Scanning transmission electron microscopy and atom probe tomography analysis of non-stoichiometry long-period-stacking-ordered structures in Mg-Ni-Y/Sm alloys

The long-period-stacking-ordered(LPSO)structure affects the mechanical,corrosion and hydrolysis properties of Mg alloys.The current work employs high angle annular dark field-scanning transmission electron microscopy(HAADF-STEM)and atom probe tomography(APT)to investigate the structural and local chemical information of LPSO phases formed in Mg-Ni-Y/Sm ternary alloys after extended isothermal annealing.Depending on the alloying elements and their concentrations,Mg-Ni-Y/Sm develops a two-phase LPSO+α-Mg structure in which the LPSO phase contains defects,hybrid LPSO structure,and Mg insertions.HAADF-STEM and APT indicate non-stoichiometric LPSO with incomplete Ni_(6)(Y/Sm)_(8) clusters.In addition,the APT quantitatively determines the local composition of LPSO and confirms the presence of Ni within the Mg bonding layers.These results provide insight into a better understanding of the structure and hydrolysis properties of LPSO-Mg alloys.

样品温度和脉冲分数对7085铝合金APT实验数据的影响

基于原子探针层析技术(APT)优异的空间和成分分辨率,针对析出强化型7085铝合金,研究了进行APT测试分析时样品温度和脉冲分数对质谱的背底噪声、化学成分、第二相分布特征的影响。结果表明:该铝合金中存在细小的MgZn2和较大尺寸的Al3(Sc,Zr)两种析出相;随着样品温度的升高,质谱的背底噪声强度不断增大,Zn、Mg、Cu和Si等元素的含量几乎不变,而Zr含量显著持续快速增加,MgZn2析出相的尺寸几乎不变,但数量密度先减小后增加。此外,随着脉冲分数的增加,背底噪声强度不断降低,并在≥25%时趋于平稳,主要合金元素的含量仍保持不变,但Zr含量不断降低,第二相析出特征的变化不明显。因此对于7085铝合金,样品温度应选择在20 K左右,脉冲分数在15%~20%之间,以提高APT的数据质量。

Re effects in model Ni-based superalloys investigated with first-principles calculations and atom probe tomography

The phase partition and site preference of Re atoms in a ternary Ni-Al-Re model alloy,including the electronic structure of different Re configurations,are investigated with first-principles calculations and atom probe tomography.The Re distribution of single,nearest neighbor(NN),next-nearest neighbor(NNN),and cluster configurations are respectively designed in the models withγandγphases.The results show that the Re atoms tend to enteringγphase and the Re atoms prefer to occupy the Al sites inγphase.The Re cluster with a combination of NN and NNN Re-Re pair configuration is not preferred than the isolated Re atom in the Ni-based superalloys,and the configuration with isolated Re atom is more preferred in the system.Especially,the electronic states are analyzed and the energetic parameters are calculated.The electronic structure analyses show there exists strong Ni-Re electronic interaction and it is mainly contributed by the d-d hybridization.The characteristic features of the electronic states of the Re doping effects are also given.It is also found that Re atoms prefer the Al sites inγside at the interface.The density of states at or near the Fermi level and the d-d hybridizations of NN Ni-Re are found to be important in the systems.

Experimental Investigation of the Early Stage of Precipitation on Binary Al-Li, Al-Cu Alloys and Ternary Al-Li-Cu Alloys by Means of Atom Probe Tomography

Aluminum-based alloys play a key role in modern engineering and are widely used in construction components in aircraft, automobiles and other means of transportation due to their light weight and superior mechanical properties. Introduction of different nano-structure features can improve the service and the physical properties of such alloys. An improvement of an Al-based alloy has been performed based on the understanding of the relationships among compositions, processing, microstructural characteristics and properties. Knowledge of the decomposition process of the microstructure during the precipitation reaction is particularly important for future technical developments. The objective of this study is to investigate the nano-scale chemical composition in the Al-Cu, Al-Li and Al-Li-Cu alloys during the early stage of the precipitation sequence and to describe whether this compositional difference correlates with variations in the observed precipitation kinetics. Investigation of the fine scale segregation effects of dilute solutes in aluminum alloys which were experienced different heat treatments by using atom probe tomography has been achieved. The results show that an Al-1.7 at.% Cu alloy requires a long ageing time of approximately 8 h at 160°C to allow the diffusion of Cu atoms into Al matrix. For the Al-8.2 at.% Li alloy, a combination of both the natural ageing condition (48 h at room temperature) and a short artificial ageing condition (5 min at 160°C) induces increasing on the number density of the Li clusters and hence increase number of precipitated particles. Applying this combination of natural ageing and short artificial ageing conditions onto the ternary Al-4 at.% Li-1.7 at.% Cu alloy induces the formation of a Cu-rich phase. Increasing the Li content in the ternary alloy up to 8 at.% and increasing the ageing time to 30 min resulted in the precipitation processes ending with δ' particles. Thus the results contribute to the understanding of Al-alloy design.

Crystallization and impact history of a meteoritic sample of early lunar crust(NWA 3163)refined by atom probe geochronology

Granulitic lunar meteorites offer rare insights into the timing and nature of igneous,metamorphic and impact processes in the lunar crust.Accurately dating the different events recorded by these materials is very challenging,however,due to low trace element abundances (e.g.Sm,Nd,Lu,Hf),rare micrometerscale U-Th-bearing accessory minerals,and disturbed Ar-Ar systematics following a multi-stage history of shock and thermal metamorphism.Here we report on micro-baddeleyite grains in granulitic mafic breccia NWA 3163 for the first time and show that targeted microstructural analysis (electron backscatter diffraction) and nanoscale geochronology (atom probe tomography) can overcome these barriers to lunar chronology.A twinned (-90°/<401>) baddeleyite domain yields a 232Th/208Pb age of 4328 ± 309 Ma,which overlaps with a robust secondary ion mass spectrometry (SIMS) 207Pb/206Pb age of 4308± 18.6 Ma and is interpreted here as the crystallization age for the igneous protolith of NWA 3163.A second microstructural domain,< 2 mm in width,contains patchy overprinting baddeleyite and yields a Th-Pb age of 2175± 143 Ma,interpreted as dating the last substantial impact event to affect the sample.This finding demonstrates the potential of combining microstructural characterization with nanoscale geochronology when resolving complex P-T-t histories in planetary materials,here yielding the oldest measured crystallization age for components of lunar granulite NWA 3163 and placing further constraints on the formation and evolution of lunar crust.

三维原子探针的电场结构模拟研究

本文针对目前世界上被广泛使用的局部电极原子探针的样品及局部电极几何结构,通过有限元方法,结合多物理场仿真技术,研究了局部电极与针状样品的距离z、样品尖端曲率半径ρ、局部电极的入口直径φ、厚度w、开口角度α和入口长度h等参数对样品尖端附近的局部电场的影响。模拟结果表明:当z与φ的取值满足z/φ≥1时,既能在样品尖端得到较高的蒸发电场强度,又能降低局部电极对离子轨迹的影响;局部电极的厚度w和开口角度α的取值对样品尖端的电场影响较小;增大局部电极入口长度h的值有利于提高样品尖端电场强度;随着原子的蒸发(样品尖端曲率半径ρ增大),为维持原子蒸发所需的电场强度,施加在样品上的电压V与样品尖端的曲率半径ρ成正比,且所需维持的电场强度越高,施加的电压V越大。

先进表征技术在锆合金显微组织研究中的应用进展

锆合金具有良好的核性能、力学性能和加工性能,是一种重要的结构材料,在核工业、航空航天和医疗设备等领域中应用前景广泛。深入了解锆合金显微组织对于掌握其性能和性质至关重要,其显微组织(如第二相、氧化膜、氢化物等)在加工和服役过程中的演变规律及对性能影响正得到材料科学、核工程领域研究者的广泛关注。先进表征技术,如电子显微分析技术、电子探针显微技术、原位表征技术及原子探针分析技术等已被应用于锆合金显微组织研究。电子显微分析技术,可对锆合金包壳的第二相、氢化物和氧化膜的显微组织特征进行表征,为锆合金包壳材料性能的优化改进提供支持。电子探针显微技术(EPMA)是高分辨率显微技术,可对锆合金的微观结构及表面特征进行分析。原位表征技术,包括透射电子显微镜原位辐照技术、原位电化学阻抗谱技术、原位拉伸实验和原位拉曼光谱。透射电子显微镜原位辐照技术,可用于研究锆合金在辐照条件下的行为及辐照引起的微观结构变化;原位电化学阻抗谱技术,可用于研究锆合金在腐蚀过程中的阻抗模量及氧化膜厚度的变化;原位拉伸实验,可实时观察锆合金的变形行为;原位拉曼光谱,可用于检测锆合金成分及结构的变化。原子探针分析技术,可对锆合金中元素偏聚现象、氧化过程、氢的分布及纳米尺度下原子分布情况的表征。综述了先进表征技术在锆合金微观组织研究中的应用进展及存在的问题,展望了锆合金显微组织的未来研究方向。本研究为深入了解锆合金的微观结构提供了参考,深化了对锆合金组织结构及性能的认识。

利用APT研究RPV模拟钢中相界面原子偏聚特征

提高了Cu含量的核反应堆压力容器(RPV)模拟钢经调质处理(880℃保温0.5h,水淬;660℃保温10h)以及400℃时效1000h后,采用原子探针层析技术(APT)研究了碳化物/α-Fe基体,富Cu相/α-Fe基体以及富Cu相/碳化物界面处溶质或杂质原子的偏聚特征。结果表明:在碳化物/α-Fe基体界面处P原子偏聚最明显;在富Cu相/α-Fe基体界面处Ni原子偏聚最明显,Mn原子也有微弱的偏聚;在富Cu相/碳化物界面处未发现溶质或杂质原子的偏聚现象。不同相界处原子偏聚不仅与界面本身微观结构有关,也与相界附近化学特性有关。

Zr-2.5Nb合金在500℃/10.3MPa过热蒸汽中腐蚀形成的O/M界面特征的APT研究

合金耐腐蚀性能的差异被认为是合金表面形成的具有保护作用的氧化物结构差异所导致的。为了表征氧化层的微结构,利用原子探针层析技术(APT)和扫描电镜(SEM)研究了Zr-2.5Nb合金在500℃/10.3 MPa过热蒸汽中腐蚀16 h后,其氧化膜/基体(O/M)界面处的三维原子分布和显微组织。结果表明:在Zr O2生成之前,存在Zr/O比接近1的氧化物前驱相; Zr O层中Nb的含量很低,位于该氧化层中的β-Nb第二相中的Nb元素几乎不向外扩散,Fe元素偏聚在Zr O2与Zr O层界面处;β-Nb第二相的抗氧化性能高于基体,Fe元素偏聚在氧化后的β-Nb第二相与基体的界面处。

利用APT研究铁素体时效钢中富Cu相和碳化物的偏析行为

铁素体时效钢样品经过880℃水淬、660℃调质处理,然后400℃时效4000 h后,利用三维原子探针层析技术(APT)研究了时效钢中晶界和基体中富Cu析出相和碳化物的偏析行为。结果表明:分析区域中Mn、Ni、Mo、C和Cu元素更容易在晶界处偏聚,形成富Cu团簇和碳化物,晶界处的纳米富Cu相为短棒状,其尺寸大小约为6 nm,团簇中的Cu原子含量为40at%。基体中的纳米团簇近似为球状,其尺寸和团簇中的Cu原子的数量密度都比晶界处小。在晶界处析出的富Cu团簇在碳化物之间,形成一种"夹层结构"。此外,富Cu团簇内部有Mn和Ni原子的偏聚,促进富Cu相的析出。

原子探针层析技术及其在矿床研究中的应用

原子探针层析技术(APT)是一种能够以亚纳米分辨率提供定量的三维元素和同位素分析的测试分析技术,具有极高的空间分辨率和低的检出限。虽然原子探针主要用于材料科学和半导体领域,但随着近年来在矿床研究中应用的不断增加,正逐渐成为矿床研究的有用手段。与传统的地质分析技术相比,原子探针具有独特的技术优势,可以测量体积<0.0007μm3的矿物的元素组成,能够在纳米尺度上揭示矿物成分的复杂性,为理解地质演化过程提供全新的认识。本文在简述原子探针层析技术的基本原理、样品的选择和处理以及针尖样品制备的基础上,重点从成矿元素赋存状态、纳米尺度包裹体和稳定同位素组成三个方面阐述了原子探针在矿床研究中的代表性应用成果。迄今为止,原子探针在矿床学中的应用主要集中在成矿元素赋存状态的分析上,尤其是与金矿相关的黄铁矿或其他化学组成相对简单的矿物。而在纳米尺度包裹体和稳定同位素组成方面,原子探针应用成果虽不如前者丰富,但也取得了一些重要的全新认识,表现出良好的应用前景。原子探针在矿床学领域迅速发展的同时,也存在一些亟需解决的问题,如复杂质谱峰的标定、三维重建失真等。尽管如此,相信随着技术的不断进步,原子探针将逐渐成为矿床研究的重要工具。

15-5PH不锈钢在580℃时效过程中的析出强化行为

对15-5PH不锈钢进行了1040℃×1 h水冷的固溶处理,随后于580℃时效不同时间。利用维氏硬度计、光学显微镜和原子探针层析技术(atom probe tomography,APT)研究了不锈钢时效过程中析出相演变规律及其对硬度的影响。结果表明:时效初期,15-5PH不锈钢的硬度迅速上升并在时效5 min后达到峰值411.0 HV0.5,随后快速下降。时效5 min的钢中富Cu相的数量密度大,强化作用明显,硬度达到峰值。随着时效时间的延长,富Cu相逐渐粗化,强化作用减弱,硬度迅速下降。时效过程中Nb(C,N)颗粒与富Cu相分布在相邻位置,且随着时效时间的延长,铌碳氮化物不断析出长大,元素富集程度不断提高。

718Plus合金时效初期强化相的析出规律

采用显微硬度计、扫描电子显微镜(SEM)、原子探针层析(APT)技术研究了在标准热处理过程中及720℃时效初期(时效至128 h)718Plus合金的显微组织以及成分的演变规律。结果表明:718Plus合金的硬度在788℃炉冷至704℃后明显上升,在720℃时效至64 h时达到最大值459.3HV±8.5HV,硬度变化与γ′相的析出长大有关。随着热处理的进行,Ti、Al、Nb元素的分配系数逐渐增大,球形γ′相的直径、体积分数逐渐增大。γ′相的析出长大由Ti、Al、Nb元素在基体中的扩散控制,扩散程度采用元素的分配系数进行表示。在整个热处理过程中,Ti、Al、Nb元素在γ′相与基体之间的分配行为造成γ′相的直径、体积分数的变化。此外,在基体中分散着纳米级γ′团簇,其尺寸和数量密度在热处理过程中基本不变。

NP550钢板淬火开裂的关键组织结构因素

为探究影响NP550含硼钢薄板淬火开裂的关键因素,采用扫描电镜、透射电镜以及三维原子探针等多尺度表征手段对NP550淬火未开裂钢板表面和淬火开裂钢板表面和心部的微观组织、合金元素分布以及力学性能进行了对比分析。结果表明,开裂钢板的裂纹起始于板厚中心区域的原奥氏体晶界处并沿原奥氏体晶界扩展。钢板心部原奥晶粒粗化、沿晶界的铁素体和脆性渗碳体的析出以及硼元素被晶界含硼相的消耗是导致开裂钢板,特别是板厚中心处强度和塑性降低的主要原因。钢板在淬火应力下发生剧烈开裂。结合淬火工艺,生产过程中应注意控制高压水的出水量,保证冷却速率,有效防止淬裂现象发生。

Elucidating the evolution of long-period stacking ordered phase and its effect on deformation behavior in the as-cast Mg-6Gd-1Zn-0.6Zr alloy

Herein,the evolution of long-period stacking ordered(LPSO)phases in the as-cast Mg-6Gd-1Zn-0.6Zr(wt.%)alloy are investigated via transmission electron microscopy(TEM)and atom probe tomography(APT).The TEM results reveal that two types of LPSO phase(a bulky interdendritic phase and a plate-like matrix LPSO phase)are formed in the as-cast sample.Most of the LPSO phases are confirmed to be of the 14H type,with a smaller proportion being of the 18R LPSO.Further,the APT results reveal that the composition of the interdendritic LPSO phase is closer to that of the ideal 14H phase compared to the matrix LPSO phase,and both the interdendritic and matrix LPSO phases exhibit a Gd/Zn ratio of 2.5,thereby indicating a deficient Zn content compared to the ideal 14H phase(i.e.,1.3).In addition,the influence of the LPSO phases on the deformation behavior is investigated at different compressive plastic strains using electron backscatter diffraction(EBSD)analysis to reveal twinning and slip behavior during deformation.The results indicate that the LPSO phase induces additional work hardening in the late stage of deformation via the suppression of{1011}compressive twinning and the activation of non-basal slip systems.

Atom Probe Tomography Study of Fe Segregation at Phase Interface in Zr–2.5Nb Alloy

β-Nb is a typical second phase in Zr-Nb-based alloys used as fuel claddings in water-cooled nuclear reactors. The segregation of alloying element Fe may affect the corrosion resistance of Zr-Nb-based alloys. In this work, the Fe segregation at the interface between β-Nb phase and a-Zr matrix in Zr-2.5Nb alloy was studied using atom probe tomography and focused ion beam. The results suggested that the Fe concentration was much lower than Nb concentration in a-Zr matrix, while Fe selectively segregated at the β-Nb/a-Zr phase interface, leading to a Fe concentration peak at some interfaces. The peak Fe concentration varied from 0.4 to 1.2 at.% and appeared at the position where Zr concentration was approximately equal to Nb concentration. The selective segregation of Fe should be affected by the heat treatment and structure defects induced by cold rolling.

原子探针层析方法研究690合金晶界偏聚的初步结果

利用脉冲电解抛光的方法制备了含有晶界的三维原子探针(3DAP)针尖样品,用原子探针层析方法(APT)研究了杂质原子在690合金晶界附近的偏聚情况。结果表明:样品经过固溶处理并在500℃～0.5 h时效后,碳化物仅在部分有利于形核的晶界位错纠结处析出,大小为5～10 nm。用三维原子探针可观察到晶界处杂质原子的偏聚现象,C主要偏聚在晶界附近1个原子层内,Si和P偏聚在晶界附近约2个原子层的厚度内。根据这些元素的偏聚数据,讨论了它们发生偏聚时的规律。

聚焦离子束快速制备锆合金三维原子探针样品

利用聚焦离子束快速精确的定位加工了锆合金的三维原子探针样品,通过合理控制加工束流和时间,制备出的针尖样品满足了三维原子探针观察样品的要求。利用三维原子探针从该样品上采集到了8 000多万的原子信息。聚焦离子束可实现三维原子探针样品的快速,便捷,高效制备。

Ni对RPV模拟钢中富Cu原子团簇析出的影响

用原子探针层析技术和时效模拟方法,研究了不同N i含量并且提高了Cu含量的反应堆压力容器(RPV)用模拟钢中富Cu、富N i和富Mn原子团簇的形成。结果表明,提高钢中的N i含量会促使富Cu原子团簇的析出,富Cu原子团簇中含有N i和Mn。实验检测到富N i的原子团簇,团簇中含有Cu和Mn,富N i原子团簇可以作为富Cu原子团簇析出时的形核区。实验还检测到富Mn原子团簇,当Mn原子团簇中含有较高的N i时,它也可以成为富Cu原子团簇析出时成核的地方。由于钢中的合金元素N i在形成富N i原子团簇后会成为富Cu原子团簇析出时成核区,因而提高N i的含量将促进富Cu原子团簇的析出,这是合金元素N i会增加压力容器钢中子辐照脆化敏感性的本质原因。

时效工艺对反应堆压力容器钢中富Cu团簇析出的影响

反应堆压力容器（RPV）模拟钢样品经880℃加热0．5h水淬，再经过660℃加热10h调质处理，随后在340～400℃进行不同时间的时效处理，测量了维氏硬度，并采用原子探针层析技术（atomprobetomography，APT）研究了富Cu团簇的析出过程。APT分析结果表明，RPV模拟钢淬火后经400℃时效100h的样品中析出了富Cu团簇，团簇的数量密度为1．69×10^23m^-3；模拟钢在调质处理后，经400℃时效1000h时效处理后才析出了富Cu团簇，团簇的数量密度为6×10^22m^-3。研究结果表明，同调质处理后时效相比，模拟钢淬火后直接时效可以更好地模拟RPV钢经中子辐照后富Cu团簇的析出。