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1.
The nucleating ability of p‐cyclohexylamide carboxybenzene (β‐NA) towards isotactic polypropylene (iPP) was investigated by differential scanning calorimetry, X‐ray diffraction, polarized optical microscopy and scanning electron microscopy. β‐NA is identified to have dual nucleating ability for α‐iPP and β‐iPP under appropriate kinetic conditions. The formation of β‐iPP is dependent on the content of β‐NA. The content of β‐phase can reach as high as 96.96% with the addition of only 0.05 wt% β‐NA. Under non‐isothermal crystallization the content of β‐iPP increases with increasing cooling rate. The maximum β‐crystal content is obtained at a cooling rate of 40 °C min–1. The supermolecular structure of the β‐iPP is identified as a leaf‐like transcrystalline structure with an ordered lamellae arrangement perpendicular to the special surface of β‐NA. Under isothermal crystallization β‐crystals can be formed in the temperature range 80–140 °C. The content of β‐crystals reaches its maximum value at a crystallization temperature of 130 °C. © 2012 Society of Chemical Industry  相似文献   

2.
In this study, the effects of melt structure (tuned by controlling the fusion temperature Tf) on non‐isothermal crystallization and subsequent melting behaviors of isotactic polypropylene (iPP) nucleated with α/β compounded nucleating agents (α/β‐CNAs) have been further investigated. The results show that under all cooling rates studied (2–40°C/min), the crystallization temperature on cooling curves increased gradually with decrease of Tf, meanwhile, when Tf was in temperature range of 166°C–179°C where ordered structures survived in the melt (defined as Region II), crystallization activation energy ΔE was found to be evidently lower compared with that when Tf > 179°C or Tf < 166°C. The results of subsequent heating showed that occurrence of Ordered Structure Effect can be observed at all the cooling rates studied; the location of the Region II was constant when cooling rate varied; Low cooling rate encouraged formation of more β‐phase triggered by ordered structure. Moreover, the role of ordered structure on β‐α recrystallization was comparatively studied by tuning the end temperature of recooling (Tend) after held at Tf, and it was found that ordered structure encouraged the formation of β‐phase with high thermal stability at low temperature part of Region II, while enhanced the β‐crystal with relatively low thermal stability at high temperature part of Region II. POLYM. ENG. SCI., 57:989–997, 2017. © 2016 Society of Plastics Engineers  相似文献   

3.
In this study, the crystallization behavior of the β‐isotactic polypropylene (β‐iPP) samples nucleated by a rare earth based β‐nucleating agent (β‐NA) WBG‐II and a metal salts compound β‐NA NAB83 (denoted as WPP and NPP, respectively) under different cooling conditions were comparatively investigated. The thermal conditions such as the cooling rate, isothermal crystallization temperature, isothermal crystallization time, and the subsequent cooling to room temperature. The results of WAXD, SEM, and nonisothermal crystallization reveal that under the same processing conditions, the crystallite size of NPP is smaller, which arrange more compactly as compared with WPP. Meanwhile, NPP has shorter crystallization rate and higher β‐nucleation selectivity, but WPP can crystallization at wider temperature range. The results of isothermal crystallization showed that NPP has higher selectivity and higher β‐nucleation efficiency, which favors the formation of high proportion of β‐phase at the isothermal crystallization temperature of 110–130°C with and without subsequent cooling; WPP has lower selectivity, which can only induce high content of β‐phase under isothermal crystallization without subsequent cooling to 25°C. In tuning the crystallization behavior and the properties of β‐PP, the joint influence of the efficiency and selectivity of the β‐NA, and the thermal conditions should be taken into consideration. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40115.  相似文献   

4.
In order to increase the isotactic content of β‐nucleated polypropylene (β‐iPP) and decrease the cost of its production, the investigation and development of novel highly efficient β‐nucleators are important issues. Nano‐CaCO3 was used as a support to prepare a supported β‐nucleator, nano‐CaCO3‐supported calcium pimelate. Fourier transform infrared spectral analysis shows that an in situ chemical reaction takes place between nano‐CaCO3 and pimelic acid. Differential scanning calorimetry results indicate that the crystallization and melting temperatures of β‐phase in supported β‐nucleator‐nucleated iPP are higher than those of calcium pimelate‐nucleated iPP. The β‐nucleating ability of the supported β‐nucleator is little influenced by the cooling rate and crystallization temperature over a wide range. The decreased content of pimelic acid in the supported β‐nucleator slightly decreases the crystallization temperature of iPP but it has no influence on the content of β‐phase in nucleated iPP. A novel supported β‐nucleator has been successfully synthesized via pimelic acid supported on the surface of CaCO3. The crystallization temperature of iPP and melting temperature of β‐phase in iPP nucleated using the supported β‐nucleator are higher than those of iPP nucleated using calcium pimelate. The concept of a supported nucleator will provide a new way to increase the efficiency of polymer additives and to decrease the amounts of them that need to be used by using nanoparticles as supports. Copyright © 2010 Society of Chemical Industry  相似文献   

5.
A highly novel nano‐CaCO3 supported β‐nucleating agent was employed to prepare β‐nucleated isotactic polypropylene (iPP) blend with polyamide (PA) 66, β‐nucleated iPP/PA66 blend, as well as its compatibilized version with maleic anhydride grafted PP (PP‐g‐MA), maleic anhydride grafted polyethylene‐octene (POE‐g‐MA), and polyethylene‐vinyl acetate (EVA‐g‐MA), respectively. Nonisothermal crystallization behavior and melting characteristics of β‐nucleated iPP and its blends were investigated by differential scanning calorimeter and wide angle X‐ray diffraction. Experimental results indicated that the crystallization temperature (T) of PP shifts to high temperature in the non‐nucleated PP/PA66 blends because of the α‐nucleating effect of PA66. T of PP and the β‐crystal content (Kβ) in β‐nucleated iPP/PA66 blends not only depended on the PA66 content, but also on the compatibilizer type. Addition of PP‐g‐MA and POE‐g‐MA into β‐nucleated iPP/PA66 blends increased the β‐crystal content; however, EVA‐g‐MA is not benefit for the formation of β‐crystal in the compatibilized β‐nucleated iPP/PA66 blend. It can be relative to the different interfacial interactions between PP and compatibilizers. The nonisothermal crystallization kinetics of PP in the blends was evaluated by Mo's method. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

6.
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   

7.
Zinc adipate (Adi‐Zn) was observed to be a highly active and selective β‐nucleating agent for isotactic polypropylene (iPP). The effects of Adi‐Zn on the mechanical properties and the β‐crystals content of nucleated iPP were investigated. The impact strength of iPP nucleated with 0.2 wt % Adi‐Zn was 1.8 times higher than that of neat iPP. In addition, wide‐angle X‐ray diffraction analysis indicated that the content of β‐crystals in nucleated iPP (kβ value) reached 0.973 with 0.1 wt % Adi‐Zn, indicating that Adi‐Zn is a highly active and selective β‐nucleating agent for iPP. Furthermore, fast scanning chip calorimetry (FSC) studies using cooling rates from 60 to 13,800 °C min?1 revealed that the formation of β‐crystals significantly depended on the cooling rates. At cooling rates below 3000 °C min?1, only β‐crystals existed. However, at cooling rates above 6000 °C min?1, β‐crystals failed to form. Moreover, a lower critical crystallization temperature that corresponded to the generation of β‐crystals was investigated using cooling‐induced crystallization, and the results are in good agreement with those of a previous study. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43767.  相似文献   

8.
The crystalline structure, morphology, and nonisothermal crystallization behavior of isotactic polypropylene (iPP) with and without a novel rare earth‐containing β‐nucleating agent (WBG) were investigated with wide‐angle X‐ray diffraction, polar optical microscopy, and differential scanning calorimetry. WBG could induce the formation of the β form, and a higher proportion of the β form could be obtained by the combined effect of the optimum WBG concentration and a lower cooling rate. The content of the β form could reach more than 0.90 in a 0.08 wt % WBG nucleated sample at cooling rates lower than 5°C/min. Polar optical microscopy showed that WBG led to substantial changes in both the morphological development and crystallization process of iPP. At all the studied cooling rates, the temperature at which the maximum rate of crystallization occurred was increased by 8–11°C in the presence of the nucleating agent. An analysis of the nonisothermal crystallization kinetics also revealed that the introduction of WBG significantly shortened both the apparent incubation period for crystallization and the overall crystallization time. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

9.
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   

10.
A novel highly efficient β‐nucleating agent for isotactic polypropylene (iPP), hexahydrophthalic barium (HHPA‐Ba), was found and its effects on the mechanical properties, the β‐phase content, and crystallization behavior of iPP were investigated, respectively. The results show that the β‐phase content of nucleated iPP (kβ value) can reach 80.2% with 0.4 wt % HHPA‐Ba. The impact strength and crystallization peak temperature of nucleated iPP are greatly increased. Compared with pure iPP, the impact strength of nucleated iPP can increase 2.4 times. Meanwhile, the spherulite size of nucleated iPP is dramatically decreased than that of pure iPP. The Caze method was used to investigate the nonisothermal crystallization kinetics of nucleated iPP and the crystallization active energy was achieved by Kissinger method. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

11.
BACKGROUND: It is a challenge for polymer processing to promote the formation of γ‐phase under atmospheric conditions in isotactic polypropylene (iPP) copolymer containing chain errors. Incorporation of an α‐nucleator in iPP copolymer seems reasonable since it can enhance non‐isothermal crystallization. Up to now, however, the issue regarding a β‐nucleated iPP copolymer still remains unclear, which is the subject of this study. RESULTS: The results indicate that the γ‐phase indeed occurs in a β‐nucleated random iPP copolymer with ethylene co‐unit (PPR) sample and becomes predominant at slow cooling rates (e.g. 1 °C min?1) where the formation of the β‐form is suppressed to a large extent. With detailed morphological observations the formation of γ‐phase in the β‐nucleated PPR sample at slow cooling rate is unambiguously attributed to the nucleating duality of the β‐nucleator towards α‐ and β‐polymorphs. The α‐crystals, induced by the β‐nucleator, serve as seeds for the predominant growth of the γ‐phase. Moreover, the presence of the β‐nucleator, acting as heterogeneous nuclei, promotes the formation of γ‐phase in the nucleated PPR sample, at least to some extent. CONCLUSION: The findings in this study extend our insights into the formation of γ‐phase in β‐nucleated iPP copolymer and, most importantly, provide an alternative route to obtain iPP rich in γ‐phase. Copyright © 2008 Society of Chemical Industry  相似文献   

12.
On the premise that shear in the slit die of an extruder was minimized as far as possible, β‐nucleated isotactic polypropylene (iPP) was extruded. Simultaneously, once the extrudate (in the melt state) left the die exit, it was stretched at various stretching rates (SRs). For iPP with a low content of β‐nucleating agent (β‐NA), the crystallinity of β‐phase (Xβ) initially increases with increasing SR, and then decreases slightly with further increase in SR. However, for iPP containing a higher content of β‐NA, with increasing SR, Xβ decreases monotonically, indicating a negative effect of SR on β‐phase formation. Small‐angle X‐ray scattering and polarized optical microscopy experiments reveal that, when SR is less than 30 cm min?1, the increasing amount of row nuclei induced by increasing SR is mainly responsible for the increase of Xβ. In contrast, when SR exceeds 30 cm min?1, the overgrowth of shish structures unexpectedly restrains the development of β‐phase, and spatial confinement is considered as a better explanation for the suppression of β‐phase. Copyright © 2011 Society of Chemical Industry  相似文献   

13.
As part of continuous efforts to understand the surprising synergetic effect between β‐nucleating agent and pre‐ordered structures of isotactic polypropylene (iPP) in significant enhancement of β‐crystallization (Ordered Structure Effect, OSE), two β‐nucleated iPP with different uniformities of stereo‐defect distribution (WPP‐A and WPP‐B) were prepared, their crystallization behaviors with variation of melt structures were studied in detail. The results revealed that β‐phase can hardly form in WPP‐A (whose stereo‐defect distribution is less uniform) because of its strong tendency of α‐nucleation caused by its less uniform stereo‐defect distribution, while WPP‐B is more favorable for β‐crystallization; As fusion temperature decreases, similar variation trends of crystallization temperature and β‐phase proportion can be observed from WPP‐A and WPP‐B, indicating the occurrence of OSE behavior, which provides unsurpassed β‐nucleation efficiency and induces β‐crystallization even in WPP‐A which is less favorable for β‐crystallization; moreover, the upper and lower limiting temperatures of Region II of WPP‐A and WPP‐B are identical, suggesting the uniformity of stereo‐defect distribution has little influence on temperature window for OSE (denoted as Region II). To explore the physical nature of Region II, self‐nucleation behavior and equilibrium melting temperature of PP‐A and PP‐B were studied. The lower limiting temperatures of exclusive self‐nucleation domain of both PP‐A and PP‐B are identical with the lower limiting temperatures of Region II in OSE (168°C); moreover, the Tm0 of both PP‐A and PP‐B are close to their upper limiting temperatures of Region II in OSE behavior (189°C). The possible explanation was proposed. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42632.  相似文献   

14.
The effects of ordered structure on isothermal crystallization kinetics and subsequent melting behavior of β‐nucleated isotactic polypropylene/graphene oxide (iPP/GO) composites were studied using differential scanning calorimetry. The ordered structure status was controlled by tuning the fusion temperature (Tf). The results showed that depending on the variation of crystallization rate, the whole Tf range could be divided into three regions: Region I (Tf > 179 °C), Region II (170 °C ≤ Tf ≤ 179 °C) and Region III (Tf < 170 °C). As Tf decreased from Region I to Region III, the crystallization rate would increase substantially at two transition points, due to the variation of the ordered structure status. Calculation of Avrami exponent n indicated that the ordered structure induced the formation of two‐dimensional growing crystallites rather than three‐dimensional growing crystallites. Moreover, in the case of isothermal crystallization, the ordered structure effect (OSE) can also greatly increase the relative content of β‐phase (βc). In Region II, OSE took place, resulting in evident increase of βc, achieving 92.4% at maximum. The variation of the isothermal crystallization temperature (Tiso) had little influence on the Tf range (Region II) of the OSE. The higher Tf in Region II was more favorable for the formation of higher βc. The ordered structure was favorable for the improvement of the nucleating efficiency of β‐nucleating agent (β‐NE), and was more effective for the improvement of lower β‐NE. © 2018 Society of Chemical Industry  相似文献   

15.
The mechanical and thermal characteristics and morphology of polyamide 6 (PA6)/isotactic polypropylene (iPP) blends (10/90 w/w) prepared with different processing procedures and incorporated with an aryl amide nucleating agent, a kind of β‐nucleating agent (β‐NA) for iPP, were investigated. The yield strength and flexural modulus of the blends decreased as β‐NA was introduced into the blends, whereas the impact strength and elongation at break improved. The crystalline structures of the blends closely depended on (1) the processing conditions and (2) competition between the β‐nucleating effect of β‐NA and the α‐nucleating effect of PA6 for iPP. Scanning electron microscopy, differential scanning calorimetry, and X‐ray diffraction were adopted to reveal the microstructures of the blends. At a low β‐NA content (<0.1 wt %), the α‐phase iPP dominated the blends, whereas the relative content of the β‐phase iPP increased remarkably when the β‐NA content was not less than 0.1 wt %. The processing conditions also showed profound influences on the supermolecular structures of iPP; this resulted in different mechanical properties of the blends. As for PA6, the crystallization behavior and crystalline structure did not exhibit obvious changes, but PA6 did play an important role in the epitaxial crystallization of iPP on PA6. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

16.
The effect of α‐ and β‐nucleating agents (NA) of various amounts on the fracture behavior of polypropylene‐co‐ethylene (CPP) was evaluated using the essential work of fracture (EWF) method. The specific EWF values of CPPs incorporated with α‐NA of different amount were all lower than that of pure CPP, while the specific nonessential work of fracture was the highest at relative low α‐NA loading (0.1 wt %), and then decreased with further increasing amount of α‐NA. Similar trend of variation was observed with increasing amount of β‐NA in CPP, and it was found that the variation of Kβ for β‐NA nucleated CPP versus NA content accorded well with the EWF versus NA content, which indicated that the addition of β‐NA could lead to effectively increased β‐crystal content and consequently improved fracture resistance of CPP. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

17.
β‐isotactic polypropylene (β‐iPP) cylindritic crystals were produced in homogeneous iPP fiber–matrix composites and heterogeneous polyamide (PA)–iPP fiber–matrix composites under different sample preparation conditions. The melt recrystallization behaviors of the β‐iPP crystals obtained in the homogeneous and heterogeneous composites were studied by optical microscopy. The experimental results show that, by heating the sample to 180 °C, the birefringence contributed by the iPP crystals in both α‐ and β‐forms disappears completely. During the cooling process, the β‐iPP crystals in the homogeneous composite appear again, while the iPP in the heterogeneous composite crystallizes in its α‐form. This demonstrates the different origins of the β‐iPP cylindrites in the homogeneous and heterogeneous composites. While the β‐iPP cylindrites in the heterogeneous composite are associated with the sample preparation procedure, the β‐iPP cylindrites in the homogeneous composite are produced by recrystallization of the molten but incompletely relaxed iPP fibers. In situ observation of the melt recrystallization process shows that the molten iPP oriented fibers crystallize first during the cooling process at relatively higher temperature in the α‐form. Abundant randomly dispersed β‐iPP nuclei formed at the surface of the recrystallized iPP fibers, which generate the β‐iPP cylindrites. Copyright © 2012 Society of Chemical Industry  相似文献   

18.
To obtain isotactic polypropylene (iPP) nanocomposites with high β‐crystal content, TMB5, calcium pimelate and calcium pimelate supported on the surface of nano‐CaCO3 were used as β‐nucleating agent and MWCNT filled β‐nucleated iPP nanocomposites were prepared. The effect of different β‐nucleating agent and MWCNT on the crystallization behavior and morphology, melting characteristic and β‐crystal content of β‐nucleated iPP nanocomposites were investigated by DSC, XRD and POM. The results indicated that addition of MWCNT increased the crystallization temperature of iPP and MWCNT filled iPP nanocomposites mainly formed α‐crystal. The β‐nucleating agent can induce the formation of β‐crystal in MWCNT filled iPP nanocomposites. The β‐nucleating ability and β‐crystal content in MWCNT filled β‐nucleated iPP nanocomposites decreased with increasing MWCNT content and increased with increasing β‐nucleating agent content due to the nucleation competition between MWCNT and β‐nucleating agents. It is found that the calcium pimelate supported on the surface of inorganic particles as β‐nucleating agent has stronger heterogeneous β‐nucleation than calcium pimelate and TMB5. The MWCNT filled iPP nanocomposites with high β‐crystal content can be obtained by supported β‐nucleating agent. POLYM. COMPOS., 36:635–643, 2015. © 2014 Society of Plastics Engineers  相似文献   

19.
Compatibilized polypropylene (PP)/polyamide (PA6) blends with and without β nucleating agent (β‐NA) are prepared, and are designated as Blend‐0.3 and Blend‐0, respectively. The melting and crystallization characteristic of the blends crystallized under different cooling rates and different crystallization temperatures are studied. It is observed that high β‐PP content can be developed in Blend‐0.3 only at slow cooling rates (<5°C/min), whereas high α‐PP content is formed at fast cooling rates. Isothermal crystallization analysis of Blend‐0 indicates that PA6 is an effective NA for α‐PP in the lower temperature range, whereas the α‐nucleating effect disappears in the higher temperature range. Blend‐0.3 can, therefore, be viewed as a system containing both α‐ and β‐NAs, simultaneously. PA6 is competing with β‐NA in inducing PP crystallization. Under the normal injection of Blend‐0.3, the melt will be cooled through the higher temperature that favors the effectiveness of β‐NA rapidly because of the faster cooling rate. However, the α‐nucleation effect from PA6 predominate at the lower temperature. This explains the difficulty in obtaining high β‐PP content in Blend‐0.3 from injection molding. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers  相似文献   

20.
In this study, the influence of β‐nucleation agent (β‐NA) on the morphology and properties of multi‐walled carbon nanotube (MWCNT) filled isotactic polypropylene (iPP) composites was explored in details. The results show that the incorporation of β‐NA has promoted the dispersion of MWCNT in the iPP matrix, which is profitable for improving the thermal stability and conductivity properties of MWCNT‐iPP composites. Besides, the 0.05 wt % β‐NA nucleated samples exhibit higher impact toughness than that of un‐β‐NA‐nucleated ones. Further SEM observations show that the morphology of MWCNT changes from large agglomerations to small clusters with doping of β‐NA. The main reason is that the incorporation of β‐NA (TMB‐5) in MWCNT filled iPP matrix has led to the formation of a charge‐transfer complex. Some of these clusters act as nucleation sites for inducing crystallization of α spherulites, which have a compete growth with β‐NA induced β crystals. Meanwhile, other clusters exist in the inter‐lamella amorphous phase of β crystals, some of them even combine two adjacent β spherulites. Accordingly, a large conductive network comes into being. Based on the investigated results, a mechanism model is proposed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

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