高压下ZrB3与NbB3力学性质的第一性原理研究

此文用密度泛函理论的赝势平面波方法的第一性原理研究了过渡金属化合物ZrB_3与NbB_3(m-AlB_2、OsB_3和MoB_3结构)在高压下的力学性质和电子结构特点,获得了在常压下,m-AlB_2是最稳定的结构,当压强升高到40GPa时发生相变,高压下最稳定是OsB_3结构.m-AlB_2-NbB_3具有最大的剪切模量204GPa,最高的德拜温度921K和最大的硬度值27.3GPa,属于潜在的超不可压缩材料.MoB_3-NbB_3、OsB_3-NbB_3和m-AlB_2-ZrB_3的硬度值分别达到了24.9GPa、22.6GPa和19.8GPa.它们的电子态主要是由M-4d态和B-2p态杂化叠加形成的,在费米能级处取值均不为零,故这些化合物都具有金属性等有益结果.     

固井水泥浆水化早期阶段水状态与电导率关系

油气井固井早期气窜现象常发生于固井水泥浆液固态转变阶段，准确掌握该阶段水泥浆的组织结构是探究固井早期气窜机理的关键。电导率方法是评价水泥浆水化进程及微观结构的有效方法之一。为此，利用电感式电导率仪研究了固井水泥浆沉降稳定性、水化速率对其电导率的影响；结合质量守恒定理和低场核磁共振技术，探究了水化早期阶段水泥浆中水状态与其电导率的关系。实验发现，在新配水泥浆中，孔溶液离子浓度和孔隙结构分布决定了水泥浆的初始电导率；随着水泥浆沉降稳定性的增加，水泥浆中孔结构分布更均匀，使其初始电导率由16.8 mS/cm增加至19.4 mS/cm；随水泥浆水化进程增加，水泥颗粒表面及孔隙中水化产物的形成改变了水泥浆的固相微观结构及孔隙结构，使分布于大孔隙中的自由水转变为小孔隙中的毛细水、凝胶水。实验结果表明，在水化早期阶段水泥浆的电导率与蒸发水、自由水含量呈线性关系。     

高压实高庙子膨润土的微观结构特征

采用水汽平衡法和渗析法吸力控制技术,借助压汞仪法(MIP)和环境扫描电镜法(ESEM)等试验手段,在自由和侧限状态下,试验研究了被确定为我国高放废物地质处置库首选缓冲材料的高庙子膨润土水化过程中的微观结构变化特征.结果表明,侧限条件与土中吸力对于高压实膨润土水化过程中的微观结构变化影响明显.在高吸力范围(3～309MPa)内,无论是处于侧限还是自由膨胀状态,高压实高庙子膨润土的含水量随控制吸力变化不大,且2种状态下数值基本一致;而当吸力低于3 MPa时,尤其是当吸力小于1 MPa时,处于不同状态下的土样中,含水量随吸力的变化特征出现了明显的差异.从微观上看,随着控制吸力的降低,自由膨胀状态下,大量的水进入了集合体间的孔隙(大孔隙)中,压实膨润土的体积膨胀主要来自于集合体间孔隙(大孔隙)的膨胀;侧限状态下,内部膨胀力逐渐积累,集合体间的孔隙(大孔隙)被压缩,较小孔隙的数量不断增加,压实膨润土中的孔隙大小趋于均一化.     

饱和状态下水泥浆体的微观结构冰冻损伤模型

为了研究水转化为冰所带来的体积膨胀对水泥浆体的微观结构的危害,量化微观结构的内部损伤,建立了一个饱水状态下水泥浆体的冰冻破坏模型.首先使用模拟水泥浆体微观结构的数值模型(HYMOSTRUC)生成一个模拟结构,根据这个模拟结构中的孔结构,分析水分在孔隙中发生的相转变;将含有冰、水和水化产物的水泥浆体微观模拟结构转变为三维...     

Ionic liquids and eutectic mixtures as solvent and template in synthesis of zeolite analogues

The challenges associated with synthesizing porous materials mean that new classes of zeolites (zeotypes)-such as aluminosilicate zeolites and zeolite analogues-together with new methods of preparing known zeotypes, continue to be of great importance. Normally these materials are prepared hydrothermally with water as the solvent in a sealed autoclave under autogenous pressure. The reaction mixture usually includes an organic template or 'structure-directing agent' that guides the synthesis pathway towards particular structures. Here we report the preparation of aluminophosphate zeolite analogues by using ionic liquids and eutectic mixtures. An imidazolium-based ionic liquid acts as both solvent and template, leading to four zeotype frameworks under different experimental conditions. The structural characteristics of the materials can be traced back to the solvent chemistry used. Because of the vanishingly low vapour pressure of ionic liquids, synthesis takes place at ambient pressure, eliminating safety concerns associated with high hydrothermal pressures. The ionic liquid can also be recycled for further use. A choline chloride/urea eutectic mixture is also used in the preparation of a new zeotype framework.     

水热条件对硅酸盐水泥的水化及其干缩性能的影响

通过强度试验、干缩测定、MIP、TG-DSC、NMR分析,研究了不同水热条件下硅酸盐水泥的早期（3 d）水化及其干缩性能。结果表明：约2 d时间的水养护温度由20℃提高到60℃,水泥的早期（3 d）水化程度显著提高,C-S-H凝胶数量显著增多,同时C-S-H凝胶的硅酸盐聚合度提高,C-S-H的表面积减小,致密度提高;水泥的3 d强度显著提高,但28 d强度明显下降;水泥的干缩显著减小。养护温度提高减小干缩的原因是由于干燥前C-S-H凝胶的化学结构等发生变化而使水泥的不可逆干缩显著减小。     

High-throughput synthesis and catalytic properties of a molecular sieve with 18- and 10-member rings

Crystalline molecular sieves with large pores and high adsorption capacities have many potential applications. Of these materials, zeolites are of particular interest owing to their stability in a wide range of experimental conditions. An aluminophosphate with very large circular channels(5) containing 18 oxygen atoms (18-ring channels) has been synthesized, but in the search for large-pore zeolites, most of the materials which have been synthesized up to now contain only 14-ring channels; the synthesis of zeolites with larger ring structures has been believed to be hindered by the low Si-O-Si bond angles available. A silicogaloaluminate (ECR-34) with unidirectional 18-ring channels was recently reported, but exhibited low micropore volume, thus rendering the material less attractive for catalytic applications. Here we report the structure and catalytic activity of the silicogermanate zeolite ITQ-33; this material exhibits straight large pore channels with circular openings of 18-rings along the c axis interconnected by a bidirectional system of 10-ring channels, yielding a structure with very large micropore volume. The conditions for synthesis are easily accessible, but are not typical, and were identified using high-throughput techniques.     

降解-CTMABr组装介-微孔分子筛的实验研究

通过考察实验影响因素以在最佳条件合成一种具有潜在应用价值的高水热稳定性材料。通过降解NaY分子筛形成其前驱体,以CTMABr（十六烷基三甲基溴化铵）为模板剂合成介-微孔分子筛。XRD和FT-IR表征结果表明材料的孔壁含有沸石结构单元,在750℃,100%水蒸汽中处理2h后介孔结构依然存在。研究认为在最佳条件下合成的材料是一种高水热稳定性的孔壁含有沸石结构单元的介孔材料,且与直接制备分子筛前驱体的过程相比,降解微孔分子筛制备前驱体有沸石回收和成本低廉两方面的优点。     

降解CTMABr组装介-微孔分子筛的实验研究

通过考察实验影响因素以在最佳条件合成一种具有潜在应用价值的高水热稳定性材料。通过降解NaY分子筛形成其前驱体,以CTMABr(十六烷基三甲基溴化铵)为模板剂合成介-微孔分子筛。XRD和FT IR表征结果表明材料的孔壁含有沸石结构单元,在750?℃,100%水蒸汽中处理2?h后介孔结构依然存在。研究认为在最佳条件下合成的材料是一种高水热稳定性的孔壁含有沸石结构单元的介孔材料,且与直接制备分子筛前驱体的过程相比,降解微孔分子筛制备前驱体有沸石回收和成本低廉两方面的优点。     

A first-order liquid-liquid phase transition in phosphorus

First-order structural phase transitions are common in crystalline solids, whereas first-order liquid-liquid phase transitions (that is, transitions between two distinct liquid forms with different density and entropy) are exceedingly rare in pure substances. But recent theoretical and experimental studies have shown evidence for such a transition in several materials, including supercooled water and liquid carbon. Here we report an in situ X-ray diffraction observation of a liquid-liquid transition in phosphorus, involving an abrupt, pressure-induced structural change between two distinct liquid forms. In addition to a known form of liquid phosphorus--a molecular liquid comprising tetrahedral P4 molecules--we have found a polymeric form at pressures above 1 GPa. Changing the pressure results in a reversible transformation from the low-pressure molecular form into the high-pressure polymeric form. The transformation is sharp and rapid, occurring within a few minutes over a pressure range of less than 0.02 GPa. During the transformation, the two forms of liquid coexist. These features are strongly suggestive of a first-order liquid-liquid phase transition.     

不同碱当量、粉煤灰和矿渣掺量对碱激发粉煤灰-矿渣地聚物力学性能及微观结构的影响

粉煤灰、矿渣复配组成碱激发复合水泥可以改善单一组分碱激发水泥的性能劣势。为了研究不同碱当量、不同粉煤灰和矿渣掺量对碱激发粉煤灰-矿渣砂浆力学性能、干燥收缩及微观结构特性的影响,采用抗压、抗折强度试验、吸水率试验、干燥收缩试验、微观扫描电子显微镜(scanning electron microscope, SEM)及傅里叶红外光谱(Fourier transform infrared spectrometer, FTIR)试验进行表征。结果表明:3、7、28 d龄期时,随着碱当量和矿渣掺量增加,粉煤灰-矿渣砂浆抗压、抗折强度呈逐渐增加趋势,吸水率和干燥收缩率呈逐渐下降趋势。其中龄期为28 d,碱当量为6%、矿渣掺量为100%时,碱激发粉煤灰-矿渣砂浆抗压强度达到峰值110.84 MPa,抗折强度达到峰值10.77 MPa,吸水率最小,为1.2%,与4%的粉煤灰-矿渣砂浆相比,碱当量为6%的砂浆干燥收缩率均减少10%以上。由微观分析知,粉煤灰-矿渣砂浆在碱激发作用下水化产物主要为铝硅酸盐凝胶和水化硅酸钙凝胶,粉煤灰掺量越大,凝胶结晶度越低。碱当量越大,体系水化产物数量越多,结构越密实。     

铁硒基超导体的高压研究进展

FeSe及其衍生化合物因表现出奇特的正常态和超导态性质,成为近年来铁基超导领域的研究热点,其中高压技术在揭示FeSe中的竞争电子序和调控高温超导方面发挥了重要作用.本文概述了利用六面砧装置对FeSe基超导体的高压研究进展,主要内容包括:(1)通过建立FeSe的完整温度-压力相图,观察到圆拱形的反铁磁相界并详细揭示了电子向列序、长程反铁磁序和超导相之间的竞争关系,结合高压下的霍尔效应测试进一步表明反铁磁临界涨落对实现高温超导具有重要作用;(2)在多个插层FeSe高温超导体中,普遍发现高压会首先抑制超导I相,然后在临界压力之上诱导出高温超导Ⅱ相,呈现出双拱形超导相图,而且最高临界温度突破50 K;(3)结合高压X射线衍射和霍尔效应测试,指出超导Ⅱ相的出现和伴随的载流子浓度提高很可能源于压力诱导的费米面重构.     

准噶尔盆地中拐地区佳二段沸石类矿物成岩作用及其对油气成藏的意义

通过岩心、铸体薄片、电子探针、包裹体等资料,对中拐地区二叠系佳木河组佳二段沸石类矿物成岩作用进行研究,并分析其对油气成藏的意义。结果表明:佳二段沸石类胶结是最主要的胶结类型,主要有浊沸石、片沸石和方沸石3种沸石类矿物;前期沸石的胶结保存了部分原始孔隙结构,为后期浊沸石和方沸石的溶蚀提供了物质基础。佳二段沸石类矿物主要分布在扇三角洲河道厚层的砂砾岩体中,其形成与火山物质密切相关;地层水化学性质、pH值以及离子的性质和比率、温度和压力等决定了沸石类型的转化:沸石从上到下的转化序列为方沸石-片沸石-浊沸石,除了沸石矿物的转化,斜长石的钠长石化也形成了部分浊沸石;浊沸石含量和溶蚀强度决定了储层质量,其次生孔隙发育带是寻找有利油气储层的目标区域。     

Electronic and structural transitions in dense liquid sodium

At ambient conditions, the light alkali metals are free-electron-like crystals with a highly symmetric structure. However, they were found recently to exhibit unexpected complexity under pressure. It was predicted from theory--and later confirmed by experiment--that lithium and sodium undergo a sequence of symmetry-breaking transitions, driven by a Peierls mechanism, at high pressures. Measurements of the sodium melting curve have subsequently revealed an unprecedented (and still unexplained) pressure-induced drop in melting temperature from 1,000 K at 30 GPa down to room temperature at 120 GPa. Here we report results from ab initio calculations that explain the unusual melting behaviour in dense sodium. We show that molten sodium undergoes a series of pressure-induced structural and electronic transitions, analogous to those observed in solid sodium but commencing at much lower pressure in the presence of liquid disorder. As pressure is increased, liquid sodium initially evolves by assuming a more compact local structure. However, a transition to a lower-coordinated liquid takes place at a pressure of around 65 GPa, accompanied by a threefold drop in electrical conductivity. This transition is driven by the opening of a pseudogap, at the Fermi level, in the electronic density of states--an effect that has not hitherto been observed in a liquid metal. The lower-coordinated liquid emerges at high temperatures and above the stability region of a close-packed free-electron-like metal. We predict that similar exotic behaviour is possible in other materials as well.     

基于HYMOSTRUC3D的固井水泥石孔隙结构演变及力学强度发展规律

固井水泥石微结构发育规律是固井工艺设计和固井质量评价的重要参考依据.以HYMOSTRUC3D软件为基础,建立了水泥水化模型,获取了CH[CH表示Ca(OH)2晶体]含量和抗压强度,并对实验结果进行了对比,模拟结果与实验结果的偏差基本都在10％以内.然后,基于水泥水化模型获取了不同水灰比(W/C,W/C=0.4、0.44、0.5、0.6、0.8、1.0、2.0)和水化龄期对固井水泥浆水化过程中C3S(3CaO·SiO2),C2S(2CaO·SiO2),C3A(3CaO·Al2O2),C4AF(4CaO·Al2O3·Fe2O3),C-S-H(Ca5Si6O16(OH)·4H2O)CH、孔隙率、孔径分布、抗压强度和三维结构等的影响.同时,采用Ryshkewitch方程、Schiller方程和二次线性方程重点讨论了抗压强度与孔隙率的关系.结果表明:在水泥水化过程中,随水化反应的进行,水泥石孔隙率逐渐减小,抗压强度增大;随水灰比增大,粗孔含量增加,细孔占比减小,孔隙率增大,孔径分布变宽,抗压强度减小.采用Ryshkewitch方程、Schiller方程和二次线性方程拟合抗压强度与总孔隙率和毛细孔隙率的相关系数都达到0.92以上,分别为0.96、0.92、0.95和0.98、0.97、0.98;毛细孔隙率是固井水泥石强度发展的主要影响因素.     

合金元素对SHS伴生金属涂层基本性能的影响

 为探究合金元素对伴生金属涂层基本性能的影响,选用Ф78 mm×8 mm×550 mm的无缝钢管,在管内壁距离管端200~350 mm处提前开设150 mm×10 mm×4 mm的长形槽,采用自蔓延高温合成技术制备添加不同含量合金元素的伴生金属涂层。通过维氏硬度测量、电子显微扫描、酸液浸泡腐蚀试验,分别探究不同合金元素对伴生金属涂层孔隙、裂纹、硬度以及耐蚀性能的影响。结果显示,添加 Nb、Cr 元素后伴生金属层硬度提高,孔隙与裂纹明显减少,金相组织趋于均匀化。伴生金属层的耐蚀性能与Cr、Nb元素添加量成正比,ZrO₂的添加量影响不大。耐蚀性最好的伴生金属涂层腐蚀仅失重0.271 g,失重率为2.71%,失重率仅为纯铁层的21.22%。结果表明,Nb、Cr元素的加入能有效改善伴生金属涂层的基本性能,而Zr元素对涂层性能影响较小。     

沸石分子筛材料中次级孔的研究——Ⅱ.Y型沸石晶内次级孔对扩散的影响

以含有次级孔的沸石的晶内扩散为研究对象,对来源于同一NaY母体的一组改性Y型沸石,进行了孔结构分析和正戊烷的扩散系数的测定。得到了具不同次级孔量的Y型沸石晶内扩散性能变化的规律。并采用随机游动方法对实际的Y型沸石晶内扩散进行模拟,得到了与实验测定一致的结果,从而可以对有次级孔的Y型沸石的晶内扩散做定量的估计。     

Effects of temperature on hydrostatic pressure-induced FE-AFE phase transition in PbLa(Zr, Sn, Ti)O3 ceramics

Hydrostatic pressure-induced ferroelectricantiferroelectric (FE-AFE) phase transition and the pressure dependence of dielectric properties in La-doped Pb(Zr,Sn, Ti)O₃ ceramics were researched; the effects of temperature on hydrostatic pressure-induced FE-AFE phase transition and dielectric properties of the samples were studied. It was found that the temperature made the FE-AFE phase transition pressure decrease, and there existed the behavior of dielectric frequency dispersion and phase transition diffusion in the dielectric-pressure spectrum. These phenomena were very useful to enrich and develop the knowledge on the diffused phase transition behavior of polycomponent relaxor ferroelectric.     

Correlation between surface charge and hydration on mineral surfaces in aqueous solutions: A critical review

Surface charges and hydration are predominant properties of colloidal particles that govern colloidal stability in aqueous suspensions. These properties usually coexist and interact with each other. The correlation between the surface charge and hydration of minerals is summarized on the basis of innovative experimental, theoretical, and molecular dynamics simulation studies. The factors affecting the adsorption behavior of ions and water molecules, such as ion concentration, ion hydration radius and valence, and surface properties, are discussed.For example, the hydration and adsorption states completely differ between monovalent and divalent ions. For ions of the same valence, the effect of surface charge on the hydration force follows the Hofmeister adsorption series. Electrolyte concentration exerts a significant effect on the hydration force at high ion concentrations. Meanwhile, the ion correlations in high-concentration electrolyte systems become long range.The interfacial water structure largely depends on surface chemistry. The hydration layer between different surfaces shows large qualitative differences.     

罗庞塬地区延长组孔隙结构特征研究

储层的孔隙结构研究是油藏精细描述、储层综合评价的重要内容,油气储集岩的微观孔隙结构对其物性具有重要的控制作用。采用铸体薄片、扫描电镜、高压压汞等多种技术手段,对罗庞塬地区延长组的孔隙结构进行了深入的分析研究。罗庞塬地区砂岩储层孔隙类型主要为粒间孔,其次为粒内孔、铸模孔、长石溶孔,另有少量裂隙孔,岩石类型为细粒一极细粒岩屑长石砂岩。铸体薄片、孔喉图像分析表明,研究区具有复杂的孔喉分布特征,不同微相孔喉分布及孔隙结构特征是造成油井产能差异的重要因素,所以研究孔隙结构是非常重要的。