La、Ce掺杂ZnO纳米晶的发光特性

共沉淀法制备了稀土镧、铈掺杂的ZnO半导体纳米晶。X射线衍射(XRD)结果表明:掺杂的ZnO纳米晶为六方纤锌矿结构,随掺杂浓度增加ZnO粒径减小。对铈掺杂纳米ZnO,以波长380nm激发,在443nm处出现了半峰宽较窄的强的蓝光发射峰;镧掺杂ZnO纳米晶则为从418~610nm的多峰宽带发射。     

Nanocrystalline gold with small size: inverse Hall–Petch between mixed regime and super-soft regime

ABSTRACT

Molecular dynamics simulations were used to study the atomic mechanisms of deformation of nanocrystalline gold with 2.65–18?nm in grain size to explore the inverse Hall–Petch effect. Based on the mechanical responses, particularly the flow stress and the elastic-to-plastic transition, one can delineate three regimes: mixed (10–18?nm, dislocation activities and grain boundary sliding), inverse Hall-Petch (5–10?nm, grain boundary sliding), and super-soft (below 5?nm). As the grain size decreases, more grain boundaries present in the nanocrystalline solids, which block dislocation activities and facilitate grain boundary sliding. The transition from dislocation activities to grain boundary sliding leads to strengthening-then-softening due to grain size reduction, shown by the flow stress. It was further found that, samples with large grain exhibit pronounced yield, with the stress overshoot decrease as the grain size decreases. Samples with grain sizes smaller than 5?nm exhibit elastic-perfect plastic deformation without any stress overshoot, leading to the super-soft regime. Our simulations show that, during deformation, smaller grains rotate more and grow in size, while larger grains rotate less and shrink in size.     

Development of a high pressure stirring cell up to 2 GPa: a new window for chemical reactions and material synthesis

ABSTRACT

A new method for stirring under high pressure conditions has been developed and tested. The key component is a Teflon cell assembly equipped with magnetic stirring function, which is capable to operate across a wide pressure range, up to at least 2?GPa, in a large volume press. The setup enables adjustable stirrer rotation rate and detection of stirring in a sample, e.g. to observe liquid–solid phase transitions at high pressure. The viscosity limit of stirring is ca. 500 times that of water at room temperature (i.e. ～500?mPas). Moreover, we show that zinc oxide nanoparticles hydrothermally synthesized at 0.5?GPa and 100°C under stirring conditions show an order of magnitude smaller size (100?nm) compared to those synthesized under non-stirring conditions (1?μm). The wide pressure range for stirring of viscous media opens interesting possibilities to produce novel materials via hydrothermal synthesis and chemical reactions.     

The influence of grain size and texture on the Young's modulus of nanocrystalline nickel and nickel–iron alloys

Hardness and Young's modulus were measured by nanoindentation on a series of electrodeposited nanocrystalline nickel and nickel–iron alloys. Hardness values showed a transition from regular to inverse Hall–Petch behaviour, consistent with previous studies. There was no significant influence of grain size on the Young's modulus of nanocrystalline nickel and nickel–iron alloys with grain sizes greater than 20?nm. The Young's modulus values for nanocrystalline nickel and nickel–iron alloys for grain sizes less than 20?nm were slightly reduced when compared to their conventional (randomly oriented) polycrystalline counterparts. The observed trend with decreasing grain size was found to be consistent with composite model predictions that consider the influence of intercrystalline defects. However, there was some notable variability of the measured values when compared to the model predictions. Three theoretical relationships were used to characterise the anisotropic elastic behaviour of these materials. As a result, texture was also considered to have an influence on the measured Young's modulus and used to explain some of the observed variability for the entire grain size range (9.8–81?nm).     

纳米晶Si在高压下的电学性质与金属化相变

 在金刚石压砧装置上,采用电阻和电容测量方法,研究了粒径为15~18 nm和80 nm的纳米晶Si在室温下、24 GPa内的电阻、电容与压力的关系。实验结果表明,它们分别在19~17 GPa和14 GPa左右发生了金属化相变。     

过渡金属Co2+离子掺杂ZnS硫化物纳米晶制备与中红外发光特性研究

利用不含有机相的简单水热法制备了Co^2+∶ZnS纳米晶,纳米晶具有立方闪锌矿结构,平均晶粒尺寸约为8.3 nm,在808 nm激光泵浦下具有2~5μm波段的中红外荧光发射,中心波长位于3400 nm和4700 nm,分别对应Co^2+离子的4T2(F)→4 A 1(F)和4T1(F)→4T2(F)的能级跃迁.进一步将制备的纳米晶在还原气氛下进行800℃热处理,获得立方闪锌矿和纤锌矿混合晶型的纳米晶,平均晶粒尺寸增大到22.5 nm左右,热处理后的纳米晶表面羟基含量更低,中红外荧光发射强度显著提高.该Co^2+∶ZnS纳米晶的制备方法简单、在制备过程中不引入有机相等荧光淬灭中心,同时证明通过后热处理过程可以进一步减少表面缺陷及羟基含量,使荧光强度得到大幅提升.     

Pressure-Induced Phase Transition in BaTiO3 Nanocrystals

The crystal structure and electric properties of BaTiO3 nanocrystals are studied by in situ high-pressure synchrotron radiation x-ray powder diffraction. The phase transition takes place not only in the samples of BaTiO3 nanocrystals that are tetragonal phase with grain sizes more than 100nm, but also in the samples of BaTiO3 nanocrystals that are cubic phase with grain sizes less than 100nm. The pressures of phase transition are found to increase with decrease of the grain size from about 4 to 10GPa for crystallites ranging from 200 to 10nm in radius. The bulk moduli are calculated according to Birch-Murnaghan state equation before and after the phase transition.     

High-pressure torsion-induced grain growth and detwinning in cryomilled Cu powders

Two mechanisms for deformation-induced grain growth in nanostructured metals have been proposed, including grain rotation-induced grain coalescence and stress-coupled grain boundary (GB) migration. A study is reported in which significant grain growth occurred from an average grain size of 46?nm to 90?nm during high pressure torsion (HPT) of cryomilled nanocrystalline Cu powders. Careful microstructural examination ascertained that grain rotation-induced grain coalescence is mainly responsible for the grain growth during HPT. Furthermore, a grain size dependence of the grain growth mechanisms was uncovered: grain rotation and grain coalescence dominate at nanocrystalline grain sizes, whereas stress-coupled GB migration prevails at ultrafine grain sizes. In addition, detwinning of the preexisting deformation twins was observed during HPT of the cryomilled Cu powders. The mechanism of detwinning for deformation twins was proposed to be similar to that for growth twins.     

纳米多晶铜的超塑性变形机理的分子动力学探讨

在聚能装药爆炸压缩形成射流的过程中, 伴随着金属药型罩的晶粒细化, 从原始晶粒30-80 μm细化到亚微米甚至纳米量级, 从微观层面研究其细化机理和动态超塑性变形机理具有很重要的科学意义. 采用分子动力学方法模拟了不同晶粒尺寸下纳米多晶铜的单轴拉伸变形行为, 得到了不同晶粒尺寸下的应力-应变曲线, 同时计算了各应力-应变曲线所对应的平均流变应力. 研究发现平均流变应力最大值出现在晶粒尺寸为14.85 nm时. 通过原子构型显示, 给出了典型的位错运动过程和晶界运动过程, 并分析了在不同晶粒尺寸下纳米多晶铜的塑性变形机理. 研究表明: 当晶粒尺寸大于14.85 nm时, 纳米多晶铜的变形机理以位错运动为主; 当晶粒尺寸小于14.85 nm时, 变形机理以晶界运动为主, 变形机理的改变是纳米多晶铜出现软化现象即反常Hall-Petch关系的根本原因. 通过计算结果分析, 建立了晶粒合并和晶界转动相结合的理想变形机理模型, 为研究射流大变形现象提供微观变形机理参考.     

爆轰合成碳包覆钴、镍磁性纳米颗粒的探索

 介绍了爆轰法合成碳包覆钴、镍纳米磁性颗粒研究的初步结果。以黑索今炸药为主体,加入钴、镍金属硝酸盐与有机碳源材料,在爆炸容器中氮气保护下用导爆管雷管引爆,成功地合成了碳包覆钴、镍纳米磁性颗粒。为了探求爆轰固体产物的形貌特征及性能,分别采用了TEM、XRD、VSM等测试手段对其进行表征。实验结果表明,爆轰产物中主要含有碳包覆纳米钴、纳米镍磁性颗粒,成球体或者椭球体,具有完好的核壳结构形貌。合成的碳包覆钴颗粒分布在30~50 nm之间,碳包覆的镍颗粒分布在25~60 nm之间,外层碳壳层主要由无定形碳和石墨构成。磁性测试表明,所得碳包金属钴、镍颗粒在室温下具有良好的软磁特性。     

纳米晶体结构与性能的模拟研究

通过分子动力学方法模拟纳米晶体（1—3nm）的结构．利用模拟的结果，进行了X射线衍射点阵常数、晶粒尺寸及点阵畸变的模拟计算，还计算了结合能及弹性模量等．结果表明纳米晶体无论是晶界和晶粒都与传统的粗晶粒晶体材料没有本质的区别，只是由于晶粒尺寸变小，以及晶界的体积分数等的作用，导致一系列的性能差异 关键词：     

Nickel nanoparticles in carbon structures prepared by solid-phase pyrolysis of nickel-phthalocyanine

Nanoscale magnetite (Fe₃O₄) (<15?nm) is known to remove arsenic efficiently but is very difficult to separate or require high magnetic fields to separate out from the waste water after treatment. Anisotropic hexagonal ferrite (BaFe₁₂O₁₉, BHF) is a well-known permanent magnet (i.e., fridge magnets) and attractive due to its low cost in making large quantities. BHF offers a viable alternative to magnetite nanocrystals for arsenic removal since it features surfaces similar to iron oxides but with much enhanced magnetism. Herein, we employ BHF nanocrystalline materials for the first time in arsenic removal from wastewater. Our results show better (75?%) arsenic removal than magnetite of the similar sizes. The BHF nanoparticles, 6.06?±?0.52?nm synthesized by thermolysis method at 320?°C do not show hexagonal phase, however, subsequent annealing at 750?°C produced pure hexagonal BHF in >200?nm assemblies. By using BHF, we demonstrate that nanoparticle removal is more efficient and fixed bed type cartridge applications are more possible.     

Synthesis of nano-polycrystalline diamond from glassy carbon at pressures up to 25 GPa

ABSTRACT

Nano-polycrystalline diamond (NPD) with various grain sizes has been synthesized from glassy carbon at pressures 15–25?GPa and temperatures 1700–2300°C using multianvil apparatus. The minimum temperature for the synthesis of pure NPD, below which a small amount of compressed graphite was formed, significantly increased with pressure from ～1700°C at 15?GPa to ～1900°C at 25?GPa. The NPD having grain sizes less than ～50?nm was synthesized at temperatures below ～2000°C at 15?GPa and ～2300°C at 25?GPa, above which significant grain growth was observed. The grain size of NPD decreases with increasing pressure and decreasing temperature, and the pure NPD with grain sizes less than 10?nm is obtained in a limited temperature range around 1800–2000°C, depending on pressure. The pure NPD from glassy carbon is highly transparent and exhibits a granular nano-texture, whose grain size is tunable by selecting adequate pressure and temperature conditions.     

The fine structure of FCC nanocrystals in Al-and Ni-based alloys

The structural perfection of nanocrystals in alloys of different chemical composition is studied by x-ray diffraction and high-resolution electron microscopy. In all the alloys studied, crystallization of the amorphous phase produces a nanocrystalline structure. The nanocrystal size depends on the chemical composition of the alloy and varies in aluminum-based alloys from 5 nm in Al₈₉Ni₅Y₆ to 12 nm in Al₈₂Ni₁₁Ce₃Si₄. Nanocrystals in nickel-based alloys vary in size from 15 to 25 nm. Al nanocrystals are predominantly defect-free, with microtwins observed only in some nanocrystals. The halfwidth of the diffraction lines is proportional to sec θ, which implies the small grain size provides the major contribution to the broadening. Nanocrystals in nickel alloys contain numerous twins, stacking faults, and dislocations.     

锐钛矿二氧化钛超细纳米晶的三声子互作用

本文通过对粒径为2.2-25.5nm的锐钛矿二氧化钛超细纳米晶在83-293 K温度范围内的变温拉曼光谱的研究,得到了三声子互作用对拉曼频率和线宽的贡献随粒径的变化关系。结果表明锐钛矿二氧化钛超细纳米晶的三声子相互作用随粒径减小而加强。     

Three-dimensional atomic scale analysis of nanostructured materials

The 3-dimensional atom probe (3DAP) has been used to provide atomic-scale microcharacterisation of a number of nanostructured materials. Grain boundary segregation has been investigated in electrodeposited nanocrystalline nickel and Ni-P. In the nanocrystalline nickel, there was no observable grain boundary segregation in the as-deposited condition. After annealing, carbon and sulphur contamination was found at the boundary of an abnormally-grown grain. In the as-deposited Ni-P alloy, only limited grain boundary segregation of P is seen, but annealing produces significant segregation and the formation of Ni₃P precipitates at grain boundaries. The phase chemistry in a melt-spun amorphous Fe-Si-Cu-Nb-B-Al (FINEMET-type) alloy has also been studied, and the hetereogeneous nucleation of Fe-Si nanocrystals at Cu precipitates shown conclusively. It is found that at early stages of crystallisation, there is only limited partitioning of the Si between the nanocrystals and the amorphous matrix. Atom probe studies of thin layered films have historically been limited by specimen preparation problems, but recent advances have now yielded data on metallic multilayer films. This has allowed atomic-scale measurements of interface chemistry in these films for the first time.     

纳米ZnO在高压下的性质与结构研究

 在金刚石压砧上测量了20 nm的ZnO和体相粉末ZnO的电阻-压力关系。研究结果表明，20 nm的ZnO在7.9 GPa 压力时出现了相变，而体相粉末ZnO在5 GPa 时有相变发生。虽然粒径小的相变压力大于粒径大的，但与以前关于体相粉末ZnO所报道的文献结果有所不同。文中对此作了解释，并对纳米ZnO在压力下的畴破裂进行了研究。     

小尺寸NaLuF4:Yb3+/Tm3+纳米晶的生长及上转换发光

为了详细地探究NaLuF₄纳米晶的生长过程,利用自主研发的可以精确控制实验参数的自动纳米合成仪制备了不同系列的NaLuF₄：Yb³⁺/Tm³⁺纳米材料。对不同反应温度下（285,295,305℃）制备的样品进行物相分析,发现随着反应时间的增加,NaLuF₄纳米晶均遵循相似的生长规律,即α-相→α-相+β-相→均匀的β-相→聚集的β-相。在不同温度下,均有一个时间段可以获得小尺寸（小于50 nm）、单分散、粒径分布窄的纯β-NaLuF₄纳米晶。另外,测试了不同温度下制备的β-NaLuF₄：Yb³⁺/Tm³⁺纳米材料的上转换发射光谱,结果表明随着反应温度的升高,样品的发光先增强后减弱。出现这种光谱规律可能是受晶体尺寸和结晶性两方面因素的影响。此外,样品在紫外区的高阶多光子发光很强。例如,361 nm发射峰强度大约是800 nm发射峰强度的2倍。     

具有强紫外上转换发射特性的小尺寸、水溶性 NaYF4∶Yb,Tm纳米晶的合成与表征

利用高温热解法合成了小尺寸、粒径均匀分布的NaYF₄∶18%Yb,0.5%Tm纳米晶,并通过配体交换的方法实现了纳米晶油溶性向水溶性的转变。通过X射线衍射仪、透射电子显微镜和荧光光谱仪对修饰前后的纳米晶进行了结构、形貌和光学性质的表征。实验结果表明:所合成的样品是纯六角相NaYF₄(β-NaYF₄),且粒径均匀分布在35 nm左右。在980 nm近红外光激发下,修饰前后的纳米晶具有强的紫外上转换发射特性,其Tm³⁺离子的五光子上转换发光强度强于四光子和三光子上转换发光强度。鉴于这种特殊的光学性质以及小的尺寸,所合成的水溶性纳米晶在生物医学领域显示出潜在的应用价值。     

Nonhydrostatic compression of gold powder to 60 GPa in a diamond anvil cell: estimation of compressive strength from x-ray diffraction data

Two gold powder samples, one with average crystallite size of ≈30?nm (n-Au) and another with ≈120?nm (c-Au), were compressed under nonhydrostatic conditions in a diamond anvil cell to different pressures up to ≈60?GPa and the x-ray diffraction patterns recorded. The difference between the axial and radial stress components (a measure of the compressive strength) was estimated from the shifts of the diffraction lines. The maximum micro-stress in the crystallites (another measure of the compressive strength) and grain size (crystallite size) were obtained from analysis of the line-width data. The strengths obtained by the two methods agreed well and increased with increasing pressure. Over the entire pressure range, the strength of n-Au was found to be significantly higher than that of c-Au. The grain sizes of both n-Au and c-Au decreased under pressure. This decrease was much larger than expected from the compressibility effect and was found to be reversible. An equation derived from the dislocation theory that predicts the dependence of strength on the grain size and the shear modulus was used to interpret the strength data. The strength derived from the published grain size versus hardness data agreed well with the present results.