LiIO_3多型性相变的进一步研究

本文用差热分析、恒温热处理、X射线衍射等方法,对LiIO_3在常压的相变过程做了进一步的研究。对于LiIO_3的常压相变机制有了较为详尽的了解 。并发现LiIO_3在高温可相对稳定存在三个相:β,η和δ,它们可分别自行熔化,其熔点相应为:432℃,421℃和416℃,从它们的热经历和存在的温度范围,表明其稳定性顺序为β>η>δ。在室温干燥空气中,与α相和β相共存的还有相,相升温放热转变为β相。在α相存在的温区里,相经过长时间热处理并不转变为α相,同时,相转变为β相的温度比α相高。与α→β的情况相同,β对→β也有诱导作用。而且的存在对α→β也有促进作用。θ相(θ_1与θ_2)与γ相一样,是相变过程的中间过渡相。     

铝-铜-镓三元系合金相图

铝-铜-镓三元系合金相图的室温截面已经用X射线方法测定出来了。室温固相截面包含11个单相(即α, γ₂, γ′, δ, ζ₁, ζ₂, η₂, θ, θ′,α_铝和镓)相区,14个双相(即α + ζ₁, α+ γ₂, α + γ′, γ₂ + γ′, γ′+ ζ₁, γ₂+δ, γ′+δ,δ +ζ₂, ζ₂+η₂, η₂+θ,η₂+ θ′, γ′ + θ′, θ′+ 镓和θ+α_铝)相区和9个三相(即α + γ′+ζ₁, α+ γ₂+ γ′, γ₂+ γ′ + δ,γ′ + δ + θ′, δ+ζ₂+θ′, ζ₂ + η₂ + θ′, η₂+ θ′ + 镓, η₂ +θ + 镓和θ +镓+ α_铝)相区。所有单相和三个二元系内室温存在的单相相同,没有新相出现。 关键词：     

Gd-Co-Cu三元系合金相图

Gd-Co-Cu三元系Gd≤34.8wt％合金相图的室温截面已经用X射线分析法测定出来。它包括五个单相区:Cu(以下简称α),Co(以下简称β),Gd₂Co₁₇(以下简称δ),GdCu₆(以下简称γ)和Gd(Co_1-xCu_x)₅(以下简称θ);七个二相区:β+δ,α+β,δ+θ,θ+γ,γ+α,θ+α,β+θ;三个三相区:α+β+θ,α+θ+γ和β+θ+δ。没有发现新相。Cu 关键词：     

Mn-Ga二元系的X射线研究

本文从44个缓冷和淬炼Mn-Ga合金摄取了德拜·谢乐照相,并配合了在富Ga部分的差热分析,初步画出了这个系统的相图。这个系统除纯Ga外共有十个相。Mn在Ga中的固溶度是几乎无可觉察的。α相是Ga在α-Mn中的原固溶体,在室温的固溶度为1.95at％Ga。β相在室温的均匀范围为8.6—19.2at％Ga,这是β-Mn结构,因此可看作是β-Mn的固溶体,由于Ga原子无规地替代了部分Mn原子而这个结构得在室温稳定存在。γ相可分成γ₁,γ₂,γ₃,三部分,γ₁是面心立方结构,γ₂是面心四方结构,γ₃是有序的面心四方结构,与Cu-Au系中的CuAuⅠ同型。在室温下稳定的是γ₃,均匀范围为37—45at％Ga,而在高温稳定的却总是γ₁。从γ₁变到γ₂,再从γ₂变到γ₃的变化是二级相变。有序度随Ga含量的递增而递增,随温度的递升而递降。整个γ相可看作是γ-Mn的固溶体,γ-Mn本身是不可能用淬炼的办法在室温获得的。δ相只存在于高温,可看作是δ-Mn的固溶体。由于Ga原子替代了部分Mn原子,因而δ一Mn结构产生了畸变而有序化。ε相是有序的六角密堆积结构,每个晶胞含8个原子,它是在约820℃从γ相同成份地转变而成的,在室温的均匀范围估计为27一30at％Ga。η相在室温约50—60at％Ga处有一宽广的均匀范围。从520到600℃,它经历一多型性变化,转变为λ相。λ相的相区随温度的递升而向富Mn的一边偏移。η和λ结构都很复杂。在富Ga的一边,存在着三个居间相χ,φ和ω,它们是由包析或包晶反应所形成的。ω相的化合式很可能相当于Mn₂Ga₉或MnGa₅,而φ相则与NiHg₄同型,在Mn_2.3Ga_7.7左右有一狭隘的均匀范围。在室温稳定存在的七个居间相中,β,ε,γ₃,X和φ是铁磁性的。铁磁性最强的是Ga含量较富的γ₃和φ相。我们测量了其中若干合金的饱和磁化强度与居里温度。 关键词：     

LiKSO4的无公度相

本文用多晶X射线衍射配合差热分析的方法研究了LiKSO₄室温以上的相变。发现当温度在熔点以下到675℃之间,晶体结沟与α-K₂SO₄的高温相同构,α相最可能的空间群为P6₃/mmc.在T_i=675℃以下出现调制结构,类似K₂WO₄,K₂MoO₄等的无公度相;参数κ的值由0.492(640℃)而随温度变化。在470℃出现整合相变κ=0.500,整合后的结构为室温相的超点阵。然后在439℃转变为室温相(空间群为P6₃)。 关键词：     

影响Salisbury屏高频响应的若干因数

应用传输线理论研究了金属薄膜Salisbury屏的反射率频谱特性，得到了Salisbury屏的反射系数公式和带宽系数的表达式.理论和数值分析表明，Salisbury屏的反射频谱是谐振型的；在谐振频率处，反射率的大小仅与金属薄膜的归一化面电阻α有关，而在其他频率处则取决于α和隔离层波阻抗η₂.反射率带宽系数Δ取决于反射率的考察值Γ_α,η₂和α.当α→α_c,η₂→η₀时，Δ取得极 关键词： Salisbury屏 反射率 频带宽度 金属薄膜     

2LiIO3·HIO3的晶体结构与相变

本文用差热分析、热失重以及X射线衍射等方法,对LiIO₃·HIO₃二元系的相平衡进行了研究,观察了以α-LiIO₃为基的固溶体和以2LiIO₃·HIO₃为基的固溶体的热学性质和晶体结构。2LiIO₃·HIO₃属六方晶系,空间群为P6₃,是α-LiIO₃的同晶型结构。20℃的点阵常数为:α=5.555?,c=4. 关键词：     

流体静压力下LiIO3晶体β→α相变的动力学过程

本文测量了在不同温度下,压力到12kbar,LiIO₃晶体β→α相变平均速率的压力关系。随压力增加,平均速率起先很快地增加,经过一个极大值,随后以比较缓慢的速率下降,文中还讨论了压力效应的物理意义。 关键词：     

铝-镉-铜三元系富铜合金相图

铝-镉-铜三元系富铜合金相图的室温固相截面已用X-射线方法测定。合金含量最高达30％(重量)铝及30％镉。室温相截面由五个单相区α,γ₂,δ,ζ₂,η₂;十个两相区α+β,α+γ₂,β+γ₂,γ₂+δ,β+δ,δ+ζ₂,ζ₂+η,η₂+δ,η₂+β,η₂+θ及四个三相区α+β+γ₂,β+γ₂+δ,β+δ+η₂,δ+ζ₂+η₂所构成。没有发现新相。     

LiIO3晶体相变的研究

本文用差热分析、恒温热处理、室温及高温X射线衍射等方法,对LiIO₃晶体的相变问题进行了研究。弄清了升温过程中γ相的本质,它是并没有稳定存在的温度区间,只能在一定温度范围,一定时间内存在的,从α相转变为β相的过渡相。熔态LiIO₃的冷凝过程不同于固态升温过程;这里存在着另一些新相——δ相。由于冷凝条件不同,因而结构也不尽相同,这些δ相在继续冷却时大部分转变为α相,但在未转变为α相之前,再度升温时,则转变为β相。从高温X射线衍射发现:差热分析曲线上所示的α←→γ和δ→α的相变温度是出现新相的温度,这时还伴随着大量的原有相的衍射线,随着时间的延长和温度的改变,原来的相才逐渐消失。同时也证实了γ→β的相变过程需要保温时间和β相的下种自催化作用。     

LiIO3-NaIO3赝二元系相图及其非晶态晶化动力学的研究

本文对LiIOO₃-NaIO₃赝二元系的相图,相变,非晶态的形成和稳定性,以及晶化的动力学过程等进行了仔细的研究,LiIO₃-NaIO₃赝二元系属共晶体系,共晶温度为325℃,共晶点成份为含50m/o LiIO₃,用共晶点附近成份的试样,在超过熔点150℃的情况下首次获得碘酸盐的非晶态,非晶态的存在降低了LiIO₃的表观相变温度,强X射线的辐照,各种空气湿度,细粒度等因素都加 关键词：     

X-ray study of molecular oxygen adsorbed on graphite

We have performed a detailed X-ray diffraction study of O₂ adsorbed on UCAR-ZYX and Le Carbon Lorraine vermicular exfoliated graphite between 15 and 50 K. At least four phases of physisorbed oxygen are found. The monolayer δ phase consists of a centered parallelogram lattice, with the molecular axes parallel to the graphite surface. The data are consistent with a triple point at 26 K. The melting transition at a coverage of one monolayer appears to be first order. At higher coverages the molecules undergo a lying-down to standing-up transition; the higher coverage ζ phase froms an approximately triangular lattice with the molecular axes perpendicular to the graphite surface. Satellite peaks around the (1, 0) Bragg peak indicate, however, that this cannot be a simple triangular lattice; possible explanations include successively incommensurate layers or a sinusoidal density modulation. For coverages in the two-layer region the ζ phase modulation peaks disappear at 37 K, and at 40 K the adsorbed oxygen appears to undergo a first order melting transition into a fluid phase. With increasing coverage, the 2D X-ray diffraction profiles and phase boundaries do not connect smoothly onto those of the 3D α and β phases. At low temperatures (T < 30 K) the ζ phase always coexists with bulk crystallites; for temperatures near the 2D melting transition the 3D peaks are not observable. These data, taken together with the heat capacity results, suggest a wetting transition with only the bilayer lamellar phase or bulk O₂ being stable at low temperatures.     

外加热型金刚石对顶压砧高压装置及高温下的压力测量

 本文报导了一种外加热型金刚石对顶压砧装置的高温高压技术，装置的压力可达20 GPa，温度可达350 ℃。采用本装置对六角结构的α-LiIO₃进行了高温高压X射线衍射实验，获得的四方结构高压相与用淬火卸压所得的ε相结构一致；建立了高温下的红宝石测试技术。发现可以根据由此法测定的Δγ_p-T曲线初步判别样品是否存在伴随有体积变化的结构相变，并可估计出该相变的压力、温度范围及相变造成的压力下降值。     

Evidence of metastability and demixion/recombination process in fast oxide-ion conductor La1.92Ca0.08Mo2O8.96

Unusual structural phenomena have been observed through high temperature X-ray diffraction in fast oxide-ion conductor La_1.92Ca_0.08Mo₂O_8.96. A demixion process occurs above 640 °C, with calcium segregation leading to the formation of CaMoO₄ impurity. It recombines at higher temperature to reform the pure cubic LAMOX phase (β-type disordered form). In addition, at lower temperature, a double reversed β/α/β phase transition (where α is the monoclinic ordered form) is observed. It is due to the metastability of the β-type structure at low temperature. Depending on the thermal history, La_1.92Ca_0.08Mo₂O_8.96 can therefore be obtained in either its α or its β form at room temperature. Sample shaping as a pellet with high relative density suppresses the low temperature phase transitions and stabilizes the cubic β form.     

Investigation of the reconstructive phase transition between metastable (α) and stable (β) modifications of the NH<Subscript>4</Subscript>LiSO<Subscript>4</Subscript> crystal

Crystals of ammonium lithium sulfate NH₄LiSO₄ in α and β modifications are studied, and conditions of their nucleation and growth are determined. The α modification of NH₄LiSO₄ and α → β phase transitions are investigated using polarized light microscopy, x-ray diffraction, and differential scanning calorimetry in the temperature range 80–530 K. It is found that, depending on the conditions of growth and storage, there exist two temperature ranges (T_{α → β} ≈ 340–350 and ≈440–450 K) in which the crystals can undergo an α → β reconstructive phase transition. The enthalpy of this transformation depends on the symmetry of the final phase. In the former case (340–350 K), the reconstructive phase transition leads to rapid destruction of the sample. In the latter case (440–450 K), the crystal structure undergoes a slow transformation (recrystallization) without noticeable distortions. The results obtained indicate that no structural phase transition occurs in the α modification of NH₄LiSO₄ at 250 K.     

Melting behavior of the oriented β-phase polypropylene texture crystallized by the temperature slope method

Isotactic polypropylene consisting of uniaxially oriented P-phase lamellae was crystallized in a temperature gradient. The β → α transition was investigated by simultaneous measurements with differential scanning calorimetry (DSC) and X-ray diffraction using synchrotron radiation (SR). To compare the transition mechanism, the β-phase sample was deformed by rolling it along the direction of the crystallization. During rolling, the β-crystal is deformed by interlamellar and interchain slip, which induces c-axis-oriented molecules along the rolling direction. The melting behavior is changed by the rolling deformation. For the as-grown β-crystal, the DSC thermogram has three peaks: the β-melting endotherm at 150°C, an exotherm by recrystallization into the °-form, and the endotherm at 167°C caused by melting of the recrystallized α-form. After the rolling deformation, the β-endotherm is extinguished by the successive exotherm. Simultaneous X-ray measurements reveal that the β → α transition is shifted to a lower temperature and that the recrystallized α-form has a c-axis-orientation caused by the rolling deformation. In the process of the β→ α transition, higher-order lamellar structure is developed earlier than formation of the crystalline structure. In this study, the heating phenomena, such as the β α transition and thickening of the β- and α-lamellae, are consistently explained by a mechanism involving melting and subsequent recrystallization.     

Synthesis,phase stability and oxide ion conductivity of Ce(IV)–Cd(II) double substituted bismuth vanadate

Bi₄V₂O_11-δ has been doped with Ce and Cd to study double substitution. The system with various dopant concentrations (0.07 ≤ x ≤ 0.30) was prepared by the standard solid-state reaction method. The correlation between the polymorphism and oxide ion performance was well investigated as a function of temperature and composition with the help of thermal analysis, X-ray diffraction (XRD) and AC impedance spectroscopy. From XRD results it is seen that the high oxide ion conducting tetragonal γ-phase is stabilized for x = 0.17. For the compositions x ≤ 0.10, monoclinic α-phase is retained at room temperature with clear evidence for two successive phase transitions α ? β and β ? γ. For x = 0.13, β ? γ phase transition is seen. However, the existence of order–disorder, γ' ? γ transition was confirmed for x = 0.17. It is seen that the highest low-temperature ionic conductivity at 320 °C is 3.19 × 10^?4 S cm^?1 which was observed for x = 0.17.     

Evolution of the spectral response of amorphous europium molybdate under annealing

The phase transformations occurring in amorphous europium molybdate Eu₂(MoO₄)₃ during annealing at atmospheric pressure are studied using optical spectroscopy and x-ray diffractometry. It is established that the metastable β phase is formed at a temperature of ～550°C, whereas the transition to the stable equilibrium α phase takes place at higher temperatures T ≥ 700°C. The spectral characteristics of the α phase, which differ substantially from those of the amorphous state and the β phase, are measured for the first time.     

Nuclear magnetic resonance study of Na (DxH1−x)3(SeO3)2 crystals

A comparison of the quadrupole perturbed deuteron magnetic resonance spectra of the α,β, and γ phase of partially deuterated sodium trihydrogen selenite crystals shows that not only in the monoclinic γ but also in the triclinic β phase the deutrons are ordered whereas they are disordered in the α phase. Spin-lattice relaxation time measurements show the existence of slow hindered rotations of the HSeO₃ and H₂SeO₃ groups at high temperatures as well as the existence of an overdamped ferroelectric soft mode which condenses at the paraelectric to ferroelectric transition.