Achieving sub-nanometre particle mapping with energy-filtered TEM

A combination of state-of-the-art instrumentation and optimized data processing has enabled for the first time the chemical mapping of sub-nanometre particles using energy-filtered transmission electron microscopy (EFTEM). Multivariate statistical analysis (MSA) generated reconstructed datasets where the signal from particles smaller than 1 nm in diameter was successfully isolated from the original noisy background. The technique has been applied to the characterization of oxide dispersion strengthened (ODS) reduced activation FeCr alloys, due to their relevance as structural materials for future fusion reactors. Results revealed that most nanometer-sized particles had a core–shell structure, with an Yttrium–Chromium–Oxygen-rich core and a nano-scaled Chromium–Oxygen-rich shell. This segregation to the nanoparticles caused a decrease of the Chromium dissolved in the matrix, compromising the corrosion resistance of the alloy.     

生物轻质高强结构及其在吸能结构中的仿生应用

在长期进化过程中，自然界中的多种动物、植物形成了独特的轻质、高强结构，以此来抵抗外界的复杂冲击载荷，保护自身完整，满足生存需要。生物轻质高强结构的优越性，启发了科研和工程人员采用结构仿生学的方法来对管状和板状两大类吸能结构进行设计优化和改进。对竹子、茎秆/树干、羽轴、骨骼四类管状生物结构和甲虫鞘翅、贝壳、柚子皮、龟壳四类板状生物结构进行综述，阐述了分层、多孔、螺旋、中空等多种结构与轻质高强特性之间的关系。在此基础上，对比和分析了相应的结构元素在单胞管、多胞管、嵌套管、波纹管等管状吸能结构和蜂窝夹芯板、复合材料板、混合结构板等板状吸能机构中起到的作用。进一步对当前仿生吸能领域存在的结构复杂、质量大、缺乏普适性的机理和过渡“桥梁”等问题做出了分析；最后对仿生吸能技术的形式简单化、结构轻量化、理论通用化、“形神兼备”化发展趋势做出展望。     

Lattice measurement and alloy compositions in metal and bimetallic nanoparticles

A new reliable method for determining the lattice spacings of metallic and bimetallic nanoparticles in phase contrast high resolution electron microscopy (HREM) images was developed. In this study, we discuss problems in applying HREM techniques to single metal (Pt and Au) and bimetallic (AuPd) nanoparticles of unknown shapes and random orientations. Errors arising from particle tilt and edge effects are discussed and analysis criteria are presented to reduce these errors in measuring the lattice parameters of nanoparticles. The accuracy of an individual particle lattice measurement is limited by an effective standard deviation which depends on the size of the individual nanoparticle. For example, the standard deviation for 20-30 A Pt or Au nanoparticles is about 1.5%. To increase the accuracy in determining the lattice spacings of nanoparticles, statistical methods have to be used to obtain the average lattice spacing of an ensemble of nanoparticles. We measured approximately 100 nanoparticles with sizes in the range of 20-30 A and found that the mean lattice spacing can be determined to within 0.2%. By applying Vegard's law to the AuPd bimetallic systems we successfully detected the presence of alloying. For 30 A nanoparticles, the estimated ultimate error in determining the composition of the AuPd alloy is about 3% provided that at least 100 particles are measured. Finally, the challenges in determining the presence of more than one alloy phases in bimetallic nanoparticle systems were also discussed.     

氧化钐包覆铁纳米复合粒子的合成及微波响应特性

以Fe和Sm2O3的微米粉体为原料，压制成块体靶材，在H2＋Ar混合气氛下蒸发，原位合成了Sm2O3包覆Fe纳米复合粒子，对其成分、结构和微波频段的电磁响应特性进行了分析。结果表明，Fe／Sm2O3复合纳米粒子具有清晰的“核／壳”结构，并通过“定量氧辅助-气-液-固”机制对其形成过程进行了探讨。电磁性能分析结果显示，由介电性稀土氧化物和铁磁性‘金属构成的“核／壳”纳米结构具有微波吸收特性，其损耗机制主要以介电型损耗为主。本文采用的物理气相方法有利于多组元的纳米结构复合，实现了稀土氧化物包覆异质金属纳米胶囊合成，为金属／稀土氧化物纳米复合材料的合成与应用提供，了试验依据。     

Revealing local variations in nanoparticle size distributions in supported catalysts: a generic TEM specimen preparation method

The specimen preparation method is crucial for how much information can be gained from transmission electron microscopy (TEM) studies of supported nanoparticle catalysts. The aim of this work is to develop a method that allows for observation of size and location of nanoparticles deposited on a porous oxide support material. A bimetallic Pt‐Pd/Al₂O₃ catalyst in powder form was embedded in acrylic resin and lift‐out specimens were extracted using combined focused ion beam/scanning electron microscopy (FIB/SEM). These specimens allow for a cross‐section view across individual oxide support particles, including the unaltered near surface region of these particles. A site‐dependent size distribution of Pt‐Pd nanoparticles was revealed along the radial direction of the support particles by scanning transmission electron microscopy (STEM) imaging. The developed specimen preparation method enables obtaining information about the spatial distribution of nanoparticles in complex support structures which commonly is a challenge in heterogeneous catalysis.     

基于等刚度条件的薄壁结构的一种材料替代轻量化设计分析方法

通过对板壳结构有限单元的弯曲应变能和膜应变能进行分析,得到一个采用不同材料的薄壁结构的刚度之间的近似解析关系式。将其与结构刚度的有限元计算分析过程相结合,提出一种不同材料但等刚度的薄壁结构的迭代设计方法和材料替代轻量化分析方法。分析得到的薄壁结构关于板壳的弯曲应变能占总的应变能的比例  的等刚度曲线,可用于直观地评价材料替代得到的等刚度结构的轻量化效果,可指导薄壁结构的轻量化设计。分析表明,材料替代对薄壁结构刚度的影响不仅与材料的弹性特性和板壳厚度相关,还与给定载荷下结构的  参数相关。对于铝板替代钢板的薄壁结构设计问题, 越高,则等刚度铝板结构的轻量化效果越明显。通过对一个悬臂薄壁钢板曲梁结构和一个典型车身接头结构的材料替代设计和轻量化分析,验证了提出的设计、分析方法的有效性和结论的正确性。     

Independent continuous and mapping method of structural topology optimization based on global stress approach

There are three difficulties in topology optimization of continuum structures. 1) The topology under multiple load case is more difficult to be optimized than under single load case, because the former becomes a multiple objective based on compliance objective functions. 2) With local constraints, such as an elemental stress limit, the topology is more difficult to be solved than with global constraints, such as the displacement or frequency limits, because the sensitivity analysis of the former has very expensive computation. 3) With the phenomenon of load illness, which is similar with stiffness illness in the structural analysis, it is not easy to get the reasonable final topological structure, because it is difficult to consider different influences between the loads with small forces and big forces, and some topology paths of transferring small forces may disappear during the iteration process. To overcome difficulties above, four measures are adopted. 1) Topology optimization model is established by independent continuous mapping (ICM) method. 2) Based on the von Mises strength theory, all elements’ stress constraints are transformed into a structural energy constraint. 3) The phenomenon of load illness is divided to classify into three cases. 4) A strategy based on strain energy is proposed to adopt ICM method with stress globalization, and the problems of the above mentioned three cases of load illness are solved in terms of different complementary approaches. Several numerical examples show that the topology path of transferring forces can be obtained more easily by substituting global strain energy constraints for local stresses constraints, and the problem of load illness can be solved well by the weighting method that takes the structural energy as a weighting coefficient.     

Transformations of gold nanoparticles investigated using variable temperature high-resolution transmission electron microscopy

Recently designed advanced in-situ specimen holders for transmission electron microscopy (TEM) have been used in studies of gold nanoparticles. We report results of variable temperature TEM experiments in which structural transformations have been correlated with specimen temperature, allowing general trends to be identified. Transformation to a decahedral morphology for particles in the size range 5–12 nm was observed for the majority of particles regardless of their initial structure. Following in-situ annealing, decahedra were found to be stable at room temperature, confirming this as the equilibrium morphology, in agreement with recently calculated phase diagrams. Other transitions at low temperature in addition to surface roughening have also been observed and correlated with the same nanoscale phase diagram. Investigations of gold particles at high temperature have revealed evidence for co-existing solid and liquid phases. Overall, these results are important in a more precise understanding of the structure and action of catalytic gold nanoparticles and in the experimental verification of theoretical calculations.     

Laser induced transition from soot generation to shell shaped carbon nanoparticles in an acetylene flow: aerosol characterization

Shell shaped carbon nanoparticles were synthesized from acetylene flow injected inside an oxygen-hydrogen diffusion flame when it was irradiated with a focused beam of a CW CO₂ laser above a certain laser power and at a certain position [1]. In the present study, the evolution of carbon nanoparticles generated under laser irradiation has been investigated together with a study on the visualization of particle generating flames. The size distributions of carbon shell nanoparticles and soots have been determined by examining the images of TEM grid on which particles were captured by local thermophoretic sampling. The variations of radii of gyration and fractal dimensions of soot and shell shaped particulate aggregates are obtained at different laser powers.     

Characterising the surface and interior chemistry of core-shell nanoparticles using scanning transmission electron microscopy

A method for extracting core and shell spectra from core-shell particles with varying core to shell volume fractions is described. The method extracts the information from a single EELS spectrum image of the particle. The distribution of O and N was correctly reproduced for a nanoparticle with a TiN core and Ti-oxide shell. In addition, the O distribution from a nanoparticle with a Cu core and a Cu-oxide shell was obtained, and the extracted Cu L_2,3-core and shell spectra showed the required change in EELS near edge fine structure. The extracted spectra can be used for multiple linear least squares fitting to the raw data in the spectrum image. The effect of certain approximations on numerical accuracy, such as treating the nanoparticle as a perfect sphere, as well as the intrinsic detection limits of the technique have also been explored. The technique is most suitable for qualitative, rather than quantitative, work.     

Key techniques and applications of adaptive growth method for stiffener layout design of plates and shells

The application of the adaptive growth method is limited because several key techniques during the design process need manual intervention of designers. Key techniques of the method including the ground structure construction and seed selection are studied, so as to make it possible to improve the effectiveness and applicability of the adaptive growth method in stiffener layout design optimization of plates and shells. Three schemes of ground structures, which are comprised by different shell elements and beam elements, are proposed. It is found that the main stiffener layouts resulted from different ground structures are almost the same, but the ground structure comprised by 8-nodes shell elements and both 3-nodes and 2-nodes beam elements can result in clearest stiffener layout, and has good adaptability and low computational cost. An automatic seed selection approach is proposed, which is based on such selection rules that the seeds should be positioned on where the structural strain energy is great for the minimum compliance problem, and satisfy the dispersancy requirement. The adaptive growth method with the suggested key techniques is integrated into an ANSYS-based program, which provides a design tool for the stiffener layout design optimization of plates and shells. Typical design examples, including plate and shell structures to achieve minimum compliance and maximum bulking stability are illustrated. In addition, as a practical mechanical structural design example, the stiffener layout of an inlet structure for a large-scale electrostatic precipitator is also demonstrated. The design results show that the adaptive growth method integrated with the suggested key techniques can effectively and flexibly deal with stiffener layout design problem for plates and shells with complex geometrical shape and loading conditions to achieve various design objectives, thus it provides a new solution method for engineering structural topology design optimization.     

High-resolution subunit detection of glutamate receptor by ultrasmall gold nanoparticles

In this study, we aimed to increase the sensitivity of protein labeling using 1.4 nm gold nanoparticles and glutamate δ2 receptor (GluD2) from the postsynaptic membrane of the Purkinje cells. The very small marker size of the particles reduces the steric hindrance between antibodies leading to a higher labeling efficiency of more than one subunit per single receptor molecule. The nanoparticles are visible in 200 kV dark‐field scanning transmission electron microscope on freeze‐fractured carbon replica of nervous tissue after plasma cleaning treatment. The different elemental composition of nanoparticles as Au nanogold or CdS quantum dot can be distinguished by energy dispersive X‐ray spectroscopy. This method ensures detection of an average of three subunits per GluD2 and often labels all four of them with 1.4 nm Au nanoparticles. It is concluded that this high‐resolution microscopic method is useful for exploring the quaternary structure of membrane proteins. Microsc. Res. Tech. 75:1159–1164, 2012. © 2012 Wiley Periodicals, Inc.     

Local Characterization Of Solids By Electron Energy Loss Spectrometry

A survey of instrumentation for electron energy loss spectrometry and applications of this technique to the local characterization of solids is presented. The use of plasmon losses and core excitation losses are compared. The statistics that determine elemental detection limits for core losses are discussed and areas for future developments in the use of electron energy loss spectrometry are emphasized.     

基于改进优化准则法的自由阻尼结构动力学拓扑优化

针对自由阻尼结构拓扑优化问题,采用模态应变能的有限元求解方法,以单元相对密度值为拓扑设计变量,以材料用量和频率改变量为约束条件,构建以多模态损耗因子加权和为目标函数的拓扑优化模型,推导了目标函数对于设计变量灵敏度的表达式。考虑到常规优化准则法用于结构动力学寻优时,目标函数存在非凸性,迭代过程中出现负值设计变量,使得优化结果不收敛或陷入局部优化,故在一般优化准则法的基础上对拓扑优化模型进行数学意义上的迭代改进。改进优化准则法解决了设计变量出现非正及迭代发散等问题,保证了全体拓扑变量参与迭代过程。通过ANSYS编程对自由阻尼板进行了仿真,并引入MAC因子来控制结构的振型跃阶,结果显示:改进算法在控制阻尼材料体积为优化前体积60%时,各阶目标函数和拓扑构型在数次迭代后趋于稳定,单元中间密度值区域相对较少,自由阻尼结构获得了有效的减振。     

Quantitative and qualitative characterization of aquatic iron oxyhydroxide particles by EF-TEM

Electron energy-loss spectroscopy (EELS) and elemental imaging under the energy-filtered transmission electron microscope are powerful tools for the characterization of iron-rich particles present in natural waters. Features present in EEL spectra (Fe-M_2,3 Fe-L_2,3 and O-K ionization edges) of goethite (α-FeOOH) have been studied with an energy filter operated at 80 keV to determine optimal quantification and elemental imaging of Fe-rich natural aquatic particles in the 30–200 nm range of thickness. For quantitative aims, the Fe-M_2,3 ionization edge cannot be used easily, but the Fe-L_2,3 edge provides more accurate results owing to a better background extrapolation. The partial cross-section of the Fe(III) M shell has been determined for iron oxide. The use of two-windows (jump-ratio) and three-windows (background stripping) imaging methods is discussed in relation to the specimen thickness.     

Independent continuous and mapping method of structural topology optimization based on the global stress approach

There are three difficulties in topology optimization of continuum structures. 1) The topology under multiple load case is more difficult to be optimized than under single load case, because the former becomes a multiple objective based on compliance objective functions. 2) With local constraints, such as an elemental stress limit, the topology is more difficult to be solved than with global constraints, such as the displacement or frequency limits, because the sensitivity analysis of the former has very expensive computation. 3) With the phenomenon of load illness, which is similar with stiffness illness in the structural analysis, it is not easy to get the reasonable final topological structure, because it is difficult to consider different influences between the loads with small forces and big forces, and some topology paths of transferring small forces may disappear during the iteration process. To overcome difficulties above, four measures are adopted. 1) Topology optimization model is established by independent continuous mapping (ICM) method. 2) Based on the von Mises strength theory, all elements’ stress constraints are transformed into a structural energy constraint. 3) The phenomenon of load illness is divided to classify into three cases. 4) A strategy based on strain energy is proposed to adopt ICM method with stress globalization, and the problems of the above mentioned three cases of load illness are solved in terms of different complementary approaches. Several numerical examples show that the topology path of transferring forces can be obtained more easily by substituting global strain energy constraints for local stresses constraints, and the problem of load illness can be solved well by the weighting method that takes the structural energy as a weighting coefficient.     

Immuno-EM using colloidal metal nanoparticles and electron spectroscopic imaging for co-localization at high spatial resolution

Multiple‐labelling immuno‐EM is a powerful tool for localizing and co‐localizing different antigens simultaneously in cells and tissues at high spatial resolution. Commonly used labels for this purpose are differently sized gold spheres. A comparison of results obtained with differently sized markers is often difficult, because the diameters of markers influence labelling efficiency. In the current study, we investigate a method for high‐resolution multiple‐labelling immuno‐EM, using equally sized colloidal markers made of different metals. Energy filtering transmission electron microscopy is used to differentiate particles based on elemental composition. The labels consist of colloidal gold, palladium and platinum‐core gold‐shell particles of approximately 6 nm in diameter, which are conjugated to different primary antibodies. Applicability of the electron spectroscopic imaging, methodology is demonstrated by labelling of actin, α‐actinin and myosin on ultra‐thin cryosections of skeletal muscle tissue.     

核-壳两亲型聚合物微胶囊的合成与性能

采用三步、一锅法制备了具有亲油内核和亲水外壳的单分散聚合物微胶囊.利用TEM等对乳液和微胶囊进行表征.乳液在NaCl水溶液中沉淀,离心分离,抽滤并用冷水洗涤,得到固体微胶粒.固体微胶粒可长时间稳定分散在水中而不分层.采用10～15%(w)固体含量的上述分散液制备的薄膜,在25℃下与水和环己烷的接触角分别为16°～20°和23°～30°,表现为两亲特性.可是,将薄膜在真空下于200℃处理0.5小时后,与水的接触角变为95-110°,而与环己烷的接触角几乎不变,表明薄膜在热的作用下完全由两亲性变为亲油疏水性.     

Chemical and physical characterization by EELS of strontium hexanoate reverse micelles and strontium carbonate nanophase produced during tribological experiments

Electron energy‐loss spectroscopy (EELS) in the analytical electron microscope has been used to characterize nanometre‐scale phases of overbased strontium 3,5‐dimethylhexanoate reverse micelles and the tribological film obtained during a friction test when the phases are used as lubricant additives. Accurate chemical, molecular and structural information on these materials are deduced by interpreting the EELS near‐edge structure. This approach allows confirmation of the composite structure of the micelles, which contain a mineral core and amorphous strontium carbonate surrounded by an organic shell. It also allows identification of the chemical composition and physical structure of the tribological film as an assembly of pure strontium carbonate microcrystals, i.e. strontianite, distributed in an amorphous intergranular phase.     

Formation of ordered groups of quantum dots during Ge/Si heteroepitaxy

A new approach to the creation of circularly ordered Ge nanoislands by epitaxy on the surface of a heterophase structure consisting of a Si(100) substrate with premade seeds in the form of SiGe nanodisks or SiGe nanorings is developed. It is shown that the spatial configuration of islands in the group is due to the nucleation of the islands in the area of local minima of the elastic energy density on the surface of a circular seed. On the basis of this approach, a number of multilayer structures with vertically aligned ring groups of quantum dots were grown. The elemental composition and luminescent properties of the ordered structures are studied.