共查询到20条相似文献,搜索用时 15 毫秒
1.
Kropewnicki ML Schaefer DJ Hehn M Dermaut W Geise HJ Chmelka BF 《Solid state nuclear magnetic resonance》2002,22(2-3):275-297
The properties of poly(p-phenylene vinylene) (PPV) films depend on the degree of orientational order present in the films. Recently, Dermaut et al. reported a novel cold-stretching technique (Macromolecules 33, 5634-5637 (2000)) in which chain alignment can be introduced into PPV precursor films by uniaxially stretching them prior to the thermal elimination reaction that forms PPV. The two-dimensional direction exchange with correlation for orientation-distribution evaluation and reconstruction (DECODER) 13C NMR technique was applied to both unstretched PPV films and PPV films that were uniaxially cold stretched to a draw ratio lambda = l/l0 = 5. The unstretched films were found to be moderately ordered, comprised of a component present at 80% with a Gaussian distribution of 60 degrees fwhm, while the remaining 20% is isotropically distributed. A distribution of 9 degrees +/- 3 degrees fwhm was measured by NMR in good agreement with IR dichroism measurements for the uniaxially cold-stretched films, establishing that a high degree of orientational order can be introduced by cold stretching PPV films. 相似文献
2.
将纳米碳化硅填加到硅橡胶中,可以获得具有非线性电导特性的纳米碳化硅/硅橡胶复合物. 本文研究了质量分数分别为5 wt%,15 wt%,30 wt%,45 wt%的纳米碳化硅/硅橡胶复合物的非线性电导特性,建立了电导率与场强的函数关系,分析了复合物的非线性电导机理,并测试了复合物的介电谱特性和击穿特性. 为了探讨非线性碳化硅/硅橡胶复合物应用于电缆终端和复合绝缘子以均匀其电场分布的可能性,应用COMSOL Multiphysics软件,对电缆终端和复合绝缘子中的电场分布进行了仿真分析. 仿真结果表明,将纳米碳化硅/硅橡胶复合物应用于电缆终端应力锥的绝缘部分,以及应用于复合绝缘子的端部,可以有效地降低其最大场强.
关键词:
纳米碳化硅/硅橡胶复合物
非线性电导特性
电场仿真 相似文献
3.
Uzi Eliav Christoph Naumann Gil Navon Philip W. Kuchel 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2009,198(2):197-203
The 2H NMR spectrum of HDO in gelatin gel, that is stretched inside silicone rubber tubing, displays a well resolved doublet. Spectra were obtained with a range of offset frequencies of partially saturating radio-frequency (RF) radiation. The resulting steady-state irradiation envelope (also referred to as a ‘z-spectrum’) has the peculiar feature that maximal suppression of the doublet occurs when the irradiation is applied exactly at the centre frequency, between the two HDO peaks. We present a quantum mechanical explanation for this phenomenon. It is shown that the phenomenon is the result of double quantum transitions. The analysis is extendable to more complex quadrupolar and dipolar-coupled systems of other nuclides. It has implications for enhancement of contrast in magnetic resonance imaging of heterogeneous systems using dipolar and quadrupolar interactions. 相似文献
4.
The relaxation times of the 1H and 133Cs nuclei in CsH3(SeO3)2 crystals were investigated using FT NMR. The 133Cs spectrum does change from seven resonance lines to one resonance line near Tm (=350 K). The presence of only one 133Cs signal is due to the liquid state resulting from the melting of the crystal. The variation in the separation of the 133Cs resonance lines with temperature indicates that the EFG at the Cs sites produced by the (SeO3)2− groups varies with temperature, which in turn means that the atoms neighboring 133Cs are displaced. And, the T1 for 133Cs is very long and undergoes significant changes near Tm. The change in the temperature dependence of T1 at Tm for the 133Cs nuclei coincides with the melting temperature. These results are compared with those obtained for MH3(SeO3)2 (M=Na, K, and Cs) crystals. 相似文献
5.
133Cs (I=7/2) nuclear magnetic resonance in a Cs2CuCl4 single crystal grown by using the slow evaporation method was measured in its three mutually perpendicular crystal planes. The 133Cs resonances of two different groups with two crystallographically inequivalent cesium nuclei, Cs(I) and Cs(II), in the unit cell were recorded. The transferred hyperfine fields for Cs(I) and Cs(II) calculated from the paramagnetic shift and the molecular susceptibility measurements could be expressed by the linear equation Hhf=AT+B. The angular dependence of the 133Cs nuclear magnetic resonance spectra showed that the Cs(I) and the Cs(II) nuclei had different values for the quadrupole coupling constant. The electric field gradient tensors of Cs(I) and Cs(II) were symmetric, and the orientations of their principal axes did not coincide. The Cs(I) ion surrounded by 11 chlorine ions had a small quadrupole parameter, a smaller charge distribution, and a small value for the transferred hyperfine field. However, the Cs(II) ion surrounded by nine chlorine ions had a larger quadrupole parameter, a larger charge distribution, and a larger value for the transferred hyperfine field. 相似文献
6.
C Srinivasan N Minadeo J Toon D Graham D Mota de Freitas C F Geraldes 《Journal of magnetic resonance (San Diego, Calif. : 1997)》1999,140(1):206-217
Evidence for competition between Li(+) and Na(+) for binding sites of human unsealed and cytoskeleton-depleted human red blood cell (csdRBC) membranes was obtained from the effect of added Li(+) upon the (23)Na double quantum filtered (DQF) and triple quantum filtered (TQF) NMR signals of Na(+)-containing red blood cell (RBC) membrane suspensions. We found that, at low ionic strength, the observed quenching effect of Li(+) on the (23)Na TQF and DQF signal intensity probed Li(+)/Na(+) competition for isotropic binding sites only. Membrane cytoskeleton depletion significantly decreased the isotropic signal intensity, strongly affecting the binding of Na(+) to isotropic membrane sites, but had no effect on Li(+)/Na(+) competition for those sites. Through the observed (23)Na DQF NMR spectra, which allow probing of both isotropic and anisotropic Na(+) motion, we found anisotropic membrane binding sites for Na(+) when the total ionic strength was higher than 40 mM. This is a consequence of ionic strength effects on the conformation of the cytoskeleton, in particular on the dimer-tetramer equilibrium of spectrin. The determinant involvement of the cytoskeleton in the anisotropy of Na(+) motion at the membrane surface was demonstrated by the isotropy of the DQF spectra of csdRBC membranes even at high ionic strength. Li(+) addition initially quenched the isotropic signal the most, indicating preferential Li(+)/Na(+) competition for the isotropic membrane sites. High ionic strength also increased the intensity of the anisotropic signal, due to its effect on the restructuring of the membrane cytoskeleton. Further Li(+) addition competed with Na(+) for those sites, quenching the anisotropic signal. (7)Li T(1) relaxation data for Li(+)-containing suspensions of unsealed and csdRBC membranes, in the absence and presence of Na(+) at low ionic strength, showed that cytoskeleton depletion does not affect the affinity of Na(+) for the RBC membrane, but increases the affinity of Li(+) by 50%. This clearly indicates that cytoskeleton depletion favors Li(+) relative to Na(+) binding, and thus Li(+)/Na(+) competition for its isotropic sites. Thus, this relaxation technique proves to be very sensitive to alkali metal binding to the membrane, detecting a more pronounced steric hindrance effect of the cytoskeleton network to binding of the larger hydrated Li(+) ion to the membrane phosphate groups. 相似文献
7.
Single-side NMR is particularly suitable for measurements of segmental anisotropy induced in elastomers by uniaxial forces or local strain. Proton transverse nuclear magnetic relaxation was investigated with the NMR-MOUSE by recording the Hahn-echo decay in cross-linked natural rubber bands. This provided information on the dependence of the Hahn-echo decay on the angle between the direction of the uniaxial stretching force and the axis Z defined direction perpendicular to the magnet pole faces of the NMR-scanner. The anisotropy effect on the Hahn-echo decay is correlated with the extension ratio, and it is more evident in the liquid-like regime of the decay. A weaker segmental anisotropy is detected by 1H solid- and Hahn-echo decays recorded by multi-pulse sequences. A qualitative understanding of the angular dependence is obtained by an analytical theory of the Hahn-echo decay adapted to the case of stretched elastomers and to strongly inhomogeneous magnetic fields. Using angular-dependent 1H residual second van Vleck moments and correlation times reported previously [P.T. Callaghan and E.T. Samulski, Macromolecules 30, 113 (1997)] from stretched natural rubber bands the segmental anisotropy measured in inhomogeneous magnetic fields by the Hahn-echo decay was numerically simulated. As an example of a macroscopic distribution of local segmental anisotropy, 1H Hahn-echo decays were measured by the NMR-MOUSE sensor in a stretched cross-linked natural rubber plate with a circular cut in the center. 相似文献
8.
《Journal of Physics and Chemistry of Solids》2003,64(6):933-937
The rotation patterns of the 133Cs (I=7/2) nuclear magnetic resonance (NMR) in a Cs2ZnCl4 single crystal grown by using the slow evaporation method were measured in two mutually perpendicular crystal planes. Two different groups of Cs resonances were recorded; this result points to the existence of two types of crystallographically inequivalent Cs(I) and Cs(II). The angular dependences of the NMR spectra led to different values for the quadrupole coupling constants and asymmetry parameters: e2qQ/h=148 kHz and η=0.11 for the Cs(I) ion, and e2qQ/h=274 kHz and η=0.66 for the Cs(II) ion. The EFG tensors of Cs(I) and Cs(II) are asymmetric, and the orientations of the principal axes of the EFG tensors do not coincide. Only, the principal Y-axes of the EFG tensors coincide for the Cs(I) and Cs(II) sites. The Cs(I) ion is surrounded by 11 chlorine ions, making it rather free and high in symmetry. The Cs(II) ion has only nine neighbors and seems to be more tight than the Cs(I) ion. 相似文献
9.
Through 13C NMR spin lattice relaxation ( T1) measurements in cubic Na2C60, we detect a gap in its electronic excitations, similar to that observed in tetragonal A4C60. This establishes that Jahn-Teller distortions (JTD) and strong electronic correlations must be considered to understand the behavior of even electron systems, regardless of the structure. Furthermore, in metallic Na2CsC60, a similar contribution to T1 is also detected for 13C and 133Cs NMR, implying the occurrence of excitations typical of JT distorted C( 2-)60 (or equivalently C( 4-)60). This supports the idea that dynamic JTD can induce attractive electronic interactions in odd electron systems. 相似文献
10.
Rotational-echo double-resonance NMR is used to probe the proximity of Cs+ network modifiers to network-forming boron in binary cesium borate glasses. Low- and high-alkali glasses show distinctly different dephasing curves, which indicate preferential association of Cs+ with four-co-ordinate boron ([4]degrees )B) at low-alkali contents only. Different [4]B sites within a given glass appear to be subject to the same 133Cs dipolar field, thus placing constraints on the possible assignments of multiple tetrahedral boron peaks to different types of medium-range order and guiding future structural modeling studies. 相似文献
11.
The structure of a sulfonated polyimide (sPI) ionomer membranes was investigated via the transport properties of various confined cations (7Li+, 23Na+, 87Rb+, 133Cs+). Their NMR spectra show large residual quadrupolar splitting depending on the orientation of the film in the static magnetic field B0. This behavior is the fingerprint of a macroscopic nematic ordering of charged interfaces. This is also confirmed by the anisotropy of the self-diffusion tensor measured by 1H and 7Li PGSE experiments on N(CH3)4+ and Li+ cations, respectively. 相似文献
12.
The paper presents the experimental results of research on the effect of an external DC electric field on the coefficient of friction of silicone rubber (elastomer) during its rubbing against a steel surface in the „pin–on–disc” experimental set-up. In the tests there were used silicone rubber samples, the pure PAG and PAO synthetic base oils and their blends with an antiwear (ZDDP) additive. The coefficient of friction μ was determined under conditions with and without an external DC electric field. A DC electric field was generated between a silicone rubber sample and a rotating steel disc (a friction pair). A sample holder was electrically isolated from other metal parts of a tribometer and was connected to one of the poles of a DC power supply, while the other pole was connected by means of the carbon brushes to a rotating steel disc. The experimental results show that the external DC electric field established between the rotating steel disc and a silicone rubber sample causes the coefficient of friction to decrease. It was also found that the coefficient of friction μ depends on the steel disc's angular velocity n, the contact pressure p, and the type of base oil and its blends with the additive used. 相似文献
13.
The (1)H NMR spectrum of glycine in stretched gelatin gel and in cromolyn liquid crystal displays a well-resolved doublet due to (1)H-(1)H dipolar interaction. Multiple spectra were obtained within a wide range of offset frequencies of partially saturating radio-frequency (RF) radiation to generate steady-state irradiation envelopes or z-spectra of glycine. Maximal suppression of the doublet occurred when the irradiation was applied exactly at the centre frequency, between the two glycine peaks. This phenomenon is due to double-quantum transitions and is similar to our previous work on quadrupolar nuclei (2)H (HDO) and (23)Na(+). When the (13)C isotopomer glycine-2-(13)C was used, the same effect was found in twice, split by (1)J(CH)+2D(CH). Additional signals in (1)H and (13)C NMR due to prochiral-chiral interactions were found when glycine-2-(13)C was dissolved in chiral anisotropic gelatin and κ-carrageenan gels. The NMR spectra were successfully simulated assuming a (2)J(HH) coupling constant of -16.5Hz and two distinct dipolar coupling constants for the -(13)CH(2)- group (D(C,HA), and D(C,HB)). 相似文献
14.
探讨可能用作燃料电池固体酸电解质的化合物CsH2PO4 (CDP)和CsH5(PO4)2(CPDP)的制备. CDP和CPDP混合物由摩尔比1∶4的Cs2CO3∶H3PO4水溶液结晶而成,而CDP和Cs2HPO4·1.5H2O (H-DCHP)混合物依其摩尔比1∶2的水溶液制备. 甲醇清洗能最有效地将CDP从其混合物中分离出来. CDP、CPDP以及H-DCHP的133Cs 和31P 魔角旋转谱以及CPDP和H-DCHP的1H魔角旋转谱均为首次报道,对各化合物的谱峰做了指认. 说明,透过确认合成的电解质以及合成过程所产生的副产物,多核固体核磁共振对于控制固体酸电解质合成的品质是一个非常有用的工具. 相似文献
15.
导电炭黑/硅橡胶复合材料介电常数与压应力的关系 总被引:1,自引:0,他引:1
以填充了导电炭黑的导电硅橡胶和绝缘硅橡胶为主体材料,分别采用质量比1:9;3:7配比进行混炼、制备,研究了压力下复合材料的介电特性.实验结果表明:在恒压下样品介电常数实部ε’随外加电场频率的增加而减小;在恒压、同频率时导电硅胶含量大的样品介电常数大;在同频率时,增大压应力,样品介电常数实部ε’都会增加,导电硅胶含量大,增幅大. 相似文献
16.
Satoru Takani 《Journal of Macromolecular Science: Physics》2016,55(9):955-967
A counterion-specific coil-globule transition (CGT) has been observed for alkali metal poly(acrylate)s (PAAM, M; Li, Na, K, Cs) in aqueous organic solvent (ethanol, dimethyl sulfoxide, acetone, acetonitrile) mixtures. In the present study we found that the reduced viscosity of PAAM, except for PAALi, in the relevant mixed solvents, except for those containing acetonitrile, significantly increased with increasing temperature. The observed temperature-induced CGT was interpreted as being caused by disintegration of the ion-clusters, i.e., the associated state of contact ion-pairs formed between the polymer charge and the counterion. In fact, the NMR line width of 23Na and 133Cs, which were used as a measure of the counterion mobility, indicated that the counterion binding was significantly weakened with increasing temperature, while the temperature effects for the PAALi and acetonitrile systems were only marginal. All these results suggested that the temperature-induced CGT behavior occurs only for systems where the ion-cluster formation promotes the CGT in the relevant solvent systems, which is also consistent with the known similar behavior of some betaine polymers. 相似文献
17.
R. D. Nevmyvako N. A. Zhuravlev T. A. Denisova Yu. M. Kadyrova K. N. Mikhalev E. G. Khaikina S. F. Solodovnikov 《Bulletin of the Russian Academy of Sciences: Physics》2014,78(4):264-266
Nuclear magnetic resonance (magic angle spinning) spectra of 7Li, 27Al, 87Rb, and 133Cs nuclei are measured in Li2 M 3Al(MoO4)4 triple molybdates (M = Rb, Cs) for the first time. Analysis of the nuclear magnetic resonance spectra reveal considerable asymmetry in the distribution of the electric charge throughout the crystal lattices of the compounds. 相似文献
18.
The 2H NMR resonance from HDO (D=2H) in human red blood cells (RBCs) suspended in gelatin that was held stretched in a special apparatus was distinct from the two signals that were symmetrically arranged on either side of it, which were assigned to extracellular HDO. The large extracellular splitting is due to the interaction of the electric quadrupole moment of the 2H nuclei with the electric field gradient tensor of the stretched, partially aligned gelatin. Lack of resolved splitting of the intracellular resonance indicated greatly diminished or absent ordering of the HDO inside RBCs. The separate resonances enabled the application of a saturation transfer method to estimate the rate constants of transmembrane exchange of water in RBCs. However both the theory and the practical applications needed modifications because even in the absence of RBCs the HDO resonances were maximally suppressed when the saturating radio-frequency radiation was applied exactly at the central frequency between the two resonances of the quadrupolar HDO doublet. More statistically robust estimates of the exchange rate constants were obtained by applying two-dimensional exchange spectroscopy (2D EXSY), with back-transformation analysis. A monotonic dependence of the estimates of the efflux rate constants on the mixing time, tmix, used in the 2D EXSY experiment were seen. Extrapolation to tmix=0, gave an estimate of the efflux rate constant at 15 degrees C of 31.5+/-2.2 s(-1) while at 25 degrees C it was approximately 50 s(-1). These values are close to, but less than, those estimated by an NMR relaxation-enhancement method that uses Mn2+ doping of the extracellular medium. The basis for this difference is thought to include the high viscosity of the extracellular gel. At the abstract level of quantum mechanics we have used the quadrupolar Hamiltonian to provide chemical shift separation between signals from spin populations across cell membranes; this is the first time, to our knowledge, that this has been achieved. 相似文献
19.
溶液阴极辉光放电-原子发射光谱法是近年来兴起的一种新型水体金属离子检测技术,它具有快速,在线和低成本检测的显著特点。以工业注射泵实现溶液阴极辉光放电激发源的流动注射进样,再以窄带滤光片分别提取Na,K,Ca,Li,Sr和Cs金属元素发射光谱信号,最后由光电倍增管和皮安表接收光谱信息光谱信号,实现了水质金属元素的检测。实验分析了注射容量分别为100和166 μL对1 mg·L-1的Na元素产生的信号强度的影响,研究发现其信号强度的相对标准偏差(RSD)分别为4.64%和1.95%,说明两种注射量稳定性都较好。为了获得更好的分析性能,实验分析了直流放电电压,狭缝的宽度以及光电倍增管供压等参数对信号强度的影响。实验结果表明,在直流放电电压为1 000 V,狭缝宽度为70 μm和光电倍增管供压为-800 V时获得了较高的信背比。采用此装置在流动注射模式下,测得了Na,K,Ca,Li,Sr和Cs六种金属元素检出限,分别为2.78,4.23,589,9.45,981和83.6 μg·L-1。实验最后对混合溶液标定物质中的Na和K元素进行了定量分析测量,测量的误差分别为7.5%和6.67%,精密度分别为1.24%和0.89%,研究结果表明基于滤光片提取光谱的流动注射分析-溶液阴极辉光放电-原子发射光谱方法具有较高的检测准确度。 相似文献
20.
Shapiro EM Borthakur A Bansal N Leigh JS Reddy R 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2000,143(1):213-216
We describe the characterization of a (23)Na temperature-dependent chemical shift and relaxation rates in the complex, Na(4)HTm[DOTP]. This is the first characterization of a (23)Na temperature-dependent chemical shift in a nonmetallic sample. The (23)Na temperature-dependent chemical shift coefficient is approximately -0. 5 PPM/ degrees C for both an aqueous solution and a 6% agarose gel of this compound. This is 50 times the magnitude of the temperature-dependent chemical shift coefficient of water protons. The relaxation times, T(1), T(2f), and T(2s) increased by 0.1, 0.01, and 0.05 ms/ degrees C, respectively. Applications of these unique properties for designing an MRI technique for monitoring heat deposition in tissue and tissue phantoms are discussed. 相似文献