The orientation and crystallinity evolution of isotactic polypropylene （iPP） induced by rolling were studied using wide angle X-ray scattering with an area detector. The tensile mechanical properties of rolled isota...The orientation and crystallinity evolution of isotactic polypropylene （iPP） induced by rolling were studied using wide angle X-ray scattering with an area detector. The tensile mechanical properties of rolled isotactic polypropylene sheets were also measured in this work. The texture component method was used to analyze the rolling texture. The rolling texture consists mainly of （010）[001], （130）[001] and [001]//RD fiber components in the sample with a rolling true strain of 1.5. The results reveal that crystallinity drastically decreases during rolling. It is suggested that amorphization is a deformation mechanism which takes place as an alternative to crystallographic intralamellar slip depending on the orientation of the lamellae. Both the orientation and crystallinity affect the tensile mechanical properties of rolled polypropylene. Crystallinity influences the elastic modulus on both directions and yield strength on transverse direction at the first stage of deformation. Orientation is the main reason for the changes of mechanical properties, especially at the latter part of deformation. The changes of both tensile strength and elongation percentage on rolling direction are larger than those on transverse direction, which results from the orientation. At last, the anisotropic mechanical properties occur on the rolling and transverse direction： high tensile strength with low elongation percentage on rolling direction and low tensile strength with high elongation percentage on transverse direction.展开更多
A relatively high predetermined crystallization temperature （135℃） was chosen to grow well developed iPP spherulites, then the partial melting was carried out at a temperature of 165℃, where the preformed spheruli...A relatively high predetermined crystallization temperature （135℃） was chosen to grow well developed iPP spherulites, then the partial melting was carried out at a temperature of 165℃, where the preformed spherulites were seen to only decrease their size but not completely melted. The crystallization behavior of partially melted isotactic polypropylene （iPP） has been carefully examined by different scanning calorimetry （DSC） and polarized light microscopy （PLM）. The experimental results show that at a special annealing temperature （165℃） the melting behavior of iPP includes two parts with different mechanism, one part is the melting of iPP spherulite outside, another is the partial lamellae perfection during longer annealing time in the unmelted spherulite. The conformational orders of the iPP melt decrease with the increase of the annealing temperature.展开更多
A study concerning the effect of vibration on the crystal structure and morphology for isotactic polypropylene(iPP) was conducted. The crystallite size, crystal structure and crystallinity of iPP under or without vibr...A study concerning the effect of vibration on the crystal structure and morphology for isotactic polypropylene(iPP) was conducted. The crystallite size, crystal structure and crystallinity of iPP under or without vibration treatment were investigated by means of differential scanning calorimetry(DSC) and wide-angle X-ray diffraction(WAXD). The results reveal that the crystallinity of the vibrated samples decreases at a high cooling rate, but it remains constant at a low cooling rate because of the chain relaxation of iPP. It has been found that vibration obviously increases the content of β-form of crystal phase and the amount of β-crystal mainly depends on the vibration amplitude.展开更多
The viscoelastic behavior of isotactic polypropylene with ultra-high molecular weight(UHPPH) and broad molecular weight distribution(MWD), produced in the presence of Ziegler-Natta catalyst, was investigated by means ...The viscoelastic behavior of isotactic polypropylene with ultra-high molecular weight(UHPPH) and broad molecular weight distribution(MWD), produced in the presence of Ziegler-Natta catalyst, was investigated by means of oscillatory rheometry at 180 and 200 ℃, whose loss modulus(G″) plots at 180 and 200 ℃ versus the natural logarithm of angular frequency(ω) present a pronounced maximum at 34.35 and 69.21 rad/s, respectively, and do not show a maximum peak at 0.01-100 rad/s for Ziegler-Natta catalyzing ethylene-propylene random copolymerization(PPR) with a conventional molecular weight and broad MWD. The fact indicates that the high molecular weight is responsible for a maximum peak of G″(ω) vs. lnω curves for UHPPH. This makes it possible to determine the plateau modulus(G 0_N) of UHPPH from a certain experimental temperature G″(ω) curve directly. For UHPPH, the G 0_N determined to be 4.28×10 5 and 3.62×10 5 Pa at 180 and 200 ℃, respectively, decreases with the increase of temperature and is independent of the molecular weight, which directly confirms reputation theoretical prediction that the G 0_N has no relation to the molecular weight.展开更多
Electron microscope and electron diffraction have been used to study epitaxial crystallization of poly(ε-caprolactone)(PCL).on highly oriented film of isotactic polypropylene(iPP).The results obtained from bright fie...Electron microscope and electron diffraction have been used to study epitaxial crystallization of poly(ε-caprolactone)(PCL).on highly oriented film of isotactic polypropylene(iPP).The results obtained from bright field(BF)electron micrograph and electron diffraction indicate that the PCL can epitaxially grow on iPP substrate and form cross-hatched lamellar texture.The c axes of PCL are ±500 apart from the c axes of iPP. The contact planes of the two kinds of crystals are(010)of iPP and(100) of PCL,respectively.展开更多
Isotactic polypropylene (iPP) with high content of ~ crystalline form was prepared by adding a series of new p form nucleators. The spherulites and morphology of//farm iPP (//-iPP) were investigated by wide-angle X-ra...Isotactic polypropylene (iPP) with high content of ~ crystalline form was prepared by adding a series of new p form nucleators. The spherulites and morphology of//farm iPP (//-iPP) were investigated by wide-angle X-ray diffraction(WAXD), polarizing microscope (PLM), scanning electron microscope (SEM) and small-angle light scattering (SALS). WAXD experimental results indicate that the amount of p form in iPP (K_x) increases with increasing /~ nucleator content from zero to 0.07 wt% or crystallization temperature T_c from 20 to 120℃ and that the highest K_x value is up to 0.95. PLM observations suggest that p spherulites exhibit bright color and that their Maltese Crosses display some concentric banding of a rather spiky, jagged character. Their !amellae are smooth and relaxed layer-plate like structure by SEM and their SALS H_v patterns arc four-petalled.展开更多
Polymerization of propylene was carried out under bulk process at 70 degrees C using the supported metallocene catalyst with four kinds of SiO2 as carrier with triethylaluminum used as cocatalyst. The morphology of th...Polymerization of propylene was carried out under bulk process at 70 degrees C using the supported metallocene catalyst with four kinds of SiO2 as carrier with triethylaluminum used as cocatalyst. The morphology of the products was studied by SEM. It was found the property of the carriers gave great effect on the fine structure of the products as well as the apperance.展开更多
The spherulite morphology of the rolled and subsequent heat-treated isotactic polypropylene （iPP） was observed by polarized microscopy, and the crystallinity evolution of materials was also measured by the wide angl...The spherulite morphology of the rolled and subsequent heat-treated isotactic polypropylene （iPP） was observed by polarized microscopy, and the crystallinity evolution of materials was also measured by the wide angle X-ray scattering （WAXS）. Rolling led to the oblate spherulites in the deformed iPP samples. The sheared crystalline lamellae broke apart into sets of crystalline blocks during rolling. As a result, the crystallinity of the iPP samples was greatly reduced during deformation, which induced the unclear spherulites and spherulite boundaries. Subsequent heat treatment resulted in the strong reerystallization of the rolled iPP samples. But the recrystaUizatinn in this work only meant the rearrangement of the macromolecule along the unbroken crystalline lamellae and the existing small crystalline blocks in the deformed spherulites. Heat treatment did not change the shape of the spherulites formed during deformation. The recrystallization also resulted in very clear spherulites and spherulite boundaries.展开更多
Extrusion-Compression molded isotactic polypropylene (iPP) composites containing 10 wt%, 20 wt%, 30 wt%, 40 wt% and 50 wt% of talc filler were studied by scanning electron microscopy (SEM), simultaneous thermal analys...Extrusion-Compression molded isotactic polypropylene (iPP) composites containing 10 wt%, 20 wt%, 30 wt%, 40 wt% and 50 wt% of talc filler were studied by scanning electron microscopy (SEM), simultaneous thermal analysis (STA) and physical testing. The scanning electron microscope (SEM) micrographs of neat iPP and composites with 10 wt%, 20 wt%, 30 wt%, 40 wt% and 50 wt% talc content show that neat PP, 10 wt%, 20 wt%, and 30wt% talc composites surface is smooth in comparison to 40 wt% and 50 wt% talc composites. It is also observed that talc is dispersed uniformly in the matrix and this uniform dispersion is not decreased even with talc content as high as 30 wt% talc. The composites of 40 wt% and 50 wt% talc contain more crack, agglomerates or larger particles. Bulk density of the composites decreases with the increase of talc content. With the increase of percentage of talc and period of immersion, the water absorption (WA) increases. Thermal analyses indicate a considerable increase of thermal stability of the composites with filler addition.展开更多
Ansa-Cyclohexyl-bis（4,5,6,7-tertrahydro-l-indenyl） zirconium dichloride （5） was used as catalyst for propylene and ethylene polymerization together with methyl aluminoxane （MAO） as the cocatalyst. Isotactic poly...Ansa-Cyclohexyl-bis（4,5,6,7-tertrahydro-l-indenyl） zirconium dichloride （5） was used as catalyst for propylene and ethylene polymerization together with methyl aluminoxane （MAO） as the cocatalyst. Isotactic polypropylene （PP） was obtained with the highest activity of 6.37× 107g PP （molZr）^-1h^-1. The mesomeso （mmmmm） pentads sequence content of PP was determined by 13C NMR spectroscopy. The dependence of the microstructure on the reaction temperature and the AI/Zr molar ratio was examined and the catalytic activity of complex 5 was compared with that of the similar ansa-zirconocene 3. The high activity of the new zirconocene 5 for propylene isospectic polymerization at high temperature （60℃） is the result of its unique bridged-group structure. Complex 5/MAO displays also high catalytic activity of 0.46× 10^6 to 9.87× 10^6g PE（molZr）^-h^-in the homo-polymerization of ethylene, The visometric molecular weight of PE ranges from 0.97×10^4 to 11.16×10^4 g.mol^- under the given conditions.^13C NMR spectroscopy analysis proves the PE to be linear polyethylene （LPE）.展开更多
Microcellular injection molding of neat isotactic polypropylene(iPP) and isotactic polypropylene/nano-calcium carbonate composites(i PP/nano-CaCO_3) was performed using supercritical carbon dioxide as the physical blo...Microcellular injection molding of neat isotactic polypropylene(iPP) and isotactic polypropylene/nano-calcium carbonate composites(i PP/nano-CaCO_3) was performed using supercritical carbon dioxide as the physical blowing agent. The influences of filler content and operating conditions on microstructure morphology of i PP and i PP/nano-CaCO_3 microcellular samples were studied systematically. The results showed the bubble size of the microcellular samples could be effectively decreased while the cell density increased for i PP/nano-CaCO_3 composites, especially at high CO_2 concentration and back pressure, low mold temperature and injection speed, and high filler content. Then Moldex 3D was applied to simulate the microcellular injection molding process, with the application of the measured ScCO_2 solubility and diffusion data for i PP and i PP/nano-Ca CO_3 composites respectively. For neat i PP, the simulated bubble size and density distribution in the center section of tensile bars showed a good agreement with the experimental values. However, for i PP/nano-CaCO_3 composites, the correction factor for nucleation activation energy F and the pre-exponential factor of nucleation rate f_0 were obtained by nonlinear regression on the experimental bubble size and density distribution. The parameters F and f_0 can be used to predict the microcellular injection molding process for i PP/nano-CaCO_3 composites by Moldex 3D.展开更多
Due to the development of the new energy industry,polypropylene with ultra-high molecular weight plays a crucial role for battery isolation membrane.This work investigated the effect of internal electron donor of Zieg...Due to the development of the new energy industry,polypropylene with ultra-high molecular weight plays a crucial role for battery isolation membrane.This work investigated the effect of internal electron donor of Ziegler-Natta catalyst system on the molecular weight of the obtained polypropylene.The scanning electron microscope(SEM)and Canon camera were used to characterize the surface morphologies of catalyst particles and polymer particles,respectively.Compared with the polypropylene particles featuring a spherical shape,these study results confirmed that the morphology duplication theory from the catalyst particle to the morphology of polymer particle was exhibited.The gel permeation chromatography(GPC)results revealed that the obtained polypropylene has a much higher average molecular weight than those prepared by conventional method.The Fourier transform infrared spectrometry(FT-IR)and X-ray photoelectron spectroscopy(XPS)revealed that the carbonyl oxygen atom on ester group was preferentially bound to Mg and Ti,as compared to the ether oxygen atom.The XPS results showed that the ratio of Ti^(3+)/Ti^(4+)could be changed by internal electron donors.When Ti3+content was nearly 99%in the Ziegler-Natta catalyst system,isotactic polypropylene with an ultra-high molecular weight of up to 1.42×10^(6)g/mol was obtained by Cat.3.This result implied that internal electron donor ID3 could reduce theβ-hydride elimination reaction to further increase the molecular weight of the obtained polymer.展开更多
The melt memory effect is a widely observed phenomenon in semi-crystalline polymers. In practical applications, various additives are usually introduced into polymers, which may affect their melt memory behavior. In t...The melt memory effect is a widely observed phenomenon in semi-crystalline polymers. In practical applications, various additives are usually introduced into polymers, which may affect their melt memory behavior. In this work, the effect of talc on the melt memory effect of metallocene-made isotactic polypropylene(M-PP) was investigated in detail by using the differential scanning calorimetry. The results indicated that the introduction of talc significantly strengthened the melt memory effect of M-PP. Specifically, the upper limit temperature of Domain II increased from 161 ℃ to 174 ℃, resulting in a substantial widening of the temperature range of Domain IIa from 1 ℃ to 14 ℃. Analysis of the crystal orientation of the M-PP containing talc cooled from various Ts suggested that the remarkably enhanced melt memory effect could be ascribed to the stabilization of oriented nuclei facilitated by talc. This stabilizing effect was likely attributable to the prefreezing effect or the sorption interaction between talc and the M-PP chains.展开更多
One-step reaction compatibilized microfibrillar reinforced iPP/PET blends （CMRB） were successfully prepared through a ＂slit extrusion-hot stretching-quenching＂ process. Crystallization behavior and morphology of C...One-step reaction compatibilized microfibrillar reinforced iPP/PET blends （CMRB） were successfully prepared through a ＂slit extrusion-hot stretching-quenching＂ process. Crystallization behavior and morphology of CMRB were systematically investigated. Scanning electronic microscopy （SEM） observations showed blurry interface of compatibilized common blend （CCB）. The crystallization behavior of neat iPP, CCB, microfibrillar reinforced iPP/PET blend （MRB） and CMRB was investigated by differential scanning calorimetry （DSC） and polarized optical microscopy （POM）. The increase of crystallization temperature and crystallization rate during nonisothermal crystallization process indicated both PET particles and mierofibrils could serve as nucleating agents and PET microfibrils exhibited higher heterogeneous nucleation ability, which were also vividly revealed by results of POM. Compared with MRB sample, CMRB sample has lower crystallization temperature due to existence of PET microfibrils with smaller aspect ratio and wider distribution. In addition, since in situ compatibilizer tends to stay in the interphase, it could also hinder the diffusion ofiPP molecules to the surface of PET phase, leading to decrease of crystallization rate. Two-dimensional wide-angle X-ray diffi：action （2D-WAXD） was preformed to characterize the crystalline structure of the samples by injection molding, and it was found that well-developed PET microfibrils contained in MRB sample promoted formation of t-phase of/PP.展开更多
文摘The orientation and crystallinity evolution of isotactic polypropylene （iPP） induced by rolling were studied using wide angle X-ray scattering with an area detector. The tensile mechanical properties of rolled isotactic polypropylene sheets were also measured in this work. The texture component method was used to analyze the rolling texture. The rolling texture consists mainly of （010）[001], （130）[001] and [001]//RD fiber components in the sample with a rolling true strain of 1.5. The results reveal that crystallinity drastically decreases during rolling. It is suggested that amorphization is a deformation mechanism which takes place as an alternative to crystallographic intralamellar slip depending on the orientation of the lamellae. Both the orientation and crystallinity affect the tensile mechanical properties of rolled polypropylene. Crystallinity influences the elastic modulus on both directions and yield strength on transverse direction at the first stage of deformation. Orientation is the main reason for the changes of mechanical properties, especially at the latter part of deformation. The changes of both tensile strength and elongation percentage on rolling direction are larger than those on transverse direction, which results from the orientation. At last, the anisotropic mechanical properties occur on the rolling and transverse direction： high tensile strength with low elongation percentage on rolling direction and low tensile strength with high elongation percentage on transverse direction.
基金supported by the National Natural Science Foundation of China(Nos.50533050 and 20634050)
文摘A relatively high predetermined crystallization temperature （135℃） was chosen to grow well developed iPP spherulites, then the partial melting was carried out at a temperature of 165℃, where the preformed spherulites were seen to only decrease their size but not completely melted. The crystallization behavior of partially melted isotactic polypropylene （iPP） has been carefully examined by different scanning calorimetry （DSC） and polarized light microscopy （PLM）. The experimental results show that at a special annealing temperature （165℃） the melting behavior of iPP includes two parts with different mechanism, one part is the melting of iPP spherulite outside, another is the partial lamellae perfection during longer annealing time in the unmelted spherulite. The conformational orders of the iPP melt decrease with the increase of the annealing temperature.
基金Supported by the National Science Funds for Distinguished Young Scholars(No.5 0 12 5 312 ) Special Funds for MajorState Basic Research Project of China(No.G19990 6 4 80 0 ) and Key Program of the National Natural Science Foundation ofChina(No.5 0 1
文摘A study concerning the effect of vibration on the crystal structure and morphology for isotactic polypropylene(iPP) was conducted. The crystallite size, crystal structure and crystallinity of iPP under or without vibration treatment were investigated by means of differential scanning calorimetry(DSC) and wide-angle X-ray diffraction(WAXD). The results reveal that the crystallinity of the vibrated samples decreases at a high cooling rate, but it remains constant at a low cooling rate because of the chain relaxation of iPP. It has been found that vibration obviously increases the content of β-form of crystal phase and the amount of β-crystal mainly depends on the vibration amplitude.
文摘The viscoelastic behavior of isotactic polypropylene with ultra-high molecular weight(UHPPH) and broad molecular weight distribution(MWD), produced in the presence of Ziegler-Natta catalyst, was investigated by means of oscillatory rheometry at 180 and 200 ℃, whose loss modulus(G″) plots at 180 and 200 ℃ versus the natural logarithm of angular frequency(ω) present a pronounced maximum at 34.35 and 69.21 rad/s, respectively, and do not show a maximum peak at 0.01-100 rad/s for Ziegler-Natta catalyzing ethylene-propylene random copolymerization(PPR) with a conventional molecular weight and broad MWD. The fact indicates that the high molecular weight is responsible for a maximum peak of G″(ω) vs. lnω curves for UHPPH. This makes it possible to determine the plateau modulus(G 0_N) of UHPPH from a certain experimental temperature G″(ω) curve directly. For UHPPH, the G 0_N determined to be 4.28×10 5 and 3.62×10 5 Pa at 180 and 200 ℃, respectively, decreases with the increase of temperature and is independent of the molecular weight, which directly confirms reputation theoretical prediction that the G 0_N has no relation to the molecular weight.
文摘Electron microscope and electron diffraction have been used to study epitaxial crystallization of poly(ε-caprolactone)(PCL).on highly oriented film of isotactic polypropylene(iPP).The results obtained from bright field(BF)electron micrograph and electron diffraction indicate that the PCL can epitaxially grow on iPP substrate and form cross-hatched lamellar texture.The c axes of PCL are ±500 apart from the c axes of iPP. The contact planes of the two kinds of crystals are(010)of iPP and(100) of PCL,respectively.
文摘Isotactic polypropylene (iPP) with high content of ~ crystalline form was prepared by adding a series of new p form nucleators. The spherulites and morphology of//farm iPP (//-iPP) were investigated by wide-angle X-ray diffraction(WAXD), polarizing microscope (PLM), scanning electron microscope (SEM) and small-angle light scattering (SALS). WAXD experimental results indicate that the amount of p form in iPP (K_x) increases with increasing /~ nucleator content from zero to 0.07 wt% or crystallization temperature T_c from 20 to 120℃ and that the highest K_x value is up to 0.95. PLM observations suggest that p spherulites exhibit bright color and that their Maltese Crosses display some concentric banding of a rather spiky, jagged character. Their !amellae are smooth and relaxed layer-plate like structure by SEM and their SALS H_v patterns arc four-petalled.
文摘Polymerization of propylene was carried out under bulk process at 70 degrees C using the supported metallocene catalyst with four kinds of SiO2 as carrier with triethylaluminum used as cocatalyst. The morphology of the products was studied by SEM. It was found the property of the carriers gave great effect on the fine structure of the products as well as the apperance.
文摘The spherulite morphology of the rolled and subsequent heat-treated isotactic polypropylene （iPP） was observed by polarized microscopy, and the crystallinity evolution of materials was also measured by the wide angle X-ray scattering （WAXS）. Rolling led to the oblate spherulites in the deformed iPP samples. The sheared crystalline lamellae broke apart into sets of crystalline blocks during rolling. As a result, the crystallinity of the iPP samples was greatly reduced during deformation, which induced the unclear spherulites and spherulite boundaries. Subsequent heat treatment resulted in the strong reerystallization of the rolled iPP samples. But the recrystaUizatinn in this work only meant the rearrangement of the macromolecule along the unbroken crystalline lamellae and the existing small crystalline blocks in the deformed spherulites. Heat treatment did not change the shape of the spherulites formed during deformation. The recrystallization also resulted in very clear spherulites and spherulite boundaries.
文摘Extrusion-Compression molded isotactic polypropylene (iPP) composites containing 10 wt%, 20 wt%, 30 wt%, 40 wt% and 50 wt% of talc filler were studied by scanning electron microscopy (SEM), simultaneous thermal analysis (STA) and physical testing. The scanning electron microscope (SEM) micrographs of neat iPP and composites with 10 wt%, 20 wt%, 30 wt%, 40 wt% and 50 wt% talc content show that neat PP, 10 wt%, 20 wt%, and 30wt% talc composites surface is smooth in comparison to 40 wt% and 50 wt% talc composites. It is also observed that talc is dispersed uniformly in the matrix and this uniform dispersion is not decreased even with talc content as high as 30 wt% talc. The composites of 40 wt% and 50 wt% talc contain more crack, agglomerates or larger particles. Bulk density of the composites decreases with the increase of talc content. With the increase of percentage of talc and period of immersion, the water absorption (WA) increases. Thermal analyses indicate a considerable increase of thermal stability of the composites with filler addition.
基金the National Natural Science Foundation of China(20374043)SINOPEC(X501025)
文摘Ansa-Cyclohexyl-bis（4,5,6,7-tertrahydro-l-indenyl） zirconium dichloride （5） was used as catalyst for propylene and ethylene polymerization together with methyl aluminoxane （MAO） as the cocatalyst. Isotactic polypropylene （PP） was obtained with the highest activity of 6.37× 107g PP （molZr）^-1h^-1. The mesomeso （mmmmm） pentads sequence content of PP was determined by 13C NMR spectroscopy. The dependence of the microstructure on the reaction temperature and the AI/Zr molar ratio was examined and the catalytic activity of complex 5 was compared with that of the similar ansa-zirconocene 3. The high activity of the new zirconocene 5 for propylene isospectic polymerization at high temperature （60℃） is the result of its unique bridged-group structure. Complex 5/MAO displays also high catalytic activity of 0.46× 10^6 to 9.87× 10^6g PE（molZr）^-h^-in the homo-polymerization of ethylene, The visometric molecular weight of PE ranges from 0.97×10^4 to 11.16×10^4 g.mol^- under the given conditions.^13C NMR spectroscopy analysis proves the PE to be linear polyethylene （LPE）.
基金Supported by the National High Technology Research and Development Program of China(2012AA040211)the National Natural Science Foundation of China(21306043)+2 种基金the Research Fund for the Doctoral Program of Higher Education of China(2012007412001920130074110013)the Fundamental Research Funds for the Central Universities
文摘Microcellular injection molding of neat isotactic polypropylene(iPP) and isotactic polypropylene/nano-calcium carbonate composites(i PP/nano-CaCO_3) was performed using supercritical carbon dioxide as the physical blowing agent. The influences of filler content and operating conditions on microstructure morphology of i PP and i PP/nano-CaCO_3 microcellular samples were studied systematically. The results showed the bubble size of the microcellular samples could be effectively decreased while the cell density increased for i PP/nano-CaCO_3 composites, especially at high CO_2 concentration and back pressure, low mold temperature and injection speed, and high filler content. Then Moldex 3D was applied to simulate the microcellular injection molding process, with the application of the measured ScCO_2 solubility and diffusion data for i PP and i PP/nano-Ca CO_3 composites respectively. For neat i PP, the simulated bubble size and density distribution in the center section of tensile bars showed a good agreement with the experimental values. However, for i PP/nano-CaCO_3 composites, the correction factor for nucleation activation energy F and the pre-exponential factor of nucleation rate f_0 were obtained by nonlinear regression on the experimental bubble size and density distribution. The parameters F and f_0 can be used to predict the microcellular injection molding process for i PP/nano-CaCO_3 composites by Moldex 3D.
基金This study was financially supported by the People’s Republic of China Ministry of Industry and Information Technology(No.gxgh2019-795)the National Natural Science Foundation of China(No.U1462102)The authors also appreciate the support provided by the Key Laboratory of Carbon Fiber and Functional Polymers.
文摘Due to the development of the new energy industry,polypropylene with ultra-high molecular weight plays a crucial role for battery isolation membrane.This work investigated the effect of internal electron donor of Ziegler-Natta catalyst system on the molecular weight of the obtained polypropylene.The scanning electron microscope(SEM)and Canon camera were used to characterize the surface morphologies of catalyst particles and polymer particles,respectively.Compared with the polypropylene particles featuring a spherical shape,these study results confirmed that the morphology duplication theory from the catalyst particle to the morphology of polymer particle was exhibited.The gel permeation chromatography(GPC)results revealed that the obtained polypropylene has a much higher average molecular weight than those prepared by conventional method.The Fourier transform infrared spectrometry(FT-IR)and X-ray photoelectron spectroscopy(XPS)revealed that the carbonyl oxygen atom on ester group was preferentially bound to Mg and Ti,as compared to the ether oxygen atom.The XPS results showed that the ratio of Ti^(3+)/Ti^(4+)could be changed by internal electron donors.When Ti3+content was nearly 99%in the Ziegler-Natta catalyst system,isotactic polypropylene with an ultra-high molecular weight of up to 1.42×10^(6)g/mol was obtained by Cat.3.This result implied that internal electron donor ID3 could reduce theβ-hydride elimination reaction to further increase the molecular weight of the obtained polymer.
基金financially supported by the National Natural Science Foundation of China (Nos. 51973037 and 52173056)PetroChina Company Limited,China。
文摘The melt memory effect is a widely observed phenomenon in semi-crystalline polymers. In practical applications, various additives are usually introduced into polymers, which may affect their melt memory behavior. In this work, the effect of talc on the melt memory effect of metallocene-made isotactic polypropylene(M-PP) was investigated in detail by using the differential scanning calorimetry. The results indicated that the introduction of talc significantly strengthened the melt memory effect of M-PP. Specifically, the upper limit temperature of Domain II increased from 161 ℃ to 174 ℃, resulting in a substantial widening of the temperature range of Domain IIa from 1 ℃ to 14 ℃. Analysis of the crystal orientation of the M-PP containing talc cooled from various Ts suggested that the remarkably enhanced melt memory effect could be ascribed to the stabilization of oriented nuclei facilitated by talc. This stabilizing effect was likely attributable to the prefreezing effect or the sorption interaction between talc and the M-PP chains.
基金financially supported by National Natural Science Foundation of China(No.20776087)National Programs for High Technology Research and Development of China(No.2008AA03Z510)
文摘One-step reaction compatibilized microfibrillar reinforced iPP/PET blends （CMRB） were successfully prepared through a ＂slit extrusion-hot stretching-quenching＂ process. Crystallization behavior and morphology of CMRB were systematically investigated. Scanning electronic microscopy （SEM） observations showed blurry interface of compatibilized common blend （CCB）. The crystallization behavior of neat iPP, CCB, microfibrillar reinforced iPP/PET blend （MRB） and CMRB was investigated by differential scanning calorimetry （DSC） and polarized optical microscopy （POM）. The increase of crystallization temperature and crystallization rate during nonisothermal crystallization process indicated both PET particles and mierofibrils could serve as nucleating agents and PET microfibrils exhibited higher heterogeneous nucleation ability, which were also vividly revealed by results of POM. Compared with MRB sample, CMRB sample has lower crystallization temperature due to existence of PET microfibrils with smaller aspect ratio and wider distribution. In addition, since in situ compatibilizer tends to stay in the interphase, it could also hinder the diffusion ofiPP molecules to the surface of PET phase, leading to decrease of crystallization rate. Two-dimensional wide-angle X-ray diffi：action （2D-WAXD） was preformed to characterize the crystalline structure of the samples by injection molding, and it was found that well-developed PET microfibrils contained in MRB sample promoted formation of t-phase of/PP.
