^29Si,^27Al Magic—Angle—Spinning Nuclear Magnetic Resonance（MAS NMR） Studies of Kaolinite and Its Thermal Transformation Products

²⁷Al,²⁹Si MAS NMR studies of kaolinite and its thermal transformation products show that in the kaolinite-mullite reaction series there is an extensive segregation of Al₂O₃ and SiO₂ and the reaction of Al₂O₃ with SiO₂ to form mullite is the main path of mullite formation. At about 850° C, the peak intensity of A1(V) reaches its maximum and with the further rise of temperature the A1(V) signal completely disappears. At about 950°C, γ-Al₂O₃ accounts for about 71% of the material phases containing Al atoms. In the series there is no obvious presence of Al-Si spinel. The²⁷Al and²⁹Si MAS NMR spectra show that there is an obvious difference between the temperature points for Al-O₂(OH)₄ octahedral sheet collapsing and Si-O₄ tetrahedral sheet breaking down.     

29Si and 27Al MAS NMR spectroscopy of mullite

A ²⁹Si and ²⁷Al magic angle spinning nuclear magnetic resonance study is reported for differently synthesized mullites. The ²⁹Si MAS NMR spectra of all samples are essentially identical. They consist of a main resonance at -86.8 ppm, a shoulder around -90 ppm and a second resonance at -94.2 ppm. The main resonance is interpreted as being due to a sillimanite-type geometry around Si and the second one is tentatively assigned to a Si environment typical for mullite. The ²⁷Al MAS NMR spectra of sinter- and fused-mullite measured at different Larmor frequencies revealed clearly the presence of three distinct Al sites in mullite, i.e. of octahedral (M1), tetrahedral (M2) and distorted tetrahedral (Al^*) sites.     

27Al, 29Si,and 23Na MAS NMR study of an Al,Si ordered alkali feldspar solid solution series

Solid-state ²⁷Al, ²⁹Si and ²³Na MAS NMR spectra have been obtained for an Al,Si ordered low albite to low microcline ion exchange series for which unit-cell parameters and ²⁹Si NMR data have previously been reported. ²⁷Al δ_i vary continuously with composition from 63.4 (±0.5) ppm for albite to 58.9 (±0.5) ppm for microcline, and parallel the ²⁹Si chemical shifts assigned to the T2m-site. The ²⁷Al and ²⁹Si chemical shifts for this series correlate well with composition-dependent lattice parameters, most notably cell volume and the angle [201]¹b. The linewidths of the ²⁹Si and ²⁷Al resonances indicate a significant amount of structural disorder in the intermediate compositions due to Na, K substitution. The 1 σ width of the distribution of average Si-O-T angles for each T-site is estimated to be about 1° for the Or33 sample. The average ²³Na δ_i varies monotonically from -8.5 (±1) ppm for albite to -24.3 (±1)ppm for Or83. Similarly, the average ²³Na nuclear quadrupole coupling constant decreases from 2.60 to 1.15 (±0.05) MHz and the asymmetry parameter of the electric field gradient increases from 0.25 to 0.6 with increasing K-content from albite to Or83. The observed variations in the quadrupole coupling parameters are consistent with simple electrostatic calculations. Higher resolution ²³Na spectra of the intermediate compositions obtained at 11.7 T indicate the presence of an inhomogeneous linebroadening which is related to the distribution of Na-environments. A model based on a random distribution of local compositions does not simulate the spectra, suggesting that the distribution of Na is skewed toward Na-rich clusters. Observation of the ²³Na NMR lineshape of Or49 after short periods of heat treatment indicate that ²³Na NMR is very sensitive to the changes in the Na, K distribution accompanying the early stages of exsolution. Reversible changes occur after heating at 530° C for 3 h, whereas heating at 600° C produces no changes, possibly bracketing the position of the coherent spinodal for Al, Si ordered alkali feldspars at this composition.     

Influence of structural factors on 29Si and 27Al NMR chemical shifts of phyllosilicates 2:1

The ²⁹Si and ²⁷Al nuclear magnetic resonance (NMR) analysis of synthetic trioctahedral phyllosilicates 2:1, with tetrahedral ratios Al _T/(Si + Al _T) ranging from 0 to 0.5, has shown that the ditrigonal distortion of tetrahedral rings (angle ) is the main factor controlling chemical shift values of tetrahedral components in both signals. The increase of ditrigonal rotation angle shifts these components towards more positive values. For each sample, the composition of tetrahedral and octahedral sheets determine the value of , and from this parameter, the mean tetrahedral Tot angle and the chemical shift values of components are deduced. For a given environment, variations on ditrigonal angle are responsibles for the observed evolution of chemical shift values with bulk composition. The comparative analysis of micas and saponite samples has demonstrated that the location of compensating charge (interlayer and octahedral sheet) does not affect chemical shift values.     

仇山酸化钙基膨润土的 27Al和 29Si 魔角旋转核磁共振谱及脱色率研究

对用不同酸度处理的仇山钙基膨润土进行了化学分析、X射线衍线（XRD）、^27Al和^29Si魔角旋转核磁共振（MAS NMR）、吡啶吸附样品的红外光谱（IR）、比表面积、阳离子交换容量（CEC）和脱色率等测定。结果表明，随着处理酸度的增加和蒙脱石中阳离子的溶出，它的d(001)的衍射强度降低，同时其Si和Al原子局域结构环境发生了显著的改变，Al原子由Al^Ⅵ变成Al^Ⅵ，Si原子由Q^Si(0Al)结构向Q^4Si(0Al)和Q^3Si(1OH)结构转变。八面体片阳离子的溶出和Si,Al原子局域结构环境的转变，显著地增加了比表面积和孔结构；Al^Ⅵ向Al^Ⅵ的转变形成了Lewis酸中心，而Si原子局域结构环境的改变形成了Br φnsted酸中心。膨润土脱色率随处理酸度增加的本质原因是在Si和Al原子局域环境的变化过程中，在其表面分别形成了Brφnsted酸中心和Lewis酸中心。     

Si,Al ordering in leucite by high-resolution 27Al MAS NMR spectroscopy

High-resolution ²⁷Al MAS NMR spectra of natural leucite recorded at H ₀=11.7T contain three resolvable resonances at ²⁷Al δ _i = 69.2, 64.7, and 61.0±0.5 ppm. These three resonances are assigned to the three inequivalent framework positions of leucite: T3, T2, and T1, respectively. Fitting the observed spectra yields a Si,Al distribution for leucite in which approximately one-half of the Al is in T1 and one-quarter in each of T2 and T3. This Si,Al distribution differs substantially from those obtained by previous workers using ²⁹Si NMR spectroscopy and X-ray diffraction. New ²⁹Si NMR spectra and revision of previously reported ²⁹Si NMR peak assignments, however, make the ²⁷Al and ²⁹Si NMR results consistent. The ²⁷Al δ _i correlate linearly with the mean T-O-T′ bond angles of the average structure, which allows the peak assignments to be made. However, this correlation lies distinctly toward higher frequency and larger bond angles than correlations for Si,Al ordered aluminosilicates, suggesting that the mean T(Al)-O-T′(Si) bond angle for each site in leucite is smaller than the mean bond angle of the average structure, which is averaged over T(Al)-O-T′(Si) and T(Si)-OT′(Si,Al) angles.     

机械研磨高岭石的固体~(29)Si、~(27)Al核磁共振光谱研究

综合多种测试方法,考察了研磨对茂名高岭石粒径、形貌与微结构等理化性质的影响。重点采用~(29)Si、~(27)Al MAS NMR光谱考察了研磨过程中结构脱羟、Si、Al配位环境变化、新活性位点形成等微结构演变等。结果表明:研磨初期,高岭石六方片层遭到破碎,颗粒粒径逐渐减小,比表面积在研磨1 h达到最大(43.8 m~2/g);此后,颗粒发生团聚,比表面积减小,样品脱羟量和表面吸附水含量均逐渐增加。核磁Si谱和Al谱分别在化学位移-100.5和14.8处出现新的信号,归属于四面体Si与八面体Al相连顶氧质子化作用而产生的Q~3 Si-OH~+-Al结构。研磨导致高岭石脱羟,Al配位状态从AlⅥ经由AlⅤ逐渐向AlⅣ转变。     

高岭石—莫来石反应系列：^27Al和^29SiMAS NMR研究

根据艰我国八个不同成因和特征的高岭土样品在４５０－１４５０℃热处理产物的ＭＡＳ ＮＭＲ谱和ＸＲＤ，ＩＲ，ＤＴＡ等研究结果，结合有关资料讨论了高岭石－莫来石反应序列的几个重要问题：１．高岭石的结构，尤其是五配位铝；２．９８０℃放热峰后的高温相是γ－Ａｌ２Ｏ３而不是Ａｌ－Ｓｉ尖晶石；３．对于莫来石化过程，认为初始莫来石８５０－９５０℃变高岭石形成，二次莫来石由分凝的ＳｉＯ２和γ－Ａｌ２Ｏ３在１２００－     

Calculation of the 29Si NMR shielding tensor in forsterite

²⁹Si NMR studies on synthetic single crystal forsterite have shown an isotropic NMR shift of –63.2 ppm relative to tetramethyl silane and shift tensor components of –24.4, –7.9 and +32.2 ppm relative to this isotropic value. The most shielded component (+32.2 ppm) lies close to the Si-O₁ vector, where Si-O₁ is the shortest bond, R(Si-O₁)=1.614Å (Weiden and Rager, Z. Naturforsch 40a, 126 (1985)). Ab initio self consistent field molecular orbital calculations using the Random Phase Approximation Localized-Orbital Local-Origin (RPA LORG) method and a polarized split valence basis set yield shift tensor components of –28.9, +2.3 and +26.6 ppm relative to the isotropic value, with the most shielded component 17.6° from the Si-O₁ axis. This good agreement is obtained for a SiO ₄ ^4– cluster with forsterite local geometry stabilized by four +1 point charges, PC, with the 相似文献   

硅藻土的29Si魔角旋转核磁共振谱研究

对广东,浙江,云南等不同矿床硅藻土的＾２９ＳｉＭＡＳＮＭＲ谱进行了讨论,谱上出现了个不同化学位移及不同强度的信号,分别为－１１０．１＊１０＾－６－－－１１２．１＊１０＾－６,－９１．１＊１０＾－６－－９１．６＊１０＾－６,－１０６．２＊１０＾－６－－１０７．１＊１０＾－６,－１００＊１０＾－６－－１０２．５＊１０＾－６。这些信号分别属于硅藻硅质,高龄石和石英的＾２９Ｓｉ共振。硅藻的硅质骨架与蛋白石     

Constraints on the structure and dynamics of the β-cristobalite polymorphs of SiO2 and AlPO4 from 31P, 27Al and 29Si NMR spectroscopy to 770 K

Nuclear magnetic resonance spectroscopic data are presented for the cristobalite polymorphs of AlPO₄ and SiO₂ from RT to 770 K, through their respective α-β transitions. The nuclear magnetic resonance (NMR) data include chemical shifts for ³¹P, ²⁷Al, and ²⁹Si, ²⁷Al quadrupole coupling parameters, and ³¹P and ²⁷Al spin-lattice relaxation rates. Also presented are electron diffraction patterns of β-cristobalite AlPO₄ that show diffuse scattering similar to that reported previously for SiO₂. For the α-phases of both AlPO₄ and SiO₂, the chemical shifts decrease approximately linearly with increasing temperature from RT to T_c and discontinuously by -2 to -3 ppm from α to β. This result is consistent with a small, continuous increase in the mean T-O-T angle (〈θ〉) of the α-phases with increasing T and an increase of 〈θ〉 by about 4° across the α-β transition for both cristobalite and its AlPO₄ analogue. Based on the ²⁹Si chemical shifts, the mean Si-O-Si angle for β-cristobalite is 152.7±1° near T_c. For AlPO₄-cristobalite, the ²⁷Al nuclear quadrupole coupling constant (C_Q) decreases approximately linearly from 1.2 MHz at RT to 0.94 MHz near T_c (493±10 K). At the α-β transition the ²⁷Al C_Q approaches zero, in agreement with the cubic average structure observed by diffraction. The satellite transitions retain a small frequency distribution above the α-β transition from electric field gradients attributed to defects. The short-range cubic symmetry of the Al-site and non-linear Al-O-P angle support a dynamically disordered model of the β-cristobalite structure. Complete averaging of the ²⁷Al quadrupole coupling in the β-phase indicates that the lifetime of any short-range ordered domains must be shorter than about 1 μs.     

29Si and 1H NMR spectroscopy of high-pressure hydrous magnesium silicates

We present NMR spectroscopic data, obtained by ¹H MAS, ¹H static spin-echo, and ²⁹Si{¹H} CP-MAS techniques, for a series of hydrous magnesium silicate samples synthesized at high pressure. This series includes chondrodite, β-Mg₂SiO₄, and phases A, B, superhydrous B, and E. Phases B and superhydrous B give very narrow ²⁹Si NMR peaks and display the most de-shielded Si^VI chemical shifts yet reported: ?170.4?ppm for B and ?166.6 for superhydrous B. The ¹H NMR spectra of B and superhydrous B confirm the presence of paired hydroxyls, as determined from refinement of the H positions from X-ray diffraction data. The ¹H MAS NMR spectra of phase B contain peaks for the two distinct hydrogen positions, with chemical shifts of +4.7 and +3.3?ppm. The static ¹H spectrum contains a powder pattern characteristic of a strongly coupled hydrogen pair, from which a dipolar coupling constant of 18.6(4)?kHz and inter-hydrogen distance of d(H–H)=1.86(2)?Å were obtained. Superhydrous B appears to give two poorly resolved ¹H MAS peaks, consistent with the presence of two distinct hydrogen pairs in the P2₁ mn crystal structure. Analysis of its spin-echo spectrum gives d(H–H)=1.83(3)?Å, slightly shorter than for phase B. β-Mg₂SiO₄, coexisting with phases B and superhydrous B, appears to give ²⁹Si{¹H} CP-MAS signal, indicating that it contains significant H concentration. The ²⁹Si chemical shifts for phases B, superhydrous B, and chondrodite, together with those reported previously for other Mg-silicates, show a good correlation with structural parameters.     

Substitution of [4]Al in layer silicates: Calculation of the Al-Si configurational entropy according to 29Si NMR Spectra

A new constructive statistical method was used to simulate the Al-Si distributions in tetrahedral layer of mica according to short range and long range order restrictions and to calculate values of configurational entropy which correspond to simulated distributions. The simulations and the calculated entropy values were constrained by the existing ²⁹Si NMR data for natural and synthetic mica samples. The results of simulation confirm previous conclusions on the importance of short range order restrictions such as Al-avoidance and homogeneous dispersion of charges (HDC) in the tetrahedral layer. The results suggest, however, that the Al-Si distribution in mica closely follows the HDC restriction only for the samples with the Al/(Si+Al) ratios in the range of 0.11–0.3. At higher values of the ratio (0.3–0.37) the degree of the HDC-type ordering decreases towards pure Al-avoidance. In the range of 0.37–0.5 two alternative models namely the HDC model and the model with partial long range order can be used to explain the observed NMR intensities.     

固体核磁光谱法研究镁铝复合氧化物的水热转化机制

复合金属氧化物广泛分布于自然界,其中镁铝复合氧化物(简称MMO)则大量分布于基性-超基性岩浆岩、蒸发河湖相和海相沉积岩等之中。本研究以镁铝水滑石(HT)煅烧产物MMO为研究对象,采用水热合成方法,通过改变反应时长,考察并揭示MMO在富硅、碱性和160℃水热条件下的结构复原特性及其转化机制。X射线衍射结果显示,该条件下MMO首先复水形成水滑石相,进而水滑石相逐渐向皂石转化,并伴有钠霞石等杂相的形成与溶解。29Si和27Al魔角旋转核磁共振谱(MAS NMR)的结果证明,在皂石结晶过程中,Al3+优先占据四面体片层的四配位位置。该研究对揭示水滑石稳定性、水滑石与硅酸盐矿物异相成核与生长、热液类型的天然皂石矿床的形成过程等具有重要指示意义。     

A 29Si NMR study of silica species in dilute aqueous solution

The speciation of silica in dilute, nearly neutral, aqueous solution has been determined by ²⁹Si NMR. Our results indicate that tetrahedral dimers in addition to monomers occur in the concentration range of dissolved amorphous silica.     

A 29Si MAS NMR study of sub-Tg amorphization of stishovite at ambient pressure

Stishovite, a high-pressure SiO₂ polymorph in which each Si is coordinated by six O atoms, transforms to an amorphous phase when undergoing heat treatment below the glass transition temperature at ambient pressure. We have applied ²⁹Si magic angle spinning nuclear magnetic resonance spectroscopy (MAS NMR) to study this amorphization process. We found that the amorphous phase generated after heating stishovite for up to 3 days at around 600 ° C consisted exclusively of four-coordinate Si, similar to glasses quenched from melts at ambient pressure. Furthermore, our data suggest that there are subtle structural differences between the amorphous phase transformed from stishovite at 600 ° C and glasses quenched from melts at ambient pressure: the amorphous phase from stishovite had a smaller mean Si-O-Si angle initially, and it gradually relaxed toward the latter with increasing heating time. There was no detectable change in the stishovite structure even after about 80% of it had been converted to the amorphous phase. The mechanism of the amorphization of stishovite is discussed in light of these results.     

Gel synthesis of magnesium silicates: A 29Si magic angle spinning NMR study

The formation of the magnesium silicate minerals forsterite, enstatite, and roedderite by heating of amorphous “protosilicate” gels precipitated from aqueous solution has been studied by ²⁹Si MAS nmr. Gentle drying of the hydrogels at 110° C gives materials with broad nmr signals that do not differ appreciably with preparation conditions, but the minerals formed by heating at 750° C or higher are greatly dependent on the precipitation and washing conditions of the original gel. The rare mineral roedderite, best known from studies of unequilibrated enstatite chondrite meteorites, becomes a major species along with forsterite when the hydrogels are washed with sodium hydroxide solution before drying and heating to 750° C.