Dielectric relaxation spectroscopy（DRS） of poly（ε-caprolactone） with different draw ratios showed that the mobility of polymer chains in the amorphous part decreases as the draw ratio increases. The activation en...Dielectric relaxation spectroscopy（DRS） of poly（ε-caprolactone） with different draw ratios showed that the mobility of polymer chains in the amorphous part decreases as the draw ratio increases. The activation energy of the α process, which corresponds to the dynamic glass transition, increases upon drawing. The enlarged gap between the activation energies of the α process and the β process results in a change of continuity at the crossover between the high temperature a process and the α and β processes. At low drawing ratios the a process connects with the β process, while at the highest drawing ratio in our measurements, the a process is continuous with the αprocess. This is consistent with X-ray diffraction results that indicate that upon drawing the polymer chains in the amorphous part align and densify upon drawing. As the draw ratio increases, the α relaxation broadens and decreases its intensity, indicating an increasing heterogeneity. We observed slope changes in the α traces, when the temperature decreases below that at which τα≈ 1 s. This may indicate the glass transition from the ‘rubbery＇ state to the non-equilibrium glassy state.展开更多
The dependence of properties on the structure and morphology of semicrystalline polymers offers an effective way to tailor the properties of these materials through structure control. To this end, establishing the str...The dependence of properties on the structure and morphology of semicrystalline polymers offers an effective way to tailor the properties of these materials through structure control. To this end, establishing the structure and property relationship is of great importance. For a right characterization of the crystal structure, several techniques can be used. Among these techniques, electron diffraction has its advantage for determining the crystal structure related to specific formation condition since it can combine with bright and dark fields observation of the sample. This feature article describes the application of electron diffraction in determining the crystal structure of semicrystalline polymers with elaborately selected examples. We focus on how the electron diffraction can be used to disclose the crystal structure, mutual orientation of different crystals, as well as the disorders included in the polymer crystals.展开更多
A semicrystalline composite, 3, 4, 9, 10 perylenetetracarboxylic dianhydride （PTCDA） doped N,N＇-di（1-naphthyl）- N,N＇-diphenylbenzidine （NPB）, has been fabricated and characterized. An organic light-emitting di...A semicrystalline composite, 3, 4, 9, 10 perylenetetracarboxylic dianhydride （PTCDA） doped N,N＇-di（1-naphthyl）- N,N＇-diphenylbenzidine （NPB）, has been fabricated and characterized. An organic light-emitting diode using such a composite in hole injection exhibits the improved performance as compared with the reference device using neat NPB in hole injection. For example, at a luminance of 2000 cd/m2, the former device gives a current efficiency of 2.0cd/A, higher than 1.6cd/A obtained from the latter device. Furthermore, the semicrystalline composite has been shown thermally to be more stable than the neat NPB thin film, which is useful for making organic light emitting diodes with a prolonged lifetime.展开更多
The large size of the crystallites in poly（L-lactide） and the low growth rate enable detailed time- and temperaturedependent X-ray scattering studies of the ordering processes to be carded out. A layer located inter...The large size of the crystallites in poly（L-lactide） and the low growth rate enable detailed time- and temperaturedependent X-ray scattering studies of the ordering processes to be carded out. A layer located intermediate between crystals and melt-like regions is observed which finally takes on crystalline order. Recrystallization processes during heating change the complete stack structure rather than the crystallites individually and produce voids in the stacks, Establishment of a new stable structure after a temperature jump in the melting range can be followed in time. DSC experiments indicate times of melting of the order of minutes.展开更多
We develop an acoustomechanical theory for semicrystalline polymers and demonstrate that acoustic radiation force is capable of causing giant deformation in these materials. When a polymer layer is subjected to combin...We develop an acoustomechanical theory for semicrystalline polymers and demonstrate that acoustic radiation force is capable of causing giant deformation in these materials. When a polymer layer is subjected to combined tensile mechanical force in plane and acoustic force （sound pressure） through thickness, it becomes initially homogeneously thin but soon inhomogeneous when the two forces reach critical conditions. Critical conditions for such acoustomechanical instability are theoretically determined based on the J2-deformation theory. We demonstrate that pull-in instability can he acoustically triggered even if the in-plane mechanical force is fixed. Bifurcation in the critical condition for acoustomechanical instability occurs when the polymer exhibits sufficiently large hardening. The findings of this study enable reliability design of novel acoustic actuated devices.展开更多
Poly(butylene 2,6-naphthalate)(PBN)is a crystallizable linear polyester containing a rigid naphthalene unit and flexible methylene spacer in the chemical repeat unit.Polymeric materials made of PBN exhibit excellent a...Poly(butylene 2,6-naphthalate)(PBN)is a crystallizable linear polyester containing a rigid naphthalene unit and flexible methylene spacer in the chemical repeat unit.Polymeric materials made of PBN exhibit excellent anti-abrasion and low friction properties,superior chemical resista nee,and outstanding gas barrier characteristics.Many of the properties rely on the presence of crystals and the formatio n of a semicrystalline morphology.To develop specific crystal structures and morphologies during cooling the melt,precise information about the melt-crystallization process is required.This review article summarizes the current knowledge about the temperature-controlled crystal polymorphism of PBN.At rather low supercooling of the melt,with decreasi ng crystal I izatio n temperature,0'-and a-crystals grow directly from the melt and organize in largely different spherulitic superstructures.Formation of a-crystals at high supercooling may also proceed via intermediate formation of a transient monotropic liquid crystalline structure,then yielding a non-spherulitic semicrystalline morphology.Crystallization of PBN is rather fast since its suppression requires cooling the melt at a rate higher than 6000 K-s_1.For this reason,investigation of the two-step crystallization process at low temperatu res requires application of sophisticated experimental tools.These in elude temperatureresolved X-ray scattering techniques using fast detectors and synchrotron-based X-rays and fast scanning chip calorimetry.Fast scanning chip calorimetry allows freezi ng the transie nt liquid-crystalline structure before its con version into a-crystals,by fast cooling to below its glass transition temperature.Subsequent an alysis using polarized-light optical microscopy reveals its texture and X-ray scatteri ng con firms the smectic arrangement of the mesogens.The combination of a large variety of experimental techniques allows obtaining a complete picture about crystallization of PBN in the entire range of melt-supercoolings down to the glass t展开更多
基金the research programme of the Dutch Polymer Institute (DPI),project#623
文摘Dielectric relaxation spectroscopy（DRS） of poly（ε-caprolactone） with different draw ratios showed that the mobility of polymer chains in the amorphous part decreases as the draw ratio increases. The activation energy of the α process, which corresponds to the dynamic glass transition, increases upon drawing. The enlarged gap between the activation energies of the α process and the β process results in a change of continuity at the crossover between the high temperature a process and the α and β processes. At low drawing ratios the a process connects with the β process, while at the highest drawing ratio in our measurements, the a process is continuous with the αprocess. This is consistent with X-ray diffraction results that indicate that upon drawing the polymer chains in the amorphous part align and densify upon drawing. As the draw ratio increases, the α relaxation broadens and decreases its intensity, indicating an increasing heterogeneity. We observed slope changes in the α traces, when the temperature decreases below that at which τα≈ 1 s. This may indicate the glass transition from the ‘rubbery＇ state to the non-equilibrium glassy state.
基金supported by the National Natural Science Foundation of China (Nos. 50833006, 21274009,51221002 and 50973008)
文摘The dependence of properties on the structure and morphology of semicrystalline polymers offers an effective way to tailor the properties of these materials through structure control. To this end, establishing the structure and property relationship is of great importance. For a right characterization of the crystal structure, several techniques can be used. Among these techniques, electron diffraction has its advantage for determining the crystal structure related to specific formation condition since it can combine with bright and dark fields observation of the sample. This feature article describes the application of electron diffraction in determining the crystal structure of semicrystalline polymers with elaborately selected examples. We focus on how the electron diffraction can be used to disclose the crystal structure, mutual orientation of different crystals, as well as the disorders included in the polymer crystals.
基金supported by the National Natural Science Foundation of China (Grant No 60606025)
文摘A semicrystalline composite, 3, 4, 9, 10 perylenetetracarboxylic dianhydride （PTCDA） doped N,N＇-di（1-naphthyl）- N,N＇-diphenylbenzidine （NPB）, has been fabricated and characterized. An organic light-emitting diode using such a composite in hole injection exhibits the improved performance as compared with the reference device using neat NPB in hole injection. For example, at a luminance of 2000 cd/m2, the former device gives a current efficiency of 2.0cd/A, higher than 1.6cd/A obtained from the latter device. Furthermore, the semicrystalline composite has been shown thermally to be more stable than the neat NPB thin film, which is useful for making organic light emitting diodes with a prolonged lifetime.
基金This work was supported by the Deutsche Forschungsgemeinschaft. Thanks are also due to the Fonds der Chemischen Industrie for financial help.
文摘The large size of the crystallites in poly（L-lactide） and the low growth rate enable detailed time- and temperaturedependent X-ray scattering studies of the ordering processes to be carded out. A layer located intermediate between crystals and melt-like regions is observed which finally takes on crystalline order. Recrystallization processes during heating change the complete stack structure rather than the crystallites individually and produce voids in the stacks, Establishment of a new stable structure after a temperature jump in the melting range can be followed in time. DSC experiments indicate times of melting of the order of minutes.
基金supported by the National Natural Science Foundation of China(51528501 and 11321062)the Fundamental Research Funds for Central Universities(2014qngz12)supported by China Scholarship Council as a visiting scholar to Harvard University
文摘We develop an acoustomechanical theory for semicrystalline polymers and demonstrate that acoustic radiation force is capable of causing giant deformation in these materials. When a polymer layer is subjected to combined tensile mechanical force in plane and acoustic force （sound pressure） through thickness, it becomes initially homogeneously thin but soon inhomogeneous when the two forces reach critical conditions. Critical conditions for such acoustomechanical instability are theoretically determined based on the J2-deformation theory. We demonstrate that pull-in instability can he acoustically triggered even if the in-plane mechanical force is fixed. Bifurcation in the critical condition for acoustomechanical instability occurs when the polymer exhibits sufficiently large hardening. The findings of this study enable reliability design of novel acoustic actuated devices.
文摘Poly(butylene 2,6-naphthalate)(PBN)is a crystallizable linear polyester containing a rigid naphthalene unit and flexible methylene spacer in the chemical repeat unit.Polymeric materials made of PBN exhibit excellent anti-abrasion and low friction properties,superior chemical resista nee,and outstanding gas barrier characteristics.Many of the properties rely on the presence of crystals and the formatio n of a semicrystalline morphology.To develop specific crystal structures and morphologies during cooling the melt,precise information about the melt-crystallization process is required.This review article summarizes the current knowledge about the temperature-controlled crystal polymorphism of PBN.At rather low supercooling of the melt,with decreasi ng crystal I izatio n temperature,0'-and a-crystals grow directly from the melt and organize in largely different spherulitic superstructures.Formation of a-crystals at high supercooling may also proceed via intermediate formation of a transient monotropic liquid crystalline structure,then yielding a non-spherulitic semicrystalline morphology.Crystallization of PBN is rather fast since its suppression requires cooling the melt at a rate higher than 6000 K-s_1.For this reason,investigation of the two-step crystallization process at low temperatu res requires application of sophisticated experimental tools.These in elude temperatureresolved X-ray scattering techniques using fast detectors and synchrotron-based X-rays and fast scanning chip calorimetry.Fast scanning chip calorimetry allows freezi ng the transie nt liquid-crystalline structure before its con version into a-crystals,by fast cooling to below its glass transition temperature.Subsequent an alysis using polarized-light optical microscopy reveals its texture and X-ray scatteri ng con firms the smectic arrangement of the mesogens.The combination of a large variety of experimental techniques allows obtaining a complete picture about crystallization of PBN in the entire range of melt-supercoolings down to the glass t
