高岭石热转变产物~(29)Si、~(27)Al魔角旋转核磁共振研究

运用魔角旋转核磁共振结合红外光谱及X射线衍射等手段 ,研究了苏州高岭石 5 60～ 160 0℃热转变产物 ,主要获得以下结论 :①高岭石 偏高岭石 莫来石的转变系列的确存在结构上的连续性。其转变经历了几个阶段 :脱羟阶段 ( 4 0 0～ 60 0℃ ) ,偏高岭石阶段 ( 60 0～ 80 0℃ ) ,相分离阶段 ( 80 0～ 110 0℃ ) ,莫来石阶段( 110 0～ 160 0℃ )。②莫来石形成过程没有出现Al2 O3的大量分凝 ,但存在SiO2 的分凝。③偏高岭石 莫来石转变过程的中间相为Al Si尖晶石和准莫来石。④引起 10 0 0℃放热反应的主要因素是准莫来石的形成。     

高岭石热转变产物^29Si、^27Al魔角旋转核磁共振研究

运用魔角旋转核磁共振结合红外光谱及X射线衍射等手段，研究了苏州高岭石的560－1600℃热转变产物，主要获得以下结论：（1）高岭石－偏高岭石－莫来石的转变系列的确存在结构上的连续性。其转变经历了几个阶段；脱羟阶段（400－600℃），偏高岭石阶段（600－800℃），相分离阶段（800－1100℃），莫来石阶段（1100－1600℃）。（2）莫来石形成过程没有出现Al2O3的大量分凝，但存在SiO2的分凝。（3）偏高岭石－莫来石转变过程的中间相为Al-Si尖晶石和准莫来石。（4）引起1000℃放热反应的主要因素是准莫来石的形成。     

机械研磨对平鲁煤系高岭石热行为的影响

对煤系高岭石进行0-2h的研磨之后，再在900℃、1000℃、1400℃的温度条件下分别对其加热1h，然后利用X射线衍射（XRD）、差热分析（DTA）、红外光谱（IR）等手段，研究机械研磨对于煤系高岭石晶体结构的破坏作用以及对其热行为的影响。结果显示，煤系高岭石被研磨1h之后，高岭石的晶体结构几乎全部跨塌。把研磨1h的煤系高岭石加热到1000℃（加热1h），便能形成结晶良好的莫来石。     

高岭石和伊利石的固体酸性受热处理温度的影响及其机理

高岭石([Al4(Si4O10)(OH)8])和伊利石(K0.75(Al1.75R0.252+)[Si3.5Al0.5O10](OH)2)是自然界常见的、具有结构代表性的两种层状硅酸盐矿物。高岭石由硅氧四面体片和铝氧八面体片按1∶1方式组成的结构单元层沿c轴方向排列而成,其片     

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－     

煅烧温度对高岭石相转变过程及Si、Al活性的影响

通过对吉林通化煤系高岭石和美国Georgia高岭石在200～1300℃热处理产物的MASNMR谱和XRD,IR,DTA等的研究,主要获得如下结论：①煅烧高岭石的相转变经历了四个阶段——脱羟阶段（约550℃）,偏高岭石阶段（550～850℃）,SiO2分凝（850～1100℃）及Al2O3分凝阶段（950～1100℃）,莫来石、方英石形成阶段（1100℃以上）;②偏高岭石-莫来石的相转变过程中存在SiO2和Al2O3的分凝,其中SiO2的分凝温度是850℃,而Al2O3的分凝温度是950℃;③1100℃开始,由偏高岭石分凝形成的非晶质SiO2一部分和Al2O3-γ发生反应生成了莫来石,一部分结晶为方英石;④煅烧高岭石Si、Al活性总体上随着煅烧温度的增高逐渐增强,其中Al的活性在900℃时达到最高,Si在1100℃时达到最高,当温度超过这两个临界点时,Si、Al活性将迅速下降。     

硅藻土的~(29)Si魔角旋转核磁共振谱

硅藻土的２９Ｓｉ魔角旋转核磁共振谱冯璜张惠芬郭九皋王辅亚王德强（中国科学院广州地球化学研究所广州５１０６４０）胡澄（南京大学固体微结构物理实验室，南京２１００９３）关键词硅藻土核磁共振微结构硅藻土轻质、吸附性强和对热、电、声极差的传导性，使其能广泛应...     

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。     

地开石-高岭石混层矿物的电子顺磁共振(EPR)研究

本文首次利用EPR研究了我国北方石炭-二叠纪煤系地层粘土岩中的粗晶(1～2mm)。与粉末状地开石、高岭石、地开石-高岭石混合样的Fe~(3+)EPR谱对比证明,这些粗晶是一种地开石-高岭石(D-K)的非规则混层矿物,其单晶的EPR表明,Fe~(3+)离子有两种位置:低对称位置,引起弱各向异性的Ⅰ线,λ～0.30;高对称位置,给出强各向异性的E线,λ～0.24。这对历来认为高岭石的Fe~(3+)谱中Ⅰ线为各向同性的看法是一个有益的修正。Ⅰ呈双线(Ⅰ_1及Ⅰ_2)是鉴定这种粗晶属于D-K混层矿物的一个特征标志。     

巯基有机硅烷嫁接高岭石对Cd(Ⅱ)的吸附性能研究

由于重金属镉离子的吸附性能较差、毒性大,因此,寻找镉离子的高效吸附材料具有重要现实意义。本文开展巯基硅烷对高岭石的嫁接改性研究,经红外光谱测试证实,成功将巯基引入到高岭石表面。同时,硅烷改性对高岭石晶体结构没有产生影响。通过批量实验考察了高岭石和巯基硅烷改性高岭石(K-SH)对Cd(Ⅱ)的吸附特征,主要探讨了p H值、时间对吸附效率的影响。矿物对Cd2+的吸附动力学符合准二级动力学模型,吸附等温方程更符合Langmuir模型,并估算的K-SH的最大吸附量是4.375 mg/g,比高岭石的大近20倍。改性高岭石表面嫁接了巯基后,可为高岭石吸附Cd(Ⅱ)提供大量的新吸附位点,通过配位复合作用显著提高对镉离子的吸附固定能力。因此,巯基硅烷改性高岭石是一种有应用前景的土壤修复材料。     

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.     

^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.     

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.     

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.     

29Si and 27Al magic-angle-spinning NMR studies of the thermal transformation of kaolinite

Thermal transformations of kaolinite of different degree of crystallinity have been monitored by ²⁷Al and ²⁹Si high-resolution NMR with magic-angle spinning (MAS NMR), X-ray diffraction, Fourier transform infrared, atomic absorption spectrophotometry and thermogravimetric analysis. NMR shows differences in the dehydroxylation process of kaolinites with different degree of crystallinity and reveals the presence of short-range order in metakaolinite. ²⁹Si NMR spectra acquired with a 30 s recycle delay of poorly and highly crystalline samples heated at 480 and 500° C, respectively, contain three distinct signals; we discuss their assignment in the light of experiments involving leaching of the samples with aqueous KOH. Ca. 40% of Si sites retain their original Q ³ symmetry just above the onset of dehydroxylation and the Q ⁴ environment is present showing that a small amount of amorphous silica has already segregated. The spectrum of samples treated at 1000° C contains a signal at -110ppm (from Q ⁴ silicons) and a faint resonance, from mullite, at ca. -87 ppm. ²⁹Si NMR also shows that cristobalite germs are already present at 950–1000° C. The ²⁷Al MAS NMR spectra of metakaolinite reveal the presence of 4-, 5-and 6-coordinated Al. Changes in the three Al populations as a function of temperature have been monitored quantitatively. Below 800° C, 4-and 5-coordinated Al appears at the expense of 6-coordinated Al, but above 800° C the amount of 6-coordinated Al increases again. We suggest a dehydroxylation scheme which accounts for the presence of 4-and 5 coordinated Al. Above 900–950° C the latter signal is no longer present in the ²⁷Al NMR spectra and new 4-and 6-coordinated Al species (mullite and γ-alumina) appear. We propose new ideas for the structure of metakaolinite.     

碱性长石Al—Si有序化进程中微结构和^29Si NMR谱的表现

笔者用Ｘ射线粉末衍射技术,对六个天然钾长石中的铝在Ｔ１Ｏ四面体位置的占位率进行了测定,它们的Ｔ１Ｏ值从０．２８变化到０．７９。对它们的透射电子显微镜研究表明,两个Ｔ１Ｏ为０．２８和０．３１的高透长石有对电子束异常过敏的调制结构,无法记录到它们的衍射像,在另外三个样品中,都见到芦席状结构,并夹杂着具一定宽度的片晶组成的格子双晶。片晶宽度随Ｔ１Ｏ的变大而增加。而在产于一个霞石正长岩中的正长石中没有观察