Atom Probe Tomography Analysis Research Articles

Atom probe study on microstructure change in severely deformed pearlitic steels: application to rail surfaces and drawn wires

Pearlitic steel is used as the material for high tensile steel wires, rails and wheels due to its high work hardening and wear resistance. These properties arise from a layered structure comprising deformable lamellar ferrite and hard lamellar cementite. This paper reviews the microstructural change in heavily drawn pearlitic steels wires and worn surfaces of pearlitic rails using atom probe tomography analysis. The cementite decomposition mechanism was elucidated for heavily drawn pearlitic steel wires. For pearlitic rail steels, atomic scale characterization of worn surfaces and of the white etching layer (WEL) were performed, and a mechanism for the formation of the WEL was proposed. The differences and similarities in microstructure and in the state of the cementite in these severely deformed pearlitic steels are discussed.

Reconstructing APT Datasets: Challenging the Limits of the Possible

Atom probe tomography (APT) has been successfully used in materials science for several decades for probing local compositional variations. In metals, the capacity to measure reliable composition at the nanoscale in 3D was successfully demonstrated in the early nineties [I, 2]. By using a few geometric ingredients, a reconstruction recipe was proposed at this time that surprisingly produced on selected materials, 3D images with an atomic scale precision of the distribution of atoms with elemental identification [3). The ability to localize precisely the 3-D coordinates of individual atoms in direct space of materials is expected to find important applications in materials science and engineering, nanoscience, physics and chemistry. It is particularly crucial in semiconductor industry, to design optical devices or electronic devices, such as light-emitting diodes (LEDs), or transistors. This ideal picture of near-perfect 3D microscope however faces two issues. First, the precision of images may vary strongly from one material to another. Compared to an optical or an electron microscope, the spatial resolution loss is not diffraction limited, since image is produced from the inverse projection of ion trajectories, ions been produced by field evaporation of surface atoms. Precision is perturbed by slight deviations of the trajectories of ions from their initial positions at the specimen surace to the ion detector. A real understanding of this trajectory taking into account first the quantum interaction of atoms/ions with the specimen surface under the presence of the strong electric field existing on the surface is mandatory. The interplay between quantum processes, and more classical deviations induced by the distribution of the electric field close to the surface is extremely complex. In metals, most of the deviations thought to be induced by the field, as it was recently demonstrated experimentally by field ion microscopy in tungsten (fig. I). In oxides, quantum effects such as in-flight dissociation of molecules may degrade significantly the spatial precision (fig. 2) [4]. The second issue concerns the global distortions induced by the presence in the sample of phases very different in term of the critical fields required to extract surface atoms. This is a current case when analyzing devices composed of complex structures of metals, oxides and semiconductors materials. The surface of the sample ideally modelled with a constant curvature radius evolves dynamically under the process of field evaporation in a complex 3D surface. The direct consequence is the presence of distortions in the projected image. After the evaporation of each atom, the field distribution around the sample must be evaluated, to understand the projection law that should necessary be taken into account to generate an accurate reconstruction [5, 6). To overcome this cumbersome calculation, an alternative model, much simpler, was developed to reproduce the imaging process in simple configurations. In multilayers systems, it was demonstrated that most of the distortions could be reduced using a fast and efficient reconstruction algorithm that predicts the analytical shape of the emitting surface all along the evaporation process [7]. If a complementary technique can be used on the same sample to verify the morphology or provide complementary information before APT analysis, then this can also greatly…

Effects of pre-strain on Cu-Mg co-clustering and mechanical behavior in a naturally aged Al-Cu-Mg alloy

Effects of pre-strain on Cu-Mg co-clusters and mechanical behavior in a naturally aged Al-Cu-Mg alloy were investigated by tensile and fatigue testing, transmission electron microscope (TEM) and atom probe tomography (APT) in present work. Results show that pre-strain contributes to increasing tension strength, not only by increasing dislocation density as previously recognized, but also through enhancing Cu/Mg ratio of Cu-Mg co-cluster and resultant critical shear stress for dislocation slip. Fatigue crack propagation (FCP) resistance is not degraded by further increasing pre-strain from 5% to 10%, in spite of a FCP resistance degradation when a pre-strain of 5% is initially applied. APT analysis indicates, comparing with 5% pre-strain, 10% pre-strain remarkably enhances Cu-Mg co-cluster size and Cu/Mg ratio during natural aging, which leads to a greater critical shear stress for dislocation slip. This undoubtedly enhances fatigue crack closure effect, and retards FCP resistance degradation when a greater pre-strain of 10% is applied.

Investigation on formation mechanism of T1 precipitate in an Al-Cu-Li alloy

The formation mechanism of T1 (Al2CuLi) precipitate in an Al-Cu-Li alloy was investigated by using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) imaging, atom probe tomography (APT) and first-principles energy calculations. The HAADF-STEM images reveal the existence of the T1 precursor phase, which is termed as T1p in this study. The T1p phase has a lattice structure identical to the Al matrix, and consists of a stacking of Li-rich and Cu-rich layers along the {111}Al planes. APT analysis further confirms the existence of T1p phase, in which the concentrations of Li and Cu are significantly lower than those in T1 plate. Based on the first-principles energy calculations, the structural evolution from T1p phase to T1 phase is proved to be energetically favorable. Correspondingly, one possible evolution process from T1p phase to T1 phase involving the change of stacking sequence is proposed and discussed.

Toward an accurate quantification in atom probe tomography reconstruction by correlative electron tomography approach on nanoporous materials

In this contribution, we propose a protocol for analysis and accurate reconstruction of nanoporous materials by atom probe tomography (APT). The existence of several holes in porous materials makes both the direct APT analysis and reconstruction almost inaccessible. In the past, a solution has been proposed by filling pores with electron beam-induced deposition. Here, we present an alternative solution using an electro-chemical method allowing to fill even small and dense pores, making APT analysis possible. Concerning the 3D reconstruction, the microstructural features observed by electron tomography are used to finely calibrate the APT reconstruction parameters.

Enhanced damage tolerance through reconstructing residual stress and Cu-Mg co-clusters by pre-rolling in an Al-Cu-Mg alloy

The damage tolerance of Al-Cu-Mg alloy sheet was successfully improved by pre-rolling with small reduction (6.1%) rather than large reduction (12.2% and 21.7%). By this 6.1% pre-rolling, most of deformation only occurs at the surface layer of sheet, but not at the center layer. A protected compressive stress gradient was created, i.e., compressive stress gradually decreased from surface to center layer. Besides, atom probe tomography analysis showed that compared to center layer, large Cu-Mg co-clusters (50–100 atoms) with higher number density formed at surface layer. This led to greater module hardening and ordering hardening in surface layer than in center layer. Both the distributions of compressive stress and Cu-Mg co-clusters were responsible for the enhanced damage tolerance of alloy sheet.

Effects of optical dopants and laser wavelength on atom probe tomography analyses of borosilicate glasses

AbstractAtom probe tomography (APT) is a novel analytical microscopy method that provides three dimensional elemental mapping with sub‐nanometer spatial resolution and has only recently been applied to insulating glass and ceramic samples. In this paper, we have studied the influence of the optical absorption in glass samples on APT characterization by introducing different transition metal optical dopants to a model borosilicate nuclear waste glass. A systematic comparison is presented of the glass optical properties and the resulting APT data quality in terms of compositional accuracy and the mass spectra quality for two APT systems: one with a green laser (532 nm, LEAP 3000X HR) and one with a UV laser (355 nm, LEAP 4000X HR). These data were also compared to the study of a more complex borosilicate glass (SON68). The results show that the analysis data quality, particularly the compositional accuracy and sample yield, was clearly linked to optical absorption when using a green laser, while for the UV laser optical doping aided in improving data yield but did not have a significant effect on compositional accuracy. Comparisons of data between the LEAP systems suggest that the smaller laser spot size of the LEAP 4000X HR played a more critical role for optimum performance than the optical dopants themselves. The smaller spot size resulted in more accurate composition measurements due to a reduced background level independent of the material's optical properties.

Dependence of Solidification for Bi2Te3\u2212xSex Alloys on Their Liquid States

The resistivity versus temperature (ρ-T) behaviours of liquid n-type Bi2Te3−xSex (x = 0.3, 0.45 and 0.6) alloys are explored up to 1050 °C. A clear hump is observed on all ρ-T curves of the three studied Bi2Te3−xSex melts during the heating process, which suggests that a temperature-induced liquid-liquid structural transition takes place in the melts. Based on this information, the solidification behaviours and microstructures of the alloys with different liquid states are investigated. The samples that experienced liquid structural transition show that the nucleation and growth undercooling degrees are conspicuously enlarged and the solidification time is shortened. As a result, the solidified lamellae are refined and homogenized, the prevalence of low-angle grain boundaries between these lamellae is increased, and the Vicker Hardness is enhanced. Atom probe tomography analyses prove that there is no segregation or nanoprecipitation within the grains, but the Te-rich eutectic structure and the evolution of composition near the Te-matrix phase boundary are investigated in a sample that experienced liquid structural transition. Our work implies that the solidification behaviours of Bi2Te3−xSex alloys are strongly related to their parent liquid states, providing an alternative approach to tailor the thermoelectric and mechanical properties even when only a simple solidification process is performed.

Quantitative assessment of carbon allocation anomalies in low temperature bainite

Low temperature bainite is a mixture of ferrite and austenite with a high dislocation density and nanoscale precipitates produced by isothermal transformation of the austenite in high-carbon high-silicon steels. The mass balance for carbon is systematically unsuitable when considering only ferrite and austenite forming the structure, but no attempt has been made to evaluate the amount of carbon located at linear defects and precipitates. Additionally, bainitic ferrite has been recently shown to have a tetragonal crystal structure, allowing greater amounts of carbon in solid solution than those expected by the paraequilibrium phase boundaries. In order to quantify the contribution of all the carbon sinks, we have followed the evolution of carbon in ferrite and austenite, along with the precipitation of cementite and η–carbide, during the isothermal bainitic transformation at 220 and 250 °C by means of in-situ synchrotron high energy X-ray diffraction and complementary transmission electron microscopy (TEM) and atom probe tomography (APT) analyses. This is the first time that the mass balance for carbon is successfully achieved by considering all the transformation products together with an estimation of the carbon segregated to linear defects.

Experimental artefacts occurring during atom probe tomography analysis of oxide nanoparticles in metallic matrix: Quantification and correction

Oxide Dispersion Strengthened (ODS) steels are promising candidates for future nuclear reactors, partly due to the fine dispersion of the nanoparticles they contain. Until now, there was no consensus as to the nature of the nanoparticles because their analysis pushed the techniques to their limits and in consequence, introduced some artefacts. In this study, the artefacts that occur during atom probe tomography analysis are quantified. The artefacts quantification reveals that the particles morphology, chemical composition and atomic density are biased. A model is suggested to correct these artefacts in order to obtain a fine and accurate characterization of the nanoparticles. This model is based on volume fraction calculation and an analytical expression of the atomic density. Then, the studied ODS steel reveals nanoparticles, pure in Y, Ti and O, with a core/shell structure. The shell is rich in Cr. The Cr content of the shell is dependent on that of the matrix by a factor of 1.5. This study also shows that 15% of the atoms that were initially in the particles are not detected during the analysis. This only affects O atoms. The particle stoichiometry evolves from YTiO2 for the smallest observed (<2 nm) to Y2TiO5 for the biggest (>8 nm).

Fluxing induced boron alloying in Fe-based bulk metallic glasses

In this work, we report on advanced insights into the effects of fluxing on Fe50Ni30P13C7 bulk metallic glasses. We find that the employed oxide fluxing agent results in significant incorporation of boron in the alloy by atom probe tomography analysis. It demonstrates that the improved glass-forming ability induced by fluxing attributes to not only the reduction of heterogeneous nucleation, but also boron alloying. In addition, the more densely packed microstructure of the fluxed alloys is also related to amount of boron addition. Such an understanding is of great importance to adequately process glass-forming liquids, in order to achieve optimized bulk metallic glass parts with enhanced thicknesses and improved mechanical properties.

On the Analysis of Clustering in an Irradiated Low Alloy Reactor Pressure Vessel Steel Weld.

Radiation induced clustering affects the mechanical properties, that is the ductile to brittle transition temperature (DBTT), of reactor pressure vessel (RPV) steel of nuclear power plants. The combination of low Cu and high Ni used in some RPV welds is known to further enhance the DBTT shift during long time operation. In this study, RPV weld samples containing 0.04 at% Cu and 1.6 at% Ni were irradiated to 2.0 and 6.4×1023 n/m2 in the Halden test reactor. Atom probe tomography (APT) was applied to study clustering of Ni, Mn, Si, and Cu. As the clusters are in the nanometer-range, APT is a very suitable technique for this type of study. From APT analyses information about size distribution, number density, and composition of the clusters can be obtained. However, the quantification of these attributes is not trivial. The maximum separation method (MSM) has been used to characterize the clusters and a detailed study about the influence of the choice of MSM cluster parameters, primarily on the cluster number density, has been undertaken.

Atomic-scale investigation of carbon atom migration in surface induced white layers in high-carbon medium chromium (AISI 52100) bearing steel

The microstructure and chemical composition of white layers (WLs) formed during hard turning of AISI 52100 steel were studied using atom probe tomography (APT) and transmission electron microscopy (TEM). APT analyses revealed a major difference in the re-distribution of the carbon (C) atoms between WLs formed above and below the Ac1 temperature, i.e. T-WL and M-WL, respectively. In T-WL, the C-atoms segregate to grain boundaries (GBs) forming interconnected or isolated C-rich clusters, ∼5 nm, with a concentration of 9.8 ± 0.3 at.%C. Apart from the GB segregation, in M-WLs, large C-rich regions were found with 24.8 ± 0.4 at.%C. Owing to the chemical composition (stoichiometry) and element partitioning of such regions, they were assigned as θ-carbides (cementite). The APT results reveal that the original θ-carbides remain un-dissolved in the M-WLs, but might be plastically deformed due to the excessive strain that exists in hard machining process. The obtained results are in good agreement with the temperatures that are reached during formation of M-WLs. The isolated nano-sized C-clusters were assigned as off-stoichiometric carbides whereas the interconnected C-rich clusters were attributed to Cottrell atmospheres, evident by the linear shape of the C-enrichment as observed in the APT reconstructions. The C-contents in the nano-sized martensitic and ferritic grains were estimated to 0.50 ± 0.06 at.%C and ∼0.46 ± 0.02 at.%C, respectively. The C-content in the ferritic grains, beyond the C-solubility limit in ferrite (<0.1 at.%) is governed by the high dislocation density inside the grains, supported by the favorable binding energy between dislocations and C-atoms compared to C-atoms and Fe in carbides. No other evidence of redistribution of the substitutional alloying elements was observed. TEM analyses showed that T-WLs comprises of an equiaxed and nano-sized grains with well-defined cell boundaries, whereas the structure in the M-WLs comprised of elongated sub-grains formed via re-orientation of the original martensite followed by breakage/partitioning into elongated sub-grains.

Enhanced analysis of nanoporous gold by atom probe tomography

Atom probe tomography (APT) analysis on nanoporous materials is typically a difficult task, owing to their inferior mechanical properties and their complex field evaporation behaviour, compared with solid consolidated materials. A method for pore infiltration by electrodeposition, detailed in this study, makes it possible to prepare APT samples of nanoporous gold (NPG) using conventional FIB processes, and obtain APT data of good quality with high yield. APT analysis of the NPG material, produced by dealloying, reveals detailed compositional variation within the structures of the nanoscale ligaments. Profiles of the ligaments show exteriors rich in Au, with Ag-rich cores that are very close to the original alloy composition. With this approach the extended analysis into NPG and other nanoporous materials becomes practical, using as a foundation for future work the sample preparation and analysis methodology of this study.

Understanding of Capping Effects on the Tip Shape Evolution and on the Atom Probe Data of Bulk LaAlO3 Using Transmission Electron Microscopy.

Two challenges exist in laser-assisted atom probe tomography (APT). First, a drastic decline in mass-resolving power is caused, not only by laser-induced thermal effects on the APT tips of bulk oxide materials, but also the associated asymmetric evaporation behavior; second, the field evaporation mechanisms of bulk oxide tips under laser illumination are still unclear due to the complex relations between laser pulse and oxide materials. In this study, both phenomena were investigated by depositing Ni- and Co-capping layers onto the bulk LaAlO3 tips, and using stepwise APT analysis with transmission electron microscopy (TEM) observation of the tip shapes. By employing the metallic capping, the heating at the surface of the oxide tips during APT analysis became more symmetrical, thereby enabling a high mass-resolving power in the mass spectrum. In addition, the stepwise microscopy technique visualized tip shape evolution during APT analysis, thereby accounting for evaporation sequences at the tip surface. The combination of "capping" and "stepwise APT with TEM," is applicable to any nonconductors; it provides a direct observation of tip shape evolution, allows determination of the field evaporation strength of oxides, and facilitates understanding of the effects of ultrafast laser illumination on an oxide tip.

Nanoscale Stoichiometric Analysis of a High-Temperature Superconductor by Atom Probe Tomography.

The functional properties of the high-temperature superconductor Y1Ba2Cu3O7-δ (Y-123) are closely correlated to the exact stoichiometry and oxygen content. Exceeding the critical value of 1 oxygen vacancy for every five unit cells (δ>0.2, which translates to a 1.5 at% deviation from the nominal oxygen stoichiometry of Y7.7Ba15.3Cu23O54-δ ) is sufficient to alter the superconducting properties. Stoichiometry at the nanometer scale, particularly of oxygen and other lighter elements, is extremely difficult to quantify in complex functional ceramics by most currently available analytical techniques. The present study is an analysis and optimization of the experimental conditions required to quantify the local nanoscale stoichiometry of single crystal yttrium barium copper oxide (YBCO) samples in three dimensions by atom probe tomography (APT). APT analysis required systematic exploration of a wide range of data acquisition and processing conditions to calibrate the measurements. Laser pulse energy, ion identification, and the choice of range widths were all found to influence composition measurements. The final composition obtained from melt-grown crystals with optimized superconducting properties was Y7.9Ba10.4Cu24.4O57.2.

Laser-Assisted Atom Probe Tomography of Deformed Minerals: A Zircon Case Study.

The application of atom probe tomography to the study of minerals is a rapidly growing area. Picosecond-pulsed, ultraviolet laser (UV-355 nm) assisted atom probe tomography has been used to analyze trace element mobility within dislocations and low-angle boundaries in plastically deformed specimens of the nonconductive mineral zircon (ZrSiO4), a key material to date the earth's geological events. Here we discuss important experimental aspects inherent in the atom probe tomography investigation of this important mineral, providing insights into the challenges in atom probe tomography characterization of minerals as a whole. We studied the influence of atom probe tomography analysis parameters on features of the mass spectra, such as the thermal tail, as well as the overall data quality. Three zircon samples with different uranium and lead content were analyzed, and particular attention was paid to ion identification in the mass spectra and detection limits of the key trace elements, lead and uranium. We also discuss the correlative use of electron backscattered diffraction in a scanning electron microscope to map the deformation in the zircon grains, and the combined use of transmission Kikuchi diffraction and focused ion beam sample preparation to assist preparation of the final atom probe tip.

Atom Probe Analysis of Ex Situ Gas-Charged Stable Hydrides.

In this work, we report on the atom probe tomography analysis of two metallic hydrides formed by pressurized charging using an ex situ hydrogen charging cell, in the pressure range of 200-500 kPa (2-5 bar). Specifically we report on the deuterium charging of Pd/Rh and V systems. Using this ex situ system, we demonstrate the successful loading and subsequent atom probe analysis of deuterium within a Pd/Rh alloy, and demonstrate that deuterium is likely present within the oxide-metal interface of a native oxide formed on vanadium. Through these experiments, we demonstrate the feasibility of ex situ hydrogen analysis for hydrides via atom probe tomography, and thus a practical route to three-dimensional imaging of hydrogen in hydrides at the atomic scale.

Quantitative transmission electron microscopy and atom probe tomography study of Ag-dependent precipitation of Ω phase in Al-Cu-Mg alloys

The close association between the Ω precipitation and various Ag additions is systematically investigated by quantitative transmission electron microscopy and atom probe tomography analysis. Our results suggest that the precipitation of Ω phase is strongly dependent on Ag variations. Increasing the bulk Ag content favors a denser Ω precipitation and hence leads to a greater age-hardening response of Al-Cu-Mg-Ag alloy. This phenomenon, as proposed by proximity histograms, is directly related to the greater abundance of Ag solutes within Ω precursors. This feature lowers its nucleation barrier and increases the nucleation rate of Ω phase, finally contributes to the enhanced Ω precipitation. Also, it is noted that increasing Ag remarkably restricts the precipitation of θ' phase.

Aging and recrystallization behavior of precipitation strengthened Al-0.25Zr-0.03Y alloy

Aging and recrystallization behavior of Al-0.25Zr-0.03Y were investigated through hardness and conductivity/resistivity measurement, transmission electron microscopy (TEM), scanning electron microscope (SEM) and atom probe tomography (APT) analysis. The results show that hardness peak of Al-0.25Zr-0.03Y is about 6HV higher than that of Al-0.25Zr with the incubation period shortened from 50 h to 5 h as well. However, compared with Al-0.25Zr-0.08Y, smaller precipitates with higher number density, higher coarsening and recrystallization resistance was found in Al-0.25Zr-0.03Y. Precipitate coarsening constant in Al-0.25Zr-0.03Y is one order of magnitude lower than that in Al-0.25Zr-0.08Y. At the same time the recrystallization temperature of Al-0.25Zr-0.03Y reached 500 °C, which is about 75 °C higher than Al-0.25Zr-0.08Y and 125°C higher than Al-0.25Zr. In the ternary alloy, the equilibrium solubility of Y in α-Al decreased by 1/4 of that in binary Al-Y at 600 °C and became negligible at 400 °C. Few primary Al3Y was found in as-cast Al-0.25Zr-0.03Y and APT analysis revealed that the amount of Y in solid solution was about 4 times higher than in that in Al-0.25Zr-0.08Y, resulting in larger nucleation driving force for Al3Y and much reduced critical nucleus size and nucleation energy. The combine contribution of diminished primary Al3Y and improved physical properties of precipitates make for the higher coarsening and recrystallization resistance of Al-0.25Zr-0.03Y.