非晶态SiO2的高温高压转变研究

利用金刚石对顶砧高压装置和激光双面加热技术, 以经700°C热处理后的吉林长白山硅藻土作为非晶态SiO₂样品,在0—4GPa, 1000—1300K温压条件下开展同步辐射X射线衍射原位测试(EDXD方法), 研究非晶态SiO₂在高温高压条件下的结晶转变方式. 测试结果表明, 在0.8—2.4GPa, 1000—1300K温压条件下, 非晶态SiO₂转变成α-石英而非β-石英或方石英, 其结晶温度较常压下非晶态SiO₂晶化所需温度明显较低, 表明压力有利于降低非晶态SiO₂转变的活化能, 并与常压下的结晶产物不同. 在3—4GPa, 1300K温压条件下, 非晶态SiO₂和石英均转变成了柯石英.     

快速加压引起的硒熔体结晶行为

开展了在513,523,533 K温度下硒熔体的快速压致凝固实验,分析了不同保温时间即0,30,60 min对凝固晶体尺寸及形貌的影响.发现随着保温时间的延长,晶粒不断发生聚集生长,晶粒尺寸变大.通过与相同温度、压力条件下非晶硒、超细晶体硒粉等温结晶的样品对比,否定了快压凝固结构为非晶硒、非晶硒晶化为晶体硒的可能性,认为硒熔体快压凝固的结构为晶体硒,在保温过程中晶体颗粒在晶界处可以发生聚集生长.分析发现熔体快速压致凝固法不能得到非晶硒的原因在于实验条件下非晶硒为不稳定相,非晶硒的晶化温度随压力关系在2 GPa前后表现出不同的变化趋势,推测压力对过冷液态硒的微观结构有影响.     

高压下尼龙1010-单壁碳纳米管复合材料的结晶行为

 采用XKY-6×1200MN型六面顶压机,在不同温度、压力条件下处理30 min后制备了尼龙1010(PA1010)-单壁碳纳米管（SWCNT）复合材料的高压结晶样品,通过X射线衍射（XRD）、差热分析仪（DSC）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）,研究了高压处理样品的结晶行为、结构变化及形貌特征。结果表明：在1.0~2.5 GPa压力下,属于高压熔体结晶;在3.0和4.5 GPa压力下属于高压退火处理;高压结晶或高压退火均有助于聚合物片层晶体的增厚,并且高压熔体结晶的增厚效果优于高压退火处理。XRD结果表明,PA1010的三斜晶型在高压处理后保持不变,高压熔体结晶或高压退火都可以使(100)晶面和(010)晶面间距减小,即高压处理致使聚合物分子链紧密堆积。DSC结果表明：在高压熔体结晶过程中,升高压力和温度可以得到片层厚度较大的PA1010晶体;在2.0 GPa、350 ℃下获得的高压结晶样品的熔点和结晶度最高,分别达到208.5 ℃和64.6%。SEM和TEM结果表明：与常压结晶样品相比,高压结晶样品内部出现c轴厚度超过150 μm的大尺寸晶体;SWCNT与PA1010基体之间形成相互穿插的网络结构,刚性的SWCNT作为高压成核剂促进PA1010晶体生长和增厚。     

低温高压及高温高压对La_(80)Al_(20)非晶态结构及超导性的影响

用X射线衍射照相、X射线衍射仪及透射电子显微镜分析了用液相淬火技术制备的La_(30)Al_(20)合金样品,结果表明样品是非晶态结构。差热分析(DTA)结果表明,非晶态样品的晶化温度T_(cr)为280℃左右,玻璃温度T_g为242℃左右。非晶态样品低温高压(流体静压法)试验结果表明:压力从0至4.77kbar,T_c从3.87K提高到4.18K。高压下,超导前的剩余电阻与常压下相比较有明显下降。非晶态样品经高温高压(25kbar,～160℃,40min)处理后,X射线衍射仪分析结果表明:发生了由非晶态→晶态的结构相变。相变产物由平衡相α-La和新的亚稳过渡相组成。其T_c从～3.9K提高到5.7K,该亚稳相结构与化学成分尚不清楚。本文并对所获得的实验结果进行了讨论。     

低温高压及高温高压对La80Al20非晶态结构及超导性的影响

用X射线衍射照相、X射线衍射仪及透射电子显微镜分析了用液相淬火技术制备的La₈₀Al₂₀合金样品,结果表明样品是非晶态结构。差热分析(DTA)结果表明,非晶态样品的晶化温度T_cr为280℃左右,玻璃温度T_g为242℃左右。非晶态样品低温高压(流体静压法)试验结果表明:压力从0至4.77kbar,T_c从3.87K提高到4.18K。高压下,超导前的剩余电阻与常压下相比较有明显下降。非晶态样品经高温高压 关键词：     

三元等原子比Fe_(33.3)Cu_(33.3)Sn_(33.3)合金的快速凝固机理与室温组织磁性研究

采用自由落体和熔体急冷两种实验技术实现了三元等原子比Fe_(33.3)Cn_(33.3)Sn_(33.3)合金的快速凝固,研究了其组织形成机理和室温磁性特征.实验发现,合金熔体在不同快速凝固条件下都没有发生液相分离,其室温组织均由初生αFe相枝晶以及CU_3SU和CU_6Sn_5二个包晶相组成计算表明,落管中合金液滴的表面冷却速率和过冷度分别达1.3×10~5 K·s~(-1)和283 K(0.19 T_L)当表面冷却速率增大至3.3×10~3 K·s~(-1),初生αFe相发生由粗大枝晶向碎断枝晶的演化.急冷快速凝固过程中,初生αFe相凝固组织沿辊面向自由面方向形成细晶区和粗晶区,其中细晶区以粒状晶为特征而粗晶区存在具有二次分枝的树枝晶随着表面冷却速率由8.9×10~6增大至2.7×10~7 K·s~(-1),αFe相平均晶粒尺寸显著减小,合金条带的矫顽力增大一倍多.     

熔体初始温度对液态金属Na凝固过程中微观结构影响的模拟研究

采用分子动力学方法对熔体初始温度热历史条件对液态金属Na凝固过程中微观结构的影响，进行了模拟研究，并采用双体分布函数g(r)曲线、键型指数法和原子团类型指数法对凝固过程中的微观结构进行了分析.结果表明：液态金属Na在不同熔体初始温度条件下以1×10¹¹K/s冷速凝固时，均形成晶化结构，其中1661和1441键型或体心立方基本原子团(14 6 0 8)在凝固过程中对微观结构的转变起决定性作用.同时发现：熔体初始温度对凝固微结构有显著影响，而对液态和过冷态的微观结构影响并不明显，只有在晶化起始温度T_c附近才充分地展现出来.不同熔体初始温度对凝固结构的晶化程度有不同的影响，虽其影响程度是随着熔体初始温度的下降呈非线性变化关系的，但仍表明是可以通过改变熔体初始温度来加以控制的.原子团类型指数法(比键型指数法)更进一步表征了晶化体系中原子团的结构特征，将有利于对液态金属凝固过程中微观结构的转变机理进行更为深入的研究.     

急冷条件下Cu-Pb偏晶合金的相分离研究

研究了Cu-Pb偏晶合金的急冷快速凝固和组织形成规律，并通过将金属熔体的热传导方程和Navier-Stokes方程相耦合, 理论分析了合金熔体的冷却速率、液固相变时间等物理参量与液相分离之间的相关性. 研究结果表明，在急冷快速凝固条件下，熔体的快速冷却对偏晶合金组织形成的影响要比熔体内部液相流动的影响更为显著. 快速凝固使液相分离受到抑制，Cu-Pb偏晶合金均可获得均匀的微观组织结构. 随着冷速的增大，晶粒尺寸明显减小，凝固组织显著细化，晶体形态由粗大枝晶向均匀细小的等轴晶过渡. 提高冷却速率，缩短液固相变时间是重力场中抑制液相分离、获得均匀偏晶组织结构的重要条件. 关键词： 偏晶合金 快速凝固 液相分离 微观结构     

碲化镉纳米晶中温度相关的能量转移

为了获得纳米晶之间以及单个纳米晶内部本体态至缺陷态两种能量转移在不同温度下对发光强度的影响,测量了碲化镉纳米晶层发光光谱随温度(78～300 K)的变化情况.碲化镉纳米晶层发光光谱显示:碲化镉纳米晶层在低温下有明显的本体(约520 nm)和缺陷(约605 nm)发光,且发光强度随温度的改变呈现出不同的变化规律.在温度变化的第一阶段(78～140 K),大尺寸碲化镉纳米晶发光效率高、表面缺陷少,小尺寸纳米晶至大尺寸纳米晶间的能量转移使得纳米晶本体发光强度逐渐升高、缺陷发光强度迅速降低.在温度变化的第二阶段(140～300 K),随着温度的升高,无辐射跃迁几率的增大使得碲化镉纳米晶缺陷态和本体态发光强度均逐渐降低.因此,能量转移仅在温度变化的第一阶段对发光强度的影响起主要作用,在第二阶段起次要作用.为了进一步验证能量转移对发光强度的影响,将碲化镉纳米晶用聚乙二醇包裹以减少纳米晶间的能量转移;将纳米晶层的干燥过程放在近真空环境下进行以减少单个纳米晶内部本体至缺陷态的能量转移.光谱结果显示在温度变化的第一阶段,这两种方式下得到的纳米晶层发光强度均逐渐降低,能量转移对发光强度的影响不再起主要作用.证实了能量转移对发光强度的影响规律的合理性.     

碲化镉纳米晶中温度相关的能量转移（英文）

为了获得纳米晶之间以及单个纳米晶内部本体态至缺陷态两种能量转移在不同温度下对发光强度的影响,测量了碲化镉纳米晶层发光光谱随温度(78~300K)的变化情况.碲化镉纳米晶层发光光谱显示:碲化镉纳米晶层在低温下有明显的本体(约520nm)和缺陷(约605nm)发光,且发光强度随温度的改变呈现出不同的变化规律.在温度变化的第一阶段(78~140K),大尺寸碲化镉纳米晶发光效率高、表面缺陷少,小尺寸纳米晶至大尺寸纳米晶间的能量转移使得纳米晶本体发光强度逐渐升高、缺陷发光强度迅速降低.在温度变化的第二阶段(140~300K),随着温度的升高,无辐射跃迁几率的增大使得碲化镉纳米晶缺陷态和本体态发光强度均逐渐降低.因此,能量转移仅在温度变化的第一阶段对发光强度的影响起主要作用,在第二阶段起次要作用.为了进一步验证能量转移对发光强度的影响,将碲化镉纳米晶用聚乙二醇包裹以减少纳米晶间的能量转移;将纳米晶层的干燥过程放在近真空环境下进行以减少单个纳米晶内部本体至缺陷态的能量转移.光谱结果显示在温度变化的第一阶段,这两种方式下得到的纳米晶层发光强度均逐渐降低,能量转移对发光强度的影响不再起主要作用.证实了能量转移对发光强度的影响规律的合理性.     

Interaction between Intermetallic Compounds <Emphasis Type="Italic">R</Emphasis>Ni<Subscript>3</Subscript> (<Emphasis Type="Italic">R</Emphasis> = Gd,Dy) and Hydrogen at Low Temperatures

The hydride phases of the intermetallic compounds GdNi₃ and DyNi₃ are synthesized at room temperature and at 273 K under a hydrogen pressure of 1–30 bar. The phase composition of the obtained samples is established using the X-ray diffraction method and the crystal-lattice parameters of the hydride phase are determined. The crystal phases are synthesized at room temperature under a hydrogen pressure of about 1 bar. At 273 K and under a pressure of 30 bar, amorphous samples are formed. The desorption of hydrogen from amorphous hydrides at 573 K leads to the formation of well-crystallized samples of the initial intermetallides. The amorphous samples are formed due to the ordering of hydrogen atoms in the metallic matrix of the hydride at low temperatures.     

Exploring the annealing temperature impacting on the magnetic coupling of nanometer soft grain and microstructure hard grain nanocomposites

Nanocomposites of 70% MgFe₂O₄ and 30% BaFe₁₂O₁₉ have been prepared by the mechano-chemical coprecipitation method. The prepared samples were annealed at different temperatures (400, 600, 800, and 1000 °C). The thermal gravimetric analysis (TGA) measurements of the as prepared samples has detected three weight losses attributed to evaporation, the decomposition of citric acid and nitrate combustion and the crystal transformation. The crystal growth of the soft phase has been proved by X-ray diffraction (XRD) and high resolution transmission electron microscope (HRTEM) measurements. The bonds have been detected by FT-IR measurements and are assigned to the two ferrite phases constituting the nanocomposites, which means that there are no intruder phases that have been detected. The vibrating sample magnetometer measurements (VSM) have displayed a gradually increasing of the saturation magnetization (Ms) with the annealing temperature, while the coercivity (H_c) and remnance (M_r) have exhibited a maximum value at the annealing temperature 600 °C. The ferromagnetic resonance (FMR) and VSM measurements have clarified the magnetic ordering changing inside the nanocomposites at the system transformation from the as prepared amorphous/hexagonal phase to the spinel/hexagonal phase with increasing annealing temperature. The porosity (P), the anisotropy (K) and the line width (ΔH) calculated parameters have been used to study the agreement between the FMR and VSM magnetic measurements.     

Phase and structural transformations in a molecular dynamics model of iron under ultrafast heating and cooling

It is shown that a system of classical particles considered in a molecular dynamics model with Pak-Doyama pairwise interatomic potential adequately describes not only the various structural states of iron (melt, bcc crystal, metal glass) but also the complex self-organization processes occurring in first-and second-order phase transitions (crystallization and vitrification, respectively). When the temperature is varied at a constant rate of 6.6×10¹¹ K/s, crystallization sets in from both the amorphous and the liquid state; at a rate of 1.9×10¹² K/s, crystallization is observed only in the amorphous state; and when heated at a rate of 4.4×10¹² K/s, the model amorphous iron transfers to the liquid state without crystallization. The energy of homogeneous formation of a crystal nucleus in the bulk of the amorphous phase of iron is calculated to be ～0.71 eV under the assumption that there is a spectrum of activation energies.     

非晶态合金La72Si28晶化过程中生成的新亚稳超导相

本文报道了在非晶态合金La₇₂Si₂₈晶化过程中生成新亚稳超导相的实验结果。非晶态合金La₇₂Si₂₈是用液态急冷法制备的,该合金经250℃,30min热处理后,得到了一个新的亚稳超导相,该相具有正交结构,其晶格参数为a=9.121?,b=6.821?,c=3.833?,超导临界温度T_c为3.02K,高于目前已知的La-Si系超导相的T_c值。 关键词：     

Quick preparation and thermal transport properties of nanostructured β-FeSi2 bulk material

This paper reports that the nanostructured β-FeSi2 bulk materials are prepared by a new synthesis process by combining melt spinning(MS) and subsequent spark plasma sintering(SPS).It investigates the influence of linear speed of the rolling copper wheel,injection pressure and SPS regime on microstructure and phase composition of the rapidly solidified ribbons after MS and bulk production respectively,and discusses the effects of the microstructure on thermal transport properties.There are two crystalline phases(α-Fe2Si5 and ε-FeSi) in the rapidly solidified ribbons;the crystal grains become smaller when the cooling rate increases(the 20 nm minimum crystal of ε-FeSi is obtained).Having been sintered for 1 min above 1123 K and annealed for 5 min at 923 K,the single-phase nanostructured βFeSi2 bulk materials with 200-500 nm grain size and 98% relative density are obtained.The microstructure of β-FeSi2 has great effect on thermal transport properties.With decreasing sintering temperature,the grain size decreases,the thermal conductivity of β-FeSi2 is reduced remarkably.The thermal conductivity of β-FeSi2 decreases notably(reduced 72% at room temperature) in comparison with the β-FeSi2 prepared by traditional casting method.     

Cu掺杂AgSbTe2化合物的相稳定、晶体结构及热电性能

利用熔融快淬结合放电等离子烧结(SPS), 制备了Cu_xAg_1-xSbTe₂(x= 0---0.3)样品. 粉末X射线衍射(XRD)分析结果显示, SPS处理以前, 含Cu样品形成NaCl型结构的固溶体, 而未加入Cu的样品析出Ag₂Te第二相. 根据热分析和XRD测量结果, Cu的加入能够有效抑制Ag₂Te的析出, 但同时会在快淬样品中产生少量非晶相. 在温度升高到540 K左右时, 非晶相发生晶化, 形成Sb₇Te亚稳相, 并最终转变成Sb₂Te₃稳定相. 对快淬样品进行低温SPS快速处理后, x =0.1样品为面心立方结构的单相化合物, 但是x =0.2, 0.3的样品分别析出第二相Sb₇Te和Sb₂Te₃. 由于析出第二相, x=0.2, 0.3样品的电导率增大, Seebeck系数减小, 热导率相应升高, 综合热电性能降低. x=0.1单相样品的功率因子与文献报道的AgSbTe₂化合物相当. 元素替代的合金化效应 增强了Cu_0.1Ag_0.9SbTe₂化合物的声子散射, 有效降低了样品的热导率. 因此, 单相样品Cu_0.1Ag_0.9SbTe₂表现出较佳的热电性能, 在620 K时热电优值达到1.     

On the control of microstructure in rapidly solidified Nd–Fe–B alloys through melt treatment

Rapidly solidified (RS) Nd₂Fe₁₄B alloys were prepared by melt-spinning under different melt treatment conditions i.e., the melt temperature was varied prior to ejection onto the quenching wheel. X-ray diffraction, transmission electron microscopy, thermal analysis and magnetic measurement were conducted on the as-quenched alloys to investigate their structural and magnetic characteristics. RS Nd₂Fe₁₄B alloys may display a variety of microstructures depending upon the thermal history of the melt before ejection: it was possible to synthesize an entirely amorphous structure, a partially amorphous structure containing nuclei and/or nanophases and a nanocrystalline structure. The relationship between the formation of crystalline nuclei or nanophases and the thermal history of the melt was studied. A lower melt ejection temperature produced a nanocrystalline microstructure, while higher melt ejection temperatures (T>1723 K) largely eliminated the presence of nuclei and associated nanophases and produced an amorphous product. The experimental results indicated that optimization of the melt treatment conditions will produce rapidly solidified Nd–Fe–B alloys with a more uniform microstructure.     

Structure of trans-1,4-polybutadiene synthesized with a new catalyst system

Abstract

The structure, phase composition, and temperature behavior of two trans-1,4-polybutadienes (TPBs) were studied by means of x-ray scattering and differential scanning calorimetry (DSC) techniques. The two samples examined were (1) PB synthesized using an immobilized titanium-magnesium catalyst and (2) a random copolymer based on PB prepared with a homogeneous vanadium-containing catalyst used as a reference material. It was found that the nascent structure of the first PB involves three phases: crystalline, mesomorphic (low-temperature form), and amorphous. In the vicinity of 65°C, a first-order phase transition occurs. The system becomes biphasic and contains the high-temperature form of the mesophase, as well as the amorphous phase, component. Above 165°C, the polymer melts to form a single-phase isotropic melt with a structure typical of liquids. The lateral dimension of crystallites reversibly changes at the crystal-mesophase transition. It is suggested that during annealing of the mesophase formed by cooling of the isotropic melt, the chains acquire an extended conformation. Loss of regularity of the structure of macromolecules of TPB causes a reduction of phase transition temperatures, an increase of the imperfection of the crystalline phase, and a contraction of the temperature range of existence of the mesophase.     

Ni熔体凝固过程中临界晶核和亚临界晶核的分子动力学模拟

本文用分子动力学模拟研究了Ni熔体以不同冷速凝固后微观结构的演变规律, 并通过理论计算确定出了Ni熔体凝固后获得理想非晶的临界条件. 模拟结果发现冷速小于10¹¹ K/s时, Ni 熔体凝固后形成晶态组织; 冷速在10¹¹ K/s到10^14.5 K/s之间时, Ni熔体凝固后形成由晶态结构与非晶态结构组成的混合组织. 冷速小于10¹⁰ K/s, Ni 熔体凝固后形成的晶态组织具有fcc结构; 冷速在10¹⁰ K/s到10^14.5 K/s之间时, Ni熔体凝固后组织中的晶态由fcc和hcp结构层状镶嵌排列构成. 通过分析模拟结果和计算结果, 确定出了Ni熔体凝固后形成理想非晶的临界冷速为10^14.5 K/s. 并发现Ni熔体中临界晶核(冷速等于10^14.5 K/s)和亚临界晶核(冷速大于10^14.5 K/s) 均由fcc和hcp组成层状偏聚结构, 这表明Ni熔体中生长的晶体、临界晶核和晶胚的结构是相同的. 关键词： 分子动力学模拟 晶体团簇 临界冷速 结构     

Aluminium-based amorphous and nanocrystalline alloys with Fe impurity

Aluminium-based rapidly quenched alloys of nominal composition of Al₉₀Fe₇Nb₃ and Al₉₄Fe₂V₄ were studied by Mössbauer spectroscopy. Samples annealed up to 573K showed amorphous structure represented by quadrupole-split doublets. From the corrected spectra areas, the values of f-factor and Debye temperature were calculated for both samples in the as-cast state. In the case of AlFeNb sample, f-factor was estimated to be f = 0.26 and for AlFeV, f = 0.31. High-temperature annealing at 773K and 873K induced a formation of nano-and microcrystalline structures. Mössbauer spectra of both compositions (with vanadium as well as with niobium) annealed at 773K showed superposition of crystalline phases with dominant contribution of Al₃Fe alloy. During annealing at 873K, phases with large grains and a small amount of the FeAl metastable phase were developed.