层状钙钛矿结构锰氧化物Ca3Mn2O7的高压结构相变

利用金刚石压砧高压装置（DAC），对Ca3Mn2O7的粉末样品进行了高压能散X射线衍射实验。结果表明，由于岩盐层易被压缩，在压力作用下层状钙钛矿结构锰氧化物Ca3Mn2O7的结构不稳定。在0－35GPa压力范围内，Ca3Mo2O7晶体结构发生了两次相变。在1．3GPa左右，由原来的四方相变为正交相，在9．5GPa左右，又由正交相向新的四方相转变。     

三聚氰胺(C3N6H6)分子晶体的压致结构相变研究

本文通过对三聚氰胺（C3N6H6）的室温高奈原位同步辐射能量散射X－ray衍射实验（EDXD），在14.7GPa压力范围内，观察到常压下为单斜晶系的三聚氰胺经历了两次压致结构相变。在1.3GPa下，三聚氰胺分子晶体从单斜相转变为三斜相；在8.2GPa又转变为正交相。本实验结果为利用三聚氰胺碳氮有机分子晶体高温高压合成超硬C3N4共价晶体的研究提供了重要信息。     

三聚氰胺（C3N6H6）的压制结构相变

本通过对三聚氰胺(C3N6H6)的室温高压原位同步辐射能量散射x-ray衍射实验（EDXRD），在14．7GPa压力范围内，观察到常压下为单斜晶系的三聚氰胺经历了两次压致结构相变。在1．3GPa下，三聚氰胺分子晶体从单斜相转变为三斜相；在8．2GPa又转变为正交相。     

超高压下CsBr的结构与相变

采用金刚石对顶压砧高压装置（DAC）、同步辐射X光源和能散法，对CsBr粉末样品进行了原位高压X光衍射实验，最高压力115GPa。观测到在53GPa左右压力下，CsBr的最强衍射峰（110）劈裂成两个峰，标志简单立方结构向四方结构的转变；在0至最高压力范围内（相应于V／V0为1至0.463)测量了晶轴比c/a；在115GPa内未观测到样品的金属化现象。     

晶粒尺寸对锐钛矿TiO2相变压力的影响

采用在位高压Raman光谱和高压同步辐射能散X射线衍射技术，在室温下对晶粒尺寸为10nm的锐钛矿TiO2进行了压致相变研究，压力范围分别为42．9GPa和23．0GPa，实验结果表明，在16．3GPa TiO2发生了一次结构相变，由原来的锐钛矿结构变为α－PbO2结构（TiO2-Ⅱ），该相变是不可逆的。同体材料TiO2的高压相变结果比较，由于晶粒尺寸的效应，纳米尺寸的锐钛矿TiO2的相变压力明显高于体材料的相变压力。     

Te/MCM41高压结构相变

本文使用金刚石对顶砧高压装置（DAC）和同步辐射X光射射，对Te/MCM41体系进行了原位高压X射线衍射实验，最高压力达到37GPa。在研究的压力范围内，观察到一个从5GPa开始，强度较小，到立方Te的相变，我们认为对应MCM41孔道内的Te。     

钙钛矿CaTiO3的超高压结构研究

利用同步辐射X射线衍射和DAC高压技术在室温下测量了钙钛矿CaTiO3在压力0-34．6GPa下的结构变化．结果表明，随着压力的增加，CaTiO3的三个晶体轴都受到不同程度的压缩，没有证据表明有相变的发生．     

纳米晶BaTiO3的高压研究

采用原位高压同步辐射X光衍射技术和Raman散射方法，对小于临界尺寸（120nm）的纳米晶BaTiO3(48nm）进行了研究，在实验压力范围内（0－21．2GPa,0-46.67GPa），纳米晶BaTiO3始终处于稳定的立方相。     

高压条件下两种金属8—羟喹啉络合物的发光行为和晶体结构变化

本测定了在高压条件下两种金属（钙和锌）的8－羟基喹啉络合物的晶体粉末样品的发光行为和原位x-光衍射光说。结果表明,压力对其发光性质产生极大的影响。随着压力的增加,8－羟基喹啉钙的发光强度在3GPa以内时大大增加。随后发光强度快速下降,到7GPa左右时几乎为零。而8－羟基喹啉锌的发光随压力的增加而逐渐降低,到7GPa左右时常压的10％。高压下的原位x－光衍射结果表明8－羟基喹啉钙的晶体在3－4GPa开始发生非晶化相变,在7GPa时该非晶化相变完成,样品的x－光衍射完全消失。而8－羟基喹啉锌在压力的作用下（至16GPa）没有发生明显的相变。     

方石英高温高压相变的实验研究

在1450℃高温下热处理天然的长白山硅藻土以获得含有一定量杂质元素的方石英,并以此为样品,利用对称型DAC装置在0-63GPa压力范围对其开展高温高压相变的实验研究。衍射方法采用同步辐射能量色散X射线衍射(EDXD)技术。实验结果表明,方石英的高压相变序列较复杂,在12、24、33GPa都有新的衍射线出现,在40GPa时仍存在明显的衍射线条而并未完全非晶化,并且为一种类似于α-PbO2型结构的高压相。在此压力下用YLF激光器加温到大约1600K,降温后样品相变为类似于斯石英的结构。随后继续加压到62．9GPa,样品未发生相变,并于此压力下给样品加温到大约1500K,降温后其结构仍不发生变化。卸压至常压,仍为类似于斯石英的结构。     

A Raman study of the nanocrystallite size effect on the pressure–temperature phase diagram of zirconia grown by zirconium-based alloys oxidation

The pressure–temperature phase diagrams of different zirconia samples prepared by oxidation of Zircaloy-4 and Zr–1%Nb–0.12O alloys were monitored by Raman spectrometry from 0.1 MPa to 12 GPa and from 300 to 640 K. These new diagrams show that the monoclinic–tetragonal equilibrium line is strongly downshifted in temperature compared to literature measurements performed on usual polycrystalline zirconia. In addition, the monoclinic–orthorhombic equilibrium line is slightly shifted to higher pressure (i.e. 6 GPa). The crystallite sizes smaller than 30 nm, are thought to be responsible for these equilibrium line displacements. The tetragonal phase obtained in temperature under high pressure can be quenched at room temperature, if the pressure is maintained, and it is destabilised and transforms completely into monoclinic phase if the pressure is released. These results confirm that coupled effects of stress, temperature and nanosized grain are responsible for the formation of the tetragonal phase near the metal/oxide interface during the oxidation of zirconium-based alloys.     

Gd1.6Nd0.4Zr2O7烧绿石的快速合成及其组织结构研究

为探索Gd₂Zr₂O₇烧绿石快速固化高放废物中锕系核素的新途径,实验用高温高压固相反应法在3～4GPa压力、1573～1673K温度范围内合成了Gd_1.6Nd_0.4Zr₂O₇烧绿石固化体,并利用X射线衍射仪、扫描电镜对样品进行了分析。结果表明：高温高压固相反应法可在极短时间（15min）内合成完全固溶的Gd_1.6Nd_0.4Zr₂O₇立方烧绿石固化体,较常用制备方法（一般合成时间不低于48h）快近200倍;用该技术合成的样品在常温常压下的相转变温度及压力得以显著提高,烧绿石相更趋稳定;样品晶格常数随Nd含量的增加及合成温度的升高而逐渐增大,随合成压力的增加而逐渐减小。这种快速高效的合成方法为未来开展高放核素的工业固化提供了一种新的技术途径和基本数据参考。     

立方烧绿石Gd_2Zr_2O_7的高温高压合成

为探索高温高压固相反应法合成Gd2Zr2O7烧绿石的可能性,以Gd2O3和ZrO2的混合粉体为原料,在5.2GPa压力、1473～1873K温度范围内进行了实验研究。通过XRD对合成样品进行了结构表征,结果证实,在5.2GPa和1873K条件下,保温保压30min,成功地合成出单一物相的、具有立方烧绿石结构的Gd2Zr2O7化合物。这种新的合成方法对于开展武器级多余钚和含钚高放废物固化具有重要的科学价值和实际意义。     

Preshock-induced phase transition in spalled U–0.75 wt% Ti

Uranium–0.75 wt% Ti samples were spalled in the range of 5–24 GPa shock pressure. One sample was preshocked to a pressure of 24 GPa, `soft' recovered, and then reloaded and spalled at 10 GPa. The spall strength of U–3/4 wt% Ti was found to range from −4.1 to −2.9 GPa when the Romanchenko correction is used in the spall strength calculation. The spall morphology of the sample that was preshocked and then spalled showed a significant change in microstructure from a parent alpha' martensite to a 2-phase eutectoid. The thermodynamically calculated temperature rise resulting from the preshock at 15–24 GPa in these samples is ∼555°C. This temperature is not sufficient to induce such a phase change. However, the preshock conditions additionally increase the flow stress of the U–34 wt% Ti, and it is postulated that this additional hardening is sufficient to increase the temperature above 885°C due to the increased amount of plastic work required during spall, thereby triggering the phase change.     

Heavy ion irradiation effects in the rare-earth sesquioxide Dy2O3

Polycrystalline pellets of the rare-earth sesquioxide Dy₂O₃ with cubic C-type rare-earth structure were irradiated with 300 keV Kr²⁺ ions at fluences up to 5 × 10²⁰ Kr/m² at cryogenic temperature. Irradiation-induced microstructural evolution is characterized using grazing incidence X-ray diffraction (GIXRD) and transmission electron microscopy (TEM). In previous work, we found a phase transformation from a cubic, C-type to a monoclinic, B-type (C2/m) rare-earth structure in Dy₂O₃ during Kr²⁺ ion irradiation at a fluence of less than 1 × 10²⁰ Kr/m². In this study, we find that the crystal structure of the top and middle regions of the implanted layer transform to a hexagonal, H-type (P6₃/mmc) rare-earth structure when the irradiation fluence is increased to 5 × 10²⁰ Kr/m²; the bottom of the implanted layer, on the other hand, remains in a monoclinic phase. The irradiation dose dependence of the C-to-B-to-H phase transformation observed in Dy₂O₃ appears to be closely related to the temperature and pressure dependence of the phases observed in the phase diagram. These transformations are also accompanied by a decrease in molecular volume (or density increase) of approximately 9% and 8%, respectively, which is an unusual radiation damage behavior.     

基于中子衍射的六方相Er1-xYxMnO3结构和磁学性能研究

为研究六方钙钛矿氧化物中磁结构和稀土离子对磁性能的影响,以六方相ErMnO3为母体,通过非磁性Y3+离子对磁性稀土Er3+离子的替代,利用X射线衍射、中子粉末衍射和磁性测量等表征手段,对六方化合物Er1-xYxMnO3的晶体结构和磁性进行系统研究。研究结果表明,Y3+离子的掺杂并未引起晶体结构和磁结构的明显改变,同时发现六方晶体结构随温度的增加呈各向异性热膨胀,在ab面内膨胀而沿着c轴收缩。中子衍射实验结果表明,Er04Y06MnO3样品的有序温度约为79 K,低温下系统的基态为反铁磁性,结构为Γ2（P63c′m′）或Γ4（P63′c′m）组态,与Er08Y02MnO3相同。磁化测试结果表明,非磁性Y3+离子掺杂量的增加削弱了磁化强度,2 K时磁性稀土离子Er3+的自旋有序在外磁场下表现出铁磁信号。该研究阐明了Er1-xYxMnO3的磁性本质和稀土磁性调控特性,为其潜在应用提供了有力指导。     

Re-evaluation of the phase relationship between plutonium and zirconium dioxides

The phase relationship between ZrO₂ and PuO₂ was examined in a low PuO₂ content region, from 3.1 to 11.2 mol% PuO₂, at temperatures between 1273 K and 1473 K, by high temperature X-ray diffractometry. The measurements were carried out in air. At 1273 K, the samples in this composition range consisted of two phases, monoclinic and cubic. Another phase, tetragonal, was observed at 1373 K. The low temperature monoclinic phase disappeared at 1473 K. It was confirmed that the monoclinic phase disappears around 1463 K; the disappearance temperature does not depend on the composition of the sample. It was, thus, inferred that there should be a eutectoid line in the phase diagram. Though the eutectoid point is not clear, the PuO₂ content at the point should be less than 3.1 mol%.     

Light ion irradiation-induced phase transformation in the monoclinic polymorph of zirconia

Ion irradiation damage experiments were performed at ∼80 K on polycrystalline samples of monoclinic, slightly sub-stoichiometric zirconia (ZrO_1.98). Following irradiation with 150 keV Ne⁺ ions, the monoclinic phase was gradually replaced by a new phase. Transmission electron microscopy (TEM) observations in cross-sectional geometry and electron microdiffraction (μD) measurements revealed that the irradiated layer in a sample irradiated to a fluence of 5 × 10²⁰ Ne/m² is partially transformed to a higher symmetry phase of high crystallinity. This phase transformation is accompanied by reduction of the initial micron-sized, highly-twinned grain distribution, to a nano-phased grain structure. Grazing incidence X-ray diffraction (GIXRD) measurements revealed that the radiation-induced phase is a tetragonal polymorph of zirconia. This was verified by the existence of strong (1 0 1) diffraction maxima and weak (1 0 2) reflections (body-centered cell). Raman spectroscopy (RS) measurements were also performed in an attempt to corroborate GIXRD results obtained from the irradiated material. RS measurements in the confocal geometry agreed with GIXRD measurements, although RS was not as definitive as GIXRD. In addition to RS showing the existence of a band corresponding to a tetragonal structure at 262 cm⁻¹, a new mystery band appeared at 702 cm⁻¹ that increased in intensity as a function of irradiation fluence.