Solvent annealing is a facile method for changing the aggregated microstructure and physical properties of polymer materials. In this paper, we addressed the effects of solvent vapor annealing, including chloroform an...Solvent annealing is a facile method for changing the aggregated microstructure and physical properties of polymer materials. In this paper, we addressed the effects of solvent vapor annealing, including chloroform and water vapor, on the polymorphic transformation in both hot-pressed film and electrospun nonwoven of isotactic polybutene-1 （PB-1） by means of in situ Fourier transform infrared spectroscopy （FTIR）. The pretty rapid transition rate caused by the increased motion of molecular chains under chloroform vapor is associated with a lowest crystallinity. Also, a decreased crystallinity with the crystal transition occurred in electrospun nonwovens resulting from the relaxation of the stretched molecular chains into amorphous state rather than realignment into crystal form I predominating the crystal transition process.展开更多
For the solid-solid transformation from form Ⅱ to form Ⅰ of isotactic polybutene-1(iPB),the temperature dependence of form Ⅰ nucleation and growth was deemed to control the transformation process.However,the relati...For the solid-solid transformation from form Ⅱ to form Ⅰ of isotactic polybutene-1(iPB),the temperature dependence of form Ⅰ nucleation and growth was deemed to control the transformation process.However,the relationship between formⅠ formation and form Ⅱ disappearance in the transformation process is not clear.In this work,the spontaneous crystal transformation from form Ⅱ to Ⅰ of iPB with 81 mol%mmmm sequence concentration is studied firstly by tracking the two processes,the decay of form Ⅱ and the yielding of form Ⅰ in a wide range of temperature spanning from 0℃ to 50℃ and in a long transformation time ranging from 5 min to 65 days with in situ FTIR and WAXD.Unlike the literature reports,the decay rate of form Ⅱ is firstly found to be lower than the yielding rate of form Ⅰ at all studied temperatures,especially at low transition temperature.This is attributed to the amorphous chains which locate near crystal lamella participating into the nucleation of form Ⅱ.The regular chain folding and growth of i PB form Ⅰ from amorphous chains containing short isotactic sequences also lead to an increase in crystallinity of form Ⅰ compared with that of initial form Ⅱ crystallized at 60℃.An increase in the annealing temperature results in decrease in crystallinity and increase in lamellae thickness of i PB formⅠ.展开更多
Isotactic polybutene-1 (iPB-1) is a semi-crystalline polymer with polymorph and puzzled structural transitions. The stable form I of iPB-1 with excellent physical and mechanical properties can hardly be obtained direc...Isotactic polybutene-1 (iPB-1) is a semi-crystalline polymer with polymorph and puzzled structural transitions. The stable form I of iPB-1 with excellent physical and mechanical properties can hardly be obtained directly from the melt;instead, metastable form II will spontaneously and slowly transform into form I. Bypassing the unstable form II formation is of great significance in polymer processing, which inspires extensive research on seeking the pathways to direct formation of form I. Methods for accelerating form II to I transition are another main focus in terms of practical approach for directly obtaining form I. Taking advantage of the solvent, an ultrafast transition of iPB-1 from form II to I within minutes has been achieved at room temperature. Such an ultrafast transition is detected after treating with dichloromethane (DCM) at 30 ℃, though the framework of isothermally crystalized iPB-1 spherulite morphology could not be fully modified. The ultrafast II-I transition of iPB-1 is attributed to the solvent-induced packed-mesophase and temperature-selected chain conformation adjustment.This ultrafast transition would shed light on understanding the mechanisms of polymorphic transitions in iPB-1.展开更多
Starting from an initial sample of butene-1/ethylene copolymer with stable form I＇, we examined the nucleation of different crystalline polymorphs （here metastable form II and stable form I＇） at different isother...Starting from an initial sample of butene-1/ethylene copolymer with stable form I＇, we examined the nucleation of different crystalline polymorphs （here metastable form II and stable form I＇） at different isothermal crystallization temperatures after being melted at different melt temperature （Tmelt）. When Tmelt was just above the melting temperature （Tm） of the crystallites, self-seeding took place. There, residue crystallites served as nuclei leading to the crystallization of the same crystalline phase. When Tmelt was a few degrees above the Tin, self-seeding was disabled due to complete melting of the initial crystals. Upon crystallization, the selection of the different polymorphs in this random copolymer was found to depend on an interplay between the domain size of segregated long crystallizable sequences and the size and energy barrier of the critical nucleus of the respective crystalline forms. Our results provide a clear understanding of the polymorphs selection during crystallization of a random copolymer as well as homo-polymers under confinement.展开更多
基金financially supported by the Special Foundation of Taishan Mountain Scholar Constructive Programthe National Natural Science Foundation of China(No.21174074)+3 种基金Shandong Provincical Key R&D Program(No.2015GGX102019)Shandong Provincial Natural Science Fund for Distinguished Young Scholars(No.JQ201213)the Nature Science Foundation of Shandong Province(No.ZR2013BM004)the Yellow River Delta Scholar program(Office of National University Science&Technology Park Administrative Committee(China University of Petroleum))
文摘Solvent annealing is a facile method for changing the aggregated microstructure and physical properties of polymer materials. In this paper, we addressed the effects of solvent vapor annealing, including chloroform and water vapor, on the polymorphic transformation in both hot-pressed film and electrospun nonwoven of isotactic polybutene-1 （PB-1） by means of in situ Fourier transform infrared spectroscopy （FTIR）. The pretty rapid transition rate caused by the increased motion of molecular chains under chloroform vapor is associated with a lowest crystallinity. Also, a decreased crystallinity with the crystal transition occurred in electrospun nonwovens resulting from the relaxation of the stretched molecular chains into amorphous state rather than realignment into crystal form I predominating the crystal transition process.
基金financially supported by the Major Science and Technology Innovation Project of Shandong Province (No. 2019JZZY010352)Natural Science Foundation of Shandong Province (ZR2019MB072)Taishan Scholar Program
文摘For the solid-solid transformation from form Ⅱ to form Ⅰ of isotactic polybutene-1(iPB),the temperature dependence of form Ⅰ nucleation and growth was deemed to control the transformation process.However,the relationship between formⅠ formation and form Ⅱ disappearance in the transformation process is not clear.In this work,the spontaneous crystal transformation from form Ⅱ to Ⅰ of iPB with 81 mol%mmmm sequence concentration is studied firstly by tracking the two processes,the decay of form Ⅱ and the yielding of form Ⅰ in a wide range of temperature spanning from 0℃ to 50℃ and in a long transformation time ranging from 5 min to 65 days with in situ FTIR and WAXD.Unlike the literature reports,the decay rate of form Ⅱ is firstly found to be lower than the yielding rate of form Ⅰ at all studied temperatures,especially at low transition temperature.This is attributed to the amorphous chains which locate near crystal lamella participating into the nucleation of form Ⅱ.The regular chain folding and growth of i PB form Ⅰ from amorphous chains containing short isotactic sequences also lead to an increase in crystallinity of form Ⅰ compared with that of initial form Ⅱ crystallized at 60℃.An increase in the annealing temperature results in decrease in crystallinity and increase in lamellae thickness of i PB formⅠ.
基金financially supported by the National Natural Science Foundation of China (Nos. 51673147, 51573131, and 21374077)
文摘Isotactic polybutene-1 (iPB-1) is a semi-crystalline polymer with polymorph and puzzled structural transitions. The stable form I of iPB-1 with excellent physical and mechanical properties can hardly be obtained directly from the melt;instead, metastable form II will spontaneously and slowly transform into form I. Bypassing the unstable form II formation is of great significance in polymer processing, which inspires extensive research on seeking the pathways to direct formation of form I. Methods for accelerating form II to I transition are another main focus in terms of practical approach for directly obtaining form I. Taking advantage of the solvent, an ultrafast transition of iPB-1 from form II to I within minutes has been achieved at room temperature. Such an ultrafast transition is detected after treating with dichloromethane (DCM) at 30 ℃, though the framework of isothermally crystalized iPB-1 spherulite morphology could not be fully modified. The ultrafast II-I transition of iPB-1 is attributed to the solvent-induced packed-mesophase and temperature-selected chain conformation adjustment.This ultrafast transition would shed light on understanding the mechanisms of polymorphic transitions in iPB-1.
基金financially supported by the National Natural Science Foundation of China(Nos.21134006 and 51525305)
文摘Starting from an initial sample of butene-1/ethylene copolymer with stable form I＇, we examined the nucleation of different crystalline polymorphs （here metastable form II and stable form I＇） at different isothermal crystallization temperatures after being melted at different melt temperature （Tmelt）. When Tmelt was just above the melting temperature （Tm） of the crystallites, self-seeding took place. There, residue crystallites served as nuclei leading to the crystallization of the same crystalline phase. When Tmelt was a few degrees above the Tin, self-seeding was disabled due to complete melting of the initial crystals. Upon crystallization, the selection of the different polymorphs in this random copolymer was found to depend on an interplay between the domain size of segregated long crystallizable sequences and the size and energy barrier of the critical nucleus of the respective crystalline forms. Our results provide a clear understanding of the polymorphs selection during crystallization of a random copolymer as well as homo-polymers under confinement.
