MgSO4水合物溶解平衡时物相的热力学判别

硫酸镁易于形成水合物,例如前次报道我们获得并讨论的用于六元体系溶解度计算合理的单独电解质Pitzer参数,及四元交互体系Na+,K+//Cl-,NO3--H2O、K+,Mg2+//NO3-,SO24--H2O、K+,Mg2+//NO3-,Cl--H2O混合参数和它们的应用。此次报道对同离子四元体系K+//Cl-,NO3-,SO24--H2O、Mg2+//Cl-,NO3-,SO24--H2O的混合参数的研究及其在体系溶解度预测中的应用。     

花岗岩与大地构造

花岗岩(广义)是地球有别于其它星球及地球上大陆地壳有别于大洋地壳的物质标志,是大陆上分布最广的岩石之一。在已有研究基础上,本文系统阐述了花岗岩大地构造的内涵、研究思路、研究内容和发展方向。花岗岩大地构造将花岗岩视为一种构造标志体、地质体,是从花岗岩角度,探索解决大地构造问题,其研究内容可概括为物理特性(构造)、物质组成(岩石地化)和年代学三大方面,具体研究内容包括:(1)巨量花岗岩浆侵位的物理特性变化及其构造意义,包括岩浆上升迁移、汇聚定位及岩体(带)形成/构建过程;(2)花岗岩体变形改造及其构造意义;(3)花岗岩物源与大陆生长及深部结构,以新老物质组成,划分造山带类型;(4)巨型花岗岩带发育过程与大陆聚散,探索超大陆和中小板块聚散的岩浆响应。花岗岩大地构造丰富了大地构造研究内容,也有助深化花岗岩体(带)形成、发育过程和构造背景的认识。它的提出是当今地球科学学科交叉、融合发展的必要。     

黑龙江省东部双鸭山二长辉长岩的年代学、矿物学、结晶过程及其地质意义

双鸭山二长辉长岩侵位于中国黑龙江省双鸭山市东北部的下白垩统含煤地层内。岩相学证据表明,双鸭山二长辉长岩中的橄榄石、斜长石、单斜辉石和钛铁矿依次是岩浆早期结晶的矿物,而黑云母及少量细小的斜方辉石是演化的岩浆分别与早期结晶的钛铁矿、橄榄石反应的产物,最后的残余岩浆结晶形成了他形的钾长石,包裹其它矿物形成嵌晶结构。根据双鸭山二长辉长岩全岩成分做结晶过程的热力学模拟计算,估计的结晶过程与岩相学研究基本一致。黑云母K-Ar法和SHRIMP锆石U-Pb法的年龄测定结果一致表明,双鸭山二长辉长岩的侵位时代为98Ma,即晚白垩世早期。这一时期,中国东北地区东部、俄罗斯远东兴安岭-鄂霍茨克一带、和日本西南部可能都是当时欧亚大陆东部活动大陆边缘的组成部分,因而晚白垩世早期俯冲相关的岩浆活动在中国东北地区东部可能也是大量存在的。     

Anomalous lightning activity over the Metropolitan Region of São Paulo due to urban effects

A significant enhancement in the number of negative cloud-to-ground (CG) lightning and a decrease in the percentage of positive CG flashes are observed over the city of São Paulo, similar to observations in other large urban areas. Strong evidence indicates that this anomalous behavior results from several mechanisms related to the urban effect. In this paper, we investigated the importance of the air pollution using CG lightning data provided by the Brazilian lightning detection network (BrasilDAT) for a 6-year period (1999–2004). Due to the large variations in the CG lightning activity in response to different meteorological processes, it is not an easy task to infer the contribution of air pollution to the enhancement in the lightning activity. In order to overcome such difficulty, two approaches were considered: (1) the weekly variation of the number of days with lightning in comparison to the mean concentration of particulate matter (PM₁₀), as well as other thermodynamical parameters; (2) the variation of the number of CG flashes and the maximum storm flash rate per individual thunderstorm for different levels of pollution. The results of both analyses suggest that: first, the enhancement in the CG lightning activity during the week days over São Paulo metropolitan region is related to the PM₁₀ concentration (pollution); second, the PM₁₀ concentration tends to increase the lifetime of the storms and, in consequence, the number of flashes per storm, and not the flash rate of the thunderstorm; and third, the effect of the pollution in the enhancement of the CG lightning activity is probably less significant compared to the effect of the urban heat island.     

白云石蛇纹石化,滑石化的热力学讨论

本文结合镁质胶凝材料方面的一些实验资料,从热力学角度讨论了MgO+SiO_2蒸发生成滑石、纤维蛇纹石;白云石的滑石化、纤维蛇纹石化和白云石与滑石间的相互转变。提出以白云石代替MgO作合成生产镁质胶凝材料更加经济。     

A creep–rupture model of synthetic fiber ropes for deepwater moorings based on thermodynamics

The synthetic fiber ropes such as polyester, aramid and high modulus polyethylene (HMPE) are increasing applied to deepwater mooring systems for oil and gas exploitation. Due to that mooring ropes generally bear tensions for a long period, synthetic fiber ropes that are composed of the viscoelastic material would present creep behaviors and even the creep rupture, which is the failure mode of greatest concern especially for HMPE ropes and on which still less study can be found. A creep damage analysis of synthetic fiber ropes is of necessity to ensure the safe and economic operation of mooring systems. Therefore further investigation on the creep–rupture behavior is beneficial to fully establishing confidence in the viability of synthetic fiber ropes for deepwater moorings. In the present study, a creep–rupture model is proposed within the framework of thermodynamics to investigate the creep and damage behaviors of synthetic fiber ropes. Methods for identifying the model parameters are also proposed in detail, which apply to any component of fiber ropes such as the fiber, yarn, strand and rope. Experimental data of aramid yarns available from the literature are utilized to validate the constitutive model. Creep and creep–rupture tests of HMPE strands at different loading levels are specially performed to further examine the present model. The present work demonstrates that the proposed model can effectively describe the viscoelastic property and damage evolution of synthetic fiber ropes at different loading levels.     

Thermodynamics and crystal chemistry of the hematite–corundum solid solution and the FeAlO3 phase

High-temperature oxide-melt calorimetry and Rietveld refinement of powder X-ray diffraction patterns were used to investigate the energetics and structure of the hematite–corundum solid solution and ternary phase FeAlO₃ (with FeGaO₃ structure). The mixing enthalpies in the solid solution can be described by a polynomial ΔH_mix=WX _hem(1?X _hem) with W=116 ± 10 kJ mol^?1. The excess mixing enthalpies are too positive to reproduce the experimental phase diagram, and excess entropies in the solid solution should be considered. The hematite–corundum solvus can be approximately reproduced by a symmetric, regular-like solution model with ΔG _excess=(W _H ?TW _S )X _hem X _cor, where W _H= 116 ± 10 kJ mol^?1 and W _S =32 ± 4 J mol^?1 K^?1. In this model, short-range order (SRO) of Fe/Al is neglected because SRO probably becomes important only at intermediate compositions close to Fe:Al=1:1 but these compositions cannot be synthesized. The volume of mixing is positive for Al-hematite but almost ideal for Fe-corundum. Moreover, the degree of deviation from Vegard's law for Al-hematite depends on the history of the samples. Introduction of Al into the hematite structure causes varying distortion of the hexagonal network of oxygen ions while the position of the metal ions remains intact. Distortion of the hexagonal network of oxygen ions attains a minimum at the composition (Fe_0.95Al_0.05)₂O₃. The enthalpy of formation of FeAlO₃ from oxides at 298 K is 27.9 ± 1.8 kJ mol^?1. Its estimated standard entropy (including configurational entropy due to disorder of Fe/Al) is 98.9 J mol^?1 K^?1, giving the standard free energy of formation at 298 K from oxides and elements as +19.1 ± 1.8 and ?1144.2 ± 2.0 kJ mol^?1, respectively. The heat capacity of FeAlO₃ is approximated as C _p (T in K)= 175.8 ? 0.002472T ? (1.958 × 10⁶)/T ²? 917.3/T ^0.5+(7.546 × 10^?6) T ² between 298 and 1550 K, based on differential scanning calorimetric measurements. No ferrous iron was detected in FeAlO₃ by Mössbauer spectroscopy. The ternary phase is entropy stabilized and is predicted to be stable above about 1730 ± 70 K, in good agreement with the experiment. Static lattice calculations show that the LiNbO₃-, FeGaO₃-, FeTiO₃-, and disordered corundum-like FeAlO₃ structures are less stable (in the order in which they are listed) than a mechanical mixture of corundum and hematite. At high temperatures, the FeGaO₃-like structure is favored by its entropy, and its stability field appears on the phase diagram.     

Thermodynamics of gas and steam-blast eruptions

Eruptions of gas or steam and non-juvenile debris are common in volcanic and hydrothermal areas. From reports of non-juvenile eruptions or eruptive sequences world-wide, at least three types (or end-members) can be identified: (1) those involving rock and liquid water initially at boiling-point temperatures (boiling-point eruptions); (2) those powered by gas (primarily water vapor) at initial temperatures approaching magmatic (gas eruptions); and (3) those caused by rapid mixing of hot rock and ground- or surface water (mixing eruptions). For these eruption types, the mechanical energy released, final temperatures, liquid water contents and maximum theoretical velocities are compared by assuming that the erupting mixtures of rock and fluid thermally equilibrate, then decompress isentropically from initial, near-surface pressure (10 MPa) to atmospheric pressure. Maximum mechanical energy release is by far greatest for gas eruptions (1.3 MJ/kg of fluid-rock mixture)-about one-half that of an equivalent mass of gunpowder and one-fourth that of TNT. It is somewhat less for mixing eruptions (0.4 MJ/kg), and least for boiling-point eruptions (0.25 MJ/kg). The final water contents of crupted boiling-point mixtures are usually high, producing wet, sloppy deposits. Final erupted mixtures from gas eruptions are nearly always dry, whereas those from mixing eruptions vary from wet to dry. If all the enthalpy released in the eruptions were converted to kinetic energy, the final velocity (v _max) of these mixtures could range up to 670 m/s for boiling-point eruptions and 1820 m/s for gas eruptions (highest for high initial pressure and mass fractions of rock (m _r) near zero). For mixing eruptions, v _max ranges up to 1150 m/s. All observed eruption velocities are less than 400 m/s, largely because (1) most solid material is expelled when m _r is high, hence v _max is low; (2) observations are made of large blocks the velocities of which may be less than the average for the mixture; (3) heat from solid particles is not efficiently transferred to the fluid during the eruptions; and (4) maximum velocities are reduced by choked flow or friction in the conduit.