共查询到20条相似文献，搜索用时 31 毫秒
1.
Bing Na Ruihua Lv Wenfei Xu Rong Chen Zunxin Zhao Yong Yi 《Polymer International》2008,57(10):1128-1133
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
2.
Blends of isotactic polypropylene (PP) and syndiotactic polystyrene (sPS) with and without β‐nucleating agent were prepared using a twin‐screw extruder at 290 °C. Blends of PP/sPS with β‐nucleating agent mainly show β crystalline form, irrespective of high (20 °C min?1) or low (2 °C min?1) previous cooling rates. This suggests that the cooling rates have little effect on the polymorphic composition of PP in PP/sPS blends. The effect of sPS on the crystallization of PP is compared with that of polyamide 6 (PA6). The increase in crystallization temperature of PP is smaller in the presence of sPS than in the presence of PA6; the fold surface free energy of PP/sPS is larger than that of PP/PA6 blends. These results reveal that compared with PA6, sPS has much weaker α‐nucleation effect on the crystallization of PP. The weak α‐nucleation effect of sPS is attributed to the high lattice mismatch between PP and sPS crystals. 相似文献
3.
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
4.
This study aims to explore the joint effects of specific β‐nucleation and rubber dispersion on morphology and mechanical behavior of materials derived from isotactic polypropylene. A β‐nucleator (N,N′‐dicyclohexylnaphthalene‐2,6‐dicarboxamide) and an amorphous EPM rubber were used for the modification of isotactic polypropylene. Four samples were investigated: neat polypropylene, the same polymer modified with 0.03 wt % of β‐nucleator or with 15 wt % of dispersed rubber particles, and finally polypropylene containing both the β‐nucleator and the rubber particles. Tensile and impact behavior were followed at room and cryogenic temperatures. It has been observed that the β‐nucleation and rubber modification have brought about a similar macroscopic softening effect on the tensile mechanical behavior. Microscopy of fracture surfaces, however, has shown different toughening mechanisms caused by specific nucleation on one hand and by rubber dispersion on the other. While a distinct synergy effect of nucleation and rubber modification on the resulting toughness was found at low temperature, no such cooperative effect manifested itself at room temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3539–3546, 2007 相似文献
5.
Yansong Yu Fangxinyu Zeng Jinyao Chen Jian Kang Feng Yang Ya Cao Ming Xiang 《Polymer International》2018,67(9):1212-1220
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
6.
This article deals with the crystallization behaviors of original (prepared in a torque rheometer), DSC crystallization and mold crystallization (quenching and slow nonisothermal crystallization) of isotactic polypropylene (iPP) mixed with β‐form nucleating agent. The microstructure and thermal stability of these samples were investigated. The wide angle X‐ray diffraction (WAXD) results indicate that fast cooling is favorable for β‐form iPP formation. With slower cooling rate and higher concentration of nucleating agent, the lamellar thickness and stability of crystal0s were enhanced. Polarized optical microscopy (POM) and scanning electron microscopy (SEM) both showed that rapid crystallized samples gave rise to tiny spherulites, whereas under slow crystallization condition, nucleated samples could be fully developed in the form of dendritic or transcrystalline structures, depending on the nucleating agent concentration. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011 相似文献
7.
A new kind of β nucleating agent, multi‐wall carbon nanotube (MWCNT)‐supported calcium pimelate was introduced into polyamide 6 (PA 6)/isotactic polypropylene (iPP; 10/90 by weight) blend and the thermal properties, morphology, and mechanical properties were investigated. The results showed that β‐iPP appeared at low content of MWCNT‐supported calcium pimelate which surmounted the α‐nucleating effect of PA 6 for iPP, and the content of β‐iPP increased with increasing content of MWCNT‐supported calcium pimelate. The impact strength, elongation at break, and flexural modulus were improved with increasing content of MWCNT‐supported calcium pimelate without significantly deteriorating the tensile strength. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012 相似文献
8.
综述了3类广泛应用的α/β复合成核剂对聚丙烯结晶动力学、结晶形态及宏观性能等方面影响的研究进展。总结了影响α/β复合成核剂调控聚丙烯结晶的主要因素在于两种成核剂的成核能力,具体表现为其成核聚丙烯结晶温度(TC)的高低:TC高的成核剂在聚丙烯结晶过程中起主导作用,TC低的成核剂基本不起成核作用,当两者的TC相接近时发生竞争成核。根据这一规律,找出了复合α、β两种成核剂的方法,并列举将其运用到调控聚丙烯的结晶过程中的实例。 相似文献
9.
The effect of a particulate nucleating agent on fractionated crystallization of polypropylene (PP) was studied. A novel method utilizing breakup of PP nanolayers was used to obtain a dispersion of PP droplets in a polystyrene (PS) matrix. An assembly with hundreds of PP nanolayers alternating with thicker PS layers was fabricated by layer‐multiplying coextusion. The concentration of an organic dicarboxylic acid salt (HPN) nucleating agent in the coextruded PP nanolayers was varied up to 2 wt %. When the assembly was heated into the melt, interfacial driven breakup of the thin PP layers produced a dispersion of PP particles in a PS matrix. Analysis of optical microscope images and atomic force microscope images indicated that layer breakup produced a bimodal particle size distribution of submicron particles and large, micron‐sized particles. Almost entirely submicron particles were obtained from breakup of 12 nm PP layers. The fraction of PP as submicron particles dropped dramatically as the PP nanolayer thickness increased to 40 nm. Only large, micron‐sized particles were obtained from 200 nm PP nanolayers. The crystallization behavior of the particle dispersions was characterized by thermal analysis and wide angle X‐ray diffraction. Only part of the PP was nucleated by HPN. It was found that HPN was not effective in nucleating the population of submicron particles. The particulate HPN was too large to be accommodated in the submicron PP particles. On the other hand, the amount of nucleated crystallization qualitatively paralleled the fraction of PP in the form of large, micron‐sized particles. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007 相似文献
10.
Six samples of isotactic polypropylene were examined to study the influence of the thermal treatments and the molecular weights and their distribution on the β‐crystallization of the polymer. The highest amount of the β‐phase was obtained by isothermal crystallization and in correspondence of high average molecular weights and wide molecular weight distributions. Small‐angle X‐ray scattering pointed out that a partial β‐crystallization seems not to influence the lamellar morphology parameters. Differential scanning calorimetry measurements, at different heating rates, allowed us to confirm that the multiple melting endotherms behavior of the β‐phase is to be correlated to a melting–recrystallization–melting mechanism. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1008–1012, 2004 相似文献
11.
《大分子材料与工程》2017,302(11)
The influence of annealing on mechanical αc‐relaxation of isotactic polypropylene (i PP) is investigated. In the sample without annealing, polymer chains in the intermediate phase are constrained by crystallites with a broad size distribution, leading to one αc‐relaxation peak with activation energy (E a) of 53.39 kJ mol−1. With an annealing temperature between 60 and 105 °C imperfect lamellae melting releases a part of the constraining force. Consequently, two αc‐relaxation peaks can be observed (αc1‐ and αc2‐relaxation in the order of increasing temperature). Both relaxation peaks shift to higher temperatures as annealing temperature increases. E a of αc1‐relaxation decreases from 38.43 to 35.55 kJ mol−1 as the intermediate phase thickness increases from 2.0 to 2.2 nm. With an annealing temperature higher than 105 °C, a new crystalline phase is formed, which enhances the constraining force on the polymer chains. So the αc1‐relaxation peak is broadened and its position shifts to a higher temperature. Moreover, the polymer chains between the initial and the newly formed crystalline phase are strongly confined. Therefore, the αc2‐relaxation is undetectable. E a of αc1‐relaxation decreases from 23.58 to 13.68 kJ mol−1 as the intermediate phase thickness increases from 2.3 to 3.0 nm. 相似文献
12.
Zishou Zhang Chunyan Chen Chunguang Wang Zhang Junping Kancheng Mai 《Polymer International》2010,59(9):1199-1204
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
13.
14.
To investigate the nucleation of metal pimelate for isotactic polypropylene (iPP) crystallization, iPP filled with a series of metal oxides with and without metal pimelate on their surface was prepared. There was a chemical reaction between pimelic acid (PA) and metal oxides MgO, CaO, BaO or ZnO, but not TiO2. The corresponding metal pimelate formed by the chemical reaction between PA and MgO, CaO, BaO or ZnO had a different influence on the crystallization behavior and melting characteristics of iPP. Addition of metal oxides increased the crystallization temperature of iPP and mainly formed α‐phase due to the heterogeneous α‐nucleation of metal oxides. The α‐nucleation of CaO could be easily changed into β‐nucleation using CaO‐supported PA, and 90.1% β‐phase was obtained. The β‐nucleation of BaO could be markedly enhanced by barium pimelate formed using supported PA. However, no β‐phase was observed for iPP filled with MgO‐ or ZnO‐supported PA. The various metal oxides with supported PA had a different influence on the crystallization behavior and melting characteristics of iPP due to the different structure of metal pimelate formed by chemical reaction between PA and the metal oxides. Copyright © 2012 Society of Chemical Industry 相似文献
15.
The effect of polystyrenes (PSs) with different architectures (three‐arm star‐shaped polystyrene (sPS), comb‐like branched polystyrene (cPS) and linear polystyrene) on their β‐nucleating efficiency for isotactic polypropylene (iPP) during crystallization and final impact and the tensile properties of iPP/PS blends were investigated by dynamic rheological measurements, SEM, DSC, polarized optical microscopy, wide angle X‐ray diffraction and mechanical property measurements. The results show that the architecture of PS has marked influence on its dispersibility in iPP and β‐nucleating efficiency. For iPP/cPS blend, plenty of short side chains reduce the probability of cPS chain entanglements, facilitating the interdiffusion between iPP and cPS chains. A favorable interfacial interaction results in good dispersibility, high β nucleating efficiency and an excellent toughening effect of cPS on iPP. However, the relatively high chain entanglement degree of sPS may not be in favor of chain diffusion between iPP and sPS and therefore relatively poor dispersibility and toughening effect are obtained. The elongation at break and impact strength of iPP were dramatically improved, especially with the addition of 1 wt% cPS. The toughening mechanism of PS on iPP is the dissipated energy caused by cavitation and the β‐nucleating effect of PS. © 2018 Society of Chemical Industry 相似文献
16.
Guoqiang Zheng Songwei Li Xiaoli Zhang Chuntai Liu Kun Dai Jingbo Chen Qian Li Xiangfang Peng Changyu Shen 《Polymer International》2011,60(7):1016-1023
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
17.
The commercial grade of isotactic polypropylene was modified by a specific β‐nucleating agent in a broad concentration range. The supermolecular structure of the specimens prepared by injection molding was characterized by X‐ray scattering and correlated with mechanical behavior. It was found that at a critical nucleant concentration of 0.03 wt % the content of the β‐modification virtually reaches a saturation level. With further addition of the nucleant, the β‐phase content increases only slightly. The long period passes through a distinct maximum at the same nucleant concentration. This singularity in structure remarkably correlates with a minimum of the yield stress and maxima of strain at break and fracture toughness. Such general behavior is also reflected in the correlation between the β‐phase concentration and fracture toughness profiles along the injection‐molded bars. It is suggested that in the critically nucleated material an optimum thickness of the amorphous interlayer with connecting chains between the β‐crystallites is established, rendering the material the highest possible ductility and toughness. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1174–1184, 2002 相似文献
18.
The effect of a β‐nucleating agent (β‐NA) on the properties and structure of a commercial impact polypropylene copolymer (IPC) was investigated. The effect of selected β‐NAs on the impact resistance, stress and strain behaviour of the IPC is reported. In addition, the IPC was fractionated according to crystallinity by preparative temperature rising elution fractionation. Fractions with varying chemical composition and crystallinity were treated with a two‐component β‐NA to investigate the effect of the β‐NA on the various fractions. The results indicate that the efficacy of the β‐NA is dependent on the chemical composition of the polymer that crystallises, more specifically on the sequence length of crystallisable propylene units. The effect of the addition of β‐NAs on the overall morphology of the IPC was also investigated, and in particular the size and distribution of the rubbery particles in these complex reactor blends were probed. © 2014 Society of Chemical Industry 相似文献
19.
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
20.
利用蒽为基础原料,自制了蒽系列的三种聚丙烯成核剂:9,10-二氢蒽-9,10-桥-α,β-马来酸酐（AMH）、9,10-二氢蒽-9,10-桥-α,β-马来酰肼（AMHD）、9,10-二氢蒽-9,10-桥-α,β-N-甘氨酸基马来酰胺（AGMA）。利用热重分析（TGA）分别考察了三者的热稳定性,采用X 射线衍射分析( XRD) 和偏光显微镜( PLM) 对其所改性等规聚丙烯（iPP）的结晶形态进行了表征,用差示扫描量热法( DSC) 研究了其结晶行为,并测试了力学性能。结果表明,AMHD和AGMA均可增强聚丙烯α晶型成核,而AMH则可诱导β-iPP的生成;该三种成核剂都有效提高了聚丙烯的结晶温度（Tc）和结晶度,其中iPP/AMHD的结晶度（Xc）提高了3.75%;同时改善了iPP的力学性能,与纯iPP试样相比,iPP/AMH抗冲击强度提高了5.60 kJ/m2,iPP/AMHD拉伸强度提高了18.02%,iPP/AGMA的弯曲强度达到53.22 MPa。 相似文献
