The influences of shearing conducted by a Brabender behavior of a commercial impact polypropylene copolymer （IPC） rheometer on phase morphology, thermal and rheological were studied. The crystallization and melting ...The influences of shearing conducted by a Brabender behavior of a commercial impact polypropylene copolymer （IPC） rheometer on phase morphology, thermal and rheological were studied. The crystallization and melting traces show that short-time annealing at 210℃ is unable to completely erase the influence of shearing on the samples. When the samples which were treated at a rotation speed of 80 r/rnin crystallize at a cooling rate of 10 K/min, their Tcs and corresponding Tms obviously rise with the increase of shearing time. Furthermore, the POM results reveal that the shearing can lead to the formation of shish-kebab and the shish-kebab amount is proportional to shearing time. The rheological measurement results show that the treated samples exhibit different G＇-ω dependences. The ＇second plateau＇ appears when the sample is treated at a rotation speed of 60 r/min or 80 r/min for 10 min, and linear G＇-ω dependence is observed at other rotation speeds. In addition, it is found that the appearance of the ＇second plateau＇ depends on the shearing time when the rotation speed is fixed. According to SEM observations, it is proposed that the ＇second plateau＇ of IPC samples should be ascribed to the aggregation of dispersion particles.展开更多
To enhance the mechanical properties of polypropylene random copolymer(PPR),polystyrene(PS)with four different contents were added to the PPR matrix through melt blending.Subsequently,using the Multi-Flow Vibration In...To enhance the mechanical properties of polypropylene random copolymer(PPR),polystyrene(PS)with four different contents were added to the PPR matrix through melt blending.Subsequently,using the Multi-Flow Vibration Injection Molding(MFVIM)technology,PPR/PS in situ microfiber composites(MFC)with different blending ratios were prepared.The results indicated that blending ratio had a great impact on the phase morphology and crystal structure of MFVIM samples,which was different from those of conventional injection molding(CIM)samples.PS ultrafine fibers could be formed under the shear field and could absorb the PPR molecular chains to form hybrid shish-kebab structures.Meanwhile,the PPR matrix could also form shish-kebab structures under the effect of strong shear.When the PS content reached 20%,under the combined action of PS in situ microfibers and highly oriented crystal structure,the tensile strength and Young’s modulus of the sample were obviously improved and the impact strength remained at a relatively high level.So a strong and tough balanced PPR based material was obtained.These results provide valuable insights for expanding the industrial and daily-life applications of PPR and show promising development prospects.展开更多
For the first time, a highly crystalline porous shish-kebab structure with a high degree of crystallinity was obtained by using a combination of two methods for the formation of porous polymeric materials. A treatment...For the first time, a highly crystalline porous shish-kebab structure with a high degree of crystallinity was obtained by using a combination of two methods for the formation of porous polymeric materials. A treatment procedure using supercritical carbon dioxide(sc CO_(2))was carried out for oriented ultrahigh molecular weight polyethylene(UHMWPE) films, which provided special conditions for the crystallization of dissolved UHMWPE macromolecules on the surface of oriented UHMWPE crystals. The prepared porous materials were investigated by scanning electron microscopy(SEM) and differential scanning calorimetry(DSC). The particularity of the obtained porous shish-kebab is the absence of the amorphous phase between lamellar crystals(kebabs). The obtained pores had an oval shape, and they were oriented in the orientation direction of the UHMWPE macromolecules. The pore size ranged from 0.05 μm to 4 μm. Controlling the conditions for the crystallization of the UHMWPE macromolecules using supercritical CO_(2) gives the possibility to control the size of both lamellar disks and pores formed.展开更多
In this study, effects of oscillatory shear with different frequencies （0-2.5 Hz） and amplitudes （0-20 mm） on the mechanical properties and crystalline morphology of linear low density polyethylene （LLDPE） were ...In this study, effects of oscillatory shear with different frequencies （0-2.5 Hz） and amplitudes （0-20 mm） on the mechanical properties and crystalline morphology of linear low density polyethylene （LLDPE） were investigated. It was found that the mechanical properties of LLDPE are improved because of the more perfect crystalline structure when LLDPE crystallizes under low-frequency and small-amplitude （0.2 Hz/4 mm） oscillatory shear. The mechanical properties can be further improved by increasing either the frequency or the amplitude of oscillatory shear. The Young＇s modulus and tensile strength of LLDPE are improved by 27% and 20%, respectively, when the frequency is increased to 2.5 Hz and the amplitude is maintained at 4 mm; while the Young＇s modulus and tensile strength are improved by 49% and 47%, respectively, when the amplitude is increased to 20 mm and the frequency is remained as 0.2 Hz. The crystallinity and microstructure of LLDPE under different oscillatory shear conditions were investigated by using differential scanning calorimetry, wide angle X-ray diffraction and scanning electron microscopy to shed light on the mechanism for the improvement of mechanical properties.展开更多
The electrospinning process was applied to fabricate the nanofibers of biodegradable poly(ε-caprolactone)(PCL) in which different contents of multiwalled carbon nanotubes(MWCNTs) were embedded. Afterward,the electros...The electrospinning process was applied to fabricate the nanofibers of biodegradable poly(ε-caprolactone)(PCL) in which different contents of multiwalled carbon nanotubes(MWCNTs) were embedded. Afterward,the electrospun nanofibers were successfully decorated with shish-kebab structure via a self-induced crystallization technique. The topographical features and the mechanical properties of the composite scaffolds were characterized,and the biocompatibility of the material was assessed by using human osteogenic sarcoma osteoblasts(MG-63 cells). The carbon nanotube(CNT) concentration is found to affect the fiber diameter and mechanical properties of electrospun nanofibers and the periodic distance of the shish-kebab architecture. Cellular attachment and proliferation assays reveal that 0.5 wt% CNT-embedded PCL scaffold shows enhanced biocompatibility with MG-63 cells than their counterparts made of neat PCL, and the collagen-like nanotopology provided by the shish-kebab structure further facilitates the cell adhesion and proliferation. The superior interactions between cells and scaffolds demonstrate that the shish-kebab-structured CNTs/PCL nanofibers may be promising candidate for tissue engineering scaffold application.展开更多
Abstract The novel shish-kebab-type liquid crystalline poly（p-phenylene）s were synthesized through Suzuki coupling reaction from 2,5-bis[（4-n-alkoxyl）benzoyloxy]1,4-dibromobenzene （monomer 1） and 1,4-benzenedibo...Abstract The novel shish-kebab-type liquid crystalline poly（p-phenylene）s were synthesized through Suzuki coupling reaction from 2,5-bis[（4-n-alkoxyl）benzoyloxy]1,4-dibromobenzene （monomer 1） and 1,4-benzenediboronic acid bistrimethylene cyclic ester （monomer 2）. Their structure and properties were characterized by GPC, DSC, X-ray diffraction and polarizing optical microscope （POM）. It was found that the polymers turned to liquid crystalline phase above their melting point. The melting point （Tm） of the polymers decreases when the length of the alkoxy tails of the mesogenic units increases. The mesophase was identified by X-ray diffraction method. The polymers could dissolve in common organic solvents and show strong blue fluorescence. The maximum absorption bands of polymers prepared from annealed films have large red-shift due to the spontaneous orientation of the liquid crystalline side chains. The same phenomena were also observed in the fluorescence spectra.展开更多
High density polyethylene （HDPE） with moderate content of crosslink network （CPE） was successfully prepared through chemical method. Specimens for structural characterization have been molded by conventional injec...High density polyethylene （HDPE） with moderate content of crosslink network （CPE） was successfully prepared through chemical method. Specimens for structural characterization have been molded by conventional injection molding （CIM） and pressure vibration injection molding （PVIM）. Influence of crosslink network on hierarchical morphology distribution and mechanical properties was systematically studied. Polarized light microscopy （PLM） revealed that both CIM and PVIM PE samples have a typical ＂skin-core＂ structure and the thickness of shear layer of CIM PE and PVIM CPE samples obviously increase. Scanning electron microscopy （SEM） showed that shish-kebab structures are clearly observed in shear layer of CIM CPE sample, indicating that the crosslink network can surely improve the formation of shish-kebab structures. Moreover, we suppose that shish-kebab structures emerged in shear and core layer of PVIM CPE sample. Wide- angle X-ray diffraction （WAXD） and small-angle X-ray scattering （SAXS） confirmed that more orientation and shish-kebab structures form even in core layer of PVIM CPE sample, which demonstrated that the hierarchical morphology was apparently altered by periodical shear and crosslink network. Finally, the mechanical properties revealed that this oriented structure increase the tensile strength from 31 MPa of CIM PE sample to 46 MPa of PVIM CPE sample. However, the tensile behavior tended to change from ductile fracture to brittle fracture.展开更多
Novel shish-kebab type liquid crystalline poly（p-phenylenevinylene） derivatives were synthesized by Stille coupling reaction from 2,5-bis[（4-n-alkoxyl）benzoyloxy]1,4-dibromobenzene （monomer l） and 1,2-bis（tribu...Novel shish-kebab type liquid crystalline poly（p-phenylenevinylene） derivatives were synthesized by Stille coupling reaction from 2,5-bis[（4-n-alkoxyl）benzoyloxy]1,4-dibromobenzene （monomer l） and 1,2-bis（tributylstannyl） ethylene （monomer 2）. The polymers with alkoxy groups are soluble in common organic solvents and exhibit blue fluorescence. Both the cast film and the annealed film have large red-shifts in fluorescence spectra and show yellow fluorescence. The polymers with CN and NO2 groups show poor solubility and green fluorescence. All the polymers possess liquid crystalline smectic phases. The melting point （Tm） of the polymers decreases when the length of the alkoxy tails of the mesogenic units increases. The polymers are easily aligned under a magnetic field of 10 Tesla. It is found that the conjugated backbone and LC side chain are aligned perpendicular and parallel to the magnetic field, respectively. The polymers show optical dichroism in fluorescence spectra, suggesting that they are available for advance materials with linear optical polarization.展开更多
Ultra-high strength and modulus polyethylene fibers can be produced from UHMW-PE(ul-tra-high molecular weight polyethylene) by gel spinning and ultra-high drawing method.The spe-cial supermolecular structure of″shish...Ultra-high strength and modulus polyethylene fibers can be produced from UHMW-PE(ul-tra-high molecular weight polyethylene) by gel spinning and ultra-high drawing method.The spe-cial supermolecular structure of″shish-kebabs″ is the intrinsic course for the fiber having highperformance.In this paper,the formation mechanism of the characteristic structure of PE fibershas been investigated by means of SEM,DSC,WAXD,SAXS and TEM,The experimental resultsshow that the extended-chain structure of PE fibers is formed originally from the bridged mole-cules in amorphous region and increased gradually during further drawing porcess.The″shish-kebab″ structure is formed by the combination of extended-chalnS and originalfolded-chains.展开更多
A new series of chiral shish-kebab type liquid crystal block copolymers that form the smectic C(Sc*) phase was synthesized by solution polycondensation. The copolymers were characterized by GPC, DSC, TG, POM, X-ray di...A new series of chiral shish-kebab type liquid crystal block copolymers that form the smectic C(Sc*) phase was synthesized by solution polycondensation. The copolymers were characterized by GPC, DSC, TG, POM, X-ray diffraction and polarimeter. The copolymers 7 entered into liquid crystal phase whin they were heated to their melting temperatures (T-m) and the copolymers 8 were in liquid crystal phase at room temperature with low viscosities. The smectic sanded texture or focal-conic texture were observed on POM. All the chiral block copolymers showed high optical activity. No racemization has happened. Temperature-variable X-ray diffraction study together with POM and polarimetric analysis realized that they are chiral smectic C(Sc*) phase. Thus we offer in this report the first example of shish-kebab type liquid crystal block copolymers that form a chiral smectic C(Sc*) phase. The variation of melting and isotropization temperatures with molecular structure was also discussed.展开更多
The novel shish-kebab-type liquid crystalline cross-conjugated （p-phenylene）s-poly（p-phenylenevinylene）s hybrid was synthesized through Gilch polymerization. Their structures and properties were characterized by N...The novel shish-kebab-type liquid crystalline cross-conjugated （p-phenylene）s-poly（p-phenylenevinylene）s hybrid was synthesized through Gilch polymerization. Their structures and properties were characterized by NMR, GPC, DSC, X-ray diffraction and polarizing optical microscope （POM）. ^1H-NMR investigation of the polymers indicates that the shish-kebab-structure has a strong ability to suppress the structural defects in the polymers. The polymers are enantiotropic liquid crystals. The melting point （Tm） of the polymers decreases when the length of the alkoxy tails of the mesogenic units increases. The mesophase was identified by X-ray diffraction method. They showed not only a smectic LC phase, but also a strong green fluorescence in chloroform. The maximum absorption band of the ＂kebabs＂ of the two, 5-bis（4＇- alkoxyphenyl）benzene at 280 nm did not appear in absorption spectra of the polymers. The same phenomena were also observed in the fluorescence spectra. These results imply that the polymers have formed a cross-conjugated uniform structure and achieved an extended n-conjugation polymer.展开更多
In the current work, a custom-made vibration injection molding device that can provide oscillatory pressure was utilized to create an injection-molded hierarchical structure. Growth competition among α, β, and γ ph...In the current work, a custom-made vibration injection molding device that can provide oscillatory pressure was utilized to create an injection-molded hierarchical structure. Growth competition among α, β, and γ phases in the injection-molded structure can be studied because of the presence of this hierarchical structure, wherein shish-kebab and spherulite layers were arranged alternately along the thickness direction. The γ crystals only existed in layers subjected to high pressure and shear stress, whereas β crystals formed between the shear layers. The change in trend of the γ fraction was similar to that of parent-to-daughter ratio. In addition, this hierarchical and alternating crystal structure can sharply increase the mechanical properties.展开更多
One-dimensional carbon nano-materials,in particular carbon nanotubes (CNTs) and carbon nanofibers (CNFs),are of scientific and technological interest due to their satisfactory properties and ability to serve as templa...One-dimensional carbon nano-materials,in particular carbon nanotubes (CNTs) and carbon nanofibers (CNFs),are of scientific and technological interest due to their satisfactory properties and ability to serve as templates for directed assembly.In this work,linear high density polyethylene (PE) was periodically decorated on CNTs and CNFs using a supercritical carbon dioxide (scCO_(2))antisolvent-induced polymer epitaxy (SAIPE) method,leading to nano-hybrid shish-kebab (NHSK) structures.The formation mechanism of different morphologies of PE lamellae on CNTs and CNFs has been discussed.Palladium nanoparticles were synthesized and immobilized on the PE/CNF NHSK structure with the assistance of scCO_(2).The obtained hierarchical nano-hybrid architecture may find applications in microfabrication and other related fields.展开更多
Liquid crystalline （LC） polymers with a shish-kebab-type moiety on their cross-conjugated （p-phenylene）s-poly（p- phenylenevinylene）s main chains were synthesized through Gilch polymerization in order to develop ...Liquid crystalline （LC） polymers with a shish-kebab-type moiety on their cross-conjugated （p-phenylene）s-poly（p- phenylenevinylene）s main chains were synthesized through Gilch polymerization in order to develop a kind of polymers available for linearly polarized white-light-emitting from single chain. In this system, the 2,5-bis（4＇-alkoxyphenyl）benzene as the ＂kebabs＂ connects with poly（p-phenylenevinylene） （PPV） main chain backbone using its molecular gravity center and the PPV as the ＂shish＂ or ＂skewer＂ （the ＂shish-kebab＂）. The polymers possess desirable properties such as excellent solubility and liquid crystalline properties. To drop the ＂kebabs＂ of the 2,5-bis（4＇-alkoxyphenyl）benzene into the orientation microgroove of aligned polyimide film, not only the ＂shish＂ of polymer main chain can be aligned by the virtue of orientation of ＂kebabs＂ but also the uniform cross-conjugated structure between the ＂kebabs＂ and ＂shish＂ can be broken. Then, the alignment of the polymer main chain showed yellow light emission and was also accompanied by orientation of the LC side chains showing blue light emission, this gave rise to a notable linearly polarized white fluorescence.展开更多
基金financially supported by the National Natural Science Foundation of China(No.51173157),National Basic Research Program of China(No.2005CB623800) and Natural Science Foundation of Zhejiang Province(No.Y4100314).
文摘The influences of shearing conducted by a Brabender behavior of a commercial impact polypropylene copolymer （IPC） rheometer on phase morphology, thermal and rheological were studied. The crystallization and melting traces show that short-time annealing at 210℃ is unable to completely erase the influence of shearing on the samples. When the samples which were treated at a rotation speed of 80 r/rnin crystallize at a cooling rate of 10 K/min, their Tcs and corresponding Tms obviously rise with the increase of shearing time. Furthermore, the POM results reveal that the shearing can lead to the formation of shish-kebab and the shish-kebab amount is proportional to shearing time. The rheological measurement results show that the treated samples exhibit different G＇-ω dependences. The ＇second plateau＇ appears when the sample is treated at a rotation speed of 60 r/min or 80 r/min for 10 min, and linear G＇-ω dependence is observed at other rotation speeds. In addition, it is found that the appearance of the ＇second plateau＇ depends on the shearing time when the rotation speed is fixed. According to SEM observations, it is proposed that the ＇second plateau＇ of IPC samples should be ascribed to the aggregation of dispersion particles.
基金supported by the National Natural Science Foundation of China(No.21627804).
文摘To enhance the mechanical properties of polypropylene random copolymer(PPR),polystyrene(PS)with four different contents were added to the PPR matrix through melt blending.Subsequently,using the Multi-Flow Vibration Injection Molding(MFVIM)technology,PPR/PS in situ microfiber composites(MFC)with different blending ratios were prepared.The results indicated that blending ratio had a great impact on the phase morphology and crystal structure of MFVIM samples,which was different from those of conventional injection molding(CIM)samples.PS ultrafine fibers could be formed under the shear field and could absorb the PPR molecular chains to form hybrid shish-kebab structures.Meanwhile,the PPR matrix could also form shish-kebab structures under the effect of strong shear.When the PS content reached 20%,under the combined action of PS in situ microfibers and highly oriented crystal structure,the tensile strength and Young’s modulus of the sample were obviously improved and the impact strength remained at a relatively high level.So a strong and tough balanced PPR based material was obtained.These results provide valuable insights for expanding the industrial and daily-life applications of PPR and show promising development prospects.
基金financially supported by the Academic leadership program Priority 2030 proposed by Federal State Autonomous Educational Institution of Higher Education I.M. Sechenov First Moscow State Medical University of the Ministry of Health of the Russian Federation (Sechenov University)The preparation and modification of UHMWPE samples were financially supported by the Russian Science Foundation (No.18-13-00145)SEM investigation was supported by the State Assignment (No.0090-2019-0002, IPAC RAS)。
文摘For the first time, a highly crystalline porous shish-kebab structure with a high degree of crystallinity was obtained by using a combination of two methods for the formation of porous polymeric materials. A treatment procedure using supercritical carbon dioxide(sc CO_(2))was carried out for oriented ultrahigh molecular weight polyethylene(UHMWPE) films, which provided special conditions for the crystallization of dissolved UHMWPE macromolecules on the surface of oriented UHMWPE crystals. The prepared porous materials were investigated by scanning electron microscopy(SEM) and differential scanning calorimetry(DSC). The particularity of the obtained porous shish-kebab is the absence of the amorphous phase between lamellar crystals(kebabs). The obtained pores had an oval shape, and they were oriented in the orientation direction of the UHMWPE macromolecules. The pore size ranged from 0.05 μm to 4 μm. Controlling the conditions for the crystallization of the UHMWPE macromolecules using supercritical CO_(2) gives the possibility to control the size of both lamellar disks and pores formed.
基金financially supported by the National Natural Science Foundation of China(Nos.51373153 and 51073139)the Zhejiang Provincial Natural Science Foundation of China(No.LY13E030002)the Zhejiang Leading Team of S&T Innovation(No.2011R50005)
文摘In this study, effects of oscillatory shear with different frequencies （0-2.5 Hz） and amplitudes （0-20 mm） on the mechanical properties and crystalline morphology of linear low density polyethylene （LLDPE） were investigated. It was found that the mechanical properties of LLDPE are improved because of the more perfect crystalline structure when LLDPE crystallizes under low-frequency and small-amplitude （0.2 Hz/4 mm） oscillatory shear. The mechanical properties can be further improved by increasing either the frequency or the amplitude of oscillatory shear. The Young＇s modulus and tensile strength of LLDPE are improved by 27% and 20%, respectively, when the frequency is increased to 2.5 Hz and the amplitude is maintained at 4 mm; while the Young＇s modulus and tensile strength are improved by 49% and 47%, respectively, when the amplitude is increased to 20 mm and the frequency is remained as 0.2 Hz. The crystallinity and microstructure of LLDPE under different oscillatory shear conditions were investigated by using differential scanning calorimetry, wide angle X-ray diffraction and scanning electron microscopy to shed light on the mechanism for the improvement of mechanical properties.
基金financially supported by the Fundamental Research Funds for the Central Universities (No. 22A201514030)China Postdoctoral Science Foundation (No. 2015M571504)+2 种基金the National Natural Science Foundation of China (Nos. 51503065 and 51273065)the Wisconsin Institute for Discovery in University of Wisconsin-MadisonChina Scholarship Council
文摘The electrospinning process was applied to fabricate the nanofibers of biodegradable poly(ε-caprolactone)(PCL) in which different contents of multiwalled carbon nanotubes(MWCNTs) were embedded. Afterward,the electrospun nanofibers were successfully decorated with shish-kebab structure via a self-induced crystallization technique. The topographical features and the mechanical properties of the composite scaffolds were characterized,and the biocompatibility of the material was assessed by using human osteogenic sarcoma osteoblasts(MG-63 cells). The carbon nanotube(CNT) concentration is found to affect the fiber diameter and mechanical properties of electrospun nanofibers and the periodic distance of the shish-kebab architecture. Cellular attachment and proliferation assays reveal that 0.5 wt% CNT-embedded PCL scaffold shows enhanced biocompatibility with MG-63 cells than their counterparts made of neat PCL, and the collagen-like nanotopology provided by the shish-kebab structure further facilitates the cell adhesion and proliferation. The superior interactions between cells and scaffolds demonstrate that the shish-kebab-structured CNTs/PCL nanofibers may be promising candidate for tissue engineering scaffold application.
基金This work was supported by China Scholarship Council and Grant-in-Aids for Scientific Research from Ministry of Education, Culture and Science of Japan.
文摘Abstract The novel shish-kebab-type liquid crystalline poly（p-phenylene）s were synthesized through Suzuki coupling reaction from 2,5-bis[（4-n-alkoxyl）benzoyloxy]1,4-dibromobenzene （monomer 1） and 1,4-benzenediboronic acid bistrimethylene cyclic ester （monomer 2）. Their structure and properties were characterized by GPC, DSC, X-ray diffraction and polarizing optical microscope （POM）. It was found that the polymers turned to liquid crystalline phase above their melting point. The melting point （Tm） of the polymers decreases when the length of the alkoxy tails of the mesogenic units increases. The mesophase was identified by X-ray diffraction method. The polymers could dissolve in common organic solvents and show strong blue fluorescence. The maximum absorption bands of polymers prepared from annealed films have large red-shift due to the spontaneous orientation of the liquid crystalline side chains. The same phenomena were also observed in the fluorescence spectra.
文摘High density polyethylene （HDPE） with moderate content of crosslink network （CPE） was successfully prepared through chemical method. Specimens for structural characterization have been molded by conventional injection molding （CIM） and pressure vibration injection molding （PVIM）. Influence of crosslink network on hierarchical morphology distribution and mechanical properties was systematically studied. Polarized light microscopy （PLM） revealed that both CIM and PVIM PE samples have a typical ＂skin-core＂ structure and the thickness of shear layer of CIM PE and PVIM CPE samples obviously increase. Scanning electron microscopy （SEM） showed that shish-kebab structures are clearly observed in shear layer of CIM CPE sample, indicating that the crosslink network can surely improve the formation of shish-kebab structures. Moreover, we suppose that shish-kebab structures emerged in shear and core layer of PVIM CPE sample. Wide- angle X-ray diffraction （WAXD） and small-angle X-ray scattering （SAXS） confirmed that more orientation and shish-kebab structures form even in core layer of PVIM CPE sample, which demonstrated that the hierarchical morphology was apparently altered by periodical shear and crosslink network. Finally, the mechanical properties revealed that this oriented structure increase the tensile strength from 31 MPa of CIM PE sample to 46 MPa of PVIM CPE sample. However, the tensile behavior tended to change from ductile fracture to brittle fracture.
基金This work was supported by the China Scholarship Council and the Grant-in-Aids for Scientific Research from Ministry of Education, Culture, Sports, Science and Technology, Japan.
文摘Novel shish-kebab type liquid crystalline poly（p-phenylenevinylene） derivatives were synthesized by Stille coupling reaction from 2,5-bis[（4-n-alkoxyl）benzoyloxy]1,4-dibromobenzene （monomer l） and 1,2-bis（tributylstannyl） ethylene （monomer 2）. The polymers with alkoxy groups are soluble in common organic solvents and exhibit blue fluorescence. Both the cast film and the annealed film have large red-shifts in fluorescence spectra and show yellow fluorescence. The polymers with CN and NO2 groups show poor solubility and green fluorescence. All the polymers possess liquid crystalline smectic phases. The melting point （Tm） of the polymers decreases when the length of the alkoxy tails of the mesogenic units increases. The polymers are easily aligned under a magnetic field of 10 Tesla. It is found that the conjugated backbone and LC side chain are aligned perpendicular and parallel to the magnetic field, respectively. The polymers show optical dichroism in fluorescence spectra, suggesting that they are available for advance materials with linear optical polarization.
文摘Ultra-high strength and modulus polyethylene fibers can be produced from UHMW-PE(ul-tra-high molecular weight polyethylene) by gel spinning and ultra-high drawing method.The spe-cial supermolecular structure of″shish-kebabs″ is the intrinsic course for the fiber having highperformance.In this paper,the formation mechanism of the characteristic structure of PE fibershas been investigated by means of SEM,DSC,WAXD,SAXS and TEM,The experimental resultsshow that the extended-chain structure of PE fibers is formed originally from the bridged mole-cules in amorphous region and increased gradually during further drawing porcess.The″shish-kebab″ structure is formed by the combination of extended-chalnS and originalfolded-chains.
基金This work was supported by the National Natural Science Foundation of China (No. 29674025) and the Natural Science Foundation of Henan Province.
文摘A new series of chiral shish-kebab type liquid crystal block copolymers that form the smectic C(Sc*) phase was synthesized by solution polycondensation. The copolymers were characterized by GPC, DSC, TG, POM, X-ray diffraction and polarimeter. The copolymers 7 entered into liquid crystal phase whin they were heated to their melting temperatures (T-m) and the copolymers 8 were in liquid crystal phase at room temperature with low viscosities. The smectic sanded texture or focal-conic texture were observed on POM. All the chiral block copolymers showed high optical activity. No racemization has happened. Temperature-variable X-ray diffraction study together with POM and polarimetric analysis realized that they are chiral smectic C(Sc*) phase. Thus we offer in this report the first example of shish-kebab type liquid crystal block copolymers that form a chiral smectic C(Sc*) phase. The variation of melting and isotropization temperatures with molecular structure was also discussed.
基金This work was supported by the National Natural Science Foundation of China (No. 20574064).
文摘The novel shish-kebab-type liquid crystalline cross-conjugated （p-phenylene）s-poly（p-phenylenevinylene）s hybrid was synthesized through Gilch polymerization. Their structures and properties were characterized by NMR, GPC, DSC, X-ray diffraction and polarizing optical microscope （POM）. ^1H-NMR investigation of the polymers indicates that the shish-kebab-structure has a strong ability to suppress the structural defects in the polymers. The polymers are enantiotropic liquid crystals. The melting point （Tm） of the polymers decreases when the length of the alkoxy tails of the mesogenic units increases. The mesophase was identified by X-ray diffraction method. They showed not only a smectic LC phase, but also a strong green fluorescence in chloroform. The maximum absorption band of the ＂kebabs＂ of the two, 5-bis（4＇- alkoxyphenyl）benzene at 280 nm did not appear in absorption spectra of the polymers. The same phenomena were also observed in the fluorescence spectra. These results imply that the polymers have formed a cross-conjugated uniform structure and achieved an extended n-conjugation polymer.
文摘In the current work, a custom-made vibration injection molding device that can provide oscillatory pressure was utilized to create an injection-molded hierarchical structure. Growth competition among α, β, and γ phases in the injection-molded structure can be studied because of the presence of this hierarchical structure, wherein shish-kebab and spherulite layers were arranged alternately along the thickness direction. The γ crystals only existed in layers subjected to high pressure and shear stress, whereas β crystals formed between the shear layers. The change in trend of the γ fraction was similar to that of parent-to-daughter ratio. In addition, this hierarchical and alternating crystal structure can sharply increase the mechanical properties.
基金the National Natural Science Foundation of China (20974102)the Program for New Century Excellent Talents in Universities (NCET)
文摘One-dimensional carbon nano-materials,in particular carbon nanotubes (CNTs) and carbon nanofibers (CNFs),are of scientific and technological interest due to their satisfactory properties and ability to serve as templates for directed assembly.In this work,linear high density polyethylene (PE) was periodically decorated on CNTs and CNFs using a supercritical carbon dioxide (scCO_(2))antisolvent-induced polymer epitaxy (SAIPE) method,leading to nano-hybrid shish-kebab (NHSK) structures.The formation mechanism of different morphologies of PE lamellae on CNTs and CNFs has been discussed.Palladium nanoparticles were synthesized and immobilized on the PE/CNF NHSK structure with the assistance of scCO_(2).The obtained hierarchical nano-hybrid architecture may find applications in microfabrication and other related fields.
基金financially supported by the National Natural Science Foundation of China(No.20574064)
文摘Liquid crystalline （LC） polymers with a shish-kebab-type moiety on their cross-conjugated （p-phenylene）s-poly（p- phenylenevinylene）s main chains were synthesized through Gilch polymerization in order to develop a kind of polymers available for linearly polarized white-light-emitting from single chain. In this system, the 2,5-bis（4＇-alkoxyphenyl）benzene as the ＂kebabs＂ connects with poly（p-phenylenevinylene） （PPV） main chain backbone using its molecular gravity center and the PPV as the ＂shish＂ or ＂skewer＂ （the ＂shish-kebab＂）. The polymers possess desirable properties such as excellent solubility and liquid crystalline properties. To drop the ＂kebabs＂ of the 2,5-bis（4＇-alkoxyphenyl）benzene into the orientation microgroove of aligned polyimide film, not only the ＂shish＂ of polymer main chain can be aligned by the virtue of orientation of ＂kebabs＂ but also the uniform cross-conjugated structure between the ＂kebabs＂ and ＂shish＂ can be broken. Then, the alignment of the polymer main chain showed yellow light emission and was also accompanied by orientation of the LC side chains showing blue light emission, this gave rise to a notable linearly polarized white fluorescence.
