The (29)Si T(1) and T(2) NMR relaxation in porous paramagnetic material SiO(2)-MnO-Al(2)O(3)

The (29)Si spin-lattice relaxation in porous silica-based material 1, doped by ions Mn(2+) at a Si/Mn ratio of 3.5, is non-exponential, independent of magic-angle spinning (MAS) rates and governed by direct dipolar coupling between electron and nucleus where an electron relaxation time is estimated to be about 10(-8)s. In the absence of mutual energy-conserving spin flips (spin diffusion) in 1, the (29)Si T(2) time increases linearly with spinning rates. None was observed in diamagnetic porous system 2. The unexpected (29)Si T(2) dependence has been interpreted in terms of the large bulk magnetic susceptibility (BMS) effects. It has been shown that editing the (29)Si Hahn-echo MAS NMR spectra eliminates wide lines, belonging to (29)Si nuclei in the proximity of paramagnetic centers, and reduces the BMS broadenings in sideband patterns for nuclei remote from these centers.     

Phosphorus donors in highly strained silicon

The hyperfine interaction of phosphorus donors in fully strained Si thin films grown on virtual Si(1-x)Ge(x) substrates with x< or =0.3 is determined via electrically detected magnetic resonance. For highly strained epilayers, hyperfine interactions as low as 0.8 mT are observed, significantly below the limit predicted by valley repopulation. Within a Green's function approach, density functional theory shows that the additional reduction is caused by the volume increase of the unit cell and a relaxation of the Si ligands of the donor.     

Nuclear spin resonance of (129)Xe doped with O(2)

Spin-lattice relaxation of (129)Xe nuclei in solid natural xenon has been investigated in detail over a large range of paramagnetic O(2) impurity concentrations. Direct measurements of the ground state magnetic properties of the O(2) are difficult because the ESR (electron spin resonance) lines of O(2) are rather unstructured, but NMR measurements in the liquid helium temperature region (1.4-4 K) are very sensitive to the effective magnetic moments associated with the spin 1 Zeeman levels of the O(2) molecules and to the O(2) magnetic relaxation. From these measurements, the value of the D[Sz(2)-(1/3)S(2)] spin-Hamiltonian term of the triplet spin ground state of O(2) can be determined. The temperature and magnetic field dependence of the measured paramagnetic O(2)-induced excess line width of the (129)Xe NMR signal agree well with the theoretical model with the spin-Hamiltonian D=0.19 meV (2.3 K), and with the reasonable assumption that the E[S(x)(2)-S(y)(2)] spin-Hamiltonian term is close to 0 meV. An anomalous temperature dependence between 1.4 K and 4.2K of the (129)Xe spin-lattice relaxation rate, T(1n)(-1)(T), is also accounted for by our model. Using an independent determination of the true O(2) concentration in the Xe-O(2) solid, the effective spin lattice relaxation time (which will be seen to be transition dependent) of the O(2) at 2.3 K and 0.96 T is determined to be approximately 1.4 x 10(-8)s. The experimental results, taken together with the relaxation model, suggest routes for bringing highly spin-polarized (129)Xe from the low temperature condensed phase to higher temperatures without excessive depolarization.     

水驱油过程的核磁共振二维谱研究

岩心水驱油过程中油水分布状况是岩心多孔介质的重要性质. 水驱油过程的研究是进一步进行提高采收率研究的基础. 核磁共振扩散-弛豫二维谱提供了岩心中流体性质的多方面信息,与核磁共振一维弛豫谱相比极大地提高了区分油水的能力. 该文通过2组岩心水驱油实验,从不同含油饱和度的扩散-弛豫二维谱中提取出水的一维弛豫谱,在原油粘度比较高的情况下获得了驱替过程中油水在不同孔隙中的分布状况以及润湿性等信息, 解决了单独用一维弛豫谱方法难以区分油水的问题. 该文的研究方法对油田提高采收率的研究有比较大的参考价值.     

Characterisation of sol-gel prepared (HfO2)x(SiO2)1-x (x=0.1, 0.2 and 0.4) by 1H, 13C, 17 O and 29Si MAS NMR, FTIR and TGA

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.     

A multinuclear solid state NMR study of the sol-gel formation of amorphous Nb2O5-SiO2 materials

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.     

Hysteresis phenomena in charging of Si Mosfet in quantizing magnetic field

We report the observation of nonequilibrium processes of charging in 2D electron layer in Si MOSFET. There were investigated the hysteresis variations of a 2D-layer charge Q_S with a gate voltage V_g or with a magnetic field H, and the hysteresis of a gate potential U_g vs magnetic field at Q_S = Const. At sufficiently low temperature T < 1K the relaxation time of a nonequilibrium state is much higher than 10³ sec. The observed phenomena may be explained qualitatively in frame of a surface potential randomness conception.     

A novel improved method for analysis of 2D diffusion-relaxation data--2D PARAFAC-Laplace decomposition

This paper demonstrates how the multi-linear PARAFAC model can with advantage be used to decompose 2D diffusion-relaxation correlation NMR spectra prior to 2D-Laplace inversion to the T(2)-D domain. The decomposition is advantageous for better interpretation of the complex correlation maps as well as for the quantification of extracted T(2)-D components. To demonstrate the new method seventeen mixtures of wheat flour, starch, gluten, oil and water were prepared and measured with a 300 MHz nuclear magnetic resonance (NMR) spectrometer using a pulsed gradient stimulated echo (PGSTE) pulse sequence followed by a Carr-Purcell-Meiboom-Gill (CPMG) pulse echo train. By varying the gradient strength, 2D diffusion-relaxation data were recorded for each sample. From these double exponentially decaying relaxation data the PARAFAC algorithm extracted two unique diffusion-relaxation components, explaining 99.8% of the variation in the data set. These two components were subsequently transformed to the T(2)-D domain using 2D-inverse Laplace transformation and quantitatively assigned to the oil and water components of the samples. The oil component was one distinct distribution with peak intensity at D=3 x 10(-12) m(2) s(-1) and T(2)=180 ms. The water component consisted of two broad populations of water molecules with diffusion coefficients and relaxation times centered around correlation pairs: D=10(-9) m(2) s(-1), T(2)=10 ms and D=3 x 10(-13) m(2) s(-1), T(2)=13 ms. Small spurious peaks observed in the inverse Laplace transformation of original complex data were effectively filtered by the PARAFAC decomposition and thus considered artefacts from the complex Laplace transformation. The oil-to-water ratio determined by PARAFAC followed by 2D-Laplace inversion was perfectly correlated with known oil-to-water ratio of the samples. The new method of using PARAFAC prior to the 2D-Laplace inversion proved to have superior potential in analysis of diffusion-relaxation spectra, as it improves not only the interpretation, but also the quantification.     

Interplay between Fe 3d and Ce 4f magnetism and Kondo interaction in CeFeAs(1-x)P(x)O probed by 75As and 31P NMR

A detailed (31)P (I = 1/2) and (75)As (I = 3/2) NMR study on polycrystalline CeFeAs(1-x)P(x)O alloys is presented. The magnetism of CeFeAsO changes drastically upon P substitution on the As site. CeFePO is a heavy fermion system without long-range order whereas CeFeAsO exhibits an Fe 3d SDW type of ordering accompanied by a structural transition from tetragonal (TT) to orthorhombic (OT) structure. Furthermore, Ce 4f(1) orders antiferromagnetically (AFM) at low temperature. At the critical concentration where the Fe magnetism is diminished the Ce-Ce interaction changes to a ferromagnetic (FM) type of ordering. Three representative samples of the CeFeAs(1-x)P(x)O (x = 0.05, 0.3 and 0.9) series are systematically investigated. (1) For the x = 0.05 alloy a drastic change of the linewidth at 130 K indicates the AFM-SDW type of ordering of Fe and the structural change from the TT to the OT phase. The linewidth roughly measures the internal field in the ordered state and the transition is most likely first order. The small and nearly constant shift from (31)P and (75)As NMR suggests the presence of competing hyperfine interactions between the nuclear spins and the 4f and 3d ions of Ce and Fe. (2) For the x = 0.3 alloy, the evolution of the Fe-SDW type of order takes place at around 70 K corroborating the results of bulk measurement and μSR. Here we found evidence for phase separation of paramagnetic and magnetic SDW phases. (3) In contrast to the heavy fermion CeFePO for the x = 0.9 alloy a phase transition is found at 2 K. The field-dependent NMR shift gives evidence of FM ordering. Above the ordering the spin-lattice relaxation rate (31)(1/T(1)) shows unconventional, non-Korringa-like behaviour which indicates a complex interplay of Kondo and FM fluctuations.     

Using liquid and solid state NMR and photoluminescence to study the synthesis and solubility properties of amine capped silicon nanoparticles

Water soluble silicon nanoparticles were prepared by the reaction of bromine terminated silicon nanoparticles with 3-(dimethylamino)propyl lithium and characterized with liquid and solid state nuclear magnetic resonance (NMR) and photoluminescence (PL) spectroscopies. The surface site dependent 29Si chemical shifts and the nuclear spin relaxation rates from an assortment of 1H-29Si heteronuclear solid state NMR experiments for the amine coated reaction product are consistent with both the 1H and 13C liquid state NMR results and routine transmission electron microscopy, ultra-violet/visible, and Fourier transform infrared measurements. PL was used to demonstrate the pH dependent solubility properties of the amine passivated silicon nanoparticles.     

Ground state of the kagomé-like S=1/2 antiferromagnet volborthite Cu3V2O7(OH)2 x 2H2O

The volborthite compound is one of the very few realizations of S=1/2 quantum spins on a highly frustrated kagomé-like lattice. Low-T SQUID measurements reveal a broad magnetic transition below 2 K which is further confirmed by a peak in the 51V nuclear spin relaxation rate (1/T1) at 1.4 K +/- 0.2 K. Through 51V NMR, the ground state (GS) appears to be a mixture of different spin configurations, among which 20% corresponds to a well defined short-range order, possibly of the sqrt(3) x sqrt(3) type. While the freezing involves all the Cu2+ spins, only 40% of the copper moment is actually frozen which suggests that quantum fluctuations strongly renormalize the GS.     

Validity of NMR pore-size analysis of cultural heritage ancient building materials containing magnetic impurities

NMR relaxation time distributions, obtained with laboratory and portable devices, are utilized to characterize the pore-size distributions of building materials coming from the Roman remains of the Greek-Roman Theatre of Taormina. To validate the interpretation of relaxation data in terms of pore-size distribution, comparison of results from standard and in situ NMR experiments with results of the mercury intrusion porosimetry (MIP) has been made. Although the pore-size distributions can be obtained by NMR in terms of either longitudinal (T₁) or transverse (T₂) relaxation times distributions, the shorter duration of the T₂ measurement makes it, in principle, preferable, although the determination of T₂ distributions is not necessarily an easy alternative to finding T₁ distributions. Among other things, the T₁ distribution is almost independent of the inhomogeneity of the magnetic field, while the T₂ distribution is strongly influenced by it. This paper was aimed at answering two questions: what are the validity limits to interpret NMR data in terms of pore-size distributions and whether the portable device can successfully be applied as a non-destructive and non-invasive tool for in situ NMR analysis of building materials, particularly those of Cultural Heritage interest.     

In situ fluid typing and quantification with 1D and 2D NMR logging

In situ nuclear magnetic resonance (NMR) fluid typing has recently gained momentum due to data acquisition and inversion algorithm enhancement of NMR logging tools. T(2) distributions derived from NMR logging contain information on bulk fluids and pore size distributions. However, the accuracy of fluid typing is greatly overshadowed by the overlap between T(2) peaks arising from different fluids with similar apparent T(2) relaxation times. Nevertheless, the shapes of T(2) distributions from different fluid components are often different and can be predetermined. Inversion with predetermined T(2) distributions allows us to perform fluid component decomposition to yield individual fluid volume ratios. Another effective method for in situ fluid typing is two-dimensional (2D) NMR logging, which results in proton population distribution as a function of T(2) relaxation time and fluid diffusion coefficient (or T(1) relaxation time). Since diffusion coefficients (or T(1) relaxation time) for different fluid components can be very different, it is relatively easy to separate oil (especially heavy oil) from water signal in a 2D NMR map and to perform accurate fluid typing. Combining NMR logging with resistivity and/or neutron/density logs provides a third method for in situ fluid typing. We shall describe these techniques with field examples.     

Fermi surface properties of CeRu2(Si1-xGex)2 in magnetic fields above the metamagnetic transitions

We report de Haas-van Alphen effect measurements on CeRu2(Si(1-x)Gex)2 to reveal electronic structure change over the broad range of chemical pressure from x=0.0 to 1.0. It is found that the Fermi surface properties change drastically across the metamagnetic crossover field (B(m)) but vary smoothly with x from those in magnetic fields above B(m) in CeRu2Si2 to those in the ferromagnetic state in CeRu2Ge2. Implications of the present results are discussed in conjunction with the magnetic phase diagram.     

A New Approach of Two-Dimensional the NMR Relaxation Measurement in Flowing Fluid

Driven-equilibrium fast saturation recovery (DEFSR), as a new method for two-dimensional (2-D) nuclear magnetic resonance (NMR) relaxation measurement based on pulse sequence in flowing fluid, is proposed. The two-dimensional functional relationship between the ratio of transverse relaxation time to longitudinal relaxation time of fluid (T ₁/T ₂) and T ₁ distribution is obtained by means of DEFSR with only two one-dimensional measurements. The rapid measurement of relaxation characteristics for flowing fluid is achieved. A set of the down-hole NMR fluid analysis system is independently designed and developed for the fluid measurement. The accuracy and practicability of DEFSR are demonstrated.     

Enhanced hyperthermia performance in hard-soft magnetic mixed Zn0.5CoxFe2.5−xO4/SiO2 composite magnetic nanoparticles

High quality Zn0.5CoxFe2.5?xO4(x=0,0.05,0.1,0.15)serial magnetic nanoparticles with single cubic structures were prepared by the modified thermal decomposition method,and Zn0.5CoxFe2.5?xO4/SiO2 composite magnetic nanoparticles were prepared by surface modification of SiO2.The magnetic anisotropy of the sample increases with the increase of the doping amount of Co2+.When the doping amount is 0.1,the sample shows the transition from superparamagnetism to ferrimagnetism at room temperature.In the Zn0.5CoxFe2.5?xO4/SiO2 serial samples,the maximum value of specific loss power(SLP)with 1974 W/gmetal can also be found at doping amount of x=0.1.The composite nanoparticles are expected to be an excellent candidate for clinical magnetic hyperthermia.     

L-赖氨酸长链烷基酯双DTPA酰胺钆(Ⅲ)配合物的合成、表征与弛豫效能

通过二乙三胺五乙酸单环酸酐(DTPA-MA)分别与L-赖氨酸的十八酯、十六酯、十四酯和十二酯的双酰化反应, 制得四种含有双DTPA螯合单元的新型配体. 它们与GdCl3·6H2O配合得到相应的双核钆(Ⅲ)配合物. 表征了配体和配合物的结构, 测试了配合物的纵向弛豫效能(R1). 结果表明: 这四种新钆配合物的R1都高于Gd-DTPA.     

Effects of T2-relaxation in MAS NMR spectra of the satellite transitions for quadrupolar nuclei: a 27Al MAS and single-crystal NMR study of alum KAl(SO4)2.12H2O

Asymmetries in the manifold of spinning sidebands (ssbs) from the satellite transitions have been observed in variable-temperature 27Al MAS NMR spectra of alum (KAl(SO4)2.12H2O), recorded in the temperature range from -76 to 92 degrees C. The asymmetries decrease with increasing temperature and reflect the fact that the ssbs exhibit systematically different linewidths for different spectral regions of the manifold. From spin-echo 27Al NMR experiments on a single-crystal of alum, it is demonstrated that these variations in linewidth originate from differences in transverse (T2) relaxation times for the two inner (m=1/2<-->m=3/2 and m=-1/2<-->m=-3/2) and correspondingly for the two outer (m=3/2<-->m=5/2 and m=-3/2<-->m=-5/2) satellite transitions. T2 relaxation times in the range 0.5-3.5 ms are observed for the individual satellite transitions at -50 degrees C and 7.05 T, whereas the corresponding T1 relaxation times, determined from similar saturation-recovery 27Al NMR experiments, are almost constant (T1=0.07-0.10 s) for the individual satellite transitions. The variation in T2 values for the individual 27Al satellite transitions for alum is justified by a simple theoretical approach which considers the cross-correlation of the local fluctuating fields from the quadrupolar coupling and the heteronuclear (27Al-1H) dipolar interaction on the T2 relaxation times for the individual transitions. This approach and the observed differences in T2 values indicate that a single random motional process modulates both the quadrupolar and heteronuclear dipolar interactions for 27Al in alum at low temperatures.     

Non-Fermi liquid states in the pressurized CeCu2(Si1-xGex)2 system: two critical points

In the archetypal strongly correlated electron superconductor CeCu2Si2 and its Ge-substituted alloys CeCu2(Si1-xGex)2 two quantum phase transitions--one magnetic and one of so far unknown origin-can be crossed as a function of pressure. We examine the associated anomalous normal state by detailed measurements of the low temperature resistivity (rho) power-law exponent alpha. At the lower critical point (at pcl, 1相似文献   

YbRh2Si2: spin fluctuations in the vicinity of a quantum critical point at low magnetic field

We report a 29Si NMR study on aligned single crystals of YbRh2Si2 which shows behavior characteristic of a quantum critical point (QCP: T(N)-->0). The Knight shift K and the nuclear spin-lattice relaxation rate 1/T(1) of Si show a strong dependence on the external field H, especially below 5 kOe. At the lowest H used in this measurement (H approximately 1.5 kOe), it was found that 1/T(1)T continues to increase down to 50 mK, whereas K stays constant with a large magnitude below 200 mK. This result strongly suggests the development of antiferromagnetic fluctuations with finite q vectors that compete with q=0 spin fluctuations in the vicinity of the QCP near H=0.5 kOe.