Dynamic mechanical studies of the sulfonated butyl rubber ionomers and their blends

Dynamic mechanical properties of sulfonated butyl rubber ionomers neutralized with different amine or metallic ion (zinc or barium) and their blends with polypropylene (PP), high-density polyethylene (HDPE), or styrene-butadiene-styrene (SBS) triblock copolymer were studied using viscoelastometry. The results showed that glass transition temperatures of ion pair-containing matrix and ionic domains (T-g1 and T-g2, respectively) of amine-neutralized ionomers were lower than those of ionomers neutralized with metallic ions, and the temperature range of the rubbery plateau on the storage modulus plot for amine-neutralized ionomers was narrower. The modulus of the rubbery plateau for amine-neutralized ionomers was lower than that of ionomers neutralized with zinc or barium ion. With increasing size of the amine, the temperature range for the rubbery plateau decreased, and the height of the loss peak at higher temperature increased. Dynamic mechanical properties of blends of the zinc ionomer with PP or HDPE showed that, with decreasing ionomer content, the T-m of PP or HDPE increased and T-g1 decreased, whereas T-g2 or the upper loss peak temperature changed only slightly. The T-g1 for the blend with SBS also decreased with decreasing ionomer content. The decrease of T-g1 is attributed to the enhanced compatibilization of the matrix of the ionomer-containing ion pairs with amorphous regions of PP or HDPE or the continuous phase of SBS due to the formation of thermoplastic interpenetrating polymer networks by ionic domains and crystalline or glassy domains.

Effect of cross-linking of high-density polyethylene. I. On spherulitic structures

Crystallization behavior and spherulitic structure of linear high-density polyethylene (HDPE), after being irradiated in its molten state by gamma -rays, was investigated by small-angle laser scattering (SALS) and differential scanning calorimetry (DSC). Significant changes in the crystallization of HDPE during cooling in air before and after being irradiated in the melt were observed. A critical minimum average molar mass between cross-links (200 carbon-carbon bonds) for spherulite formation in such an irradiated HDPE network was obtained.

Brittle-ductile transition in high-density polyethylene/glass-bead blends: Effects of interparticle distance and temperature

The toughness of high-density polyethylene (HDPE)/glass-bead blends containing various glass-bead contents as a function of temperature was studied. The toughness of the blends was determined from the notch Izod impact test. A sharp brittle-ductile transition was observed in impact strength-interparticle distance (ID) curves at various temperatures. The brittle-ductile transition of HDPE/glass-bead blends occurred either with reduced ID or with increased temperature. The results indicated that the brittle-ductile-transition temperature dropped markedly with increasing glass-bead content. Moreover, the correlation between the critical interparticle distance (ID.) and temperature was obtained. Similar to the ID, of polymer blends with elastomers, the ID, nonlinearly increased with increasing temperature. However, this was the first observation of the variation of the ID, with temperature for polymer blends with rigid particles. (C) 2001 John Wiley & Sons, Inc. J Polym. Sci Part B: Polym. Phys 39: 1855-1859, 2001.

Controlling factors for the occurrence of heteroepitaxy of polyethylene on highly oriented isotactic polypropylene

The controlling factors for the epitaxial crystallization of high-density polyethylene (HDPE) on highly oriented isotactic polypropylene (iPP) substrates have been studied in detail by means of transmission electron microscopy and electron diffraction. The results obtained in this work indicate that the crystallization process must be considered in the investigation of epitaxial growth of polymers on polymeric substrates, because of the unique morphological and crystallization characteristics of polymers. Crystallization rate has an important effect on the epitaxial crystallization of polymers. Higher rates result in the formation of thicker epitaxial layers. Isothermal crystallization temperature is another factor affecting epitaxial growth of polymers. Lower temperatures are favorable to epitaxial crystallization of polymers. There exists a critical epitaxial temperature at given experimental conditions, above which no epitaxial growth occurs at all. The influence of crystal dimensions of both the substrates and the deposited polymers on epitaxial growth confirms that secondary nucleation is an important controlling factor for the occurrence of epitaxial crystallization in polymers. The requirement satisfying the secondary nucleation criterion is that the substrate crystal dimension in the matching direction must be greater than the crystal thickness of the deposited polymer. Once the requirement of the secondary nucleation is satisfied, subsequent epitaxial growth is based on the lamellar growth habit of the deposited polymer itself. (C) 1998 Published by Elsevier Science Ltd. All rights reserved.

Critical crystallization temperature for the occurrence of epitaxy between high-density polyethylene and isotactic polypropylene

The crystallization behavior of high-density polyethylene (HDPE) on highly oriented isotactic polypropylene (iPP) at elevated temperatures (e.g., from 125 to 128 degrees C), was studied using transmission electron microscopy and electron diffraction. The results show that epitaxial crystallization of HDPE on the highly oriented iPP substrates occurs only in a thin layer which is in direct contact with the iPP substrate, when the HDPE is crystallized from the melt on the oriented iPP substrates at 125 degrees C. The critical layer thickness of the epitaxially crystallized HDPE is not more than 30 nm when the HDPE is isothermally crystallized on the oriented iPP substrates at 125 degrees C. When the crystallization temperature is above 125 degrees C, the HDPE crystallizes in the form of crystalline aggregates and a few individual crystalline lamellae. But both the crystalline aggregates and the individual crystalline lamellae have no epitaxial orientation relationship with the iPP substrate. This means that there exists a critical crystallization temperature for the occurrence of epitaxial crystallization of HDPE on the melt-drawn oriented iPP substrates (i.e., 125 degrees C). (C) 1997 John Wiley & Sons, Inc.

Crystallization behavior of blends of high-density polyethylene with novel linear low-density polyethylene

Blends of high-density polyethylene (HDPE) with novel linear low-density polyethylene (LLDPE) samples in the whole range of compositions were investigated by means of differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD). The LLDPEs are ethylene/octene-1 copolymers prepared with a single-site catalyst, with a narrower distribution of branches compared to Ziegler-Natta type polymers. It was found that cocrystallization or separate crystallization in the blends profoundly depends on the content of branches in the LLDPE, while the critical branch content of the novel LLDPE for separate crystallization is much lower than that of commercial LLDPE (prepared with Ziegler-Natta catalysts). This implies that the miscibility of linear and branched polyethylene is also affected by the distribution of branches. The marked expansion of the unit cell in cocrystals, which are formed by HDPE with the novel LLDPE, indicates that the branches are included in the crystal lattice during the cocrystallization process. The result is very helpful to understand the phenomenon that the unit cell dimensions of commercial branched polyethylene are larger than those of linear polyethylene.

Morphology and mechanical properties of PP/HMWPE blends

Mechanical properties and morphology of blends of polypropylene (PP) with high molecular weight polyethylene (HMWPE) prepared by coprecipitation from xylene solution are investigated. Compared to blends of PP with commercial high-density polyethylene (HDPE), the mechanical properties of the blends of PP/HMWPE are much superior to those of PP/HDPE blends. Not only is the tensile strength stronger, but also the elongation at break is much higher than that of the PP/HDPE blends of the same composition. These differences increase with increasing HMWPE and HDPE content. Scanning electron microscopy of the fracture surface resulting from the tensile tests shows that the compatibility in PP/HMWPE blends is much better than that in PP/HDPE blends. This is most likely attributable to the enhanced chain entanglement of HMWPE with the PP in the amorphous phase due to the lower crystallinity, owing to the high molecular weight of the HMWPE, and a much more flexible chain. The thermal behavior and spherulite morphology of both blends are also investigated.

Chemiluminescence studies of radiation induced oxidation of various polyethylenes

The chemiluminescence (CL) emission from three kinds of polyethylene, HDPE, LLDPE and LDPE, which had been exposed to 80 kGy dose from Co-60 in both air and nitrogen, has been examined. CL measurement was done under both nitrogen and oxygen atmosphere. The results show that the CL emission from irradiated samples does not result from irradiation itself, but from the oxidation reactions occurring during and after irradiation. Addition of 1 phr of an antioxidant, Irganox 1010, can effectively inhibit the radiation induced oxidation in LLDPE and LDPE. In the case of HDPE, however, it was found that pure HDPE has the best resistance to radiation-induced oxidation of the polymers examined in this work. However, incorporation of Irganox 1010 was found to have not only a stabilizing effect against radiation induced oxidation, but also to promote the oxidation in some cases.

Studies on the electrical conductivity of carbon black filled polymers

The conductivity mechanism for a carbon black (CB) filled high-density polyethylene (HDPE) compound was investigated in this work. From the experimental results obtained, it can be seen that the relation between electrical current density (J) and applied voltage across the sample (V) coincides with Simmons's equation (i.e., the electrical resistivity of the compound decreases with the applied voltage, especially at the critical voltage). The minimum electrical resistivity occurs near the glass transition temperature (T-g) of HDPE (198 K). It can be concluded that electron tunneling is an important mechanism and a dominant transport process in the HDPE/CB composite. A new model of carbon black dispersion in the matrix was established, and the resistivity was calculated by using percolation and quantum mechanical theories. (C) 1996 John Wiley & Sons, Inc.

COMPATIBILIZATION OF HIGH-DENSITY POLYETHYLENE/POLYISOPRENE BLENDS WITH POLYETHYLENE/POLYISOPRENE THREAD-THROUGH COPOLYMERS

The compatibilization of high density polyethylene (HDPE)/polyisoprene (PI) blends with polyethylene/polyisoprene (PE/PI) ''thread-through'' copolymers was investigated. The proliferating structure of PE/PI with segments chemically identical to HDPE and PI, respectively, is different from that of graft copolymers. Studies showed that the dispersed domain size in the blends was significantly reduced and interfacial adhesion was improved by the compatibilization action of the copolymer. In the differential scanning calorimetry (DSC) analysis, the crystallization peak of HDPE in the blends became broad with adding the copolymer and fractionated crystallization appeared in the HDPE/PI blend compatibilized with the copolymer at a weight ratio of 30/70 while it appeared in the blend without copolymer at a weight ratio of 20/80. DMA results showed that by adding the copolymer, both the glass transition temperature (T-g) of the PI component and the alpha-relaxation of HDPE shifted to lower temperature, demonstrating the enhanced penetration of the two components. Mechanical properties of the blends were improved, especially the elongation at break, by the presence of the copolymers. The characteristic yielding at the fractured surface of the blends compatibilized with the copolymer indicates the fractural behavior of the material changed from brittle to tough.

高密度聚乙烯／低密度聚乙烯／乙烯－醋酸乙烯共聚物共混体系的结晶行为

通过ＤＳＣ和ＷＡＸＤ研究了高密度聚乙烯／低密度聚乙烯／乙烯－醋酸乙烯共聚物（ＨＤＰＥ／ＬＤＰＥ／ＥＶＡ）三元共混体系的热行为和结晶性能。发现当ＨＤＰＥ含量小于４０％时，ＥＶＡ对ＬＤＰＥ起稀释剂作用，促进ＨＤＰＥ、ＬＤＰＥ的晶相分离，使ＨＤＰＥ、ＬＤＰＥ单独结晶．当ＨＤＰＥ含量高于４０％时，ＬＤＰＥ片晶进入ＨＤＰＥ晶相。形成与ＬＤＰＥ在片晶水平上的共晶。

STRUCTURE AND PROPERTIES OF MALEATED HIGH-DENSITY POLYETHYLENE

Possible changes in the structure and properties of maleated polyethylene (HDPE-MA) at different degrees of grafting (D.G.) were examined. At the level of 1.6 maleic anhydride (MA)/100 ethylene units E, 70-80% of crystallinity of the parent PE was retaine

高密度聚乙烯／超高分子量聚乙烯共混物高取向薄膜形态结构与力学性能的研究

高密度聚乙烯／超高分子量聚乙烯共混物高取向薄膜形态结构与力学性能的研究张伟广，赵勇，杨德才中国科学院长春应用化学研究所，高分子物理开放实验室，长春，１３００２２）关键词ＨＤＰＥ、ＵＨＭＷＰＥ、共混物、形态结构、力学性能如何提高高分子材料抗张强度和模量...

THE THERMAL-STABILITY OF POLYETHYLENE BLENDS DURING HEAT-PROCESSING AND SHORT-TERM PHOTOOXIDATION

The melt flow behaviour of LDPE/HDPE blends with various compositions have been determined by melt flow index (MFI) measurement. The effects of stabilizers, photo-sensitizers, multiple extrusions and short-term photooxidation have been studied. The results show that there is no marked thermal stability difference between homopolymers and blends without multiple extrusions, no matter whether stabilizers or photo-sensitizers are added. Multiple extrusions or photo-sensitizers reduce their thermal stability, shown by the decrease in MFI. The decrease in MFI of photooxidized samples does not imply serious structural change and shows that the active species formed during photooxidation induce a crosslinking reaction in the melt indexer. Multiple extrusions increase the number of active species formed in LDPE or blends and lead to an obvious decrease in MFI. It is suggested that LDPE and LDPE-rich blends after short-term photooxidation can be characterized by MFI measurement. In contrast, HDPE cannot be characterized by this method due to its linear structure.

高密度聚乙烯与其他聚烯烃共混物高取向薄膜结晶结构的电子显微学研究

本文用透射电子显微镜方法研究了高密度聚乙烯(HDPE)与其它聚烯烃[包括线性低密度聚乙烯(LLDPE)、低密度聚乙烯(LDPE)、等规聚丙烯(iPP)、聚丁烯-1(PB-1)等]共混物高取向薄膜的结晶结构,其中聚烯烃组分含量为10%。在共混物熔体拉伸薄膜中,HDPE以高取向的片晶形式存在,片晶的生长方向垂直于拉伸方向。共混物中LLDPE、LDPE与HDPE形成共晶。与HDPE不相容的iPP、PB-1在共混体系中未观察到明显的相区存在。聚烯烃组分的加入,不仅影响HDPE的片晶尺寸,同时影响结构的对称性,即由纯HDPE的非对称“近单晶”结构变为对称的纤维结构。