iPP, produced from iPP and a small amount of MAH‐grafted‐iPP, was investigated by polarizing optical microscopy (POM), at Tc = 121–135oC. Nucleation processes at a given Tc were faster for modified PP as compared to neat iPP. The induction time for nucleation increased nonlinearly with increasing Tc and decreased for modified PP, probably as a result of promoted heterogeneous nucleation due to the presence of carbonyl groups of MAH‐grafted‐PP. The average spherulite sizes were decreased by modification, and the growth rate was enhanced in maleated PP and modified PP. The induction time approach was applied to the results obtained by POM to compare the tendency for heterogeneous nucleation of neat and MAH‐modified PP. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3107–3118, 2000  相似文献   

7.
Crystallization behaviour of isotactic polypropylene/linear low density polyethylene (iPP/LLDPE) blends has been investigated by optical microscopy and DSC. Crystallization of iPP depends upon blend composition and thermal history. When blended with LLDPE, the crystallization temperature of iPP, Tc, decreased slightly. Crystallinity did not change in the range 0-80wt% LLDPE; there were only slight changes in the crystalline structure, but LLDPE seemed to resist forming the β type of spherulites. Below 80 wt% of LLDPE, iPP was a continuous phase. The iPP spherulite growth rate was almost constant; however, overall crystallization decreased due to decreasing primary nuclei density.  相似文献   

8.
The isothermal crystallization kinetics and morphology development of isotactic polypropylene (iPP) blended with small loading of nanostructure of polyhedral oligomeric silsesquioxane (POSS) were studied with differential scanning calorimetry (DSC), polarized optical microscopy (POM), and wide-angle X-ray diffraction (WAXD). The crystallization behaviors of iPP/POSS composites presented an unusual crystallization behavior during isothermal and nonisothermal crystallization conditions. The exothermic morphologies of isothermal and nonisothermal crystallization of iPP/POSS composites changed remarkably with increasing POSS. Moreover, the developments of spherulitic morphology for iPP/POSS composites showed that the major dispersed POSS molecules became nanocrystals first and then aggregated together forming thread- or network-like morphologies, respectively, depending on POSS content, which was observed. It implies that these major POSS nanocrystals' morphologies appeared as an effective nucleating agent and promoted the nucleation rate of iPP, whereas the minor dispersed POSS molecules that had slight miscibility between iPP retarded the nucleation and growth rates of iPP in the remaining bulk region. Therefore, the isothermal crystallization showed a single exothermic peak at pure iPP and POSS-1.0, whereas at POSS-2.0 and POSS-3.0, displayed the multi-exothermic peaks during isothermal crystallization. These faces indicated that POSS molecules were both influence on the transport of iPP chain in the melted state and on the free-energy of formation the critical nuclei of iPP assisted by the POSS structures were observed. Therefore, we postulated that the crystallization mechanisms of multi-exothermic peaks in isothermal crystallization may proceed to combine the “nucleating agent inducing nucleation of iPP event assisted by the POSS domains” that the nucleation of iPP does occur preferentially on the surfaces of the POSS “threads” or “networks” structures, and “nucleation and growth of iPP in the remaining bulk melted iPP region retarded by dispersed POSS molecules”. Therefore, effects of POSS content on the isothermal and nonisothermal crystallization behaviors of iPP/POSS composites due to the POSS molecules partially miscible with iPP, at very small loading of POSS molecules, promoted or retarded the rates of nucleation and growth of iPP depending on the POSS content and crystallization temperature were discussed.  相似文献   

9.
The crystallization kinetics and morphology development of pure isotactic polypropylene (iPP) homopolymer and iPP blended with atactic polypropylene (aPP) at different aPP contents and the isothermal crystallization temperatures were studied with differential scanning calorimetry, wide‐angle X‐ray diffraction, and polarized optical microscopy. The spherulitic morphologies of pure iPP and larger amounts of aPP for iPP blends showed the negative spherulite, whereas that of smaller amounts of aPP for the iPP blends showed a combination of positive and negative spherulites. This indicated that the morphology transition of the spherulite may have been due to changes the crystal forms of iPP in the iPP blends during crystallization. Therefore, with smaller amounts of aPP, the spherulitic density and overall crystallinity of the iPP blends increased with increasing aPP and presented a lower degree of perfection of the γ form coexisting with the α form of iPP during crystallization. However, with larger amounts of aPP, the spherulitic density and overall crystallinity of the iPP blends decreased and reduced the γ‐form crystals with increasing aPP. These results indicate that the aPP molecules hindered the nucleation rate and promoted the molecular motion and growth rate of iPP with smaller amounts of aPP and hindered both the nucleation rate and growth rate of iPP with larger amounts of aPP during isothermal crystallization. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1093–1104, 2007  相似文献   

10.
In this work, 2,2′-methylene-bis-(4,6-di-t-butylphenylene)phosphate lithium (NA03) was synthesized and its crystal structural characterization was obtained by single crystal X-ray diffusion. The crystal data showed geometrically the cell parameter of NA03 matched with isotactic polypropylene (iPP), the a cell dimension was about two times to the value of cell edge of (010)iPP. The disregistry was 2.89%, which was under the upper limit between the lattice matching spacing of host and guest crystals. Then NA03 was proved to be a highly effective nucleating agent for iPP through studying crystallization behaviors, crystallization morphologies, and mechanical properties of iPP nucleated with NA03. The outstanding nucleation efficiency could be attributed to the lattice matching between nucleating agent and iPP. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

11.
Dodecyl amine functionalized graphene oxide (DA‐GO)/isotactic polypropylene (iPP) nanocomposites were prepared via solution mixing method. Fourier transform infrared (FTIR), thermogravimetric analysis (TGA), and X‐ray photoelectron spectroscopy (XPS) verified that the DA was successfully grafted onto the surface of graphene oxide. The crystallization behavior of iPP/DA‐GO nanocomposites was investigated by differential scanning calorimetry (DSC) and polarized optical microscope (POM). The DSC results of both isothermal and non‐isothermal crystallization process indicated that the addition of DA‐GO can decrease the half‐time crystallization (t1/2) and elevate crystallization peak temperature (Tp) of iPP. The results of isothermal crystallization kinetics showed that the overall crystallization rates of iPP/DA‐GO nanocomposites, especially with higher DA‐GO content, were much faster than that of neat iPP. During the non‐isothermal crystallization process, the nucleation ability (Φ) of nanocomposites containing 0.05, and 0.5 wt % DA‐GO were 0.83 and 0.69, respectively. And the crystallization activation energy of iPP decreased from 348.7 (neat iPP) to 309.2 and 283.1 kJ/m 2 by addition of 0.05 and 0.5 wt % DA‐GO, respectively. The decrease of Φ and indicated DA‐GO has strong heterogeneous nucleation effect and can promote the crystallization of iPP significantly. Additionally, POM micrographs showed the DA‐GO in iPP matrix can form more nucleation sites for the spherulite growth. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40000.  相似文献   

12.
Isothermal crystallization behavior of isotactic polypropylene (iPP) synthesized using metallocene catalyst was investigated in this work. The isotacticity of the polypropylene was characterized by 13C‐NMR spectroscopy. It was found that the melting temperature (Tm) of the iPP is 123.51°C and the crystallization temperature (Tc) is 93°C. The iPP synthesized in this work did not show a general increase of Tm with an increase of crystallization temperature Tc, due to the short crystallization time of 20 min and low molecular weight (number average molecular weight = 6,300). The iPP showed a tendency of increasing heat of fusion (ΔHf) with decreasing crystallization temperature. All the spherulites of iPP samples showed negative birefringence. For the iPP sample crystallized at the highest Tc (= 123°C, just below Tm), the spherulite showed a pronounced Maltese Cross and a continuous sheaf‐like texture aligning radially, which suggests that R‐lamellaes are dominant in this spherulite. The crystalline structure of the iPP was also investigated by X‐ray diffraction. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 231–237, 2005  相似文献   

13.
The thermal properties and morphology development of isotactic polypropylene (iPP) homopolymer and blended with low molecules weigh atactic polypropylene (aPP) at different isothermal crystallization temperature were studied with differential scanning calorimeter and wide-angle X-ray scattering. The results of DSC show that aPP is local miscible with iPP in the amorphous region and presented a phase transition temperature at Tc=120 °C. However, below this transition temperature, imperfect α-form crystal were obtained and leading to two endotherms. While, above this transition temperature, more perfect α- and γ-form crystals were formed which only a single endotherm was observed. In addition, the results of WAXD indicate that the contents of the γ-form of iPP remarkably depend both on the aPP content and isothermal crystallization temperature. Pure iPP crystallized was characterized by the appearance of α- and γ-forms coexisting. Moreover, the highest intensity of second peak, i.e. the (0 0 8) of γ-form coexisting with (0 4 0) of α-form, and crystallinity were obtained for blended with 20% of aPP, the γ-form content almost disappeared for iPP/aPP blended with 50% aPP content. Therefore, detailed analysis of the WAXD patterns indicates that at small amount aPP lead to increasing the crystallinity of iPP blend, at larger amount aPP, while decreases crystallinity of iPP blends with increasing aPP content. On the other hand, the normalized crystallinity of iPP molecules increases with increasing aPP content. These results describe that the diluent aPP molecular promotes growth rate of iPP because the diluent aPP molecular increases the mobility of iPP and reduces the entanglement between iPP molecules during crystallization.  相似文献   

14.
Amorphous poly(ethylene isophthalate) (PEI) was synthesized, and was used for preparing an inclusion compound (IC) with γ‐cyclodextrin (γ‐CD). Coalesced polymer was produced by washing the PEI‐γ‐CD‐IC with hot water. Wide angle X‐ray diffraction, Fourier transform infrared, and differential scanning calorimetry analyses were employed to verify formation of PEI‐γ‐CD‐IC and to compare the as‐synthesized and coalesced PEI samples. These observations suggested that the conformations and morphology/chain‐packing of PEI were changed via coalescence from its γ‐CD inclusion compound. The glass‐transition temperature of the amorphous coalesced PEI is 15–20°C higher than the Tg observed for the as‐synthesized sample, even when observed in the second heat after cooling from well above Tg at 260°C. The amorphous as‐synthesized PEI retains its randomly‐coiling structure, while coalesced PEI has at least partially retained, the highly extended and parallel chains from the narrow channels of the inclusion compound, resulting in better/tighter packing among the PEI chains manifested by a higher Tg. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 6049–6053, 2006  相似文献   

15.
The crystallization kinetics of isotactic polypropylene (iPP) and nucleated iPP with substituted aromatic heterocyclic phosphate salts were investigated by means of a differential scanning calorimeter under isothermal and nonisothermal conditions. During isothermal crystallization, Avrami equation was used to describe the crystallization kinetics. Moreover, kinetics parameters such as the Avrami exponent n, crystallization rate constant Zt, and crystallization half‐time t1/2 were compared. The results showed that a remarkable decrease in t1/2 as well as a significant increase in overall crystallization rate was observed in the presence of monovalent salts of substituted aromatic heterocyclic phosphate, while bivalent and trivalent salts have little effect on crystallization rate of iPP. The addition of monovalent metal salts could decrease the interfacial free energy per unit area perpendicular to PP chains σe value of iPP so that the nucleation rate of iPP was increased. During nonisothermal crystallization, Caze method was used to analyze the crystallization kinetics. It also showed that monovalent metal salts had better nucleation effects than bivalent and trivalent metal salts. From the obtained Avrami exponents of iPP and nucleated iPP it could be concluded that the addition of different nucleating agents changed the crystal growth pattern of iPP. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3307–3316, 2006  相似文献   

16.
The influence of molecular weight and its distribution on the nucleation density, crystallization, thermal and mechanical behavior of isotactic polypropylene based composites has been investigated. The composites were prepared by compression molding. The ability of carbon and Kevlar fibers to nucleate the polypropylene has been studied during isothermal and nonisothermal crystallization, by optical microscopy and differential scanning calorimetry (DSC), as function of crystallization temperature Tc and iPP molecular weight. Two extreme crystallization conditions were tested: quenching and slow crystallization to obtain crystals and amorphous phases of different structure. The ability of fibers to enhance mechanical properties in polypropylene based composites was examined by tensile tests at room temperature. It was found that nucleation density, crystallization parameters, and the results of tensile tests strongly depend on the molecular weight M w of iPP, molecular weight distribution, and thermal history of polypropylene. The numerical values of the nucleation density have been found to strongly depend on the nature of fiber. In fact, Kevlar fiber has shown a better nucleating ability than carbon fiber. The results of tensile tests have been related to the sample morphology. The analysis of fractured specimens also provided useful information about fiber-matrix adhesion.  相似文献   

17.
A supercooled melt of isotactic polypropylene (iPP) was extruded through a capillary die. Polarized light microscopy (PLM), wide‐angle X‐ray diffraction (WAXD), and differential scanning calorimetry (DSC) were used to investigate the effects of the relatively weak wall shear stress (σw), extrusion temperature (Te), and crystallization temperature (Tc) on the structure and morphology of β‐form isotactic polypropylene (β‐iPP). β‐cylindrites crystals could be observed by PLM in the extruded specimen even at a lower σw's (0.020 MPa), and the β‐iPP content increased with decreasing Te. Under a given Te of 150°C, the increase in σw positively influenced the β‐iPP content. The DSC and WAXD results indicate that the total crystallinity and β‐iPP content increased when Tc was set from 105 to 125°C; the other experimental parameters were kept on the same level. Although Tc was above 125°C, the β‐iPP content obviously decreased, and the total crystallinity continued to increase. On the basis of the influences of σw, Te, and Tc on the β‐iPP crystal morphology and structure, a modified model is proposed to explain the growing of shear‐induced β‐iPP nucleation. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

18.
The thermal properties of isotactic polypropylene (iPP) reinforced with polyaniline‐grafted‐short glass fibers (PAn‐g‐SGF) at 10, 20, and 30 wt% concentration and iPP blended with 5 wt% PP‐grafted‐maleic anhydride (PP‐gMA) and 30 wt% of PAn‐g‐SGF were investigated. iPP crystallizes into a spherulitic morphology, the microfiller promoted larger spherulite size and higher dynamic modulus, but the overall degree of crystallinity decreased as the concentration of PAn‐g‐SGF increased. The melting temperature, Tm, was not influenced by the microfiller. However, the crystallization temperature, Tc, as determined by DMA, first decreased reaching a minimum at ca. 20 wt%, and then increased, in contrast with Tc determined by DSC, it increased as concentration increased. The initial reduction in Tc observed by DMA seems to be associated with the crystallites growing from the microfiller into the matrix, the overall molecular dynamics then being less affected. On the other hand, increase in Tc above 20 wt% concentration suggests that the percolation threshold could be responsible for these results. Addition of the maleic anhydride copolymer produced higher shear modulus, transition temperatures, and activation energy, suggesting higher interaction between microfiller and polymer matrix. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers  相似文献   

19.
The isothermal and nonisothermal crystallization kinetics of nonnucleated and nucleated isotactic polypropylene (iPP) were investigated by DSC and a polarized light microscope with a hot stage. Dibenzylidene sorbitol (DBS) was used as a nucleating agent. It was found that the crystallization rate increased with the addition of DBS. The influence of DBS on fold surface energy, σe, was examined by the Hoffman and Lauritzen nucleation theory. It showed that σe decreased with the addition of DBS, suggesting that DBS is an effective nucleating agent for iPP. Ozawa's theory was used to study the nonisothermal crystallization. It was found that the crystallization temperature for the nucleated iPP was higher than that for nonnucleated iPP. The addition of DBS reduced the Ozawa exponent, suggesting a change in spherulite morphology. The cooling crystallization function has a negative exponent on the crystallization temperature. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2089–2095, 1998  相似文献   

20.
The structure, phase structure, morphology, crystallization and melting behavior of isotactic polypropylene (iPP) blended with a master batch (MB), formed by high density polyethylene and hydrogenated hydrocarbon resin (iPP/MB), have been in details investigated by using X-ray diffraction, optical microscopy and differential scanning calorimetry. It was found that the structure and morphology depend on crystallization conditions. A new family of α spherulites of iPP (type I spherulites) can be activated using appropriate crystallization conditions. Nucleation of these spherulites has been explained by using the approach of nucleus migration in polymer blends. Type I spherulites present specific morphological, kinetic and thermal behaviors. In particular it was found that the growth rate of type I spherulites, at a given Tc, is higher than the growth rate of spherulites grown from plain iPP.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号