皂化环烷酸串级萃取体系计算机模拟的研究

溶剂萃取法是目前国内外广泛采用的分离提纯和富集稀土元素的方法之一，与其它方法相比较，具有许多优点，为了改变稀土萃取分离工艺的研究方法还比较落后的状态，研究和解决这个问题已令人瞩目。计算机的数学模拟法就是其中较为先进的方法之一。本论文用计算机的数学模拟法对皂化环烷酸分离钇和镧系元素的串级萃取体系进行了初步的研究。在分析皂化环烷酸和皂化P507串级萃取体系特点的基础上，提出了皂化环烷酸分离钇(Y)和镧系元素(Nd,Er)串级萃取体系的静态数学模型，对模型参数及其求法做了较为详细的讨论，分别用矩辄法和逐级计算法解算，并将计算结果与实验结果进行比较，发现矩阵法的计算精度较逐级计算法为好。可以得出：所提出的模型对氨化环烷酸分离钆和镧系元素的串级萃取体系是基本适用的，并且预计，对皂化弱酸类萃取剂分离金属离子的串级萃取体系也将具有一定的通用性；初步尝试了一种实验方法，对皂化的串级萃取体系，根据串级条件，只做单级实验就可以用电子计算机模拟地计算出各组份的逐级浓度，实验结果表明，这种方法对氨化环烷酸萃取体系是可行的。对皂化环烷酸分离钇(Y)和镧系元素(Nd)的串级萃取体系进行了改变工艺条件的计算。所建立的模型为非线性方程组，用改进牛顿法解非线性方程组，对解的初值要求较为严格，为了方便并且较快地找到一组初值，首先用逐级计算法解算，其结果就作为矩法的初值，并对端级模型作了简化，对工艺参数改变（洗液的酸度、料液的总浓度、料液的组成以及级数）进行了相应条件下的单级实验，求得了各模型参数，然后进行模拟计算，得到了与萃取规律相符的计算结果，又进行了常级模拟实验加以比较，计算值与实际串级萃取体系的实验值相比较，端级结果比较一致，中间各级有时误差较大，我们希望能够能过对计算结果的比较，从而对工艺条件加以筛选，这方面的工作还需要进行较为深入的研究，模型和计算方法都有待于进一步的完善。论文中，还对近年来李涵等提出的单一稀土线性规则进行了进一步探讨，结果表明对非稀土元素如Cu(Ⅱ)，Co(Ⅱ)，Ni(Ⅱ)等单一元素的萃取，该线性规则仍然成立。

数学模拟法优化设计氨化体系稀土分离工艺

应用数学模拟法对氨化环烷酸体系分离钇与镧系元素的萃到过程及氨化P_(507)体系分离稀土元素的萃取过程分别进行了优化工艺设计。采用复合形优化法，在进料浓度和进料量一定的情况下，选取 Q = (N · Zo · VOE)/(x(1, 1)·VAE)为目标函数。选取N、NF、Zo、VOE、Hw和VAW为六个优化参数，选取二出口产品的纯度和收率为约束条件。首先对氨化环烷酸体系分离Y与镧系元素（Nd）的串级萃取过程进行了优化工艺设计。优化设计中所用的串级计算采用了占计算机内存较小的求解稀疏矩阵的方法。在满足出口产品Y的纯度不小于99.98%的情况下，得到了一组优化工艺参数和该优化工艺条件下的各级二相数据。并与已有实验结果进行了对比，论证了其合理性。其次，将逐级计算法引入了优化设计过程，对氨化环烷酸体系分离Y与Nd的过程再次进行了计算，并与矩阵法结果作了对比，认为逐级计算法可以与优化方法结合设计工艺。用此方法对氨化环烷酸体系分离Y与Nd，Er的串级萃取过程进行了优化工艺设计，在满足出口产品Y纯度≥99.99%的情况下，得到了一组优化工艺参数，同时给出了优化工艺条件下的各级二相数据，对比已有实验，结果比较满意。利用所提出的方法对文献报道的从江西矿分离高纯Y的实际过程进行了计算，所得的结果与串级理论设计出的结果比较接近。由于文献已进行了实验验证，故可以认为本文所得的结果基本可靠。最后，在分析了氨化P_(507)体系萃取稀土元素的特点以后，提出了逐级计算法与复合优化法相结合来优化工艺参数。在水相出口级、进料级、有机相出口级建立单级分配模型，采用所建立的模型和方法对氨化P_(507)体系分离Nd, Sm的串级萃取过程进行了优化工艺设计，得到了一组优化参数及优化工艺下的二相各级各组分浓度，并在优化的工艺条件下做了验证实验，实验结果与计算结果基本吻合。

对金属稀土金属有机配合物的合成、结构及催化性质研究

合成出三类18种双金属稀土金属有机配合物：第一类：Ln-Li双金属π－烯丙基稀土配合物－LiLn(π-C_3H_5)_4 nD(Ln=La、Tb, n=3; Ln=Y、Dy, n=2.5; Ln=Ce、Pr、Nd、Sm、Gd、Er, n=2; D=二氧六环）。第二类：Ln-Mg双金属π－烯丙基稀土配合物-(π-C_3H_5)_2CnCl_5Mg_2(tmed)_2 (Ln=Ce、Nd)和(π-C_4H_7)_2LnCl_5Mg_2(tmed)_2 (Ln=La、Ce、Nd; C_4H_7=i-C_4H_7)。第三类：Ln-Al双金属配合物－[(CF_3CO_2)_3LnHAlR_2·2THF]_2 (Ln=Y、Nd, R=i-Bu; Ln=Eu, R=Et)。用四园X－ray衍射仪在低温下测定了LiCe(π-C_3H_5)_4·4D、[(CF_3CO_2)_3YHAl(i-Bu)_2 2THF]_2、[(CF_3CO_2)_3NdHAl(i-Bu)_2 2THF]_2和[(CF_3CO_2)_3EuHAlEt_2·2THF]_2的晶体结构。对[(CF_3CO_2)_3YHAl(i-Bu)_2·2THF]_2和LiLn(π-C_3H_5)_4 nD类配合物进行了较详细的NMR研究。二维C－H相关NMR谱表明在[(CF_3CO_2)_3YHAl(i-Bu)_2·2THF]_2配合物中6个CF_3CO_2~-有2个羰基的C与H成键，该结果解释了Ln-Al双金属配合物中相应羰基的非平面结构现象。研究表明LiLn(π-CC_3H_5)_4·nD可催化异戊二烯和苯乙烯均聚合；不同配合物中均以Y配合物的活性为最高。(π-C_3H_5)_2CeCl_5Mg_2(tmed)_2对异戊二烯、丁二烯、苯乙烯以及甲基丙烯酸甲酯（MMA）的聚合有较低的催化活性；(π-C_4H_7)_2LnCl_5Mg_2(tmed)_2也对苯乙烯和异戊二烯的聚合有一定的催化活性。分别以LiCe(π-C_3H_5)_4·4D和(π-C_3H_5)_2CeCl_5Mg_2(tmed)_2作为稀土配位催化剂的模型配合物，研究了其催化所得聚异戊二烯的端基结构。表明聚合物均具有烯丙基端基(-CH_2-CH=CH_2)。证明单体在Ce~(3+)和π－烯丙基之间发生了插入反应，聚合按π－烯丙基机理进行。该结果首次为稀土配位催化共轭双烯烃聚合的活性链端π－烯丙基机理提供了直接的实验证据。(π-C_3H_5)_2CeCl_5Mg_2(tmed)_2-Al(i-Bu)_3(Al/Ce(摩尔比)=4))体系对异戊二烯的聚合具有较高的催化活性，所得聚合物仍具有－CH_3-CH=CH_2端基，而没有i-Bu端基。该结果又一次为上述π-烯丙基机理提供了直接的实验证据。发现Ln(CF_3CO_2)_3-AlEt_3体系可催化THF开环聚合。首次实现稀土催化THF开环聚合。研究了Y(CF_3CO_2)_3-HAl(i-Bu)_2-ECH（环氧氯丙烷）体系催化THF开环聚合法性及聚合机理。讨论了各种聚合条件对该体系催化活性的影响。研究了[(CF_3Co_2)YHAl(i-Bu)_2·2THF]_2在ECH存在下催化THF聚合活性并认为该双金属配合物为Y(CF_3CO_2)_3-HAl(i-Bu)_2-ECH体系的活性体。[(CF_3CO_2)_3YHA(i-Bu)_2·2THF]_2和[(CF_3CO_2)_3EuHAlEt_2·2THF]_2均可催化ECH和MMA聚合，所得PMMA的间同(rr)含量可达76.5％。

Microstructure and mechanical properties of Mg-4.5Zn-xNd (x=0, 1 and 2, wt%) alloys

Microstructure and mechanical properties of Mg-4.5Zn-xNd (x = 0, 1 and 2, wt%) alloys heat-treated at 603 K for 2 It have been investigated. T-phase (an Mg-Zn-Nd ternary phase) was observed in the Nd containing alloys. The optimal mechanical properties were obtained in the Mg-4.5Zn-1Nd alloy, and the ultimate tensile strength and yield strength were 228 and 79 MPa, respectively. Through comparing with the Mg-4.5Zn alloy, the increments of ultimate tensile strength and yield strength were 51 and 17 MPa.

Investigation of Chemical Bond Characteristics, Thermal Expansion Coefficients and Bulk Moduli of alpha-R2MoO6 and R2Mo2O7 (R = rare earths) by Using a Dielectric Chemical Bond Method

Theoretical researches are performed on the alpha-R2MoO6 (R = Y, Gd, Tb Dy, Ho, Er, Tm and Yb) and pyrochlore-type R2Mo2O7 (R = Y, Nd, Sm, Gd, Tb and Dy) rare earth molybdates by using chemical bond theory of dielectric description. The chemical bonding characteristics and their relationship with thermal expansion property and compressibility are explored. The calculated values of linear thermal expansion coefficient (LTEC) and bulk modulus agree well with the available experimental values. The calculations reveal that the LTECs and the bulk moduli do have linear relationship with the ionic radii of the lanthanides: the LTEC decreases from 6.80 to 6.62 10(-6)/K and the bulk modulus increases from 141 to 154 GPa when R goes in the order Gd, Tb Dy, Ho, Er, Tm, and Yb in the alpha-R2MoO6 series; while in the R2Mo2O7 series, the LTEC ranges from 6.80 to 6.61 10(-6)/K and the bulk modulus ranges from 147 to 163 GPa when R varies in the order Nd, Sm, Gd, Tb and Dy.

Geochemistry and isotopic ratios of samples obtained during R/V Akademik Nikolaj Strakhov cruise ANS24

New petrological and geochemical data were obtained for basalts recovered during cruise 24 of the R/V "Akademik Nikolay Strakhov" in 2006. These results significantly contributed to the understanding of the formation of tholeiitic magmatism at the northern end of the Knipovich Ridge of the Polar Atlantic. Dredging was performed for the first time both in the rift valley and on the flanks of the ridge. It showed that the conditions of magmatism have not changed since at least 10 Ma. The basalts correspond to slightly enriched tholeiites, whose primary melts were derived at the shallowest levels and were enriched in Na and depleted in Fe (Na-TOR type). The most enriched basalts are typical of the earlier stages of the opening and were found on the flanks of the ridge in its northernmost part. Variations in the ratios of Sr, Nd, and Pb isotopes and lithophile elements allowed us to conclude that the primary melts generated beneath the spreading zone of the Knipovich Ridge were modified by the addition of the enriched component that was present both in the Neogene and Quaternary basalts of Spitsbergen Island. Compared with the primitive mantle, the extruding magmas were characterized by positive Nb and Zr anomalies and a negative Th anomaly. The formation of primary melts involved melting of the metasomatized depleted mantle reservoir that appeared during the early stages of opening of the Norwegian-Greenland Basin and transformation of the paleo-Spitsbergen Fault into the Knipovich spreading ridge, which was accompanied by magmatism in western Spitsbergen during its separation from the northern part of Greenland.

Geochemistry and petrology of the volcanic rocks from the Sulu Sea

Major-, trace-, and rare-earth element analyses of the basaltic rocks recovered from the basement of the Sulu Sea and of lithic clasts from the pyroclastic unit representing the acoustic basement of the Cagayan Ridge, are presented. The major and trace elements were measured by X-ray fluorescence techniques, and rare-earth elements by instrumental neutron activation analysis. These data show that the Sulu Sea basalts are back-arc tholeiites and the lithic clasts are basalts, basaltic andesites, and andesites typical of volcanic arc suites erupted on continental crust. Petrogenetic modeling is used to show that the Sulu Sea basalts were derived from a heterogeneous mantle, probably representing subcontinental lithosphere, with contributions from a subduction component. The Sulu Sea is interpreted as a back-arc basin formed by rifting of an Oligocene to early Miocene volcanic arc leaving the Cagayan Ridge as a remnant arc. This event occurred during northward subduction of the Celebes Sea basement beneath the Oligocene to early Miocene arc.

Energetics of rare earth manganese perovskites A1-xA ' xMnO3 (A = La, Nd, Y and A ' = Sr, La) systems

High temperature reaction calorimetry using molten lead berate as solvent has been used to study the thermochemistry of NdMnO3, YMnO3, La1-xSrxMnO3 (with 0 < x < 0.5), and Ln(0.5)Ca(0.5)MnO(3) (with Ln = La, Nd, Y), The enthalpies of formation of these multicomponent oxides from their binary constituents have been calculated from the measured enthalpy of drop solution, The energetic stability of the perovskite depends on the size of the A cation, The enthalpy of formation of YMnO3 (smallest A cation) is more endothermic than those of NdMnO3 and LaMnO3. The energetics of the perovskite also depends on the oxidation state of the B site's ions. In the La1-xSrxMnO3 system, the energetic stability of the structure increases with the Mn4+/Mn3+ ratio, The new values of the enthalpies of oxidations, with reliable standard entropies, were used to plot the phase stability diagram of the lanthanum-manganese-oxygen system in the temperature range 300-1100 K, The LaMnO3/MnO phase boundary evaluated in this study agrees with the one published by Atsumi et nl. calculated from thermogravimetric and conductivity measurements.

Resistometric studies of solute-vacancy interactions and clustering kinetics in an FCC matrix [AlZn Alloy with Ag, Ce, Dy, Li, Nb, Pt, Sb, Y, or Yb]

Al-4.4 a/oZn and Al-4.4 a/oZn with Ag, Ce, Dy, Li, Nb, Pt, Y, or Yb, alloys have been investigated by resistometry with a view to study the solute-vacancy interactions and clustering kinetics in these alloys. Solute-vacancy binding energies have been evaluated for all these elements by making use of appropriate methods of evaluation. Ag and Dy additions yield some interesting results and these have been discussed in the thesis. Solute-vacancy binding energy values obtained here have been compared with other available values and discussed. A study of the type of interaction between vacancies and solute atoms indicates that the valency effect is more predominant than the elastic effect.

Precipitation response of the magnesium alloy WE43 in strained and unstrained conditions

The precipitation behavior of the magnesium alloy WE43 (Mg-4%Y-2.3%Nd-0.5%Zr) has been studied in strained and unstrained conditions using Transmission Electron Microscopy (TEM). Ageing treatments were carried out at three temperatures, namely 210 degrees C, 230 degrees C and 260 degrees C. The precipitation sequence during static aging of solution treated (ST) samples has been identified as ST —> beta'' —> beta' followed by the formation of beta(1) and equilibrium beta precipitates form after very long ageing periods. Dynamic precipitation was observed during high temperature deformation, leading to the formation of beta' and intermediate beta(1) precipitates. The strained samples, when further heat treated, resulted in the transformation of beta(1) into beta equilibrium precipitates. The sequence of dynamic precipitation is ST —> beta(1) —> beta and ST —> beta'. (C) 2014 Elsevier B.V. All rights reserved.

Serrated Plastic Flow During Nanoindentation in Nd-Based Bulk Metallic Glasses

The microstructure of Nd_{60}Al_{10}Ni_{10}Cu_{20-x}Fex (x = 0, 5, 7, 10, 15, 20) alloys can change from homogeneous phase to a composite structure consisting of amorphous phase plus clusters or nanocrystals by adjusting the Fe content. The effect of microstructure on the plastic deformation behavior in this alloy system is studied by using nanoindentation. The alloys with homogeneous amorphous structure exhibit pronounced flow serrations during the loading process of nanoindentation. The addition of Fe changes the plastic deformation behavior remarkablely. No flow serration is observed in the alloys with high Fe content for the indentation depth of 500 nm. The mechanism for the change of plastic serrated flow behavior is discussed.

Avances en espectrometría de masas con fuente de plasma: Análisis simultáneo de elementos mayores y trazas mediante Q-ICP-MS y análisis isotópicos de Sm-Nd mediante HR-MC-ICP-MS. Aplicación en estudios geoquímicos

186 p. : il.

Dual-wavelength competitive output in Nd:Y3Sc1.5Al3.5O12 ceramic disk laser

In this paper, we demonstrated a dual-wavelength competitive output in Nd:Y3SC1.5Al3.5O12 ceramic disk laser. Different dual-wavelength output behaviors for Nd:YSAG and Nd:YAG ceramic disk laser were investigated and discussed. By applying the energy transfer model, we suggested the reasonable explanation for this new phenomenon as the disordered replacing of Al3+ ions by Sc3+ ions. The main advantage of the dual-wavelength ceramic laser is the possibility to serve as the seed source to generate Terahertz radiation. (C) 2008 Elsevier B.V. All rights reserved.

Magnetic characterisation of large grain, bulk Y-Ba-Cu-O superconductor-soft ferromagnetic alloy hybrid structures

Large grain, bulk Y-Ba-Cu-O (YBCO) high temperature superconductors (HTS) have significant potential for use in a variety of practical applications that incorporate powerful quasi-permanent magnets. In the present work, we investigate how the trapped field of such magnets can be improved by combining bulk YBCO with a soft FeNi, ferromagnetic alloy. This involves machining the alloy into components of various shapes, such as cylinders and rings, which are attached subsequently to the top surface of a solid, bulk HTS cylinder. The effect of these modifications on the magnetic hysteresis curve and trapped field of the bulk superconductor at 77 K are then studied using pick-up coil and Hall probe measurements. The experimental data are compared to finite element modelling of the magnetic flux distribution using Campbell's algorithm. Initially we establish the validity of the technique involving pick-up coils wrapped around the bulk superconductor to obtain its magnetic hysteresis curve in a non-destructive way and highlight the difference between the measured signal and the true magnetization of the sample. We then consider the properties of hybrid ferromagnet/superconductor (F/S) structures. Hall probe measurements, together with the results of the model, establish that flux lines curve outwards through the ferromagnet, which acts, effectively, like a magnetic short circuit. Magnetic hysteresis curves show that the effects of the superconductor and the ferromagnet simply add when the ferromagnet is saturated fully by the applied field. The trapped field of the hybrid structure is always larger than that of the superconductor alone below this saturation level, and especially when the applied field is removed. The results of the study show further that the beneficial effects on the trapped field are enhanced when the ferromagnet covers the entire surface of the superconductor for different ferromagnetic components of various shapes and fixed volume. © 2014 Elsevier B.V. All rights reserved.