The recovery of amorphous PET fiber in global chain orientation but nearly random segmental orientation (GOLR) state was studied by the hot shrinkage measurement above the glass transition temperature. The relaxation ...The recovery of amorphous PET fiber in global chain orientation but nearly random segmental orientation (GOLR) state was studied by the hot shrinkage measurement above the glass transition temperature. The relaxation curves in the form of di-exponential decay were acquired and the change of two special times with the variation of treating temperature and residual recovery ratio ' was discussed.展开更多
This work extends our previous understanding concerning the nonlinear responses of entangled polymer solutions and melts to large external deformation in both simple shear and uniaxial extension. Many similarities hav...This work extends our previous understanding concerning the nonlinear responses of entangled polymer solutions and melts to large external deformation in both simple shear and uniaxial extension. Many similarities have recently been identified for both step strain and startup continuous deformation, including elastic yielding, i.e., chain disentanglement after cessation of shear or extension, and emergence of a yield point during startup deformation that involves a deformation rate in excess of the dominant molecular relaxation rate. At a sufficiently high constant Hencky rate, uniaxial extension of an entangled melt is known to produce window-glass-like rupture. The present study provides evidence against the speculation that chain entanglements tie up into "dead knots" in constant-rate extension because of the exponentially growing chain stretching with time. In particular, it is shown that even Instron-style tensile stretching, i.e., extending a specimen by applying a constant velocity on both ends, results in rupture. Yet, in the same rate range, the same entangled melt only yields in simple shear, and the resulting shear banding is clearly not a characteristic of rupture. Thus, we conclude that chain entanglements respond to simple shear in the manner of yielding whereas uniaxial extension is rather effective in causing some entanglements to lock up, making it impossible for the entanglement network to yield at high rates.展开更多
Distributed Lagrange Multiplier/Fictitious Domain （DLM/FD） method was employed to simulate the channel flow with polymer suspension. The polymer molecules were modeled as Finitely Extensible Nonlinear Elastic （FENE...Distributed Lagrange Multiplier/Fictitious Domain （DLM/FD） method was employed to simulate the channel flow with polymer suspension. The polymer molecules were modeled as Finitely Extensible Nonlinear Elastic （FENE） chains and FENE chain cluster. The coiled stretched transition of FENE chains was examined and the change in configuration of FENE chains was presented. The average velocity profile of the fully developed channel flow with 64 FENE chains was given and fitted well with the power-law curve. The change of chain cluster configuration was also simulated. These simulations show that DLM/FD method is capable of simulating the motion of not only FENE chain, but also FENE chain cluster.展开更多
Two kinds of aliphatic alternating polyesteramide prepolymers were prepared through melt polycondensation from N,N＇-bis（2-hydroxyethyl）-adipamide and adipic acid or sebacic acid. Chain extension of them was conduct...Two kinds of aliphatic alternating polyesteramide prepolymers were prepared through melt polycondensation from N,N＇-bis（2-hydroxyethyl）-adipamide and adipic acid or sebacic acid. Chain extension of them was conducted with 2,2＇-（1,4- phenylene）-bis（2-oxazoline） and adipoyl biscaprolactamate as combined chain extenders. The chain extended polyesteramides （ExtPEAs） were characterized by IR, 1H-NMR, differential scanning calorimetry, thermogravimetric analysis, wide angle X-ray scattering, tensile test and enzymatic degradation. The results showed that the ExtPEA（4,m）s were mainly constituted with the diester adipamide alternating units. ExtPEA（4,4） and ExtPEA（4,8） had Tm of 83.8℃ and 85.8℃ and initial decomposition temperature above 310.0℃. They crystallized similarly as Nylon-66 did and were flexible thermoplastic materials with tensile strength up to 25.64 MPa and strain at break up to 737%.展开更多
A series of polyesteramide prepolymers[PrePEA（0/4,8）s] having mixed alternating bisesterdiamide units was synthesized via melt polycondensation from N,N＇-bis（2-hydroxyethyl）oxamide（0） and N,N＇-bis（2-hydroxyet...A series of polyesteramide prepolymers[PrePEA（0/4,8）s] having mixed alternating bisesterdiamide units was synthesized via melt polycondensation from N,N＇-bis（2-hydroxyethyl）oxamide（0） and N,N＇-bis（2-hydroxyethyl）-adipamide（4） with sebacic acid（8） at different molar ratios.Chain extension of them was conducted with 2,2＇-（1,4-phenylene）-bis（2-oxazoline） and adipoyl biscaprolactamate as combined chain extenders.The chain extended polyesteramides[ExtPEA（0/4,8）s] were characterized by proton nuclear magnetic resonance（1H NMR）,gel permeation chromatography（GPC）,differential scanning calorimetry（DSC）,thermogravimetry analysis（TGA）,wide angle X-ray scattering,tensile test and enzymatic degradation.The results show that ExtPEA（0/4,8）s were crystalline polyesteramides.They had Tm up to 136.5 ℃ and initial decomposition temperature above 297.5 ℃.They crystallized in similar crystallites into Nylon-66 and degraded under the catalysis of protease or lipase.They are thermoplastic materials with tensile strength up to 21.5 MPa and elongation at break above 64.0％.展开更多
High molecular weight aliphatic segmented poly（ether ester amide）s（PEEAs） were synthesized via melt polycondensation and chain extension. An oligomeric polyamide（PA） terminated mainly with -COOH groups（HOOC-PA-...High molecular weight aliphatic segmented poly（ether ester amide）s（PEEAs） were synthesized via melt polycondensation and chain extension. An oligomeric polyamide（PA） terminated mainly with -COOH groups（HOOC-PA-COOH） was prepared from the reaction of nylon 610 salt with sebacic acid. Melt polycondensation of HOOC-PA-COOH with polyethylene glycol（PEG）, such as PEG400, PEG600, PEG1000 and PEG1500, was conducted at 200 ℃, and several segmented PEEA prepolymers（PrePEEAs） were prepared. Chain extension of PrePEEAs was carried out at 190 ℃ using 2,2＇-（1,4-phenylene）-bis（2-oxazoline） and adipoyl biscaprolactamate as combination chain extenders. Chain extended PEEAs（ExtPEEAs） were characterized by gel permeation chromatography（GPC）, Fourier transform infrared spectrophotometer（FTIR）, proton nuclear magnetic resonance（1H NMR）, differential scanning calorimetry（DSC）, wide angle X-ray scattering（WAXS）, thermogravimetry analysis（TGA）, and tensile test. The ExtPEEAs exhibited Mn up to 98700, Tm from 164.2 ℃ to 176.1 ℃, initial decomposition temperature above 320.6 ℃, tensile strength up to 34.80 MPa, and strain at break from 111.92% to 353.12%. Aliphatic segmented PEEAs with good thermal and mechanical properties were prepared.展开更多
基金the National Key Project for Fundamental Research, "Macromolecular Condensed State" of the State Science and Technology Commissi
文摘The recovery of amorphous PET fiber in global chain orientation but nearly random segmental orientation (GOLR) state was studied by the hot shrinkage measurement above the glass transition temperature. The relaxation curves in the form of di-exponential decay were acquired and the change of two special times with the variation of treating temperature and residual recovery ratio ' was discussed.
基金supported, in part, by the National Science Foundation of the United States (DMR-0821697, CMMI-0926522, DMR-1105135)
文摘This work extends our previous understanding concerning the nonlinear responses of entangled polymer solutions and melts to large external deformation in both simple shear and uniaxial extension. Many similarities have recently been identified for both step strain and startup continuous deformation, including elastic yielding, i.e., chain disentanglement after cessation of shear or extension, and emergence of a yield point during startup deformation that involves a deformation rate in excess of the dominant molecular relaxation rate. At a sufficiently high constant Hencky rate, uniaxial extension of an entangled melt is known to produce window-glass-like rupture. The present study provides evidence against the speculation that chain entanglements tie up into "dead knots" in constant-rate extension because of the exponentially growing chain stretching with time. In particular, it is shown that even Instron-style tensile stretching, i.e., extending a specimen by applying a constant velocity on both ends, results in rupture. Yet, in the same rate range, the same entangled melt only yields in simple shear, and the resulting shear banding is clearly not a characteristic of rupture. Thus, we conclude that chain entanglements respond to simple shear in the manner of yielding whereas uniaxial extension is rather effective in causing some entanglements to lock up, making it impossible for the entanglement network to yield at high rates.
文摘Distributed Lagrange Multiplier/Fictitious Domain （DLM/FD） method was employed to simulate the channel flow with polymer suspension. The polymer molecules were modeled as Finitely Extensible Nonlinear Elastic （FENE） chains and FENE chain cluster. The coiled stretched transition of FENE chains was examined and the change in configuration of FENE chains was presented. The average velocity profile of the fully developed channel flow with 64 FENE chains was given and fitted well with the power-law curve. The change of chain cluster configuration was also simulated. These simulations show that DLM/FD method is capable of simulating the motion of not only FENE chain, but also FENE chain cluster.
基金financially supported by the National Natural Science Foundation of China (Nos.50873013 and 21244006)
文摘Two kinds of aliphatic alternating polyesteramide prepolymers were prepared through melt polycondensation from N,N＇-bis（2-hydroxyethyl）-adipamide and adipic acid or sebacic acid. Chain extension of them was conducted with 2,2＇-（1,4- phenylene）-bis（2-oxazoline） and adipoyl biscaprolactamate as combined chain extenders. The chain extended polyesteramides （ExtPEAs） were characterized by IR, 1H-NMR, differential scanning calorimetry, thermogravimetric analysis, wide angle X-ray scattering, tensile test and enzymatic degradation. The results showed that the ExtPEA（4,m）s were mainly constituted with the diester adipamide alternating units. ExtPEA（4,4） and ExtPEA（4,8） had Tm of 83.8℃ and 85.8℃ and initial decomposition temperature above 310.0℃. They crystallized similarly as Nylon-66 did and were flexible thermoplastic materials with tensile strength up to 25.64 MPa and strain at break up to 737%.
基金Supported by the National Natural Science Foundation of China（Nos.50873013, 21244006）.
文摘A series of polyesteramide prepolymers[PrePEA（0/4,8）s] having mixed alternating bisesterdiamide units was synthesized via melt polycondensation from N,N＇-bis（2-hydroxyethyl）oxamide（0） and N,N＇-bis（2-hydroxyethyl）-adipamide（4） with sebacic acid（8） at different molar ratios.Chain extension of them was conducted with 2,2＇-（1,4-phenylene）-bis（2-oxazoline） and adipoyl biscaprolactamate as combined chain extenders.The chain extended polyesteramides[ExtPEA（0/4,8）s] were characterized by proton nuclear magnetic resonance（1H NMR）,gel permeation chromatography（GPC）,differential scanning calorimetry（DSC）,thermogravimetry analysis（TGA）,wide angle X-ray scattering,tensile test and enzymatic degradation.The results show that ExtPEA（0/4,8）s were crystalline polyesteramides.They had Tm up to 136.5 ℃ and initial decomposition temperature above 297.5 ℃.They crystallized in similar crystallites into Nylon-66 and degraded under the catalysis of protease or lipase.They are thermoplastic materials with tensile strength up to 21.5 MPa and elongation at break above 64.0％.
基金Supported by the National Natural Science Foundation of China（Nos.21244006, 50873013）.
文摘High molecular weight aliphatic segmented poly（ether ester amide）s（PEEAs） were synthesized via melt polycondensation and chain extension. An oligomeric polyamide（PA） terminated mainly with -COOH groups（HOOC-PA-COOH） was prepared from the reaction of nylon 610 salt with sebacic acid. Melt polycondensation of HOOC-PA-COOH with polyethylene glycol（PEG）, such as PEG400, PEG600, PEG1000 and PEG1500, was conducted at 200 ℃, and several segmented PEEA prepolymers（PrePEEAs） were prepared. Chain extension of PrePEEAs was carried out at 190 ℃ using 2,2＇-（1,4-phenylene）-bis（2-oxazoline） and adipoyl biscaprolactamate as combination chain extenders. Chain extended PEEAs（ExtPEEAs） were characterized by gel permeation chromatography（GPC）, Fourier transform infrared spectrophotometer（FTIR）, proton nuclear magnetic resonance（1H NMR）, differential scanning calorimetry（DSC）, wide angle X-ray scattering（WAXS）, thermogravimetry analysis（TGA）, and tensile test. The ExtPEEAs exhibited Mn up to 98700, Tm from 164.2 ℃ to 176.1 ℃, initial decomposition temperature above 320.6 ℃, tensile strength up to 34.80 MPa, and strain at break from 111.92% to 353.12%. Aliphatic segmented PEEAs with good thermal and mechanical properties were prepared.
