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1.
Polypropylene (PP) pipe is extraordinarily important in modern construction and transportation engineering owing its predominant advantages over metal such as good dimensional stability, low cost, and light weight. However, low toughness and hoop strength always stand in the way of the wide application. In this study, two kinds of β‐nucleating agents (NAs) (WBG‐II and NAB‐83) were added in isotactic polypropylene and thereafter, the crystalline composition, morphology, and alignment were investigated under the combination effects of rotation extrusion and NA. The experimental results showed that both NAB‐83 and WBG‐II could promote numerous β crystals, but dot‐like NAB‐83 could only induce randomly distributed isotropic spherulites. On the contrary, by adjusting the temperature gradient along the extrusion to rotation section, WBG‐II first dissolved into PP melts and then self‐assembled into fiber‐like nuclei before the formation of PP crystals. Compared to homogeneous crystallization, fibrous WBG‐II nuclei lowered the energy barrier for PP crystals; therefore, epitaxial β lamellae grew on these fibrous NAs and stacked into β‐form hybrid shish kebabs. Meanwhile, the alignment of these highly oriented structures deflected from the axis driven by the helical movement caused by die rotation. Consequently, PP pipe with outstanding hoop tensile performance as well as excellent toughness was prepared. J. VINYL ADDIT. TECHNOL., 25:E195–E202, 2019. © 2018 Society of Plastics Engineers  相似文献   

2.
Investigation of microstructure and properties is critical for the development and application of polymer materials. Polypropylene random copolymer (PPR) and β‐nucleated PPR are widely used in water pipe production. The effect of melt shear flow on the crystalline structure and mechanical properties of PPR containing β‐nucleating agent needs in‐depth understanding. In this paper, we demonstrated the preparation of PPR and PPR containing 0.1 wt% calcium pimelate (Ca‐Pim) samples by conventional injection molding (CIM) and oscillation shear injection molding (OSIM). The multilayer structures and morphologies of the samples were characterized by SEM, two‐dimensional X‐ray scattering and DSC. The mechanical properties and the microstructures of samples prepared by these two injection molding methods were compared. Compared with samples prepared by CIM, the stronger shear provided by OSIM induced the formation of a thicker layer of a shish‐kebab structure and a higher content of γ crystals, and dramatically suppressed the β‐nucleating effect of Ca‐Pim. The OSIM samples have more shish‐kebab structures and higher crystallinities than CIM samples and therefore the former exhibit better rigidity than the latter. The β crystals in the core layer and the thicker layer of shish‐kebab structure endow OSIM‐PPR/0.1 wt% Ca‐Pim with excellent impact toughness. © 2017 Society of Chemical Industry  相似文献   

3.
The oriented “shish–kebab” structure and β‐crystal can enhance the mechanical properties of polypropylene products. In this regard, equipment and β‐nucleation agents have been developed or modified to form shish–kebab and β‐crystal. However, the effect of shish–kebab/β‐crystal proportion on the mechanical properties of polypropylene remains unclear. The answer is crucial but remains a challenge because of the difficulty in manipulating the shish–kebab proportion. In this work, we used a self‐made multiflow vibrate‐injection molding, which can provide a controllable shear flow, to produce samples with different shear‐layer thicknesses. The shish–kebab proportion was represented by R, which is the thickness ratio of the shear layer to that of the whole sample. Results showed that the tensile strength exponentially increased, whereas the elongation at break exponentially decreased, with R. The impact strength remained constant with R, indicating that the shish–kebab and β‐crystal possessed similar toughening effects. This work proposes a schematic to interpret the strengthening mechanism involved and presents a method of establishing and controlling the mechanical properties of polypropylene samples by using shish–kebab structures and β‐crystals. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45052.  相似文献   

4.
A two‐step process for preparing glass fibers (GFs) reinforced β‐nucleated PP composites was designed and developed. The complementary approach combined GFs reinforcement and β‐nucleating agents regulation using N,N′‐dicyclohexyl‐2,6‐napthalene‐dicarboxamide (TMB‐5) in the presence of maleic anhydride grafted polypropylene (PP‐g‐MA) through extrusion blending. The influence of TMB‐5 and GFs on the mechanical properties and crystallization behavior of PP was studied by mechanical test, wide‐angle X‐ray diffraction, differential scanning calorimetry, and scanning electron microscopy. A distinct complementary effect of GFs and β‐nucleating agent TMB‐5 on mechanical properties and crystallization behavior of PP was observed. Results showed that addition of 20 wt % GFs and 0.1 wt % TMB‐5 into PP matrix with the two‐step process could lead to significant increase to its mechanical properties: specifically 64.8% improvement in tensile strength, 107.1% enhancement in flexural modulus, and 167.7% increasement in notched impact strength compared to that of neat PP. Furthermore, with the combination of TMB‐5 and GFs, not only led to promoted interfacial adhesion, but also significantly improved overall comprehensive mechanical properties. The complementary process provided an alternative approach for the development of PP with balanced toughnesss and stiffness. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45768.  相似文献   

5.
All‐polyethylene composites exhibiting substantially improved toughness/stiffness balance are readily produced during conventional injection molding of high density polyethylene (HDPE) in the presence of bimodal polyethylene reactor blends (RB40) containing 40 wt% ultrahigh molar mass polyethylene (UHMWPE) dispersed in HDPE wax. Scanning electron microscopy (SEM) and differential scanning calorimetry (DSC) analyses shows that flow‐induced crystallization affords extended‐chain UHMWPE nanofibers forming shish which nucleates HDPE crystallization producing shish‐kebab structures as reinforcing phases. This is unparalleled by melt compounding micron‐sized UHMWPE. Injection molding of HDPE with 30 wt% RB40 at 165 °C affords thermoplastic all‐PE composites (12 wt% UHMWPE), improved Young's modulus of 3400 MPa, tensile strength of 140 MPa, and impact resistance of 22.0 kJ/m2. According to fracture surface analysis, the formation of skin‐intermediate‐core structures accounts for significantly improved impact resistance. At constant RB40 content both morphology and mechanical properties strongly depend upon processing temperature. Upon increasing processing temperature from 165 °C to 250 °C the average shish‐kebab diameter increases from the nanometer to micron range, paralleled by massive loss of self‐reinforcement above 200 °C. The absence of shish‐kebab structure at 250 °C is attributed to relaxation of polymer chains and stretch‐coil transition impairing shish formation.  相似文献   

6.
Branched and linear polyacetals prepared by cationic bulk polymerization were molded under high‐injection rate and pressure, and the resultant 1‐mm‐thick specimens were investigated regarding the crystalline morphology, mechanical properties, and transparency. The branched polyacetal exhibited shear‐induced transformation of crystalline morphology, namely, the spherulites, the elongated spherulites, and shish‐kebab morphology parallel to the flow direction, with increasing shear viscosity. The degree of orientation of the branched polyacetal, calculated from the intensity distribution on the Debye ring of the (100) diffraction by WAXS, linearly and significantly increased with the increase of the logarithm of the shear viscosity. The difference of the crystalline morphology greatly influenced the mechanical properties and transparency of the branched and linear polyacetals. The branched polyacetal with the shish‐kebab morphology had approximately 20% higher tensile strength and modulus as compared with those with the spherulites morphology, and showed translucent with a higher light transmittance over a wide range of wavelength of incident light. The results indicate that a large number of fibrous crystals in the shish‐kebab morphology result in the self‐reinforcement of specimens parallel to the flow direction and diminishment of the scattering of incident light. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3182–3392, 2006  相似文献   

7.
The crystallization structures of Polypropylene (PP) injection‐molded bars nucleated by nucleating agent were detected from the skin layer to the core zone, layer by layer. α‐phase nucleating agent 1,3:2,4‐bis (3,4‐dimethylbenzylidene) sorbitol (DMDBS, Millad 3988), β‐phase nucleating agent aryl amides compounds (TMB‐5), and their compounds were introduced into PP matrix, respectively. The relative content of β‐phase PP in the different zones of an injection‐molded bar was characterized and calculated by Wide angle X‐ray diffraction (WAXD) and Differential scanning calorimetry (DSC). The results show that, whether in pure PP or in nucleated PP, both β‐phase PP and α‐phase PP grow in the skin layer of the injection‐molded bar. However, in the intermediate layers and the core zone, the crystallization structures of PP are dependent on the used nucleating agent. β‐phase is the main crystallization structure of TMB‐5 (0.1 and 0.2 wt%) nucleated PP, and α‐phase in DMDBS (0.1 and 0.2 wt%) nucleated PP. Compounding nucleating agents with 0.1 wt% DMDBS and 0.1 wt% TMB‐5 induces PP crystallization almost in β‐phase; however, PP nucleated by 0.2 wt% DMDBS and 0.2 wt% TMB‐5 crystallizes exclusively in α‐phase. The crystallization mechanism of PP nucleated by compounding nucleating agents was further studied in this work. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers  相似文献   

8.
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   

9.
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   

10.
This paper presented a simple and facile method to prepare high-performance polypropylene sheet through hybrid shish kebab crystals. The experimental results showed that fibrous rare earth nucleating agent (WBG) was a kind of rigid particle with properties of easier alignment along flow and more stability when compared with oriented molecule, so during the processing of WBG-modified polypropylene samples, WBG fibrils acted as “shish” to direct the oriented crystallization of coiled polymer chains perpendicular to the fibril, into hybrid shish kebab with reinforcement function. As a result, the tensile and yield strengths of WBG-modified polypropylene sheets were improved significantly.  相似文献   

11.
The crystalline morphology and dynamical crystallization of antibacterial polypropylene composite and pure polypropylene were investigated via differential scanning calorimeter (DSC), wide angle X‐ray diffraction (WAXD), and real‐time hot‐stage optical microscopy (OM). The results reveal that the crystalline morphology of antibacterial PP composites changes with variations of the crystallization conditions and compositions. The crystalline phase consists of both α‐PP and β‐PP crystals. The content of β‐PP decreases with the increase in antibacterial agent content and cooling rate. With the addition of β‐nucleating agent, the morphologies of all dynamically crystallized antibacterial PP composites show no obvious spherulitic morphology, and the decrease of crystal perfection and the increase of nucleation density of antibacterial PP composite system could be observed. With the increase of antibacterial agent content, the overall crystallization rates of the antibacterial PP composite increase dramatically, while the content of β‐PP in all antibacterial PP composite decrease distinctly under given cooling conditions. These results can be explained by the interruptive effect of antibacterial agent on interactions of β‐nucleating agent components and the obstructing effect of antibacterial agent on the mobility of PP chains in melts. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

12.
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   

13.
Calcium salts of suberic (Ca‐Sub) and pimelic (Ca‐Pim) acids were synthesized and implemented as in different grades of isotactic polypropylene (iPP). Propylene homopolymer, as well as random and block copolymers containing these additives, crystallized iPP into pure or nearly pure β modification in the isothermal and nonisothermal crystallization experiments. Recently, Ca‐Sub proved to be the most effective β‐nucleating agent of iPP. The Ca‐Sub nucleating agent widens the upper crystallization temperature range of pure β‐iPP formation up to 140°C. In this study the effect of the these additives on the crystallization, melting characteristics, and structure of the PP were studied. The degree of crystallinity of β‐iPP was markedly higher than that of α‐iPP. A widening in the melting peak of the samples crystallized in a high temperature range was first observed and discussed in regard to literature results of the same phenomenon for α‐iPP. The morphology of the β‐iPP samples was revealed by scanning electron microscopy. Independent of the type of polymer or nucleating agent, hedritic structures were found in the early stages of growth of the β‐spherulites. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2357–2368, 1999  相似文献   

14.
The melting and crystallization behaviors, morphology, and mechanical properties of polypropylene (PP)/surface‐treated calcium sulfate (CaSO4) whisker (T‐CSW), β‐PP/T‐CSW, and β‐PP/polypropylene‐graft‐maleic anhydride (PP‐g‐MAH)/T‐CSW composites had been investigated via differential scanning calorimetry (DSC), wide angle X‐ray diffraction (WAXD), polarized light microscopy (PLM), scanning electron microscopy (SEM), and mechanical tests. We found that T‐CSW was an α‐nucleating agent and increased the crystallization temperatures of PP, but PP‐g‐MAH and high loadings of T‐CSW had weakly negative effects on the crystallization rates of PP. The T‐CSW restrained the formation of β‐spherulites, and the spherulitic size decreased in the composites. PP‐g‐MAH improved the compatibility and adhesion between T‐CSW and the matrix. The notched impact strength was improved, and the tensile strength was enhanced at low levels of T‐CSW, while the flexural modulus was weakened for β‐PP/T‐CSW and β‐PP/PP‐g‐MAH/T‐CSW composites versus PP/T‐CSW composites. POLYM. COMPOS., 37:2121–2132, 2016. © 2015 Society of Plastics Engineers  相似文献   

15.
In this article, microporous polypropylene (PP) membranes were produced with TMB‐5 as β‐crystal nucleating agent by biaxial stretching. Influences of different concentration of TMB‐5 were studied using differential scanning calorimetry and X‐ray diffraction. It was found that the highest crystallinity was reached when the nucleating agent content was 0.5 wt %. The effect of stretching temperature and stretching ratio on pore size distribution and porosity of the membranes were investigated by scanning electron microscopy and mercury porosimeter, respectively. And physical properties, such as tensile strength, permeability, and puncture resistance of the microporous membrane prepared at the optimized conditions, were evaluated. Compared with commercial PP separator membrane, the as‐prepared microporous membrane shows similar uniform pore size distribution and exhibits slightly higher porosity and ionic conductivities. When used as lithium‐ion separator, the experimental film shows more stable cycling performance than the commercial one. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45825.  相似文献   

16.
Summary: Polyhydroxybutyrate (PHB) is an ideal bioplastic, however, this polymer undergoes a severe embrittlement process because of its spherulitic structure, rendering the material brittle. Using a series of in‐situ rheo techniques, we have previously observed only the rapid initial stage of shish formation, we term a partial shish, which existed at high shears in medium‐molecular‐weight PHB, = 360 000. The shish kebab morphology is anticipated to remove or severely lessen this embrittlement process whilst providing new properties and applications. For medium and ultra high‐molecular‐weight (MMWT, = 360 000/UHMWT, = 5 × 106) PHB 99/1 and 99.5/0.5 blends only a partial shish is identified. However, the initial shish formation stage and subsequent stages were observed at 98/2 and 97/3 blend ratios resulting in a complete shish, we term the full shish, and fiber formation was evident. We believe this fiber morphology achieved by high molecular weights is crucial to sustaining the shish kebab structure for an excessive period.

Left: In‐situ rheo‐light scattering micrograph; 97/3 MMWT/UHMWT PHB at 100 s?1 for 1 s shear shish held at 75 s. Right: In situ rheo‐optical micrograph; PHB fiber morphology observed at 50 s?1 for 2 s shear 98/2 MMWT/UHMWT PHB after 1 min.  相似文献   


17.
Monoclinic (α) and hexagonal (β) polypropylene (α‐ and β‐PP) were stained in the vapor of a ruthenium tetroxide solution prepared in situ. The effect of staining on the fusion behavior was investigated using a DSC. A staining duration between 10 and 24 h was found suitable for obtaining a good electron contrast between the crystalline and amorphous regions for TEM examination without causing severe damage to the crystals. The spherulites of the water‐quenched α‐PP were found to be composed of very fine cross‐hatched lamellae whose long period was about 10 nm. In comparison, the β‐PP spherulites crystallized isothermally at 130°C had a category 2 morphology and the lamellae have a long period of 20 nm. The morphology of the spherulite boundary varied depending on the contact angle between the lamellae of the neighboring spherulites. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1529–1538, 1999  相似文献   

18.
Magnesium salt (M‐HOS) whisker and β‐nucleating agent were introduced into polypropylene and their effects on the crystalline structures, morphologies, mechanical properties, and thermal resistance of polypropylene (PP) were investigated. The results of wide angle X‐ray diffraction (WAXD), differential scanning calorimetry (DSC), and polar optical microscopy (POM) examinations suggested that the presence of the whisker did not cause any negative effect on the occurrence of β‐modification, and β‐phase became absolutely dominant form in β‐nucleated samples. The mechanical and thermal properties tests demonstrated that there is an excellent synergy between the β‐nucleating agent and the whisker. For PP composite containing 0.1 wt% of the β‐nucleating agent and 10 wt% of the whiskers, the Izod notched impact strength, elongation at break, flexural modulus, and heat deflection temperature were increased by 108, 194, 31, and 40%, respectively, compared with those of neat PP. By combining the toughening effect of α–β transition with the reinforcing effect of the whisker, simultaneous improvement in toughness, flexural modulus, and thermal performance of PP was successfully achieved. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers  相似文献   

19.
Shish‐kebab, which is endowed with superior strength and modulus, provides the potential to fabricate self‐reinforced polymer products. However, the injection‐molded product usually exhibits a typical skin–core structure, and the shish‐kebab is only located in an extremely thin shear layer. Therefore, the controlling and tailoring of crystal structures in complex flow field to improve the mechanical properties of the injection‐molded sample are still a great challenge. Herein, for the first time, high‐density polyethylene sample with a novel macroscopic alternating skin–core structure is achieved using a melt multi‐injection molding technique. Results show that, with increasing the amount of melt injection, the layers of skin–core structure increase in the form of arithmetic progression, and therefore the tensile strength of the samples progressively increases due to an increase of shish‐kebab content. This study demonstrates a new approach to achieve multilayer homogeneous materials with excellent tensile strength via macroscopic structural design during the practical molding process.  相似文献   

20.
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   

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