快速制备肼—高岭石插层复合物的方法及意义

将一定浓度的肼溶液与高岭土混合，施以机械研磨，不仅加快了肼分子插入高岭石的速率(10分钟内可使插层率达96％)，而且超细效果明显。在加温120℃后，插入高岭石层间的肼分子挥发，产生的气体能进一步将高岭土剥离，最后得到—2μm＞90％的超细高岭土粉体，且片状晶形完好。这种技术为制备“双90”超细高岭土提供了新的思路和方法。     

不同产地煤系高岭土的矿物学特征及插层复合物的制备

金洋、蒙西和雪纳高岭土化学成分以SiO₂和Al₂O₃为主,K、Na、Ca、Mg含量低,而Fe、Ti含量较高;矿物成分以高岭石为主,还含有少量一水软铝石、石英、蒙脱石等。XRD和IR分析结果表明,金洋和蒙西高岭石的有序度较高,HI结晶指数分别为1.19和1.23,而雪纳高岭石的衍射峰峰形弥散,对称程度差,HI结晶指数仅有0.56。二甲基亚砜和甲酰胺与煤系高岭土相互作用后均能进入高岭石层间并撑大其晶面间距,其中金洋高岭土的插层率最高,雪纳次之,蒙西高岭土的插层效果最差。     

高岭土/吡啶插层复合物的制备与表征

以高岭土／甲醇插层复合物作为中间体，用“取代法”制备了高岭土／吡啶插层复合物，产物用X射线粉晶衍射、热分析和傅利叶变换红外光谱进行了表征。在保持吡啶润湿的条件下，高岭土的层间距增加到1．22nm。吡啶的插层率达到了90．20％。高岭土／吡啶插层复合物不稳定，干燥后其层间距减少到0．86nm。高岭土／吡啶插层复合物的红外光谱表明：吡啶分子与高岭土的内表面羟基形成了氢键。吡啶分子在高岭土层间可能以垂直于高岭土层片的方式排列，且氮原子面对八面体层片。     

高岭石/醋酸钾插层复合物的制备及其影响因素

利用浸泡法制备了高岭石/醋酸钾插层复合物,进行X射线衍射分析,探讨了影响插层的因素。结果表明,醋酸钾对高岭石的插层作用与高岭石的结晶度、插层剂浓度、pH值密切相关。高岭石结晶度越高,越有利于插层作用的进行;高浓度的插层剂(≥30%)可以在较短的时间(12 h)内完成插层作用,而低浓度的插层溶液则需要非常长的时间(≥144 h)才能完成,且获得的插层率较低;pH=10的弱碱性条件最有利于插层的进行;温度对高岭石的插层作用影响不大,在室温就可获得较好的插层效果。     

煤系高岭石的原始晶粒尺寸及结晶度对插层作用的影响

采用SEM、XRF、XRD和IR研究了大同、平朔和淮北煤系高岭石的结构、粒度及其特性,探讨了粒度大小对高岭石插层作用的影响及其机理。研究发现:粒度中等且结晶有序的平朔煤系高岭石插层率最高,其次为晶体粗大但结晶有序的大同高岭石,粒度最小且结晶无序的淮北高岭石插层率最低。研究认为高岭石原始晶粒粒度对高岭石插层作用有重要影响,中等粒度最有利于高岭石插层作用的进行,粒度过大或过小均不利于高岭石插层作用的进行,其原因是由于不同粒度的高岭石插层作用过程中导致的差异弹性变形引起的。结晶有序度对高岭石插层作用也有重要影响,结构无序不利于插层作用的进行。     

大同粗晶高岭石-二甲基亚砜插层复合物的制备及表征

首先研究了大同高岭石的矿物学特征,结果表明大同高岭石晶粒粗大,主要由高岭石组成,样品的有序度高,Hinckley指数为1.12。在此基础上,用二甲基亚砜对大同高岭石进行插层,采用XRD、IR和TG-DSC研究插层复合物的结构。XRD结果表明DMSO已插入高岭石层间,d001由原来的0.717nm增至1.13nm,插层率达96.01%;红外光谱证明DMSO中的S=O基团与高岭石的外羟基发生了化学键合作用;热分析结果显示插层复合物于120℃~240℃发生DMSO的脱嵌作用,高岭石的脱羟基温度在400℃~750℃。     

甲酰胺在高岭石层间的定向研究

甲酰胺插层作用使高岭石层间距从0．717nm膨胀为1．020nm。其增加值(0．303nm)小于甲酰胺的范得瓦尔分子直径(0．47nm)。DRIFT光谱研究表明插层作用破坏了原高岭石层间氢键，并分别在高岭石Si—O基与甲酰胺NH基和高岭石OH基与甲酰胺C=O基之间形成氢键，甲酰胺HN基还部分嵌入高岭石复三方孔洞。     

插层-磨剥法制备不同径厚比的高岭石

通过对醋酸钾/高岭石插层复合物的机械磨剥制备了不同径厚比的高岭石样品,并利用X射线粉晶衍射(XRD)、激光粒度仪、扫描电子显微镜(SEM)、透射电子显微镜(TEM)和傅里叶变换红外光谱(FTIR)表征了4个样品的粒径、结构以及形貌。实验结果表明:随着插层磨剥次数的增加,高岭石的结晶度指数(HI)由原矿的1.29降至0.69,结晶度降低,晶体结构在一定程度上遭到破坏。同时,4个样品的粒径及厚度逐渐减少,径厚比依次增大至11.7。此外,经过3次插层磨剥洗涤后,部分剥离的片层发生卷曲,但很少完全卷曲成纳米卷。     

二甲基甲酰胺对高岭石插层的分子动力学模拟

通过对高岭石-二甲基甲酰胺插层复合物随层间域中二甲基甲酰胺分子数逐渐增加的分子动力学模拟,发现高岭石层间距可被小分子的插层大幅度扩增,但需要借助外界条件克服插层能垒。通过对层间距为1.26 nm模型的界面结构和界面作用的计算,发现二甲基甲酰胺在高岭石层间域中呈单层分布。二甲基甲酰胺的分子平面斜交于层间域表面60°左右,其HC=O官能团的O原子作为质子受体与层间域铝氧面的羟基形成较强的氢键,而甲基则与硅氧面以疏水作用相结合。由于高岭石层间域的铝氧面具有反应活性较高的表面羟基,相比于硅氧面表现出对二甲基甲酰胺更强的亲和性。     

高岭石有机插层复合物的研究现状及发展趋势

综述了高岭石-有机物插层复合物发展历程,分析了高岭石插层复合物制备方法、插层反应影响因素及插层应用,并阐述了有机插层复合物的研究重点及发展趋势。     

有机化合物在高岭石结构中的夹层作用实验研究

详细研究了某些有机化合物在高岭石层间的夹层作用及其稳定性。极性化合物水合联胺与高岭石的夹层作用,其最大层间膨胀值可达11.33Å,且较稳定。红外吸收光谱表明,极性有机物对层间的OH基有扰动作用。脂肪酸盐和丙烯酰胺可分别通过水合联胺及甲酰胺做夹带剂与高岭石进行夹层作用,作用结果,其层间距可分别从7Å扩大到11Å及11.05Å,前者在常温下比较稳定;后者在加热时是稳定的,但温度超过300℃,d₀₀₁值又恢复到7Å。     

蒙脱石作为尿素缓释基质的试验研究

采用一定的方法可使尿素进入蒙脱石层间,形成蒙脱石尿素夹层复合体。在一定范围内,随着尿素夹入量的增加,复合体的晶面间距（d001）逐渐增大。与钙基蒙脱石-尿素夹层复合体相比,钠基蒙脱石-尿素夹层复合体的尿素夹入量较大,并且置于土壤后尿素分子释放较快。蒙脱石-尿素夹层复合体在尿素的不断释放过程中,其出d001值逐渐减小并趋向于恢复到夹层作用前蒙脱石的d001值。蒙脱石可望在农业上作为尿素缓释基质。     

Relative performance of lime stabilized amended clay liners in different pore fluids

Successful design of soil liner and covers for landfills and waste impoundments involves selection of liner material and assessment of chemical compatibility of the liner material. In this work locally available materials with different mineralogy have been evaluated from the viewpoint of liner application. Many local soils may not meet the requirements of liner material; often it is necessary to amend these soils with commercially available processed bentonite. Clay liners may be attacked by chemical waste or leachate, concentrated organic chemicals can attack compacted clay effectively destroying the characteristics of liner material. Thus the main aim of this work has been to assess the suitability of different types of locally available materials for their potential use as liners for waste containment facilities. The materials studied are kaolinitic red earth, illite and fly ash. Based on literature survey and experimental work in this laboratory, 20% by weight of bentonite has been chosen for amending selected materials. Addition of 20% bentonite to selected liner material improved the hydraulic conductivity and adsorption capacity of the amended mixture but, reduced the volume stability. To improve the volume stability of the amended material and to have better resistance towards chemicals attack, stabilizing the amended mixture with 1% by weight of lime has been considered. The relative advantages and disadvantages of four materials namely; red earth with 20% bentonite, illite with 20% bentonite, fly ash with 20% bentonite and illite alone, stabilized with 1% by weight of lime were brought out. The chemical compatibility of the materials to electrolyte solution (0.5 N NaCl), alkaline solution (0.5 N NaOH), acid (0.5 N HCl) and organic fluid (CCl₄) has been studied. The relative efficiency of the selected materials with selected pore fluids was compared.     

煤系高岭石有机夹层作用的实验研究

本文利用ＸＲＤ和ＩＲ研究了丙烯酰胺和脂肪酸盐与煤系高岭石的夹层作用及稳定性。通过极性有机化合物作夹带剂，成功地合成了高岭石－丙烯酰胺、高岭石－脂肪酸盐有机复合体。夹层作用完成后，层面间距从７．１８Ａ分别扩大到１１．２２Ａ和１１．３２Ａ。有机化合物能在高岭石层间形成稳定的夹层主要与夹层分子和高岭石内表面羟基形成氢键有关。     

原料组分对动力学相似材料性质影响的试验研究

随着振动台、离心机等动力学模型试验方法的不断发展,对于动力学相似材料的要求也愈加精细。在满足动力学相似理论的基础上,如何快速、准确地配制出性质合理的相似材料是试验中至关重要的一步。本文以粒度不同的河沙、重晶石粉、铁粉、云母片为原料,以速干水泥为胶结物,对不同材料混合的动力学相似材料性质进行了试验研究。试验结果表明:（1）级配良好的骨料所配置的相似材料密度较大,且颗粒间断级配越大,骨胶比对相似材料密度影响越大;（2）以河砂为骨料、水泥为胶结物,可以配制出密度为1.5~2.2g ·cm-3、动泊松比0.2~0.4、动弹性模量2.5~5.5 GPa的动相似材料;（3）铁粉的增重效果比重晶石粉显著,且铁粉试件的动、静弹性模量随铁粉增加而显著增大,而重晶石粉比例的变化对重晶石粉试件的动、静弹性模量影响不大,在配制"高重低强"的动力学相似材料时,重晶石粉是更理想的原料;（4）随着云母用量的不断增加,试件的密度、动泊松比和动、静弹性模量均显著降低,云母片是很好的减强剂,可以用来模拟岩体间软弱夹层或结构面。     

高岭土的深加工与新材料

煅烧高岭土由于晶体结构的改变而引起理化性能的变化，所表现出的性能更加优异。利用高岭土的特殊层状结构，将一些强极性有机小分子插入到结构层间，生成有机插层材料，这种新的复合物将黏土矿物和有机化合物的各自特性有机结合，极大地开阔了高岭土的应用领域和“档次”。以高岭土为原料而开发成功的Sialon材料，由于所具备的优越的力学性能、高温性能及化学稳定性等，在冶金、航空、化工机械和药学等方面显现出了极好的应用前景。地聚物材料是以偏高岭土、碱激发剂为主要原料，具有与陶瓷性能相似的一种新材料。     

Stabilization of swelling clays by Mg(OH)2. Changes in clay properties after addition of Mg-hydroxide

Stabilization of the swelling clay structure is attempted by intercalation of Mg(OH)₂ and the development of a brucite interlayer between the clay layers. The properties of the product obtained by applying the technique, formulated as described in a previous work, are considered here. The materials used were Wyoming bentonite (USA), Fuller's Earth (UK), kaolinite, illite, lignite, and silica gels. The Mg(OH)₂-clay products were examined by the methylene blue dye test, X-ray diffraction analysis (XRD), differential thermal analysis (DTA), and derivative thermogravimetry analysis (DTGA). From the results obtained it is concluded that: the Mg-hydroxide is adsorbed by swelling clays both on their external and internal surface, whereas it is adsorbed on the external surface by non-swelling clays. The internally adsorbed phase of Mg-hydroxide forms an ill-defined interlayer of brucite, retarding swelling, whereas the external phase covers the particles modifying drastically their surface properties, like the adsorption of the MB dye. The material produced after precipitation of Mg-hydroxide on swelling clays (smectites) did not re-expand on wetting or after glycolation. The adsorption of MB dye was also reduced by some 80–90%, due to coating effect, preventing the measurements of the external surface area of the clay by polar molecules. The principal forces involved in the process are believed to be physical adsorption on the external surface, along with chemisorption and some chemical bonding, mostly in the internal surface. Cementation due to crystallization and, in the long term, some pozzolanic reactions take also place. Internal adsorption of the Mg-hydroxide is postulated to be in the form of positively charged mono- and/or small polymers and it is, chiefly, diffusion controlled. Since Mg-hydroxide is internally adsorbed by swelling clays, whereas Ca-hydroxide(lime) is not, and the (Mg, Ca)-clay aggregates are more stable than the Ca-clay or the Mg-one, the combination of the two hydroxides could give better results in soil stabilization than each hydroxide alone.     

微波辐射制备高岭石/聚丙烯酰胺插层复合物

本文将微波技术引入到制备高岭石/有机物插层复合物的研究中,以DMSO为前驱体,研究了微波辐射对高岭石的有机插层、取代、原位聚合作用.发现微波能加快插层和置换反应,极大地缩短反应时间.微波辐射下插层时间为30 min时,插层率即可达到75%以上,置换反应50 min,置换率达到77%以上.同时发现微波在反应中对高岭石具有剥片效果.采用X射线衍射、FT-IR光谱、TG、TEM等技术对插层复合物及微波作用机理进行了探讨.     

Experimental Study on the Solubility of Cr^2 in Olivine,Orthopyroxene and Spinel Solid Solutions

Experiments have been performed on the system MgO-SiO2-Cr-O at 0-2.88 GPa and 1100-1450℃,focusing on the stability of Cr^2 in olivine(O1),orthopyroxene(Opx) and spinel(Sp) and its partitioning between these phases.Analytical reagent grade chemicals,MgO,SiO2,Cr2O3.and Cr were used to make starting mixtures.Excess Cr(50%) was then added in these mixtures to ensure that the resultant phases were in equilibrium with the metal Cr.Flux of BaO B2O3(%) was added for facilitating experimental equilibrium and crystal growth.Cr was used as capsule material.All phases in the product were identified by X-ray and analyzed by electron microprobe,The contents of CrO in the different phases(O1,Opx and Sp)were calculated according to stoichiometry.The obtained results of calculation indicate that Cr^3 in Ol and Opx is negligible.The experimental results show;(a) with increasing temperature and decreasing pressure,Cr^2 solubility in Ol,Opx and Sp increases;(b) with in creasing temperature,the partitioning coefficient of Mg and Cr^2 between Ol and Opx decreases,that between Opx and Sp increases,and that between Ol and Sp remains almost unchanged;(c) the effect of pressure on all partitioning coefficients is negligible.