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1.
《Polymer Composites》2017,38(12):2707-2717
Maleic anhydride‐grafted polypropylene (Ma‐PP) and β nucleation agents (β‐NA) were used to modify the glass fiber (GF)/isotactic polypropylene (iPP) composite. The interface adhesion, degree of orientation, and crystalline morphologies of the PP/GF composites molded by multiflow vibrate‐injection molding (MFVIM) and conventional injection molding (CIM) were studied by polarized light microscopy (PLM), scanning electronic microscopy (SEM), and X‐ray measurements. Results prove that the interface adhesion was improved by the Ma‐PP; γ crystal was generated by the MFVIM due to the instant high pressure and shear during the multiflow; and a hierarchical structure which has a strengthened skin and a toughened core was formed. As a result, the final PP/GF/β‐NA composite has a 60% increase in tensile strength and 80% improvement in impact strength compare with the CIM pure PP/GF composite. Based on the observations, a modified model is proposed to interpret the strengthening and toughening mechanism. Our work paves the way to obtain high‐performance GF/iPP composites. POLYM. COMPOS., 38:2707–2717, 2017. © 2015 Society of Plastics Engineers  相似文献   

2.
In this work, isotactic–polypropylene (iPP) specimens were prepared by a modified injection molding machine, in which high temperature preshear (HTPS) can be imposed on the molten polymer during the plasticizing stage. The effect of HTPS on the microstructure and mechanical property of iPP was investigated. It was found that spherulite size in core region of iPP part decreased steadily with the increasing HTPS duration, indicating that HTPS could substantially enhance iPP nucleation. Moreover, β ‐iPP formation correlated strongly with HTPS duration. That is, in the absence of HTPS, β ‐iPP existed only in intermediate region; with moderate HTPS duration, β ‐iPP could be unexpectedly formed in core region; however, long HTPS duration inhibited β ‐iPP formation in both intermediate region and core region. Based on the relationship between β ‐iPP formation and HTPS duration, metastable nuclei, instead of α ‐row nuclei, were proposed to be responsible for the development of β ‐iPP. Notched Izod impact test showed that moderate HTPS duration enhance the impact strength of injection molded iPP by decreasing the thickness of shear region and elevating β ‐iPP crystallinity in core region. Dynamic mechanical test indicated that with the increase of HTPS duration, the storage modulus of injection‐molded iPP improves drastically. POLYM. ENG. SCI., 55:2714–2721, 2015. © 2015 Society of Plastics Engineers  相似文献   

3.
The influence of a mixed additive of lanthanum stearate and stearic acid on the crystalline characteristics of isotactic polypropylene (iPP) has been investigated. The results of the wide‐angle X‐ray diffraction (WAXD) measurements and the melting behaviour examination by differential scanning calorimetry (DSC) show that the additive might induce a high proportion of β‐form and act as a β‐form nucleating agent. The relative content of β‐form estimated by WAXD is 33.1% in a PP containing 2.5% (by weight) of the additive. Isothermal crystallization at 130 °C, examined by DSC, reveals that the additive considerably accelerates the overall rate of crystallization: the half crystallization period t1/2, decreases from 11.7 min for pure PP to 7.3 min for PP containing 2.5% of the additive. However, the additive has no obvious influence on the nucleation mechanism and crystal growth mode. Polarized light microscopy (POM) examinations indicate that the addition of the additive to PP causes spherulites to become much finer. © 2003 Society of Chemical Industry  相似文献   

4.
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   

5.
Large amount of work has been published on the tacticity‐properties relationship of isotactic polypropylene (iPP). However, the stereo‐defect distribution dependence of morphology and mechanical properties of β‐nucleated iPP (β‐iPP) is still not clear. In this study, two different iPP resins (PP‐A and PP‐B) with similar average isotacticity but different uniformities of stereo‐defect distribution were selected, their β‐iPP injection molding specimens were prepared, and the morphology evolution and tensile behaviors were studied by means of differential scanning calorimetry (DSC), 2D wide‐angle X‐ray diffraction (2D‐WAXD) and scanning electron microscope (SEM). DSC results showed that with the same concentration of β‐nucleating agent (0.3 wt % WBG‐II), PP‐B with more uniform stereo‐defect distribution exhibited more amount of β‐phase than that of PP‐A with less uniform stereo‐defect distribution, indicating that PP‐B is more favorable for the formation of β‐phase. SEM results showed that PP‐B formed more amount of β‐crystals with relatively high structural perfection, while in PP‐A a mixed morphology of α‐ and β‐phase with obviously higher amount of structural imperfection emerges. The results of room‐temperature tensile test indicated that the yield peak width of PP‐B was obviously wider, and the elongation at break of PP‐B was higher than that of PP‐A, showing a better ductile of PP‐B. The morphology evolution results of SEM, 2D‐WAXD and DSC suggest that, a combination of lamellar deformation and amorphous deformation occurred in PP‐A, while only amorphous deformation mainly took place in PP‐B, which was thought to be the reason for the different tensile behaviors of the samples. In the production of β‐PP products via injection molding, the uniformity of stereo‐defect distribution was found to be an important factor. PP with more uniform distribution of stereo‐defect favors the formation of large amount of β‐phase with high perfection, which exhibit superior ductile property. The related mechanism was discussed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40027.  相似文献   

6.
It is widely believed that β ‐nucleating agent is beneficial for effectively toughening isotactic polypropylene (iPP). However, for the injection molding process, the shearing and thermo‐mechanical conditions make the nucleation and crystallization process complicated. In this paper, the effects of injection rate on crystallization of β ‐nucleated iPP were studied by scanning electron microscope (SEM), two‐dimensional wide‐angle X‐ray diffraction and differential scanning calorimetry (DSC). It is observed that with increasing injection rate, the content of β ‐crystals exhibits different tendencies in the skin, intermediate layers, and core zone. Specifically, for the intermediate layer, the β ‐crystals content first increases with increasing injection rate to 85 cm·s?1, and begins to decrease afterward. By simulating the injection process, the most likely explanation for the β ‐crystal change is the comparatively high shear rate and low shearing time that the melt experienced. Variations in β ‐form content are mainly responsible for the mechanical properties of β ‐nucleated iPP. The results of this study provide a valuable way to control the iPP toughness in the injection molding process. POLYM. ENG. SCI., 57:172–182, 2017. © 2016 Society of Plastics Engineers  相似文献   

7.
The morphological development of a special polymeric nucleating agent [acrylonitrile–styrene copolymer (SAN)] in the isotactic polypropylene (iPP) matrix in the process of injection molding has been investigated by means of wide‐angle X‐ray diffraction and scanning electron microscope. The current experimental results indicate that the shear field, in combination with the temperature gradient, has great influence on the morphological distribution of SAN in the process of injection molding. For injection‐molded SAN/iPP specimens with higher SAN concentration (≥4%), SAN assembles to many microspheres and disperses uniformly in the isotropic core region; while from isotropic core region to oriented skin region, these SAN microspheres are gradually stretched into fibrils as a result of shear effect. On the contrary, for the specimens with lower SAN concentration (<4%), only microspheres can be observed in the core region and the skin region. At the same time, SAN has been proved to be a kind of special β‐nucleating agent. The addition of SAN into iPP helps enhances the crystallinity and the content of β crystal form of injection‐molded specimen. The morphology and the distribution of SAN in iPP matrix have great influence on the SAN's nucleating activity, which will ultimately affect the final crystalline structures of injection‐molded specimens. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

8.
The melting behavior and crystalline forms of isotactic polypropylene (iPP) samples crystallized under different conditions of pressure and temperature were investigated using differential scanning calorimeter (DSC) and wide‐angle X‐ray diffraction (WAXD), respectively. When treated with dynamic supercritical CO2(Sc‐CO2), iPP samples undergo the formation of β‐crystal that does not occur on the treatment with atmospheric pressure and static supercritical CO2(Sc‐CO2) pressure. In addition, the relative content of β‐crystal has deep dependence on melt state and depressurization rate. Depressurization plays very critical role in the formation of β‐crystal by means of imposing three‐dimensional tensile field during cell growth. The tensile field induced α‐row nuclei where the formation of β‐crystal occurred. This finding will provide one new method to induce β‐crystal in iPP parts. POLYM. ENG. SCI. 56:980–986, 2016. © 2016 Society of Plastics Engineers  相似文献   

9.
The nucleation ability of isotactic poly(propylene) (iPP) to ammonium 2,2′‐methylene‐bis‐(4,6‐di‐t‐butylphenylene) phosphate (An) was investigated in the present work comparing with sodium 2,2′‐methylene‐bis‐(4,6‐di‐t‐butylphenylene) phosphate (NA‐11). Scanning electron microscope (SEM) revealed the crystalline morphology of both An and NA‐11 with planar surface characteristics. The observation of the fracture surface of nucleation iPP samples by SEM showed An particles were dispersed uniformly in polymer and had a better compatibility with iPP matrix than NA‐11 particles. Differential scanning calorimeter (DSC) showed that the melting temperature of An was 262°C significantly lower than that measured from NA‐11 group (above 400°C). Crystallization behaviors of iPP/NA‐11 and iPP/An were also investigated by DSC analysis, respectively. The results showed the crystallization peak temperature and the crystallinity of iPP/An were almost near to that of iPP/NA‐11. Furthermore, mechanical and optical properties of iPP were strongly improved in the presences of An and NA‐11. The flexural strength of iPP was elevated 34 and 35% and the haze value was reduced from 40.4 to 15.1 and 14.9% by the addition of 0.15 wt% NA‐11 and An, respectively. These results demonstrate that the nucleating agent of An described here is a good nucleating agent for the crystallization of iPP as well as NA‐11. POLYM. ENG. SCI., 55: 22–28, 2015. © 2014 Society of Plastics Engineers  相似文献   

10.
We report here the synthesis and characterization of a reactive liquid crystal (RLC) as a novel polymeric nucleating agent for the promotion of the nucleation efficiency of isotactic polypropylene (iPP). The RLC was synthesized by an in‐situ photo‐polymerization and was then grafted onto the molecular chain of iPP by the reactive blending. The phase transition and crystalline morphologies of RLC‐iPP in the β‐nucleation were studied. It is found that the nucleation efficiency of β‐crystals of iPP can be increased to 42% with a very small amount of RLC grafting, which is much higher than the reported nucleation efficiency of polymeric nucleating agents up to now (23%). In addition, we found that the nucleation efficiency of β‐crystals is strongly related to the concentration of RLC for the reactive blending. The nucleation efficiency was decreased from 42% to about 17% with the increase of RLC concentration from 0.5% to 4%. We propose a possible nucleation mechanism for this interesting phenomenon. It is expected that this new β‐nucleation RLC will have potential industrial applications in the future. POLYM. ENG. SCI., 54:2112–2120, 2014. © 2013 Society of Plastics Engineers  相似文献   

11.
By adding a polymeric β‐nucleating agent (acrylonitrile–styrene copolymer, SAN), in situ microfibril reinforced isotactic polypropylene (iPP)/SAN blend parts with high contents of β‐form crystals and transcrystals were molded via water‐assisted injection molding (WAIM). Thanks to the unique stress and temperature fields occurring during the WAIM, SAN microfibers formed across the whole residual wall of iPP/SAN blend parts with relatively large thickness. Numerical simulations on high‐pressure water penetration and cooling stages of the WAIM were carried out to reveal the stress and temperature fields. Comprehensive analysis of both experimental and simulated results showed that not only the shear flow field but also elongational flow field occurring during the WAIM was responsible for the formation of SAN microfibers and unique crystal morphology distribution in the WAIM iPP/SAN blend part. Moreover, during the WAIM, the high cooling rate also played an important role in the formation of both phase and crystal morphologies. The preferential formation of transcrystals in the inner layer of WAIM iPP/SAN blend part could be ascribed to the strong elongation, rather than the strong shear. It was believed that the quantification of stress and temperature fields of the WAIM via numerical simulation could provide a guidence for molding high‐performance products. POLYM. ENG. SCI., 55:1698–1705, 2015. © 2014 Society of Plastics Engineers  相似文献   

12.
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   

13.
This article presents the effects of nanoclay and supercritical nitrogen on the crystallization and thermal behavior of microcellular injection‐molded polyamide‐6 (PA6) nanocomposites with 5 and 7.5 wt% nanoclay. Differential scanning calorimetry (DSC), X‐ray diffractometry (XRD), and polarized optical microscopy (POM) were used to characterize the thermal behavior and crystalline structure. The isothermal and nonisothermal crystallization kinetics of neat resin and its corresponding nanocomposite samples were analyzed using the Avrami and Ozawa equations, respectively. The activation energies determined using the Arrhenius equation for isothermal crystallization and the Kissinger equation for nonisothermal crystallization were comparable. The specimen thickness had a significant influence on the nonisothermal crystallization especially at high scanning rates. Nanocomposites with an optimal amount of nanoclay possessed the highest crystallization rate and a higher level of nucleation activity. The nanoclay increased the magnitude of the activation energy but decreased the overall crystallinity. The dissolved SCF did not alter the crystalline structure significantly. In contrast with conventionally injection‐molded solid counterparts, microcellular neat resin parts and microcellular nanocomposite parts were found to have lower crystallinity in the core and higher crystallinity near the skin. POLYM. ENG. SCI., 46:904–918, 2006. © 2006 Society of Plastics Engineers  相似文献   

14.
The study of crystallization behavior and crystalline morphology of polymer melt under shear flow is of great interest due to the strong effect of flow field on the final properties of polymer products in the practical processing. In this respect, the shearing hot stage provides a unique tool which monitors sensitively the changes in crystalline structure induced by precise experimental conditions. Herein, the impacts of both melting temperature and shear rate on the crystallization behavior of isotactic polypropylene (iPP) melt are investigated. Under static conditions, there are only random spherulite structures. Once shear is involved, the cylindrite‐layers appear near both surfaces of the sample, which is consistent with the skin‐core structure in the injection molded parts. Meanwhile, the β‐crystals can be developed and are related to the molecular orientation, depending on the applied melting temperatures and shear rates. More interestingly, the crystallinity of β‐crystal in the pure iPP can reach 15%. The above results indicate that the melting temperature and shear rate are important factors in determining the β‐form crystal development of iPP matrix.  相似文献   

15.
The non‐isothermal crystallization behavior, the crystallization kinetics, the crystallization activation energy and the morphology of isotactic polypropylene (iPP) with varying content of β‐nucleating agent were investigated using differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). The DSC results showed that the Avrami equation modified by Jeziorny and a method developed by Mo and co‐workers could be successfully used to describe the non‐isothermal crystallization process of the nucleated iPPs. The values of n showed that the non‐isothermal crystallization of α‐ and β‐nucleated iPPs corresponded to a tridimensional growth with homogeneous and heterogeneous nucleation, respectively. The values of crystallization rate constant showed that the rate of crystallization decreased for iPPs with the addition of β‐nucleating agent. The crystallization activation energy increased with a small amount (less than 0.1 wt%) of β‐nucleating agent and decreased with higher concentration (more than 0.1 wt%). The changes of crystallization rate, crystallization time and crystallization activation energy of iPPs with varying contents of β‐nucleating agent were mainly determined by the ratio of the content of α‐ and β‐phase in iPP (α‐PP and β‐PP) from the DSC investigation, and the large size and many intercrossing lamellae between boundaries of β‐spherulites for iPPs with small amounts of β‐nucleating agent and the small size and few intercrossing bands among the boundaries of β‐spherulites for iPPs with large amounts of β‐nucleating agent from the SEM examination. Copyright © 2010 Society of Chemical Industry  相似文献   

16.
Tensile strength of isotactic polypropylene (iPP)/glass fiber (GF) composites and neat iPP molded respectively by gas-assisted injection molding (GAIM) was examined. For comparison, tensile strength of the counterparts, which were molded by conventional injection molding (CIM) under the same processing conditions but without gas penetration, was also examined. Tensile strength of the CIM parts steadily increases with the increase of the GF content. For neat iPP molded by GAIM, as the gas pressure increases the tensile strength increases. However, for the iPP/GF composites, the tensile strength generally decreases when the gas pressure increases. And, at a given content of GF, tensile strength of the parts molded by GAIM is unexpectedly lower than that of the counterparts molded by CIM. At a given gas pressure, the higher the fiber content, the lower the tensile strength. In addition, scanning electron microscope (SEM) results show that foaming structure should be responsible for the poor tensile strength of the composites molded by GAIM. The poor adhesion between the glass fibers and the matrix and the unique properties of the gas used in GAIM process are the substantial factors in the formation of foaming structure.  相似文献   

17.
Molten polymers are usually exposed to varying levels of shear flow and temperature gradient in most processing operations. Many studies have revealed that the crystallization and morphology are significantly affected under shear. A so‐called “skin‐core” structure is usually formed in injection‐molded semicrystalline polymers such as isotactic polypropylene (iPP) or polyethylene (PE). In addition, the presence of nucleating agent has great effect on the multilayered structure formed during injection molding. To further understand the morphological development in injection‐molded products with nucleating agent, iPP with and without dibenzylidene sorbitol (DBS) were molded via both dynamic packing injection molding (DPIM) and conventional injection molding. The structure of these injection‐molded bars was investigated layer by layer via SEM, DSC, and 2 days‐WAXD. The results indicated that the addition of DBS had similar effect on the crystal size and its distribution as shear, although the later decreased the crystal size more obviously. The combination of shear and DBS lead to the formation of smaller spherulites with more uniform size distribution in the injection‐molded bars of iPP. A high value of c‐axis orientation degree in the whole range from the skin to the area near the core center was obtained in the samples molded via DPIM with or without DBS, while in samples obtained via conventional injection molding, the orientation degree decreased gradually from the skin to the core and the decreasing trend became more obvious as the concentration of DBS increased. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

18.
The influence of γ‐quinacridone as a β‐crystal nucleating agent in injection molded isotactic polypropylene (iPP) is discussed. Samples are injection molded and characterized via polarized‐light optical microscopy and X‐ray diffraction. Mold‐filling simulation is used to understand the shear and cooling processes during sample preparation. The cooling rate associated with the quench near the mold wall is estimated to be greater than 600 K s?1 using simulation, confirming previous studies that β‐crystal growth is not supported at that cooling rate. The non‐nucleated samples form β‐crystals at a distance of 100–300 µm from the skin and in the core of the sample, which is not expected based on quiescent cooling data. Since the mold‐filling simulation does not predict shear in the core, the formation of the β‐crystals formed in this region is attributed to shear‐induced crystallization effects in the injection unit of the molding machine that are not modeled in flow simulation, as they are typically excluded from any molding simulation analysis. This “melt‐memory” effect has shown to be significant, and it is suggested that the prediction of final properties of injection moldings requires understanding and knowledge of the entire shear history of the material including that of the injection unit.  相似文献   

19.
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   

20.
This article is principally concerned with the morphology and crystallinity of isotactic polypropylene (iPP) parts molded by injection molding, during which a self‐interference flow (SIF) occurs for the melt in the cavity. Scanning electron microscopy shows that a transverse flow takes place in SIF samples. Wide‐angle X‐ray diffraction and differential scanning calorimetry show that SIF moldings exhibit a γ phase, in addition to α and β phases, and high crystallinity. Meanwhile, the results for iPP moldings made by the conventional flow process, that is, conventional injection molding, are reported for comparison. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2791–2796, 2003  相似文献   

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