纳米结构Cu固体材料的低温热容性能研究

采用真空热压技术在高真空和温度为523K的情况下,通过不同压力将直径平均大约为45nm的Cu纳米粉末压制成纳米结构Cu固体材料,将X射线衍射、扫描电镜与物性测试仪(PPMS)相结合,研究了低温下纳米结构Cu固体材料的比热容随温度和材料密度的变化.研究结果表明:低温比热容随着纳米结构Cu固体材料密度的降低而升高;纳米结构Cu固体材料的低温比热容大于粗晶Cu,其增加率在10K左右达到极大.基于缺陷的热振动效应,探讨了这些现象的物理机理.     

纳米Cu固体材料的X射线衍射与正电子湮没研究

采用自悬浮-冷压法,在不同压力下制得纳米Cu固体材料并对其在不同温度和保温时间下进行退火,利用X射线衍射(XRD)和正电子湮没寿命谱(PAS)分析对材料的结构和微观缺陷进行了表征。XRD分析表明,压制而得的样品晶粒度为20 nm,低于300 ℃退火3 h后并未发现晶粒显著长大;PAS分析表明,压制后的样品缺陷主要为单空位和空位团,大空隙很少,随着退火温度的升高和退火时间的延长,单空位通过扩散结合成空位团,大空隙也在温度较高时分解为空位团,导致空位团的含量增加,而单空位和大空隙的含量降低。     

纳米Cu固体材料的X射线衍射与正电子湮没研究

 采用自悬浮-冷压法,在不同压力下制得纳米Cu固体材料并对其在不同温度和保温时间下进行退火,利用X射线衍射(XRD)和正电子湮没寿命谱(PAS)分析对材料的结构和微观缺陷进行了表征。XRD分析表明,压制而得的样品晶粒度为20 nm,低于300 ℃退火3 h后并未发现晶粒显著长大;PAS分析表明,压制后的样品缺陷主要为单空位和空位团,大空隙很少,随着退火温度的升高和退火时间的延长,单空位通过扩散结合成空位团,大空隙也在温度较高时分解为空位团,导致空位团的含量增加,而单空位和大空隙的含量降低。     

ICF物理实验用纳米Cu块体靶材的制备研究

 采用自悬浮定向流法制备了金属纳米粉体并采用真空手套箱专利技术和冷压法在高压（1.5 GPa）作用下保压40 min后，成功制备出了相对密度达97％和显微硬度达1.85 GPa的金属Cu纳米晶材料。经XRD分析，其晶粒大小为20 nm。正电子湮没(PAS)实验结果表明，其空隙大小和数量与采用惰性气体冷凝法原位压制(IGC)的样品相比，空位簇数量较多，微空隙的大小和数量基本相当。激光惯性约束聚变（ICF）模拟实验表明：采用该方法制备的纳米Cu块体材料靶的激光转换效率比常规Cu材料靶高5倍。     

材料物理的新进展—纳米固体材料

纳米固体材料（ｎａｎｏｍｅｔｅｒ ｓｉｚｅｄ ｍａｔｅｒｉａｌｓ）的出现，引起了国际上物理、材料、化学及工程科学家们的很大兴趣．这是由晶粒或颗垃尺寸为 １—１５ ｎｍ（１ｎｍ＝１０－９ｍ）的超细金属、陶瓷、高分子组成的固体材料．与固体中传统的晶体、非晶体不同的是，纳米晶体材料中存在着既无长程序、又无短程序的新的固态结构．由于其特殊的原子组态，已观察到一系列不寻常的物理学和力学效应。同时也为制备相图限制之外的合金或具有特殊结合键的新型材料提供了可能性．     

纳米固体材料的性能与界面微观结构

综述了纳米陶瓷ＴｉＯ２和纳米金属Ａｇ的力学性能，以及纳米离子导体ＣａＦ２和ＰｂＦ２等的离子导电性能，结合其界面微观结构特征，对上述纳米固体材料的优异性能进行了初步解释     

ZnO纳米块体材料的制备及其性能的研究

采用连续成型方式压制了纳米ZnO素坯，考察了素坯密度、烧结时间、致密化温度等参数与 成型方式的关系.用场发射扫描电镜表征了烧结体微观组织特征.测定了ZnO纳米块体材料中 硬度随烧结温度的变化规律.结果表明，采用连续成型方式可使素坯密度提高56％、烧结时 间缩短了3h、致密化温度降低200℃.场发射扫描电镜显示烧结体内部密度及颗粒尺寸分布 均匀.硬度测定结果显示ZnO纳米块体材料中显微硬度随烧结温度的变化不是单调的，而是随 烧结温度的升高显微硬度先升高后降低，拐点对应的晶粒尺寸为50—60nm. 关键词： ZnO纳米块体 连续成型 硬度     

W/Cu梯度功能材料的高热负荷性能研究

用等离子体喷涂和热压方法制作了W/Cu梯度功能材料(FGM)样品,用大功率ND∶YAG激光对其进行了高热负载模拟实验.结果表明,在100～400MW@m-2的瞬时(脉冲宽度为4ms)热负载下,经过200～700次热循环,未发现有W-Cu复合体开裂.在123MW@m-2的功率密度下作用700次,发现钨表面有再结晶现象及严重的晶界腐蚀和裂纹,再结晶的平均晶粒尺寸约为5～10μm,垂直于表面呈柱状结构,再结晶层厚度约20～30μm.由于激光的淬冷效应,晶粒生长的趋势并不明显.在398MW@m-2功率密度下出现了明显的腐蚀坑,坑内呈疏松的蜂窝结构,坑的边缘出现了明显沉积区,能谱分析表明沉积区集聚了大量的金属杂质.等离子体喷涂试样比热压试样更易产生晶界的断裂的裂纹.在相同的热负荷条件下,W/Cu FGM的重量损失低于石墨材料的重量损失.     

纳米Cu颗粒等温晶化过程的分子动力学模拟研究

采用分子动力学方法和镶嵌原子势,模拟了500个Cu原子(简称Cu₅₀₀) 组成的纳米颗粒的等温晶化过程.利用修正的均方位移、键对分析技术和内在结构(IS) 等方法对该过程中的结构和动力学行为进行分析研究.结果显示:与块体金属不同的是, Cu₅₀₀纳米颗粒在某一温度保温时,其晶化时间并不是一个定值, 而是存在一个统计分布,并且保温温度越低其晶化时间的分布范围越广, 最长晶化时间越长.在低温晶化时, Cu₅₀₀经历了一系列中间构型的转变才达到晶态, 表现出多步晶化的特征.文章作者研究了颗粒的初始构型对晶化进程的影响, 发现颗粒的初始结构特征和能量状态对其随后的晶化过程有着重要的影响, 同一温度下,颗粒初始构型的IS能量越低其晶化时间越长,这一点在低温时尤其明显.     

高压对复合氧化物纳米固体内部缺陷结构的影响

 详细研究了不同压力下压制的NiFe₂O₄纳米固体材料的正电子寿命谱，分析了材料内部界面上缺陷结构随压制压力的变化，并与La_0.7Sr_0.3MnO₃纳米固体的缺陷结构随压力的变化进行了比较。实验结果表明，随着压制压力的增加，NiFe₂O₄纳米固体内部界面上自由体积缺陷和微孔隙缺陷的体积均被明显地压缩了，但自由体积缺陷的压缩幅度要高得多，反映出NiFe₂O₄纳米固体界面上原子排列的有序程度在高压下逐渐增强的规律。对具有不同微结构变化特征的复合氧化物纳米固体材料，其内部的缺陷结构在高压下具有不同的变化规律，进而引起其宏观物性的不同变化。     

Investigation of microstructure thermal evolution in nanocrystalline Cu

The microstructure of nanocrystalline Cu prepared by compacting nanoparticles (50-60 nm in diameter) under high pressures has been studied by means of positron lifetime spectroscopy and X-ray diffraction. These nanoparticles were produced by two different methods. We found that there are order regions interior to the grains and disorder regions at the grain boundaries with a wide distribution of interatomic distances. The mean grain sizes of the nanocrystalline Cu samples decrease after being annealed at 900 °C and increase during aging at 180 °C, which are observed by X-ray diffraction, revealing that the atoms exchange between the two regions. The positron lifetime results clearly indicate that the vacancy clusters formed in the annealing process are unstable and decomposed at the aging time below 6 hours. In addition, the partially oxidized surfaces of the nanoparticles hinder grain growth when the samples age at 180 °C, and the vacancy clusters inside the disorder regions, which are related to Cu₂O, need longer aging time to decompose. The disorder regions remain after the heat treatment in this work, in spite of the grain growth, which will be good for the samples keeping the properties of nanocrystalline material.     

Optical properties of nanocrystalline silver halides

A review of quantum confinement effects in nanocrystals of silver bromide (AgBr) and silver iodide (AgI) is presented. AgBr is an indirect gap semiconductor while AgI has a direct band-to-band lowest energy transition. An examination of the low-temperature optical properties of quantum confined AgBr grown using a variety of synthetic techniques will be made. The dynamics of some of the involved excitonic processes will be measured and discussed in reference to a possible breakdown in the momentum selection rules as the nanocrystals are made smaller. Other explanations for this behavior such as impurity exclusion and surface effects will also be considered, as will the dynamics associated with the trapping of excitons at intrinsic iodide impurities in AgBr. Absorption measurements on AgI nanocrystals will be discussed and compared with the exciton photophysics in AgBr. Both AgBr and AgI display an increasing blue shift of their luminescence, arising from the recombination of excitons, as the crystallite size decreases. The luminescence intensity arising from this process increases with decreasing size in AgBr but it disappears in small crystals of AgI. This leads to the conclusion that in the latter material nonradiative decay channels are opening up as the size decreases.     

金属间化合物Cu4Al纳米微粉的热稳定性研究

 对采用自悬浮定向流法制备的Cu4Al纳米微粉进行了差热分析(DTA)，发现在258,423和537 ℃存在不同量值的吸热峰。参照DTA曲线上吸热峰所对应的温度，分别对粉末样品进行了模拟退火实验，热处理后样品的X射线衍射（XRD）分析证实258和423 ℃处无结构相变发生，537 ℃处的吸热峰则对应于从Cu4Al向Cu₃Al的相转变，并且伴随着Cu₃Al晶粒的长大。对比实验结果表明，Cu₄Al纳米微粉在440 ℃以下具有非常好的热稳定性，超过537 ℃将发生结构相变。     

Effect of KI/LiF/CdCl2 on photoluminescent and electroluminescent properties of nanocrystalline (Zn-Cd)S: Cu films

The effect of KI/LiF/CdCl₂ on photoluminescent and electroluminescent (EL) spectra have been reported for (Zn-Cd)S:Cu films. Nanocrystalline films of (Zn-Cd)S:Cu have been prepared using chemical deposition technique in aqueous alkaline bath and their subsequent condensation on substrates. Important results in terms of XRD, SEM, absorption spectra, PL and EL spectra, voltage and frequency dependence of EL brightness are presented. Also, EL brightness waves, EL decay and dependence of EL brightness on nature of electrode material are presented and discussed. SEM studies show best growth conditions in the presence of CdCl₂. Results of XRD studies are associated to ZnS and CdS. Both the studies show average particle sizes to be in the nano order. PL and EL emissions from different films show emission peaks in the blue–green region. Results of absorption spectra show a slight change in band gaps owing to the addition of impurities. Voltage dependence of EL brightness shows effectiveness of acceleration–collision mechanism. Frequency dependence of EL brightness first shows an increase in brightness in the lower frequency range, followed by saturation at higher frequencies. Brightness waves consist of primary and secondary waves, which depend on voltage and frequency of excitation. EL cells with Al electrode give better brightness compared with cells with Ag electrodes. The lifetimes of EL emission are found to be of the order of microseconds.     

Effects of Co and W alloying elements on the electrodeposition aspects and properties of nanocrystalline Ni alloy coatings

Depending on deposition current density and alloying elements, various types of surface structure (surface morphology and grain orientation) were observed for Ni and Ni alloy nanocrystalline coatings. It was found that the variation of surface morphology with current density is in a good agreement with the variation of grain orientation. An increase in the current density produced larger grains and also reduced the charge transfer resistance and growth inhibition intensity which may change the surface structure of the coatings. For Ni coatings, the effect of surface structure on the corrosion resistance was detected to be superior to that of grain size. In the case of Ni-Co coating and at different deposition current densities, Co content and surface structure were recognized as the major factors influencing the corrosion resistance. Surface structure was also a more important factor determining the corrosion resistance of Ni-W coatings. In Ni-Co-W coatings, surface structure and grain size of the coatings were found to be independent of deposition current density. This is believed to be due to the simultaneous contrary effects of Co and W elements.     

Mechanical properties of nanocrystalline copper under thermal load

The material properties of nanocrystallines are known to generally have a strong dependence on their nanoscale morphology, such as the grain size. The Hall-Petch effect states that the mechanical strength of nanocrystalline materials can vary substantially for a wide range of grain sizes; this is attributed to the competition between intergranular and intragranular deformations. We employed classical molecular dynamics simulations to investigate the morphology-dependent mechanical properties of nanocrystalline copper. The degradation of material properties under thermal load was investigated during fast strain rate deformation, particularly for the grain size. Our simulation results showed that the thermal load on the nanocrystalline materials alters the grain-size behavior of the mechanical properties.     

Defect thermodynamic and transport properties of nanocrystalline Gd-doped ceria

Nanocrystalline CeO₂-doped (5, 7.5, 10, and 15 mol%) Gd₂O₃ powders, with a particle size of about 17 nm, were synthesized through the combustion of glycine/nitrate gels. Dense nanocrystalline materials were obtained by hot uniaxial sintering. Optical microscopy, scanning electron microscopy and transmission electron microscopy examinations, as well as X-ray diffraction analyses, have allowed us to characterize these polycrystals. The grain sizes, included between ∼10 and 80 nm, depend on both the sintering temperature and the amount of dopant. A comparison of the transport properties of these nanocrystalline samples to the values obtained with coarsened grained materials of same composition shows that the ionic conductivity passes through a maximum for mean grain sizes included between 300 and 500 nm. Furthermore, an enhancement of the ionic conductivity is observed when the amount of dopant increases. This was attributed to a grain-size-dependent gadolinium segregation at the periphery of the grains confirmed by X-ray photoelectron spectroscopy characterizations. Paper presented at the 11th EuroConference on the Science and Technology of Ionics, Batz-sur-Mer, France, 9–15 Sept. 2007.     

Critical properties of the paramagnetic-to-ferromagnetic transition in nanocrystalline Gd diluted with Fe

Nanocrystalline Gd_0.946Fe_0.054 of average grain size 68 nm was prepared by melt-spinning. The magnetic behavior in the vicinity of the paramagnetic to ferromagnetic transition was investigated via dc magnetization and ac susceptibility measurements. The transition temperature and effective critical exponents for the order parameter and zero-field susceptibility were determined using Arrott-Noakes and Kouvel-Fisher analyses. The values obtained were T_C=291.71±0.07 K, β_eff=0.385±0.009, and γ_eff=1.24±0.03, respectively. Correction to scaling analysis indicated that the asymptotic exponents were both smaller than the effective ones within the reduced-temperature range investigated, contrary to the behavior seen in monocrystalline Gd. This behavior can be explained in terms of a crossover from 3D short-range Heisenberg universality class to the 3D Ising universality class due to increased anisotropy induced by the high magnetic fields used in the measurements and also possibly due to strain.