Characterization of local chemical ordering and deformation behavior in high entropy alloys by transmission electron microscopy

Short-range ordering(SRO)is one of the most important structural features of high entropy alloys(HEAs).However,the chemical and structural analyses of SROs are very difficult due to their small size,complexed compositions,and varied locations.Transmission electron microscopy(TEM)as well as its aberration correction techniques are powerful for characterizing SROs in these compositionally complex alloys.In this short communication,we summarized recent progresses regarding characterization of SROs using TEM in the field of HEAs.By using advanced TEM techniques,not only the existence of SROs was confirmed,but also the effect of SROs on the deformation mechanism was clarified.Moreover,the perspective related to application of TEM techniques in HEAs are also discussed.

Lattice Distortion Analysis Directly from High Resolution Transmission Electron Microscopy Images —the LADIA Program Package

Direct strain mapping from high resolution transmission electron microscopy images is possible for coherent structures. At proper imaging conditions the intensity peaks in the image have a constant spatial relationship with the projected atom columns. This allows the determination of the geometry of the projected unit cell without comparison with image simulations. The fast procedure is particularly suited for the analysis of large areas. The software package LADIA is written in the PV-WAVE code and provides all necessary tools for image processing and analysis. Image intensity peaks are determined by a cross-correlation technique, which avoids problems from noise in the low spatial frequency range. The lower limit of strain that can be detected at a sampling rate of 44 pixels/nm is≈2%.

High-resolution Transmission Electron Microscopy Characterization of the Structure of Cu Precipitate in a Thermal-aged Multicomponent Steel

High-dispersed nanoscale Cu precipitates often contribute to extremely high strength due to precipitation hardening,and whereas usually lead to degraded toughness for especially ferritic steels.Hence,it is important to understand the formation behaviors of the Cu precipitates.High-resolution transmission electron microscopy(TEM)is utilized to investigate the structure of Cu precipitates thermally formed in a high-strength low-alloy(HSLA)steel.The Cu precipitates were generally formed from solid solution and at the crystallographic defects such as martensite lath boundaries and dislocations.The Cu precipitates in the same aging condition have various structure of BCC,9 R and FCC,and the structural evolution does not greatly correlate with the actual sizes.The presence of different structures in an individual Cu precipitate is observed,which reflects the structural transformation occurring locally to relax the strain energy.The multiply additions in the steel possibly make the Cu precipitation more complex compared to the binary or the ternary Fe-Cu alloys with Ni or Mn additions.This research gives constructive suggestions on alloying design of Cu-bearing alloy steels.

Structural characterization of Al_(0.55)Ga_(0.45)N epitaxial layer determined by high resolution x-ray diffraction and transmission electron microscopy

Structural characteristics of Alo.55 Gao.45N epilayer were investigated by high resolution x-ray diffraction（HRXRD）and transmission electron microscopy（TEM）;the epilayer was grown on GaN/sapphire substrates using a high-temperature A1 N interlayer by metal organic chemical vapor deposition technique.The mosaic characteristics including tilt,twist,heterogeneous strain,and correlation lengths were extracted by symmetric and asymmetric XRD rocking curves as well as reciprocal space map（RSM）.According to Williamson-Hall plots,the vertical coherence length of AlGaN epilayer was calculated,which is consistent with the thickness of AlGaN layer measured by cross section TEM.Besides,the lateral coherence length was determined from RSM as well.Deducing from the tilt and twist results,the screw-type and edge-type dislocation densities are 1.0×10~8 cm^（-2） and 1.8×10^（10） cm^（-2）,which agree with the results observed from TEM.

High-resolution transmission electron microscopy and bulk magnetometry study of LaFe_(11.5)Si_(1.5) compound

This paper studies the microstructural and magnetic properties of LaFe11.5Si1.5 compound by means of highresolution transmission electron microscope and bulk magnetometry measurements. The crystalline structure is accompanied with the noncrystalline and nanocrystalline structures. This characteristic is the reflection of the crystalline process held by quenching. The inverse susceptibilities diverge and deviate from Curie-Weiss law under low applied magnetic fields. This paper proposes the possible mechanism between the anomalous susceptibilities and microstructure, and offers a perspective on the magnetic properties of metastable intermetallic compounds.

Scanning transmission electron microscopy: A review of high angle annular dark field and annular bright field imaging and applications in lithium-ion batteries

Scanning transmission electron microscopy（STEM） has been shown as powerful tools for material characterization,especially after the appearance of aberration-corrector which greatly enhances the resolution of STEM. High angle annular dark field（HAADF） and annular bright field（ABF） imaging of the aberration-corrected STEM are widely used due to their high-resolution capabilities and easily interpretable image contrasts. However, HAADF mode of the STEM is still limited in detecting light elements due to the weak electron-scattering power. ABF mode of the STEM could detect light and heavy elements simultaneously, providing unprecedented opportunities for probing unknown structures of materials. Atomiclevel structure investigation of materials has been achieved by means of these imaging modes, which is invaluable in many fields for either improving properties of materials or developing new materials. This paper aims to provide a introduction of HAADF and ABF imaging techniques and reviews their applications in characterization of cathode materials, study of electrochemical reaction mechanisms, and exploring the effective design of lithium-ion batteries（LIBs）. The future prospects of the STEM are also discussed.

High Resolution Electron Microscopy Observations of Structural Changes in Iron Nitride Films Annealed in Vacuum

Iron-nitride films were prepared by reactive sputtering, and the effect of annealing treatment on the structures was investigated by means of in-situ electron microscopy and high resolution electron microscopy (HREM). As-deposited films were observed to be a mixed structure of a few ultrafine epsilon-Fe2-3N particles existing in the amorphous matrix. it was found that the structure-relaxation in the amorphous occurred at 473 K, and the ultrafine grains began to grow at the higher annealing temperatures. The transition of the amorphous to epsilon-Fe2-3N was almost completed at 673 K. It is considered that the formation of the ideal epsilon-Fe3N is originated from the ordering of the nitrogen atoms during the annealing in vacuum. On the other hand, gamma'-phase (Fe4N) was seen to precipitation of epsilon-phase at 723 K. Two possible modes are proposed in the precipitation of gamma'-phase, depending on the heating rate and crystallographic orientation relationships, i.e. [121](epsilon)//[001](gamma), (2(1) over bar0$)(epsilon)//(110)(gamma) and [100](epsilon)//[110](gamma), (001)(epsilon)//(111)(gamma). In addition, alpha-Fe particles were observed to form from the gamma'-phase at high temperatures. We assumed that these structural changes are due to the diffusion of nitrogen and iron atoms during the annealing, except for the case of the precipitation of the gamma'-phase as depicted above. The results obtained in this work are in a good agreement with the assumption.

Visualization of atomic scale reaction dynamics of supported nanocatalysts during oxidation and ammonia synthesis using in-situ environmental(scanning) transmission electron microscopy

Reaction dynamics in gases at operating temperatures at the atomic level are the basis of heterogeneous gas-solid catalyst reactions and are crucial to the catalyst function.Supported noble metal nanocatalysts such as platinum are of interest in fuel cells and as diesel oxidation catalysts for pollution control,and practical ruthenium nanocatalysts are explored for ammonia synthesis.Graphite and graphitic carbons are of interest as supports for the nanocatalysts.Despite considerable literature on the catalytic processes on graphite and graphitic supports,reaction dynamics of the nanocatalysts on the supports in different reactive gas environments and operating temperatures at the single atom level are not well understood.Here we present real time in-situ observations and analyses of reaction dynamics of Pt in oxidation,and practical Ru nanocatalysts in ammonia synthesis,on graphite and related supports under controlled reaction environments using a novel in-situ environmental(scanning) transmission electron microscope with single atom resolution.By recording snapshots of the reaction dynamics,the behaviour of the catalysts is imaged.The images reveal single metal atoms,clusters of a few atoms on the graphitic supports and the support function.These all play key roles in the mobility,sintering and growth of the catalysts.The experimental findings provide new structural insights into atomic scale reaction dynamics,morphology and stability of the nanocatalysts.

Three-Dimensional Analysis of Melanosomes Isolated from B16 Melanoma Cells by Using Ultra High Voltage Electron Microscopy

Melanosomes, isolated by centrifugal separation from culture broth of B16 melanoma cells derived from mouse, were observed by scanning electron microscopy (SEM), and by transmission electron microscopy (TEM). Some interesting structural features were found inside and outside of the melanosomes. By SEM observation, the melanosomes were ellipsoid shape, their surface was not smooth and was covered with rough substructure, 10 to 20 nm particles. By TEM, uneven structure and micro particles were observed in the melanosomes. Furthermore, three-dimensional analysis was tried by using the ultra-high voltage electron microscopy(UHVEM). Micrographs of the melanosomes were taken at various tilted angles by UHVEM, after preparing 500 nm thickness specimens stained with lead citrate. From the micrographs collected, the three-dimensional structures were reconstructed by using i-mode software. Melanin stained by lead and non stained parts was clearly observed in the reconstructed structure. Non stained parts were round, regular size, and distributed widely in the melanosomes.

A Transmission Electron Microscopy Study of Plate Martensite Formation in High-carbon Low Alloy Steels

The martensitic microstructures in two high-carbon low alloy steels have been investigated by classical and automated crystallographic analysis under a transmission electron microscope. It is found that the martensitic substructure changes from consisting mostly of transformation twins for 1.20 mass% carbon （C） steel to both transformation twins and planar defects on {101}M for 1.67 mass% C steel. In the 1.67 mass% C steel it is further found that small martensite units have a rather homogeneous substructure, while large martensite units are more inhomogeneous. In addition, the martensite units in both steels are frequently found to be of zigzag patterns and have distinct crystallographic relationships with neighboring martensite units, e.g. kink or wedge couplings. Based on the present findings the development of martensite in high-carbon low alloy steels is discussed and a schematic of the martensite formation is presented. Moreover, whether the schematic view can be applied to plate martensite formation in general, is discussed.

以硫化态前驱物制备的NiMoS/γ-Al_2O_3催化剂表面活性相HRTEM研究

采用硫化态前驱物四硫代钼酸铵溶液浸渍载体γ-Al2O3制备了硫化态NiMoS/γ-Al2O3加氢精制催化剂,对催化剂进行了XRD和HRTEM表征,并以FCC柴油为原料,考察了催化剂的加氢精制性能。结果表明,该加氢催化剂的活性组分与载体γ-Al2O3的相互作用较弱,不存在难以还原硫化的Mo—O—Al桥键,催化剂表面MoS2分散度较好,MoS2的晶粒较大,堆积层数较高,大部分MoS2以Ⅱ型的NiMoS相存在;硫化态NiMoS/γ-Al2O3加氢精制催化剂具有优于工业催化剂CK-2的脱硫、脱氮和脱芳烃性能。

用HRTEM研究DOC和DPF对柴油机颗粒排放的影响

利用高分辨率透射电镜(HRTEM)对安装了排气后处理装置的CY4102-CE4B柴油机排放的颗粒进行观察,对比了ESC循环中工况7与工况10后处理装置中,柴油氧化催化器(DOC)与颗粒捕集器(DPF)前后颗粒的微观形貌与结构。研究结果表明:组成颗粒的基本粒子均呈近似球形,与发动机工况和后处理装置无关;经DOC后组成颗粒的基本粒子的轮廓比在DOC前更清晰,次级粒子由葡萄状结构向链状结构转化,但经DPF后,又向葡萄型结构转化;低速低负荷时,组成基本粒子的内核与外壳不甚明晰,呈无定型结构,基本结构单元的尺寸较小,薄层呈波浪状;而高速高负荷时,组成基本粒子的内核与外壳更加清晰,呈石墨结构,层状结构也更加明显,薄层几乎呈直线段。

Deformation defects and electron irradiation effect in nanostructured Al-Mg alloy processed by severe plastic deformation

In order to explore the exact nature of deformation defects previously observed in nanostructured Al-Mg alloys subjected to severe plastic deformation, a more thorough examination of the radiation effect on the formation of the planar defects in the high pressure torsion （HPT） alloys was conducted using high-resolution transmission electron microscopy （HRTEM）. The results show that high density defects in the HRTEM images disappear completely when these images are exposed under the electron beam for some duration of time. At the same time, lattice defects are never observed within no-defect areas even when the beam-exposure increases to the degree that holes appear in the areas. Therefore, it is confirmed that the planar defects observed in the HPT alloys mainly result from the significant plastic deformation and are not due to the radiation effect during HRTEM observation.

GaAs/Al_(0.3)Ga_(0.7)As QWIP暗电流特性HRTEM研究

采用金属有机物化学气相沉积法（MOCVD）生长GaAs/Al0.3Ga0.7As量子阱材料，制备300μm×300μm台面，内电极压焊点面积为20μm×20μm，外电极压焊点面积为80μm×80μm的单元样品两种。用变温液氮制冷系统对样品进行77~300 K暗电流特性测试。结果显示，器件暗电流曲线呈现出正负偏压的不对称性。利用高分辨透射扫描电镜（HRTEM）获得样品纳米尺度横断面高分辨像，分析结果表明：样品横断面处存在不同程度的位错及不均匀性。说明样品内部穿透位错造成相位分离是引起量子阱光电性能变差的根本原因，不同生长次序中AlGaAs与GaAs界面的不对称性与掺杂元素的扩散现象加剧了暗电流曲线的不对称性。

非均匀GaAs/AlGaAs量子阱红外探测器材料表征和器件性能研究

本文利用分子束外延(MBE)技术成功生长了GaAs/AlGaAs非均匀量子阱红外探测器材料,并对相关微结构作了细致表征。分析比较了非均匀量子阱结构和常规量子阱红外探测器性能差异,并对比研究了不同势阱宽度下非均匀量子阱红外探测器的性能变化。通过高分辨透射电子显微镜(HRTEM)结合能谱仪(EDS)对非均匀量子阱红外探测器材料微结构进行了分析,并利用二次离子质谱仪(SIMS)对非均匀势阱掺杂进行了表征。结果表明,该量子阱外延材料晶体质量很好,量子阱结构和掺杂浓度也与设计值符合较好。对于非均匀量子阱红外探测器,通过改变每个阱的掺杂浓度和势垒宽度,可以改变量子阱电场分布,而与传统的均匀量子阱红外探测器相比,其暗电流显著下降(约一个数量级)。在不同阱宽下,非均匀量子阱的跃迁模式发生改变,束缚态到准束缚态跃迁模式下(B-QB)的器件具有较高的黑体响应率以及较低的暗电流。

大别山双河地区超高压变质岩矿物超微构造的HRTEM研究

报道了大别山双河地区超高压榴辉岩和硬玉石英岩矿物超微构造及缺陷结构的高分辨透射电镜研究结果。在天然变形绿辉石晶内的自由位错、位错倾斜壁、位错环、位错网、亚晶界、堆垛层错等亚构造中 ,发现了纳米级水分子团 ,这种球形状水分子团包体的存在是导致绿辉石晶体水解弱化和塑性变形的重要因素。在榴辉岩矿物中广泛发育的层错、(10 0 )变形双晶、晶畴结构、界面与晶面的交叉滑移、晶格畸变等变形构造及缺陷结构 ,指示超高压岩石经历了快速折返。在硬玉单晶大约 5 0 0nm的微晶畴内 ,发现了C2 /c和P2 1/n两种结构 ,C2 /c结构的晶体学参数对应于硬玉 ,而P2 1/n结构的晶体学参数对应于绿辉石 ,纳米级P2 1/n出溶结构的存在 ,表明在退变质过程中 ,硬玉在纳米尺度上部分转变为绿辉石 ,并且未能达到平衡。也说明在主体岩石的抬升过程中 ,硬玉晶体伴随有复杂的非平衡退变质作用。对于大别山超高压变质岩的p T轨迹描述及其构造解释具有重要意义。

316LN不锈钢在除氧高温水中表面氧化膜的多层结构

在钛合金高压釜中对316LN不锈钢进行了除氧高温水中浸泡试验。采用X射线衍射、扫描电镜观察和透射电镜测试浸泡试验后316LN不锈钢表面生成氧化膜的特征。结果表明:外层氧化物中富铁、含镍且铬含量很低;内层氧化膜中富铬含铁和镍,表现为两个细分区域。靠近金属基体的过渡区中主合金元素和氧的浓度梯度大;而在该过渡区与外层氧化膜之间的准均匀区,元素浓度梯度较小,表现为铬含量逐渐增大,镍和铁含量逐渐减小。在内层氧化膜与外层氧化膜之间出现主要合金元素及氧含量的陡变。

高变质煤HRTEM图像中芳香晶格条纹的MASK R-CNN识别

近年来,人工智能的兴起推动了我国煤炭行业在绿色环保、智能生产等方面的发展。针对芳香晶格条纹识别过程中存在的解译慢、周期长和误判率高等问题,提出了一种基于MASK R-CNN的智能提取方法。该智能提取方法通过调整特征参数和优化网络结构,对条纹特征的识别算法进行改进:①跳过前期预处理过程,以端到端的模式进行芳香晶格条纹的特征提取训练,实现从原始HRTEM中自动识别芳香晶格条纹的功能;②突破常规神经网络提取目标物外轮廓的思维桎梏,实现对线要素的快速准确分割。以人工解译结果为标准,通过智能提取结果和传统提取结果在精度评价、识别效果和参数提取等方面的对比,验证该智能提取方法的有效性。结果表明,在识别精度方面,智能提取方法的准确率、精准率、召回率和交并比的数值为91.2%,85.2%,83.4%和72.9%,分别高于传统提取方法的89.9%,62.1%,75.4%和51.6%;在识别效果方面,智能提取方法对细节的处理更加智能,提取的线条连贯性和平滑性更好,同时噪音更少;在长度和取向等参数的统计分析方面,智能提取结果与人工解译结果在取向和长度分布图上的匹配度更高。综上所述,该智能提取方法通过MASK R-CNN进行芳香晶格条纹的自动识别,降低工作成本,提高工作效率,为煤大分子结构研究提供更快捷可靠的数据支持。

La_(0.7)Ca_(0.3)MnO_3薄膜微观结构的HRTEM表征

利用透射电子显微镜研究了衬底温度600～800℃条件下采用脉冲激光法在(001)LaAlO3(LAO)衬底上制备的La0.7Ca0.3MnO3(LCMO)薄膜的微观结构。结果表明薄膜由大量柱状晶组成且与LAO衬底形成良好外延关系。LCMO薄膜与LAO衬底的取向关系可以描述为:(ⅰ)(100)f∥(001)s、[011]f∥[100]s;(ⅱ)(011)f∥(001)s、[100]f∥[100]s。LCMO显示层状畴结构,即在衬底上初始生长的薄膜为(ⅱ)型畴,在此之上生长的薄膜为(ⅰ)类和(ⅱ)类型畴的混合体。薄膜中可观察到一些反向畴与孪晶等缺陷。薄膜与衬底界面少见错配位错,薄膜以Stranski-Krastanov模式生长。

一种强化汽车铝合金析出相的原子分辨电子显微学和谱学研究

原子分辨率的电子显微学和谱学技术是研究析出强化铝合金微结构的最有力的手段和方法,特别是原子分辨率的EDS能谱成像技术为更深入地研究和认识铝合金中的析出强化相颗粒结构及其与铝基体的界面匹配关系至关重要。然而,迄今为止,对于汽车轻量化用Al⁃Mg⁃Si合金中Mg、Si合金元素的亚稳析出聚集颗粒,原子分辨率的EDS能谱成像很难实现。本工作为国内首次报道对汽车用Al⁃Mg⁃Si合金中轻质Mg、Si元素的析出颗粒成功实现原子分辨率的EDS能谱成像的案例。作者利用最先进的透射电子显微镜技术研究了一种典型汽车用Al⁃Mg⁃Si合金在250℃时效强化过程中工艺-微结构-性能的演变关系。研究结果表明,富Mg合金在高温峰值时效阶段析出相的主要类型为β′相(Mg_(9)Si_(5))。通过先进原子分辨率的能谱成像揭示了β′相与Al基体界面层的精细原子结构和元素分布。β′相颗粒最外层总是以Mg原子层对接Al基体,这有助于帮助理解析出相界面能问题。本文的研究结果清楚解答了该合金硬度和屈服强度均得到显著提升的微结构原因。