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An advanced NMR protocol for the structural characterization of aluminophosphate glasses 总被引:1,自引:0,他引:1
In this work a combination of complementary advanced solid-state nuclear magnetic resonance (NMR) strategies is employed to analyse the network organization in aluminophosphate glasses to an unprecedented level of detailed insight. The combined results from MAS, MQMAS and (31)P-{(27)Al}-CP-heteronuclear correlation spectroscopy (HETCOR) NMR experiments allow for a detailed speciation of the different phosphate and aluminate species present in the glass. The interconnection of these local building units to an extended three-dimensional network is explored employing heteronuclear dipolar and scalar NMR approaches to quantify P-O-Al connectivity by (31)P{(27)Al}-heteronuclear multiple quantum coherence (HMQC), -rotational echo adiabatic passage double resonance (REAPDOR) and -HETCOR NMR as well as (27)Al{(31)P}-rotational echo double resonance (REDOR) NMR experiments, complemented by (31)P-2D-J-RESolved MAS NMR experiments to probe P-O-P connectivity utilizing the through bond scalar J-coupling. The combination of the results from the various NMR approaches enables us to not only quantify the phosphate units present in the glass but also to identify their respective structural environments within the three-dimensional network on a medium length scale employing a modified Q notation, Q(n)(m),(AlO)(x), where n denotes the number of connected tetrahedral phosphate, m gives the number of aluminate species connected to a central phosphate unit and x specifies the nature of the bonded aluminate species (i.e. 4, 5 or 6 coordinate aluminium). 相似文献
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O'Dell LA Gunawidjaja PN Holland MA Mountjoy G Pickup DM Newport RJ Smith ME 《Solid state nuclear magnetic resonance》2008,33(1-2):16-24
The HfO2-SiO2 system is attracting interest as a possible new dielectric material in semiconductor devices. Knowledge of the location of hafnium within the silica network and the effect hafnium has on the structure will be central to the successful use of this material system in this application. Here, sol-gel techniques have been used to manufacture (HfO2)x(SiO2)1-x samples (x=0.1, 0.2 and 0.4, each heat treated at 250, 500 and 750 degrees C) and these have been characterised by magic angle spinning (MAS) NMR (1H, 13C, 17 O, 29Si), Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis. 29Si MAS NMR showed that increasing the hafnia content decreases the connectivity of the silicate network, i.e. increases the range of differently connected SiO4 (Qn) units with more having increased numbers of non-bridging oxygens (i.e. lower n). FTIR and 17 O MAS NMR showed unequivocally that the x=0.4 sample phase-separated at higher temperatures, while in the x=0.1 sample the hafnium was homogeneously mixed into the SiO2 phase without any phase separation. 相似文献
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Gunawidjaja PN Holland MA Mountjoy G Pickup DM Newport RJ Smith ME 《Solid state nuclear magnetic resonance》2003,23(1-2):88-106
The effects of different heat treatment schemes (i.e. successively or directly heated to particular temperatures) and atmospheres (air or nitrogen) on the solid-state NMR spectra obtained from (TiO(2))(0.15)(ZrO(2))(0.05)(SiO(2))(0.80) sol-gel materials are investigated. A combination of 1H, 13C, 17O and 29Si NMR is used. 29Si MAS NMR indicates that the extent of condensation of the silica-based network strongly depends on the maximum temperature the sample has experienced, but the condensation is largely independent of the details of the heat treatment scheme and atmosphere used. For sol-gel produced silicate-based materials the results show that the equilibrium structure at each temperature is reached rapidly compared to the time (2h) spent at that temperature. The 17O NMR results confirm that a nitrogen atmosphere does significantly reduce loss of 17O from the structure but care must be taken since there could be differential loss of 17O from the regions having different local structural characteristics. 相似文献
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Using a multitude of modern solid-state NMR techniques including 11B-MQMAS-NMR, 11B-13C-REDOR NMR, 13C-11B-REAPDOR NMR, 15N-11B-REAPDOR NMR and 13C-2D-RFDR NMR experiments, the network organization in the quaternary high performance ceramic SiBN3C has been studied. Carbon is found to agglomerate into domains with predominant carbon-carbon bonding. The NMR results are compatible with carbon atoms involved in a graphite-like bonding scheme. The network adopted is quite similar to the corresponding one in the related ternary ceramic Si3B3N7, consisting of domains characterized by predominant Si-N bonding and domains of predominant B-N bonding with the carbon agglomerates located within the B-N domains of the network. The homogeneity with respect to the elemental distribution down to the nm regime, observed using electron spectroscopic imaging techniques puts an upper limit of ca. 1 nm to these agglomerates. 相似文献
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Drake KO Carta D Skipper LJ Sowrey FE Newport RJ Smith ME 《Solid state nuclear magnetic resonance》2005,27(1-2):28-36
Multinuclear 1H, 13C, 17O, 29Si MAS and 93Nb static NMR is reported from a series of sol-gel prepared (Nb2O5)x(SiO2)(1-x) materials with x=0.03, 0.075 or 0.30. 13C NMR shows that by 500 degrees C the organic precursor fragments have been removed although some residual carbon remains as a separate phase. The 29Si NMR typically shows three Q-species (Q2,3,4) in the initial gels, and that with increasing heat treatment the average n of the Qn-species increases as the organic fragments and hydroxyl groups are removed. 17O shows unequivocally that the x=0.03 and 0.075 samples are not phase separated, while at the much higher niobia-content of x=0.30 Nb-O-Nb signals are readily detected, a definite indication of the atomic scale phase separation of Nb2O5. The x=0.03 and 0.075 samples heated to 750 degrees C are thus representative of amorphous niobium silicates. Comparison is made to other sol-gel prepared metal silicates especially with another Group Va metal tantalum. The effects of tantalum and niobium on the silica network are very different and it is suggested here that most of the niobium is present as NbO4, forming part of the silicate network. 相似文献
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A combination of two-dimensional nuclear magnetic resonance (NMR) proton relaxometry and differential interference contrast
optical microscopy is used to compare the pore structures of hydroxyethyl methacrylate-based hydrogels used in conventional
contact lenses with three silicone hydrogels primarily developed for continuous-wear contact lenses. It is shown that both
types of hydrogel have a connected network of nanopores but that, in addition, the silicone hydrogels contain pores on the
micrometer scale that enhances their permeability. The potential of other two-dimensional NMR relaxation and diffusion methods
for detailed characterization of hydrogels is discussed. 相似文献
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An algorithm is presented for solving the structures of silicate network materials such as zeolites or layered silicates from solid-state 29Si double-quantum NMR data for situations in which the crystallographic space group is not known. The algorithm is explained and illustrated in detail using a hypothetical two-dimensional network structure as a working example. The algorithm involves an atom-by-atom structure building process in which candidate partial structures are evaluated according to their agreement with SiOSi connectivity information, symmetry restraints, and fits to 29Si double quantum NMR curves followed by minimization of a cost function that incorporates connectivity, symmetry, and quality of fit to the double quantum curves. The two-dimensional network material is successfully reconstructed from hypothetical NMR data that can be reasonably expected to be obtained for real samples. This advance in “NMR crystallography” is expected to be important for structure determination of partially ordered silicate materials for which diffraction provides very limited structural information. 相似文献
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Jian-Hua Ma Li-Qun Zhang You-Ping Wu 《Journal of Macromolecular Science: Physics》2013,52(8):1128-1141
For styrene-butadiene rubber (SBR) compounds filled with the same volume fraction of carbon black (CB), precipitated silica and carbon–silica dual phase filler (CSDPF), filler-rubber interactions were investigated thru bound rubber content (BRC) of the compounds and solid-state 1H low-field nuclear magnetic resonance (NMR) spectroscopy. The results indicated that the BRC of the compound was highly related to the amount of surface area for interaction between filler and rubber, while the solid-state 1H low-field NMR spectroscopy was an effective method to evaluate the intensity of filler-rubber interaction. The silica-filled compound showed the highest BRC, whereas the CB-filled compound had the strongest filler-rubber interfacial interaction, verified by NMR transverse relaxation. The strain sweep measurements of the compounds were conducted thru a rubber process analyzer; the results showed that the CSDPF-filled compound presented the lowest Payne effect, which is mainly related to the weakened filler network structure in polymer matrix. The temperature sweep measurement, tested by dynamic mechanical thermal analysis, indicated that the glass transition temperature did not change when SBR was filled with different fillers, whereas the storage modulus in rubbery state and the tanδ peak height were greatly affected by the filler network structure of composites. 相似文献
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综合采用红外光谱(FTIR)、核磁碳谱 (13C NMR)、差示扫描量热(DSC),热失重测试(TGA)等多种表征手段,研究了聚硅芳炔(PAR)和聚硅乙炔(PMR)两种含硅炔基树脂的固化行为,讨论了树脂固化物的结构与热稳定性的关系。结果表明:PAR和PMR树脂的固化机理不同,PAR主要通过炔基间的加成和Diels-Alder反应实现分子间的固化交联,并最终形成由苯环和稠芳环组成的芳构网络;PMR则主要通过硅氢基、炔基、烯基之间的加成反应实现固化,并成形饱和的碳硅Si—C(sp3)网络结构。固化成型的芳构网络和Si—C(sp3)网络结构分别赋予了PAR和PMR树脂固化物良好的热稳定性能,它们的热分解温度Td5均大于600 ℃,900 ℃残重率均达到85%以上。 相似文献
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Chekmenev EY Hu J Gor'kov PL Brey WW Cross TA Ruuge A Smirnov AI 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2005,173(2):322-327
This communication reports the first example of a high resolution solid-state 15N 2D PISEMA NMR spectrum of a transmembrane peptide aligned using hydrated cylindrical lipid bilayers formed inside nanoporous anodic aluminum oxide (AAO) substrates. The transmembrane domain SSDPLVVA(A-15N)SIIGILHLILWILDRL of M2 protein from influenza A virus was reconstituted in hydrated 1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine bilayers that were macroscopically aligned by a conventional micro slide glass support or by the AAO nanoporous substrate. 15N and 31P NMR spectra demonstrate that both the phospholipids and the protein transmembrane domain are uniformly aligned in the nanopores. Importantly, nanoporous AAO substrates may offer several advantages for membrane protein alignment in solid-state NMR studies compared to conventional methods. Specifically, higher thermal conductivity of aluminum oxide is expected to suppress thermal gradients associated with inhomogeneous radio frequency heating. Another important advantage of the nanoporous AAO substrate is its excellent accessibility to the bilayer surface for exposure to solute molecules. Such high accessibility achieved through the substrate nanochannel network could facilitate a wide range of structure-function studies of membrane proteins by solid-state NMR. 相似文献
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Proton nuclear magnetic resonance (NMR) magnetization exchange is used to investigate residual dipolar couplings in a series of cross-linked poly(styrene-cobutadiene) elastomers. A new model for the dipolar unit is used for the evaluation of the signal decay in magnetization exchange experiments. It takes into account an extended residual dipolar coupling network along the polymer chain. It is shown that in the regime of short mixing times, information about the residual dipolar coupling between methine and methylene protons can be obtained which is not affected by other inter- and intramolecular dipolar couplings. The dynamic order parameter of methine-methylene protons is measured and correlated with cross-link density. This study certifies the quality of a filter for magnetization from residual dipolar couplings which exploit magnetization exchange. The filter can be used to generate contrast in NMR images of heterogeneous elastomers. The first proton NMR parameter image of a dynamic order parameter is presented for a phantom made from poly(styrene-cobutadiene) samples with different cross-link densities. 相似文献
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介绍一体化核磁共振波谱仪梯度-场频联锁-匀场系统的设计方案. 该方案使用嵌入式以太网、FPGA(Field Programmable Gate Array,现场可编程门阵列)、EMI(External Memory Interface, 外部存储器接口)和高速串行总线等技术构建了基于以太网的通信系统和使用并行运算的控制系统, 并具备CAN(Controller Area Network,控制器局域网)总线通信的能力. 梯度放大器通过LVDS(Low-Voltage Differential Signaling,低压差分信号传输)接口与主控系统的梯度波形发生器连接,实现与谱仪工作站的交互. 系统采用插板式结构和通用性电路的设计方法,具有很好的扩展能力和适应性,能够满足不同谱仪的需求. 系统在11.7 T(500 MHz)NMR系统中进行了有效的锁场、匀场和梯度特性的测试,证明了该方案的可行性. 相似文献
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Yung KT 《Magnetic resonance imaging》2003,21(2):135-144
Gels consist of crosslinked polymer network swollen in solvent. The network of flexible long-chain molecules traps the liquid medium they are immersed in. Some gels undergo abrupt volume change, a phase transition process, by swelling-shrinking in response to external stimuli changes in solvent composition, temperature, pH, electric field, etc. We report that during volume phase transition changes of NMR longitudinal relaxation time T(1), NMR transverse relaxation time T(2), and diffusion coefficient D of the PMMA gel, and D of the NIPA gel. We describe how the gels were synthesized and the reason of using the snapshot FLASH imaging sequence to measure T(1), T(2), and D. Since T(1), T(2) and D maps have identical field of view and data are extracted from identical areas from their respective maps, these values can be correlated quantitatively on a pixel-by-pixel basis. Thus a complete set of NMR parameters is measured in-situ: the gels are in their natural state, immersed in the liquid, during the phase transition. The results of spectroscopic method agree with that of snapshot FLASH imaging method. For the PMMA gel T(1), T(2) and D decrease when gels undergo volume phase transition between deuterated acetone concentration of 30% and 40%. At its contracted state, T(1) is reduced to a little less than one order of magnitude, T(2) over two orders of magnitude, and D over one order of magnitude, smaller from values of PMMA gel at the swollen state. At an elevated temperature of 54 degrees C the thermosensitive NIPA gel is at a contracted state, with its D reduced to almost one order of magnitude smaller from that of the swollen NIPA at room temperature. 相似文献
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The COmponent-REsolved (CORE) strategy has been employed, for the first time to solid state NMR spectroscopy. CORE was used to extract two time-dependent spectral components in 24 29Si{1H} NMR spectra, recorded on a meso-structured silica material under conditions of cross polarization evolution. No prior assumptions were made about the component bandshapes, which were both found to be skewed to higher chemical shifts. For the silica fragments close to protons this skewness could be rationalized by a distribution of the degree of condensation in the silica network; however, for the other component the non-Gaussian shape was unexpected. We expect that the same strategy could be applied to a range of experiments in solid-state NMR spectroscopy, where spectral distributions or kinetic parameters need to be accurately extracted. 相似文献
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Li-Min Zhao 《Journal of luminescence》2006,118(2):317-324
A new monomer, TBBA-APMES, has been synthesized by grafting 3-aminopropyl-methyl-diethoxylsiliane (APMES) to 4-tert-butylbenzoic acid (TBBA) and characterized by H NMR, C NMR and Fourier transform infrared (FT-IR). The monomer acts as a functional ligand for Tb and La ion and as a sol-gel precursor. Luminescent hybrid materials consisting of terbium-lanthanum complex covalently bonded to a silica-based network have been obtained in situ via a sol-gel approach. Through the co-hydrolysis and polycondensation, Tb3+ and La3+ can be introduced in the same molecular hybrids through the chemical Si-O network and fluorescent enhancement is observed. The luminescent behavior has been studied with the different ratios of Tb3+-La3+, suggesting that the luminescence intensities of hybrids can be enhanced obviously by the existence of La3+. The enhanced fluorescence effect may be due to the strengthening of intramolecular energy transfer efficiency by La3+. 相似文献