Novel polyaryletherketones containing various pendant groups .1. Synthesis and characterization

Novel high glass transition temperature polyaryletherketones, containing pendant amido, alkyl, and carboxyl groups with reduced viscosity above 0.54 dL/g, were synthesized via solution nucleophilic polycondensation reaction of phenolphthalin, 2',2 ''-diisopropyl-5',5 ''-dimethylphenolphthalin, and 3,3'-bis(4-hydroxyphenyl)isobenzopyrrolidone with bis(4-nitrophenyl)ketone in the presence of potassium carbonate. By ion exchange with Na+ and K+, four ionomers were also prepared. A new monomer simultaneously containing carboxyl and algyl substituents was synthesized by reduction reaction of 2',2 ''-diisopropyl-5',5 ''-dimethyl-phenolphthalein. The resulting polymers were soluble in a few polar aprotic solvents; transparent, colorless, and tough films could easily be cast from DMF or DMSO solution. The mechanical properties of the films were excellent; and their tensile strength, elongation at break, and tensile moduli were in the range of 67.1-97.1 MPa, 7.8-165%, and 1.47-2.27 GPa, respectively. The prepared polymers showed fairly good thermal stability and resonably high glass transition temperatures above 210 degrees C. (C) 1997 John Wiley & Sons, Inc.

Synthesis and characterization of aromatic liquid crystalline poly(ester-imide)s derived from an imidodicarboxylic acid

A new class of liquid crystalline poly(ester-imide)s was synthesized by melt polycondensation. The basic physical properties of the resulting polymers were investigated by differential scanning calorimetry (d.s.c.), wide-angle X-ray diffraction (WAXD), polarized light microscopy, scanning electron microscopy (SEM), thermogravimetric analysis (t.g.a.), and rheological and mechanical testing. All of these poly(ester-imide)s were amorphous, as reflected by the results obtained from the WAXD and d.s.c. studies. Characterization and comparison of these poly(ester-imide)s with the corresponding polyesters suggested that the introduction of imide groups into the polyester chain is favourable for the formation of liquid crystalline phases. These results, together with the rheological studies, suggested that there existed a form of strong inter- or intramolecular electron donor-acceptor interaction which played a significant role in the liquid crystalline properties of the poly(ester-imide)s. The polymer products thus obtained exhibited good mechanical properties, with flexural strengths and moduli as high as 174 MPa and 6.9 GPa, respectively. The morphology of the fracture surfaces of extruded rod samples showed a sheet-like structure which consisted of ribbons and fibres oriented along the flow direction. The glass transition temperatures and thermal stabilities of the polymers were improved by the incorporation of imide groups. Copyright (C) 1996 Elsevier Science Ltd.

THE PHYSICAL AND CHEMICAL-PROPERTIES OF SYNTHETIC AND NATURAL JADEITE FOR JEWELRY

Jadeite was synthesized from its glass of stoichiometric composition NaAlSi2O6, and a colouring agent Cr2O3 (0.3-0.6 wt%) was added to achieve the emerald colour. The conditions employed were a pressure range of 3.0-5.0 GPa and a temperature range of 1150

合成压力、温度对人工翡翠宝石编织结构影响的研究

在1.8～5.5GPa、1150～1450℃范围内均可实现由具有翡翠成份的非晶玻璃态到翡翠结构(单斜晶系)结晶态的转化。发现人工翡翠宝石的显微织构随合成压力、温度的变化很大,但其晶胞参数变化不大。晶粒细密编织紧凑的人工翡翠显微结构特征,宏观上表现出质地细腻、色泽纯正、最富有观赏价值的特点;其最佳合成条件为:压力5,1 GPa,温度1150℃。热稳定性实验表明,人工翡翠与天然翡翠具有相同的稳定性。

Genesis of Th-230 excess in basalts from mid-ocean ridges and ocean islands: Constraints from the global U-series isotope database and major and rare earth element geochemistry

Based on Th-230-U-238 disequilibrium and major element data from mid-ocean ridge basalts (MORBs) and ocean island basalts (OIBs), this study calculates mantle melting parameters, and thereby investigates the origin of Th-230 excess. (Th-230/U-238) in global MORBs shows a positive correlation with Fe-8, P (o), Na-8, and F-melt (Fe-8 and Na-8 are FeO and Na2O contents respectively after correction for crustal fractionation relative to MgO = 8 wt%, P (o)=pressure of initial melting and F (melt)=degree of melt), while Th-230 excess in OIBs has no obvious correlation with either initial mantle melting depth or the average degree of mantle melting. Furthermore, compared with the MORBs, higher (Th-230/U-238) in OIBs actually corresponds to a lower melting degree. This suggests that the Th-230 excess in MORBs is controlled by mantle melting conditions, while the Th-230 excess in OIBs is more likely related to the deep garnet control. The vast majority of calculated initial melting pressures of MORBs with excess Th-230 are between 1.0 and 2.5 GPa, which is consistent with the conclusion from experiments in recent years that D (U)> D (Th) for Al-clinopyroxene at pressures of > 1.0 GPa. The initial melting pressure of OIBs is 2.2-3.5 GPa (around the spinel-garnet transition zone), with their low excess Ra-226 compared to MORBs also suggesting a deeper mantle source. Accordingly, excess Th-230 in MORBs and OIBs may be formed respectively in the spinel and garnet stability field. In addition, there is no obvious correlation of K2O/TiO2 with (Th-230/U-238) and initial melting pressure (P (o)) of MORBs, so it is proposed that the melting depth producing excess Th-230 does not tap the spinel-garnet transition zone. OIBs and MORBs in both (Th-230/U-238) vs. K2O/TiO2 and (Th-230/U-238) vs. P (o) plots fall in two distinct areas, indicating that the mineral phases which dominate their excess Th-230 are different. Ce/Yb-Ce curves of fast and slow ridge MORBs are similar, while, in comparison, the Ce/Yb-Ce curve for OIBs shows more influence from garnet. The mechanisms generating excess Th-230 in MORBs and OIBs are significantly different, with formation of excess Th-230 in the garnet zone only being suitable for OIBs.

南海新生代碱性玄武岩的特征及其地球动力学意义

南海是西太平洋最大的边缘海之一，位于欧亚板块、印-澳板块以及太平洋板块之间。南海海底扩张停止(15.5Ma, Briais et al., 1993) 后的板内火山作用，影响着中国南部、中南半岛、大洋基底和分裂的微大陆片段的广大地区。对南海新生代玄武岩进行地球化学研究，不仅对于理解南海板内火山作用的深部地幔过程有着重要意义，而且对南海形成演化及含油气盆地形成的深部动力学机制有着深远意义。 南海新生代玄武岩K-Ar/Ar-Ar年龄为3.8-7.9Ma, 表明为晚中新世以来的岩浆活动产物，与周边地区的碱性火山岩在年龄上的一致性。岩石学特征表明，南海新生代玄武岩的矿物组合为橄榄石、单斜辉石、斜长石，与特征的碱性玄武岩的矿物组合一致。由橄榄石所计算的南海底潜在地幔温度(Tp)平均值为1661℃, 暗示南海地区下的地幔可能存在热量异常，为海南地区存在地幔柱的观点提供了证据。单斜辉石富钙、钛，由单斜辉石-熔体平衡温压计计算的岩浆房深度分别为：碱玄岩岩浆房深度约49km（对应压力为1.46～1.48 GPa）；粗面玄武岩岩浆房约25km（对应压力为0.76 GPa）；玄武岩岩浆房约15km（对应压力为0.44GPa）。由碱玄岩→粗面玄武岩→玄武岩，平衡温度(K)依次降低:从1535～1498→1429→1369。由斜长石微晶所计算的岩浆喷出地表的温度为989℃。 主量元素特征表明，岩石类型主要为碱玄岩，有少量的粗面玄武岩和玄武岩，属于碱性系列。微量元素方面，大离子亲石元素(LILE)以及高场强元素（HFSE）特别是Nb、Ta、Ti、Y等元素均呈现富集现象，Yb、Sc、Sr以及K、U、Th等生热元素相对亏损，微量元素及稀土元素分布岩石类似板内OIB微量元素的全球平均值。同位素地球化学研究表明，源区存在两个混合端员并具Dupal Pb异常：一个为DMM，位于软流圈或岩石圈地幔中；另一个为EM2源区，可能来自位于核-幔边界处的海南地幔柱而非大陆底岩石圈地幔。研究表明，南半球Dupal异常不存在全球范围内的地区专属性，本区存在的Dupal异常与南半球Dupal异常可能不存在联系。在南海新生代玄武岩的成因过程中，海南地幔柱在为岩石圈地幔的部分熔融作用提供所需的热量同时，也在物质上作出了贡献。南海盆新生代碱性玄武岩由不同程度的部分熔融作用，以及岩浆在上升期间或者在高位岩浆房中的橄榄石等矿物分离结晶作用所形成，同时还可能发生了堆晶作用。构造环境判别表明，玄武岩浆在上升到地表过程中几乎未受到地壳混染。 南海新生代玄武岩的地球化学研究表明，在玄武质岩浆的深部地幔演化过程中，海南地幔柱可能起着重要的作用。通过引入海南岛地幔柱这个概念，本文建立了一个新的有关南海形成演化的初步的概念性模型：（1）50-32Ma，印度洋板块-欧亚板块碰撞及其所导致的太平洋板块后退的综合效应为南海地区提供了一个伸展环境，此伸展环境为地幔柱物质的上升提供了通道；（2）32-21Ma，当地幔柱柱头到达软流圈时, 通过侧向物质流开始同扩张中心发生相互作用，促进了南海的扩张，并在26-24Ma期间发生了洋脊重新就位事件，使扩张中心从原来的18°N附近(即现今西北海盆的中心)调整到15.5°N附近（即现今的东部亚盆）；（3）21-15.5Ma, 随着地幔柱效应的逐渐增强，热点-洋脊相互作用越来越强烈，在大约21Ma发生了洋脊的再次重新就位事件，诱发了西南海盆的扩张；（4）15.5-现在，由于印澳板块前缘与巽他大陆碰撞，使得南海大约在15.5Ma停止扩张,并沿着南沙海槽及吕宋海沟向菲律宾岛弧及巴拉望地块之下俯冲，而南海热点继续活动，在地表处直到第四纪还有碱性玄武岩喷出。

高温高压下H2O-CH4体系PVTx性质的分子动力学模拟研究

Geological fluids are important components in the earth system. To study thephysical chemistry properties and the evolution of fluid system turns out to be one of the most challenging issues in geosciences. Besides the conventional experimental approaches and theoretical or semi-theoretical modeling, molecular level computer simulation(MLCS) emerges as an alternative tool to quantificationally study the physico-chemical properties of fluid under extreme conditions in order to find out the characteristics and interaction of geological fluids in and around earth. Based on our previous study of the intermolecular potential for pure H2O and thestrict evaluation of the competitive potential models for pure CH4 and the ab initio fitting potential surface across H2O-CH4 molecules in this study, we carried out more than two thousand molecular dynamics simulations for the PVTx properties of pure CH4 and the H2O-CH4 mixtures. Comparison of 1941 simulations with experimental PVT data for pure CH4 shows an average deviation of 0.96% and a maximum deviation of 2.82%. The comparison of the results of 519 simulations of the mixtures with the experimental measurements reveals that the PVTx properties of the H2O-CH4 mixtures generally agree with the extensive experimental data with an average deviation of 0.83% and 4% in maximum, which is equivalent to the experimental uncertainty. Moreover, the maximum deviation between the experimental data and the simulation results decreases to about 2% as temperature and pressure increase,indicating that the high accuracy of the simulation is well retained in the high temperature and pressure region. After the validation of the simulation method and the intermolecular potential models, we systematically simulated the PVTx properties of this binary system from 673 K and 0.05 GPa to 2573 K and 10 GPa. In order to integrate all the simulation results and the experimental data for the calculation of thermodynamic properties, an equation of state (EOS) is developed for the H2O-CH4 system covering 673 to 2573 K and 0.01 to 10 GPa. Isochores for compositions < 4 mol% CH4 up to 773 K and 600 MPa are also determined in this thesis.

NCMAS系统熔体结构和动力学性质压力效应的分子动力学研究

Molecular dynamics simulations were used to study the pressure dependence of the structure and the dynamic properties of forsterite melt (Mg_2SiO_4), diopside melt (CaMgSi_2O_6), anorthite melt (CaAl_2Si_2O_8), jadite melt (NaAlSi_2O_6) and albite melt (NaAlSi3O8) from 0 GPa to 25 GPa at about 2000 K and the following conclusions have been reached. Firstly, the ratio of NBO to T (NBO and T denote the content of non-bridging oxygen and the total content of Si~(4+) and Al~(3+) respectively) is closely related to the pressure and the composition of the melts. It decreases monotonously in forsterite, diopside and anorthite melts while increases at the initial stage and then decreases in jadite and albite melts with increasing pressure. At a fixed pressure, the shear viscosity of the melts decreases with increasing NBO/T and the variation rate is almost 150 times higher in fully polymerized melts than that in de-polymerized melts in comparison with anorthite melts. Secondly, it is generally accepted that the formation of the Si and A1 will promote the diffusion of the network-forming ions. The hypothesis is frequently employed to explain the emergence of the maximum self-diffusion coefficient of the network-forming ions in fully polymerized melts. However, I detected that the pressure corresponding to the peak of the self-diffusion coefficient of the network-forming ions is lower than that corresponding to the maximum content of Si and A1, and that there exists an approximately linear relationship between the self-diffusion coefficient of the ions and the breaking frequency of the bonds under a given pressure, which is different from the present understanding about the mechanism of self-diffusion. Thirdly, the relationship between the self-diffusion coefficient of Si~(4+), Al~(3+) and O~(2-) and the shear viscosity of the melts evolves from the Stokes-Einstein equation and Sutherland-Einstein equation to the Eyring equation with increasing pressure. And the key to obtain self-diffusion coefficient from shear viscosity under difference pressures is to determine A. in the Eyring equation. For Si~(4+) and O~(2-), this could be done using the linear relationship between A, and NBO% in anorthite melts. However, this method is inapplicable in other kinds of melts.

分子水平上研究地质流体的物理化学性质

Geological fluids exist in every geosphere of the Earth and play important roles in many processes of material transformations, energetic interchanges and geochemical interactions. To study the physicochemical properties and geochemical behaviors of geological fluids turn Girt to be one of the challenging issues in geosciences. Compared with conventional approaches of experiments and semi-theoretical modeling, computer simulation on molecular level shows its advantages on quantitative predictions of the physicochemical properties of geological fluids under extreme conditions and emerges as a promising approach to find the characteristics of geological fluids and their interactions in different geospheres of the Earth interior.This dissertation systematically discusses the physicochemical properties of typical geological fluids with state-of-the-art computer simulation techniques. The main results can be summarized as follows: (1) The experimental phase behaviors of the systems CH4-C2H6 and. CO2 have been successfully reproduced with Monte Carlo simulations. (2) Through comprehensive isothermal-isobaric molecular dynamics simulations, the PVT data of water hia^e been extended beyond experimental range to about 2000 K and 20 GPa and an improved equation of state for water has been established. (3) Based on extensive computer simulations, am optimized molecular potential for carbon dioxide have been proposed, this model is expected to predict different properties of carbon dioxide (volumetric properties, phase equilibria, heat of vaporization, structural and dynamical properties) with improved accuracies. (4) On the basis of the above researches of the end-members, a set of parameters for unlike interactions has been proposed by non-linear fitting to the ab initio potential surface of CO2-H2O and is superior to the common used mixing rule and the results of prior workers vs/Ith remarkable accuracies, then a number of simulations of the mixture have been carried out to generate data under high temperatures and pressures as an important complement to the limited experiments. (5) With molecular dynamics simulations, various structural, dynamical and thermodynamical properties of ionic solvations and associations have been oomprehensively analyzed, these results not only agree well with experimental data and first principle calculation results, but also reveal some new insights into the microscopic ionic solvation and association processes.

岩石圈深部温压条件下芳烃的演化特征

在密闭体系中, 400~700℃和1~3 GPa的条件下进行了褐煤加水的模拟实验, 分析了实验产物中芳烃的演化特征, 并讨论了高压高温对有机质的演化的影响. 实验结果表明, 高压抑制了液态烃的裂解, 压力升高有利于有机质降解产物的环化、聚合和芳构化; 温度升高, 芳烃的成熟度增加, 压力增加会抑制或延迟油气的生成和有机质成熟, 并且温度越低, 抑制作用越明显. 高压对有机质热演化的影响是非线性的. 该研究结果不仅加深了对俯冲带地幔有机质稳定性的认 识, 而且对认识深层油气成藏及保存也有启示意义.

深部岩石圈温压条件下烃类存在的实验研究

在密闭体系中压力高达3 GPa, 温度高达700℃的条件下进行了褐煤加水的模拟实验, 分析了实验产物中的烷烃生物标志化合物的变化规律, 并讨论了高压高温对有机质演化的影响. 实验结果表明, 高压抑制了液态烃的生成, 使高峰值后移; 相同压力条件下, 温度升高有利于有机质的成熟演化; 压力增加会抑制或延迟油气的生成和有机质成熟. 高碳数烷烃在地幔高压力条件下仍可以存在, 这不仅突破了“生油窗”的传统概念, 而且还加深了在异常高压高温区寻找油带富集区的认识.

4GPa,室温至33O℃条件下方解石Ⅲ的原位Ⅹ衍射

利用能量色散X射线衍射技术,结合金刚石压腔外加热技术,在4.07～4.75 GPa,25～330℃条件下,进行了方解石Ⅲ的X衍射测量.结果表明,在实验的温压范围内,方解石Ⅲ稳定存在.随温度升高,方解石的晶胞参数逐渐增大.

高温高压和不同氧逸度下上地幔矿物岩石电导率的实验研究

借助于YJ-3000t六面顶高压设备和Solartron-1260阻抗/增益相位分析仪，在1.0~4.0 GPa和1073~1473 K及NNO (Ni+NiO)、IM (Fe+Fe3O4)、IW (Fe+FeO) 和MMO (Mo+MoO2) 4种固态氧缓冲剂控制氧分压条件下就位测量了单晶辉石、辉石岩、单晶橄榄石和二辉橄榄岩的电导率。取得如下结果： 1、在实验选择的频率范围10-1~107 Hz，无论从阻抗谱的Nyquist图还是Bode图均可以看出，电导率对频率具有很强的依赖性； 2、随着温度升高，电导率增大，Lg σ与1/T之间符合Arrhenius线性关系式； 3、在 IM和NNO固态氧缓冲约束条件下，随着压力升高，电导率降低，获得了一系列表征样品体系载流子特征的指前因子、活化能、活化焓和活化体积等Arrhenius参数； 4、在给定压力和不同氧缓冲剂控制下，按照NNO、IM、IW和MMO氧逸度降低的顺序，电导率减小； 5、在2.0 GPa和NNO控制下，按照 (001)、(100)、(010) 的顺序，透辉石的电导率和指前因子减小，活化焓增大，电学性质在不同晶面方向上存在各向异性； 6、样品中的小极化子导电机制可为电导率、指前因子、活化焓和活化体积等随温度、压力及氧逸度的变化规律提供合理解释。

高温高压下岩石部分熔融及熔体形态学研究

熔体形态学作为现代岩石学的前沿领域之一，其主要研究矿物颗粒之间熔体形态特征、连通性以及与周围矿物的相互作用关系。该学科在我国还不被广大地学工作者所熟悉。本论文以斜长角闪岩为初始物料，在850-1100℃和2.0-4.0 GPa条件下，进行了岩石的部分熔融实验，并对作为实验产物的熔体进行了形态学方面的研究。同时就目前形态学研究的基础理论和实验方法作了初步介绍。 利用YJ－3000吨六面顶高压装置，我们以天然的块状斜长角闪岩为样品，在高温高压条件下进行了斜长角闪岩的脱水部分熔融实验，测量了熔体与矿物相接触时所形成的二面角。结果表明： 1、熔体的形态分布与熔融程度具有明显依赖关系，当熔融程度小于5%时，熔体被矿物颗粒分隔开来，以熔块的形式相互独立；当熔融程度大于5%时，薄膜状或管状熔体沿矿物颗粒边缘形成一个相互连通的熔融网络。 2、当熔体相互隔离时，二面角平均值大于60°；当熔体相互连通时，二面角平均值小于60°。在熔体相互连通的测量实验中，英安质和安山质成分的熔体与石榴子石的二面角分布在56－58°之间，与单斜辉石的二面角分布在50－53°之间。 3、根据界面化学理论推导表面张力和界面能的最小化是推动熔体连通的两个驱动力。 4、二面角大小受体系温度、压力及物质组成等物理化学条件的影响，随着温度升高，固－液界面的表面张力减弱，二面角减小，熔体越容易相互连通。 5、通过对二面角的原位测量，不仅可以判断熔体的相互连通性，还能反演熔体的熔融过程。

高温高压下榴辉岩和斜长角闪岩的弹性波速度和衰减的研究

本论文选取了斜长角闪岩和榴辉岩作为实验样品，在压力为1.0-3.0 GPa和温度为室温-1300 ℃的条件下，进行了弹性纵波速度和弹性波衰减的实验研究。实验是在YJ-3000吨压力机上进行的，利用超声脉冲透射的方法，首次获得了在压力大于1.0GPa和温度高于800 ℃的条件下的岩石的声波衰减及其各向异性的实验数据。取得如下主要结论：1．榴辉岩的Vp值随压力的升高而增大，在P < 2.0GPa时，上升的速率较快，表明微裂隙逐渐闭合；当P > 2.0GPa时，上升的速率变慢，且表现出很好的线性趋势，这时测得的纵波速度表明了榴辉岩本征的纵波速度，这与前人的实验结果相同。斜长角闪岩的Vp值随压力的变化与榴辉岩的变化相似，不同的是斜长角闪岩的微裂隙闭合压力为1.5GPa。榴辉岩的Vp的Av_p(％)随压力的升高基本保持不变，而斜长角闪岩的Av_p(％)随压力的升高逐渐增大。2.榴辉岩和斜长角闪岩在1.0-3.0 GPa压力下的Vp值随温度的升高而降低，但Vp值在不同的温度阶段，不同的方向上降低的速率和形式不同。如在1.0GPa压力下，当温度小于500 ℃时，Vp值下降较快，说明温度对纵波速度的影响较小；当T > 500 ℃时，Vp值下降的缓慢，说明榴辉岩内部可能发生了结构和应力状态的变化。斜长角闪岩在升温的初始阶段，Vp缓慢下降，并表现出很好的线性趋势。当T > 647 ℃时，Vp下降的速率增大，线性趋势也较好，当T > 1051 ℃时，Vp下降的速率又变小，且比初始时下降的速率要小。榴辉岩Vp的Av_p(％)值随温度的升高而下降，在不同的压力上其下降的速率不同。如在1.0GPa条件下，Av_p(％)随温度的升高而快速下降；在3.0GPa条件下，Av_p(％)值随温度下降缓慢。而斜长角闪岩的Vp的Av_p(％)随温度的变化较复杂，如在1.0GPa条件下，当T < 647 ℃时，Av_p(％)值随温度的升高缓慢增加，当T > 647 ℃时，Av_p(％)值快速增大，当温度达到922 ℃时，Av_p(％)上升到最大值，此后又随温度而减小。3．榴辉岩和斜长角闪岩的弹性波的Q值随压力的升高而增大，其增大的速率和幅度与Vp值的增大形式相同。榴辉岩的Q值的A_Q(％)随压力而升高，而斜长角闪岩的Q值的A_Q(％)随压力基本保持不变。4．榴辉岩和斜长角闪岩的弹性波的Q值随温度的升高而降低，在不同的压力下其降低的速率不同。如在1.0GPa压力下，Q值降低的速率较大；3.0GPa压力下，当T < 300 ℃时，榴辉岩的Q值快速下降，随后下降的幅度减慢，当T > 700 ℃时，榴辉岩的Q值很低，且减小的幅度很小。斜长角闪岩的Q值随温度的变化在1.0-3.0GPa条件下，Q值很小的幅度和趋势相似：当T < 647 ℃时，Q值下降的缓慢，当647 ℃ < T < 1051 ℃时，Q值快速下降，随后下降速率又变小。榴辉岩Q值的A_Q(％)随温度的升高而降低，在1.0和2.0GPa压力下降低较快；3.0GPa压力下A_Q(％)降低较缓慢。斜长角闪岩Q值的A_Q(％)随温度的升高开始缓慢降低，当647 ℃ < T < 105l ℃时，A_Q(％)快速增大，当T > 105l ℃时，A_Q(％)又降低。