In this research, the morphologies, isothermal-crystallization kinetics, and spherulite growth of aliphatic polyketone/polyamide-6 blends were studied. A single glass-transition temperature （Tg） was determined, and ...In this research, the morphologies, isothermal-crystallization kinetics, and spherulite growth of aliphatic polyketone/polyamide-6 blends were studied. A single glass-transition temperature （Tg） was determined, and the composition dependence of Tg for these blends was well described by the Kwei equation. The strong intermolecular interaction between the two polymer components was confirmed by melting-point depression. The isothermal-crystallization kinetics were analyzed on the basis of the Avrami approach. A linear increase in the radii of the spherulites with time was observed for all compositions. All the spherulites continued to grow at nearly identical growth rates. With increasing polyamide-6 content, the size of the spherulites in the polyketone/polyamide-6 blends gradually decreased, and the number of spherulites in the blends increased.展开更多
Hydroxyapatite/poly（L-lactide） （HA/PLLA） nanocomposites were prepared by the solvent mixing method. The isothermal crystallization behavior was studied by differential scanning calorimetry （DSC） and polarized op...Hydroxyapatite/poly（L-lactide） （HA/PLLA） nanocomposites were prepared by the solvent mixing method. The isothermal crystallization behavior was studied by differential scanning calorimetry （DSC） and polarized optical microscopy （POM）. The results show that the crystallization behavior of HA/PLLA composites was strongly affected by the content of HA and crystallization temperature, and the addition of HA could promote nucleation and enhance the crystallization rate. When isothermal crystallization was carried out at 110℃, the HA/PLLA nanocomposite with 1% HA content crystallized most rapidly among all the composites and the half crystallization time was only 1.0 min. Banded spherulites were observed for the HA/PLLA composites, but no banded spherulites were seen in the crystals of PLLA under the same condition.展开更多
The morphologies of poly(L-lactic acid)(PLLA)spherulites,when crystallized within the pre-existed poly(oxymethylene)(POM)crystal frameworks,have been investigated.PLLA/POM blend is a melt-miscible crystalline/crystall...The morphologies of poly(L-lactic acid)(PLLA)spherulites,when crystallized within the pre-existed poly(oxymethylene)(POM)crystal frameworks,have been investigated.PLLA/POM blend is a melt-miscible crystalline/crystalline blend system.Owing to the lower melting point but much faster crystallization rate than PLEA,POM crystallized first upon cooling from the melt state and then melted first during the subsequent heating process in this blend system.Lamellar assembly of PLLA crystals within the pre-existed POM spherulitic frameworks was directly observed with the polarized light microscopy by selectively melting the POM frameworks.The investigation indicated that PLLA crystals fully replicated the spherulitic morphology and optical birefringence of the POM crystal frameworks,which was independent of T_(o).On the other hand,POM could also duplicate the pre-existed PLLA morphologies.The result obtained provides us a possibility to design the lamellar assembly and crystal structures of polymer crystals in miscible crystalline/crystalline polymer blends.展开更多
Poly(L-lactic acid)(PLLA)has drawn much attention due to its excellent medical and pharmaceutical applications for decades.As a semi-crystalline polymer,morphology and crystal structure of PLLA greatly determine its p...Poly(L-lactic acid)(PLLA)has drawn much attention due to its excellent medical and pharmaceutical applications for decades.As a semi-crystalline polymer,morphology and crystal structure of PLLA greatly determine its properties.Here,w e demonstrate,for PLLA films,a nonconventional texture featuring two types of spherulites emerging in pairs to form a distinct nested structure where a small spherulite(〜10μm)is embedded in a large one(100μm to 300μm).In addition to the size,the molecular weight and polymorph are different in the large and small spherulites.Crystallographic a-form and relatively low molecular weight are identified in the large spherulites,while meta-stable a'-form and relatively high molecular weight in the small ones.These differences suggest that the polydisperse PLLA polymers fractionate during film formation and the high-molecular-weight fraction crystallizes into the small spherulites with meta-stable structure because of its complicated polymer entanglement and high viscosity.In contrast,the rest of polymers crystallize into the large spherulites with the thermodynamically stable polymorph.Furthermore,this texture exhibits accelerated PLLA degradation initiated from the small spherulites,which is distinct from the typical PLLA spherulites.Insights provided by this work may lead to new texture-properties relationship associated with polydispersity of molecular weight.展开更多
Isotactic polypropylene（i PP） samples obtained by pressure vibration injection molding（PVIM） and conventional injection molding（CIM） were studied by polarized-light microscopy（PLM）, respectively. It was found ...Isotactic polypropylene（i PP） samples obtained by pressure vibration injection molding（PVIM） and conventional injection molding（CIM） were studied by polarized-light microscopy（PLM）, respectively. It was found that the alternating bright and dark banded spherulites were generated in the transitional region of PVIM parts. It is the first time that the banded spherulites of isotactic polypropylene were observed in polymer processing. What＇s more, the banded spherulites were proved to be constituted of α-form crystal by hot stage polarized-light microscopy（HT-PLM） and wide angle X-ray diffraction（WAXD）. Morphology of the banded spherulites was also studied by scaning electronical microscopy（SEM）.展开更多
The ring-banded spherulite is a special morphology of polymer crystals and has attracted considerable attention over recent decades. In this study, a new phase field model with polymer characteristics is established t...The ring-banded spherulite is a special morphology of polymer crystals and has attracted considerable attention over recent decades. In this study, a new phase field model with polymer characteristics is established to investigate the emergence and formation mechanism of the ring-banded spherulites of crystalline polymers. The model consists of a nonconserved phase field representing the phase transition and a temperature field describing the diffusion of the released latent heat. The corresponding model parameters can be obtained from experimentally accessible material parameters.Two-dimensional calculations are carried out for the ring-banded spherulitic growth of polyethylene film under a series of crystallization temperatures. The results of these calculations demonstrate that the formation of ring-banded spherulites can be triggered by the self-generated thermal field. Moreover, some temperature-dependent characteristics of the ring-banded spherulites observed in experiments are reproduced by simulations, which may help to study the effects of crystallization temperature on the ring-banded structures.展开更多
The method for measuring the spherulite growth rate and studying the morphology of polypropylene - based blends by image processing technology is described. The main advantages of this method, as compared to existing ...The method for measuring the spherulite growth rate and studying the morphology of polypropylene - based blends by image processing technology is described. The main advantages of this method, as compared to existing techniques, are: better reliability; reproducibility; ease of manipulation. Such an approach provides a means of measuring the rate of spherulite growth. In this study, isotactic polypropylene (PP), polystyrene (PS)/PP, and polybutylene terephthalate (PBT)/PP have been studied. The results show that the technology of image analysis is very useful in the study of the kinetics of crystallization of polymer.展开更多
The surface morphology of free-surface PCL ringed spherulites was investigated by using atomic force microscopy. The spherulites were obtained by crystallization of PCL/PVC blends of different compositions. It was fou...The surface morphology of free-surface PCL ringed spherulites was investigated by using atomic force microscopy. The spherulites were obtained by crystallization of PCL/PVC blends of different compositions. It was found that the ringed spherulite exhibited regularly fluctuating rings on its surface. Compared with the bright-dark ring pattern of the spherulite under a polarizing microscope, it was proved that the optical characteristics of the ringed spherulite under polarizing microscope coincided with its surface characteristics. The bright rings in polarizing micrographs of the spherulite coincided with the convex rings on its surface, while the dark rings coincided with the concave rings.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
A series of PCL/MDI/BDO segmented polyurethanes have been synthesized by two-step method in solution.The hard segment content ranges from 10% to 48% by weight, and the molecular weight of PCL diols is 1500. Hard segme...A series of PCL/MDI/BDO segmented polyurethanes have been synthesized by two-step method in solution.The hard segment content ranges from 10% to 48% by weight, and the molecular weight of PCL diols is 1500. Hard segment spherulites have been observed in compression molded specimens of all of the samples except the one of the lowest hard segment content. The difficulty in sphernlite formation was explained as only in a small temperature range,the microphase separation rate may be faster than the crystallization rate and all these processes are very slow due to the hydrogen bonding between hard and soft segments and the interactions between hard segments themselves. PCL soft segments of molecular weight 1500 is still crystallizable and may form different crystalline superstructures.展开更多
Several NNW-trending Cretaceous rhyolite dikes in the northeastern Cheongsong area of southern Korea contain spherulitic fabrics and are locally quarried as an ornamental stone. The dikes, part of the Cheongsong dike ...Several NNW-trending Cretaceous rhyolite dikes in the northeastern Cheongsong area of southern Korea contain spherulitic fabrics and are locally quarried as an ornamental stone. The dikes, part of the Cheongsong dike swarm, contain a variety of spherulites which are characterized by radial array of acicular intergrowths from fibrous quartz and alkali feldspars. They are classified as some simple, multiple and compound spherulite types from flower-like patterns, and the types are different each other in spatial distribution within the dikes. The various radial fabrics suggest that they crystallized under the different cooling mechanisms and processes in rapidly cooling dikes. Spheroids lacking a flower-like pattern may be precipitated after compositional segregation in a supercooled magma. Simple acicular spherulites could be crystallized by devitrification of true glass which cooled rapidly below the transformation temperature, whereas layered multiple spherulites could result from a crystallization of supercooled magma at relatively rapid cooling rates above the transformation temperature. Acicular multiple spherulites could be produced from a combination of the above three mechanisms operating at slower cooling rates.展开更多
A new spherulite-like structure of main chain thermotropic aromatic copolyesters formed in solution cast specimens was observed and was studied by means of polarizing microscopy, X-ray diffraction, SEM and IR spectrom...A new spherulite-like structure of main chain thermotropic aromatic copolyesters formed in solution cast specimens was observed and was studied by means of polarizing microscopy, X-ray diffraction, SEM and IR spectrometry. Results indicate that the spherulite-like structure of main chain thermotropic aromatic copolyesters formed from the casting solution (phenol/Cl2CH2CH2Cl2) is not a real crystal but only a high oriented arrangement of the macromolecular chains as a spherulite. This resulted from the interaction between the needle-like crystal of phenol and the rigid mesomorphic groups of molecular chain. The parallel packing of extended copolyester molecules along the needle-like crystal of phenol leads to the formation of the spherulite-like structure.展开更多
文摘In this research, the morphologies, isothermal-crystallization kinetics, and spherulite growth of aliphatic polyketone/polyamide-6 blends were studied. A single glass-transition temperature （Tg） was determined, and the composition dependence of Tg for these blends was well described by the Kwei equation. The strong intermolecular interaction between the two polymer components was confirmed by melting-point depression. The isothermal-crystallization kinetics were analyzed on the basis of the Avrami approach. A linear increase in the radii of the spherulites with time was observed for all compositions. All the spherulites continued to grow at nearly identical growth rates. With increasing polyamide-6 content, the size of the spherulites in the polyketone/polyamide-6 blends gradually decreased, and the number of spherulites in the blends increased.
基金supported by the National Natural Science Foundation of China(Key Project No.50733003 and Project No.20604030)the International Cooperation fund of Science and Technology(Key project 20071314) from the Ministry of Science and Technology of Chinathe fund from Chinese Academy of Sciences(KGCX-YW-208)
文摘Hydroxyapatite/poly（L-lactide） （HA/PLLA） nanocomposites were prepared by the solvent mixing method. The isothermal crystallization behavior was studied by differential scanning calorimetry （DSC） and polarized optical microscopy （POM）. The results show that the crystallization behavior of HA/PLLA composites was strongly affected by the content of HA and crystallization temperature, and the addition of HA could promote nucleation and enhance the crystallization rate. When isothermal crystallization was carried out at 110℃, the HA/PLLA nanocomposite with 1% HA content crystallized most rapidly among all the composites and the half crystallization time was only 1.0 min. Banded spherulites were observed for the HA/PLLA composites, but no banded spherulites were seen in the crystals of PLLA under the same condition.
基金financially supported by the National Natural Science Foundation of China(Nos.21674033,21374027)National Key R&D Program of China(No.2017YFB0307704)
文摘The morphologies of poly(L-lactic acid)(PLLA)spherulites,when crystallized within the pre-existed poly(oxymethylene)(POM)crystal frameworks,have been investigated.PLLA/POM blend is a melt-miscible crystalline/crystalline blend system.Owing to the lower melting point but much faster crystallization rate than PLEA,POM crystallized first upon cooling from the melt state and then melted first during the subsequent heating process in this blend system.Lamellar assembly of PLLA crystals within the pre-existed POM spherulitic frameworks was directly observed with the polarized light microscopy by selectively melting the POM frameworks.The investigation indicated that PLLA crystals fully replicated the spherulitic morphology and optical birefringence of the POM crystal frameworks,which was independent of T_(o).On the other hand,POM could also duplicate the pre-existed PLLA morphologies.The result obtained provides us a possibility to design the lamellar assembly and crystal structures of polymer crystals in miscible crystalline/crystalline polymer blends.
基金supported by the National Natural Science Foundation of China(Nos.51625304 and 51873182).
文摘Poly(L-lactic acid)(PLLA)has drawn much attention due to its excellent medical and pharmaceutical applications for decades.As a semi-crystalline polymer,morphology and crystal structure of PLLA greatly determine its properties.Here,w e demonstrate,for PLLA films,a nonconventional texture featuring two types of spherulites emerging in pairs to form a distinct nested structure where a small spherulite(〜10μm)is embedded in a large one(100μm to 300μm).In addition to the size,the molecular weight and polymorph are different in the large and small spherulites.Crystallographic a-form and relatively low molecular weight are identified in the large spherulites,while meta-stable a'-form and relatively high molecular weight in the small ones.These differences suggest that the polydisperse PLLA polymers fractionate during film formation and the high-molecular-weight fraction crystallizes into the small spherulites with meta-stable structure because of its complicated polymer entanglement and high viscosity.In contrast,the rest of polymers crystallize into the large spherulites with the thermodynamically stable polymorph.Furthermore,this texture exhibits accelerated PLLA degradation initiated from the small spherulites,which is distinct from the typical PLLA spherulites.Insights provided by this work may lead to new texture-properties relationship associated with polydispersity of molecular weight.
文摘Isotactic polypropylene（i PP） samples obtained by pressure vibration injection molding（PVIM） and conventional injection molding（CIM） were studied by polarized-light microscopy（PLM）, respectively. It was found that the alternating bright and dark banded spherulites were generated in the transitional region of PVIM parts. It is the first time that the banded spherulites of isotactic polypropylene were observed in polymer processing. What＇s more, the banded spherulites were proved to be constituted of α-form crystal by hot stage polarized-light microscopy（HT-PLM） and wide angle X-ray diffraction（WAXD）. Morphology of the banded spherulites was also studied by scaning electronical microscopy（SEM）.
基金Project supported by the National Key Basic Research Program of China(Grant No.2012CB025903)the National Natural Science Foundation of China(Grant No.11402210)+1 种基金the Northwestern Polytechnical University Foundation for Fundamental Research(Grant No.JCY20130141)the Ministry of Education Fund for Doctoral Students Newcomer Awards of China
文摘The ring-banded spherulite is a special morphology of polymer crystals and has attracted considerable attention over recent decades. In this study, a new phase field model with polymer characteristics is established to investigate the emergence and formation mechanism of the ring-banded spherulites of crystalline polymers. The model consists of a nonconserved phase field representing the phase transition and a temperature field describing the diffusion of the released latent heat. The corresponding model parameters can be obtained from experimentally accessible material parameters.Two-dimensional calculations are carried out for the ring-banded spherulitic growth of polyethylene film under a series of crystallization temperatures. The results of these calculations demonstrate that the formation of ring-banded spherulites can be triggered by the self-generated thermal field. Moreover, some temperature-dependent characteristics of the ring-banded spherulites observed in experiments are reproduced by simulations, which may help to study the effects of crystallization temperature on the ring-banded structures.
基金This project was supported by China Doctoral Special Foundation
文摘The method for measuring the spherulite growth rate and studying the morphology of polypropylene - based blends by image processing technology is described. The main advantages of this method, as compared to existing techniques, are: better reliability; reproducibility; ease of manipulation. Such an approach provides a means of measuring the rate of spherulite growth. In this study, isotactic polypropylene (PP), polystyrene (PS)/PP, and polybutylene terephthalate (PBT)/PP have been studied. The results show that the technology of image analysis is very useful in the study of the kinetics of crystallization of polymer.
基金This work was supported by The National Natural Science Foundation of China and also The State Science and Technology Commission of China under The National Key Project for Fundamental Research "Macromolecular Condensed State".
文摘The surface morphology of free-surface PCL ringed spherulites was investigated by using atomic force microscopy. The spherulites were obtained by crystallization of PCL/PVC blends of different compositions. It was found that the ringed spherulite exhibited regularly fluctuating rings on its surface. Compared with the bright-dark ring pattern of the spherulite under a polarizing microscope, it was proved that the optical characteristics of the ringed spherulite under polarizing microscope coincided with its surface characteristics. The bright rings in polarizing micrographs of the spherulite coincided with the convex rings on its surface, while the dark rings coincided with the concave rings.
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A series of PCL/MDI/BDO segmented polyurethanes have been synthesized by two-step method in solution.The hard segment content ranges from 10% to 48% by weight, and the molecular weight of PCL diols is 1500. Hard segment spherulites have been observed in compression molded specimens of all of the samples except the one of the lowest hard segment content. The difficulty in sphernlite formation was explained as only in a small temperature range,the microphase separation rate may be faster than the crystallization rate and all these processes are very slow due to the hydrogen bonding between hard and soft segments and the interactions between hard segments themselves. PCL soft segments of molecular weight 1500 is still crystallizable and may form different crystalline superstructures.
文摘Several NNW-trending Cretaceous rhyolite dikes in the northeastern Cheongsong area of southern Korea contain spherulitic fabrics and are locally quarried as an ornamental stone. The dikes, part of the Cheongsong dike swarm, contain a variety of spherulites which are characterized by radial array of acicular intergrowths from fibrous quartz and alkali feldspars. They are classified as some simple, multiple and compound spherulite types from flower-like patterns, and the types are different each other in spatial distribution within the dikes. The various radial fabrics suggest that they crystallized under the different cooling mechanisms and processes in rapidly cooling dikes. Spheroids lacking a flower-like pattern may be precipitated after compositional segregation in a supercooled magma. Simple acicular spherulites could be crystallized by devitrification of true glass which cooled rapidly below the transformation temperature, whereas layered multiple spherulites could result from a crystallization of supercooled magma at relatively rapid cooling rates above the transformation temperature. Acicular multiple spherulites could be produced from a combination of the above three mechanisms operating at slower cooling rates.
基金This work was supported by the National Key Project for Fundamental Research"Macromolecular Condensed State",The State Science and Technology Commission of China.
文摘A new spherulite-like structure of main chain thermotropic aromatic copolyesters formed in solution cast specimens was observed and was studied by means of polarizing microscopy, X-ray diffraction, SEM and IR spectrometry. Results indicate that the spherulite-like structure of main chain thermotropic aromatic copolyesters formed from the casting solution (phenol/Cl2CH2CH2Cl2) is not a real crystal but only a high oriented arrangement of the macromolecular chains as a spherulite. This resulted from the interaction between the needle-like crystal of phenol and the rigid mesomorphic groups of molecular chain. The parallel packing of extended copolyester molecules along the needle-like crystal of phenol leads to the formation of the spherulite-like structure.
