Substrate Templating upon Self‐Assembly of Hydrogen‐Bonded Molecular Networks on an Insulating Surface

Molecular self‐assembly on insulating surfaces, despite being highly relvant to many applications, generally suffers from the weak molecule–surface interactions present on dielectric surfaces, especially when benchmarked against metallic substrates. Therefore, to fully exploit the potential of molecular self‐assembly, increasing the influence of the substrate constitutes an essential prerequisite. Upon deposition of terephthalic acid and trimesic acid onto the natural cleavage plane of calcite, extended hydrogen‐bonded networks are formed, which wet the substrate. The observed structural complexity matches the variety realized on metal surfaces. A detailed analysis of the molecular structures observed on calcite reveals a significant influence of the underlying substrate, clearly indicating a substantial templating effect of the surface on the resulting molecular networks. This work demonstrates that choosing suitable molecule/substrate systems allows for tuning the balance between intermolecular and molecule–surface interactions even in the case of typically weakly interacting insulating surfaces. This study, thus, provides a strategy for deliberately exploiting substrate templating to increase the structural variety in molecular self‐assembly on a bulk insulator at room temperature.     

微生物拌和渗滤砂土固化试验研究

河道崩岸现象频发,严重威胁河流航运和两岸人民的生命安全。微生物矿化技术作为一种新型的土体改良技术,在河道护岸方面具有一定的应用前景。本文选用3种不同颗粒粒径范围的砂土进行微生物拌和渗滤固化,并基于无侧限抗压强度试验、碳酸钙含量、崩解率及吸水率测试,分析颗粒粒径、渗滤次数及拌和配比对微生物固化效果的影响,探究拌和法和渗滤法结合的固化机制。研究结果表明：拌和法在砂土试样中生成的碳酸钙大多起填充作用,胶结程度较低,而后续渗滤固化能够显著改善土体特性。拌和配比为2:8、粒径为0.3 ~ 0.6 mm时试样的固化效果较好,抗压强度最高可达1.86 MPa;试样的碳酸钙含量和抗压强度随渗滤次数增加呈非线性增长,而强度上限随粒径增大呈上升趋势。试验得出崩解率最低为2%,吸水率最低降至9.26%,较一般黏性土而言,固化试样抵抗水的侵蚀性较强且具有一定的渗水性,在河道护岸及施工工艺方面具有一定应用价值。     

有机膦系抑制方解石阶梯面生长的分子动力学研究

有机膦系化合物是工业冷却水系统中常用阻垢剂,对有机膦酸阻垢剂的阻垢性能及机理进行研究,能为新型阻垢剂开发应用提供合理的理论依据。根据周期性键链（PBC）理论模型,运用分子动力学方法（MD）,模拟了工业冷却水循环过程中5种有机膦阻垢剂与方解石4种阶梯面的相互作用机理。结果表明,有机膦酸分子与方解石（104）4个阶梯面的结合能均为负值,相互作用为放热过程,阻垢剂分子对方解石（104）阶梯面的生长具有良好的抑制作用。通过计算结合能,得出阻垢剂分子的吸附能力由强到弱依次为HDTMP、EDTMP、ATMP、NDP、AMP;同时观察到有机膦酸分子主要吸附在晶面的活性生长点,即阶梯面的终端拐角位置与阶梯拐点位置,占据了晶面上结晶的活性位置,抑制了晶面的进一步生长。根据有机膦酸与阶梯面结合能数据,得到4种终端阶梯面的吸附能力由强到弱依次为CO₃-CO₃、CO₃-Ca、Ca-CO₃、Ca-Ca,即稳定性越强则吸附能力越弱。     

改性聚丙烯酰胺对方解石的助滤性能

研究了聚丙烯酰胺 ( PAM)、羟甲基化聚丙烯酰胺 ( HMPAM)、磺甲基化聚丙烯酰胺 ( SMPAM)和氨甲基化聚丙烯酰胺 ( AMPAM)对细粒方解石的助滤性能。结果表明 :在相同的相对分子质量下 ,改性 PAM对细粒方解石的助滤效果为 :SMPAM>HMPAM>PAM>AMPAM。     

Isotopic and fluid inclusion study of hydrothermal and metamorphic carbonates in the Larderello geothermal field and surrounding areas, Italy

Fluid inclusions have been studied on six calcite veins from the shallow part (480 to 1515 m below ground level) of the Larderello geothermal field and outcropping in peripheral zones of the geothermal area. Oxygen and carbon isotopic analyses have been carried out on these carbonate veins, as well as on the dolostone layers found inside the Paleozoic metamorphic units of the deep part of the field (from 1939 to 3177 m below ground level). Fluid inclusion observations suggest that boiling processes probably occurred during calcite precipitation in most of the veins. The fluids that formed or interacted with the calcite veins below the uppermost reservoir (made up of Mesozoic marine carbonates), and with the calcite hydrothermal veins of Sassa, were characterised by an apparent salinity from 1.3 to 5.3 wt.% NaCl eq. and a homogenisation temperature from 137 to 245°C. The fluid inclusions related to the calcite veins hosted above the uppermost reservoir show a wide range of apparent salinity (from 1.7 to 22.2 wt.% NaCl eq.) and homogenisation temperatures from 224 to 296°C. Apparent salinity/homogenisation temperature covariations of the latter veins are interpreted as being the result of a mixing process between a low-temperature, high-salinity fluid and a higher-temperature, moderate-salinity fluid. The oxygen isotopic compositions of the calcite veins (δ¹⁸O from 10.34 to 11.45‰) located below the Mesozoic carbonates and in the outcrops (δ¹⁸O from 9.42 to 17.07‰) indicate that the vapour in equilibrium with these veins was isotopically similar to the present-day discharge steam. The aqueous fluids in equilibrium with these veins could be meteoric water that interacted with the Mesozoic carbonates of the upper reservoir. The δ¹³C values of the CO₂ produced at Larderello and the constant concentration of this gas over time are, however, indicative of a deep source inside the reservoir that is probably related to the decarbonation reaction within the metamorphic units that form the present-day deep reservoir. Fluid inclusion salinities (up to 22.2 wt.% NaCl eq.) and isotopic results (δ¹⁸O from 13.43 to 21.99‰, δ¹³C between −1.26 and −0.18‰) on the calcite veins hosted above the uppermost reservoir suggest that the water circulating in these veins has strongly interacted with Mesozoic carbonates or Neogene sediments containing evaporite layers. The isotopic values (δ¹⁸O from 14.09 to 19.91‰, δ¹³C from −4.09 to 1.90‰) of dolomite samples present in the Paleozoic metamorphic rocks indicate a reaction with fluid of variable temperatures under different water/rock ratios. The isotopic composition of one sample reveals equilibrium with present-day discharge fluids. This fact aside, the remaining data indicate that the Paleozoic dolomitic layers do not seem to contribute significantly to the production of CO₂.     

石灰石和方解石预处理酸性含氟废水的试验研究

稀有金属矿冶炼厂废水成分复杂、酸性强、含氟高、含有多种重金属离子。采用天然石灰石或方解石对其进行中和沉淀预处理, 使pH值升至2.5～3.5, 可以去除大部分氟;然后再投加石灰乳和混凝剂PAM, 使其pH值达8.5 左右, 这样能有效地去除其中的氟和重金属离子。该废水处理工艺形成的化学沉淀少、操作简单方便, 与传统的石灰乳中和法相比, 该工艺能较大幅度地降低酸性废水的处理成本。     

1-羟基乙叉-1,1-二膦酸抑制方解石螺旋生长的分子模拟研究

为研究阻垢剂的阻垢机理,我们利用HyperChem分子模拟软件,对1-羟基乙叉-1,1-二膦酸(1-hydroxy ethylidene-1．1- diphosphonic acid)HEDP抑制方解石的螺旋生长,进行了计算机分子模拟。首先,根据方解石晶体生长形貌,通过分子模拟软件生成有螺旋位错的方解石{104}面,同时基于半经验分子轨道理论,对离解后的HEDP结构优化以获得其部分电荷分布。进而用分子力学计算HEDP在{104}面螺旋位错扭折点的吸附能,及该处吸附HEDP后,Ca2 和CO32-分别沿法线向它趋近时吸附能的变化。得到结果是,在趋近扭折点过程中,HEDP与{104}面的吸附作用越来越强烈。之后,在Ca2 、CO32-趋近螺旋位错台阶时都遇到很高的势垒。计算结果表明,HEDP牢牢吸附在扭折点上,并且吸附后的HEDP阻碍了Ca2 、CO32-的沉积, 从而抑制在扭折点周围碳酸钙分子的快速生长。     

方解石去除水中磷酸盐的影响因素研究

通过试验研究了方解石去除水中磷酸盐的影响因素。结果表明：Ca^2＋促进了方解石对磷酸盐的去除，并且Ca^2＋浓度越高，对磷酸盐去除的促进作用越强；当碳酸钙饱和度（SICaCO3）〈0时，方解石的除磷效率随HCO3^-浓度的增加而降低，而当SICaCO3≥0时，HCO3^-浓度的增加反而会使方解石的除磷效率提高；温度越高、反应时间越长，方解石对磷的去除率越高；重复使用可以提高方解石去除磷酸盐的效率；当Ca^2＋浓度较低时，随着pH值（5～9）的增加方解石的除磷效率明显下降，而当Ca^2＋浓度较高时，pH值（5～9）对方解石除磷性能的影响则较小；方解石去除磷酸盐的性能受粒径和温度的影响较大。     

云南龙陵县勐兴铅锌矿床蚀变特征及找矿潜力

勐兴铅锌矿床是保山-镇康Pb、Zn、Hg、稀有金属矿成矿带内的大型铅锌矿床,矿床由一套层纹状灰岩、泥灰岩所包裹,其产状与围岩基本一致,形态受层间滑动-破劈理带控制,具有一层为主,多层含矿及尖灭再现、分支复合现象。通过大比例尺钻孔编录、平-剖面蚀变组合划分以及镜下矿物学特征研究表明:①矿区方解石化发育最广泛。②矿区蚀变组合可以划分为方解石-硅化带、黄铁矿化带、肉红色-灰绿色硅化灰岩带。③矿区近矿蚀变岩可划分为肉红色夹绿色纹层状微晶含白-绢云母灰岩、浅肉红色夹浅黄绿色薄层状微晶含泥质-绢云母灰岩、灰白色夹黑色纹层状微晶含泥质-绢云母灰岩。结合前人认识以及近期勘查成果,认为矿床为沉积-改造型,其深部可能受到与岩体(隐伏)、岩脉的叠加成矿作用,具有寻找铅锌多金属矿的潜力。     

Characteristics of pulsed photo-stimulated luminescence and thermoluminescence for the identification of gamma irradiated poultry eggs

Pulsed photo-stimulated luminescence (PPSL) is a simple screening method that can be employed qualitatively at the spot for the detection of eggs treated with ionizing radiation.Due to the variations in the results during storage,the eggs of ostrich,duck,hen,and quail were irradiated to doses of 0,1,2,and 3 kGy.Most of the samples were incorrectly identified during storage after four months of irradiation.Thermoluminescence (TL) technique was also tried by using egg shells in order to confirm the irradiation treatment in eggs.TL glow curves were recorded between the temperatures 50℃to 400℃at the rate of 5°/s for all the control and irradiated samples.On the basis of integrated areas of first glow curves (TL1),the glow curve ratios (TL1/TL2) and the shapes of maxima of TL1, the irradiation treatment of all the eggs was confirmed.Furthermore,the presence of calcite and aragonite minerals that cause the TL signal in the egg shells were studied using X-ray diffraction spectrometry.