The wideline proton NMR spectra of polyethylene powder samples were analyzed in terms of contributions from three components： （1） a rigid part with immobile chains, （2） a soft region with liquid-like character wh...The wideline proton NMR spectra of polyethylene powder samples were analyzed in terms of contributions from three components： （1） a rigid part with immobile chains, （2） a soft region with liquid-like character which produces a Lorentzian contribution to the spectrum, and （3） an intermediate region in which the rotation of methylene groups about C-C bonds is partially hindered. The relative mass fractions as well as chain mobilities varied greatly among samples produced by different polymerization techniques. The NMR crystallinity agreed well with that estimated by WAXD and was much higher than DSC crystallinity, indicating an inclusion of the contribution from a crystalline-amorphous interphase. The crystalline defects in the rigid part could be significantly affected by processing parameters when employing the same type of polymerization technique. The intermediate region in the NMR spectra was analyzed according to the comparison between bimodal high density polyethylene and corresponding linear unimodal one. It was found that the mass fraction of the NMR interphase could be an indication of the percentage of tie molecules between crystalline lamellae and thus may significantly affect the mechanical properties of polymeric material.展开更多
The morphology of some polyetherester-ureas were studied by ^(13)C CP/MAS and ~1H wide-line NMR spectroscopy. It was found that the HDI and MDI based polymers have well crystallized hard segments, whereas the TDI and ...The morphology of some polyetherester-ureas were studied by ^(13)C CP/MAS and ~1H wide-line NMR spectroscopy. It was found that the HDI and MDI based polymers have well crystallized hard segments, whereas the TDI and HMDI based ones have not. For HDI/MDI based polymers, the presented results suggest that the distribution of two kinds of hard segment units is mainly in a block form. The influences of the different hard segment and chain length on the mobility of the soft segment were also studied.展开更多
NMR spectra acquired with experiments using frequency-sweeps such as the wide-band uniform-rate smooth truncation(WURST)spin-echo and Carr-Purcell-Meiboom-Gill(CPMG)sequences cannot be absorptively phased by using onl...NMR spectra acquired with experiments using frequency-sweeps such as the wide-band uniform-rate smooth truncation(WURST)spin-echo and Carr-Purcell-Meiboom-Gill(CPMG)sequences cannot be absorptively phased by using only conventional zerothand first-order phase correction.Implementation of phase correction up to the secondorder is described for obtaining absorptive spectra,which have more desirable line shapes and noise properties than magnitude spectra.The relationship of the second-order phase to the parameters of frequency sweeps is derived.The second-order phasing in the frequency-domain is equivalent to a point spread in the time-domain signal.The application of second-order phase correction is demonstrated with a wideline 35Cl CPMG spikelet spectrum.展开更多
基金Project supported by the National Natural Science Foundation of China （No. 20490205） and CSC-DAAD Collaboration Project （2004）.
文摘The wideline proton NMR spectra of polyethylene powder samples were analyzed in terms of contributions from three components： （1） a rigid part with immobile chains, （2） a soft region with liquid-like character which produces a Lorentzian contribution to the spectrum, and （3） an intermediate region in which the rotation of methylene groups about C-C bonds is partially hindered. The relative mass fractions as well as chain mobilities varied greatly among samples produced by different polymerization techniques. The NMR crystallinity agreed well with that estimated by WAXD and was much higher than DSC crystallinity, indicating an inclusion of the contribution from a crystalline-amorphous interphase. The crystalline defects in the rigid part could be significantly affected by processing parameters when employing the same type of polymerization technique. The intermediate region in the NMR spectra was analyzed according to the comparison between bimodal high density polyethylene and corresponding linear unimodal one. It was found that the mass fraction of the NMR interphase could be an indication of the percentage of tie molecules between crystalline lamellae and thus may significantly affect the mechanical properties of polymeric material.
文摘The morphology of some polyetherester-ureas were studied by ^(13)C CP/MAS and ~1H wide-line NMR spectroscopy. It was found that the HDI and MDI based polymers have well crystallized hard segments, whereas the TDI and HMDI based ones have not. For HDI/MDI based polymers, the presented results suggest that the distribution of two kinds of hard segment units is mainly in a block form. The influences of the different hard segment and chain length on the mobility of the soft segment were also studied.
基金the National High Magnetic Field Laboratory(NHMFL,USA)through NSF DMR-1644779 and the State of Florida.
文摘NMR spectra acquired with experiments using frequency-sweeps such as the wide-band uniform-rate smooth truncation(WURST)spin-echo and Carr-Purcell-Meiboom-Gill(CPMG)sequences cannot be absorptively phased by using only conventional zerothand first-order phase correction.Implementation of phase correction up to the secondorder is described for obtaining absorptive spectra,which have more desirable line shapes and noise properties than magnitude spectra.The relationship of the second-order phase to the parameters of frequency sweeps is derived.The second-order phasing in the frequency-domain is equivalent to a point spread in the time-domain signal.The application of second-order phase correction is demonstrated with a wideline 35Cl CPMG spikelet spectrum.
