Carbide and nitride phase characterization in a transition metal carbo-nitride using x-ray spectroscopy and atom probe tomography.

A multi-phase hafnium carbo-nitride was investigated by various analytical methods. Incomplete homogenization between mixed HfC-HfN starting powders subjected to hot isostatic pressing resulted in both carbon-rich and nitrogen-rich phases. The compositions of these two phases were quantified in detail by wavelength dispersive spectroscopy and atom probe tomography, with the atom probe tips having either a small or a large shank angle geometry. For each of the two phases, an agreement of the compositions obtained by wavelength dispersive spectroscopy and atom probe tomography was found. However, the quality of the mass spectrum and hit multiplicity (single hits) were generally higher for the carbon-rich as compared to the nitrogen-rich carbo-nitride. Though the atom probe tip geometry does not appear to influence the composition, the mass resolving power did improve with the larger shank angle geometry while the hit multiplicity deteriorated slightly. Finally, our results demonstrate that hafnium carbide requires less thermal assistance to field evaporate than hafnium nitride.

Evolution of nanoscale clusters in γ' precipitates of a Ni-Al-Ti model alloy.

The evolution of phase separation and ordering processes determines the structure and properties of Ni-based superalloys. Here we use atom probe tomography to clarify the origin of γ particles occurring in ordered (L12) γ' precipitates in a Ni86.1Al8.5Ti5.4 alloy. Particularly, we elucidate the evolution from nanoscaled Ni-rich heterogeneities (Ni-rich clusters) to γ spheres and then γ plates inside γ' precipitates from the compositional and the thermodynamic point of view. We find that Ni supersaturation of γ' precipitates is relieved by formation of Ni-rich clusters, which results in an energetically more favorable state. Subsequently, coalescence introduces necking between the Ni-rich clusters and leads to the formation of γ particles. Our results demonstrate that phase separation of γ' precipitates is characterized by different stages with various governing driving forces.

Statistical analysis of composition fluctuations and short-range order in stoichiometric Ni-Cr-Mo alloys.

In the solution treated state Ni-Cr-Mo based alloys exhibit short-range order characterized by the appearance of diffuse intensity spots in electron diffraction patterns at {1 ½ 0} positions. This short-range order appears due to of the formation of chemical heterogeneities. In the present work we report on the investigation of short-range order in Ni-33 at% Cr and Ni-16.7 at% Cr-16.7 at% Mo alloys using transmission electron microscopy. Chemical heterogeneities and their sizes are analyzed by statistical methods applied to three-dimensional atom probe data obtained on the same alloys. The obtained chemical heterogeneities are correlated to regions of short-range order in Ni-33 at% Cr and Ni-16.7 at% Cr-16.7 at% Mo alloys.

Sr-Al-Si co-segregated regions in eutectic Si phase of Sr-modified Al-10Si alloy.

The addition of 200 ppm strontium to an Al-10 wt% Si casting alloy changes the morphology of the eutectic silicon phase from coarse plate-like to fine fibrous networks. In order to clarify this modification mechanism the location of Sr within the eutectic Si phase has been investigated by a combination of high-resolution methods. Whereas three-dimensional atom probe tomography allows us to visualise the distribution of Sr on the atomic scale and to analyse its local enrichment, transmission electron microscopy yields information about the crystallographic nature of segregated regions. Segregations with two kinds of morphologies were found at the intersections of Si twin lamellae: Sr-Al-Si co-segregations of rod-like morphology and Al-rich regions of spherical morphology. Both are responsible for the formation of a high density of multiple twins and promote the anisotropic growth of the eutectic Si phase in specific crystallographic directions during solidification. The experimental findings are related to the previously postulated mechanism of "impurity induced twinning".

Phase separation in equiatomic AlCoCrFeNi high-entropy alloy.

The microstructure of the as-cast AlCoCrFeNi high entropy alloy has been investigated by transmission electron microscopy and atom probe tomography. The alloy shows a very pronounced microstructure with clearly distinguishable dendrites and interdendrites. In both regions a separation into an Al-Ni rich matrix and Cr-Fe-rich precipitates can be observed. Moreover, fluctuations of single elements within the Cr-Fe rich phase have been singled out by three dimensional atom probe measurements. The results of investigations are discussed in terms of spinodal decomposition of the alloying elements inside the Cr-Fe-rich precipitates.

Microstructural investigation of Sr-modified Al-15 wt%Si alloys in the range from micrometer to atomic scale.

Strontium-modified Al-15 wt%Si casting alloys were investigated after 5 and 60 min of melt holding. The eutectic microstructures were studied using complementary methods at different length scales: focused ion beam-energy selective backscattered tomography, transmission electron microscopy and 3D atom probe. Whereas the samples after 5 min of melt holding show that the structure of eutectic Si changes into a fine fibrous morphology, the increase of prolonged melt holding (60 min) leads to the loss of Sr within the alloy with an evolution of an unmodified eutectic microstructure displaying coarse interconnected Si plates. Strontium was found at the Al/Si eutectic interfaces on the side of the eutectic Al region, measured by 3D atom probe. The new results obtained using 3D atom probe shed light on the location of Sr within the Al-Si eutectic microstructure.

Modification of Mo-Si alloy microstructure by small additions of Zr.

Molybdenum and its alloys are potential materials for high-temperature applications. However, molybdenum is susceptible to embrittlement because of oxygen segregation at the grain boundaries. In order to alleviate the embrittlement small amounts of zirconium were alloyed to a solid solution of Mo-1.5Si alloy. Two Mo-based alloys, namely Mo-1.5Si and Mo-1.5Si-1Zr, were investigated by the complementary high-resolution methods transmission electron microscopy and atom probe tomography. The Mo-1.5Si alloy shows a polycrystalline structure with two silicon-rich intermetallic phases Mo(5)Si(3) and Mo(3)Si located at the grain boundaries and within the grains. In addition, small clusters with up to 10 at% Si were found within the molybdenum solid solution. Addition of a small amount of zirconium to Mo-1.5Si leads to the formation of two intermetallic phases Mo(2)Zr and MoZr(2), which are located at the grain boundaries as well as within the interior of the grain. Transmission electron microscopy shows that small spherical Mo-Zr-rich precipitates (<10nm) decorate the grain boundaries. The stoichiometry of the small precipitates was identified as Mo(2)Zr by atom probe tomography. No Si-enriched small precipitates were detected in the Mo-1.5Si-1Zr alloy. It is concluded that the presence of zirconium hinders their formation.

Effect of decomposition of the Cr-Fe-Co rich phase of AlCoCrCuFeNi high entropy alloy on magnetic properties.

Splat-quenched, as-cast and aged (2h at 600 °C after casting) AlCoCrCuFeNi high entropy alloys were investigated by means of transmission electron microscopy and three-dimensional atom probe (3D-AP). 3D-AP revealed anti-correlated fluctuations of the Cr and Fe-Co compositions in Cr-Fe-Co-rich regions of the as-cast alloy. The ferromagnetic behavior of AlCoCrCuFeNi high entropy alloy was correlated with the decomposition of the Cr-Fe-Co-rich regions into ferromagnetic Fe-Co-rich and antiferromagnetic Cr-rich domains, the size of which was determined by statistical analysis of 3D-AP data. The splat-quenched alloy showed a softer magnetic behavior as compared to the as-cast and aged alloys. The aged alloy possessed a higher saturation magnetization and coercivity as compared to the as-cast alloy.

Analysis of clustering in Al-Mg-Si alloy by density spectrum analysis of atom probe data.

Early stages of cluster formation in an Al-Si-Mg alloy were investigated by atom probe tomography and evaluated by a newly developed statistical method based on the nearest neighbour distributions. After solutionising and quenching, an alloy sample was naturally aged for one week. The atom probe data then measured was analysed for Mg, Si or Mg-Si clusters. For comparison specimen artificial aged with well developed precipitates was also investigated. A general approach for the analysis of density spectra was set up, which reduced the problem to the solution of an integral equation. Application of the method to the atom probe data set allowed us to detect clusters and to evaluate the atomic fractions within these clusters. This is also possible for an arbitrary number of nucleated phases. The higher-order next nearest neighbour distributions were used for the estimation of cluster sizes. Combining the density distribution method with a Monte Carlo simulation we found very small Si-Si and Mg-Mg clusters consisting of only a few atoms in the naturally aged state.

Positive effect of natural pre-ageing on precipitation hardening in Al-0.44at% Mg-0.38at% Si alloy.

Age hardening in a purely ternary Al-Mg0.4-Si0.4 (0.44 at% Mg, 0.38at%Si) alloy that is similar to AA6060 was investigated by hardness measurement, TEM and three-dimensional atom probe (3D-AP). In particular, the effect of natural pre-ageing before artificial ageing, which is known to have a positive effect in this alloy, was studied by comparing three different conditions: natural ageing only, artificial ageing for 1.5h at 180 degrees C only and combined natural pre-ageing and subsequent artificial ageing for 1.5h at 180 degrees C. Natural ageing influences the mechanical properties significantly. Naturally aged alloys exhibit a hardening response that is governed by the presence of small clusters. Subsequent artificial ageing of naturally aged specimens increases the value of peak hardness, which is attributed to the increase of the number density of needle-shaped precipitates as compared to the samples without natural ageing. It is assumed that besides these precipitates, the small Si clusters formed at room-temperature storage remain stable during artificial ageing.

A new approach for explanation of specimen rupture under high electric field.

Failure of needle-shaped specimens under the action of high electric fields is one of the most serious problems in many field-ionization devices and methods. It was shown that the length of what was removed during discharge part of specimens in most of the cases was several orders greater than that of an initial radius of the specimen apex. Experimental results obtained in this work indicate that electrical breakdown in field-ion microscopes is initiated by the impact of nanoparticles detached from a point anode in a high electric field. A new approach for explanation of an observed specimen failure in a high electric field was proposed, where the formation and expansion of the cathode plasma play the key role in the mechanical rupture and melting of field-ion tips. The expanding plasma behaves as a dynamic capacitor plate characterized by a high velocity and increasing field strength at the specimen tip. The field rise rate at a constant voltage in a dynamic plasma-to-tip capacitor is of the order of >10(20)V/m/s. The present experimental data along with the ecton model of the vacuum breakdown allow the results to be discussed as a mechanical sample failure under the action of the superhigh positive field pulse induced by the cathode plasma expansion.

The influence of Cu addition on precipitation in Fe-Cr-Ni-Al-(Cu) model alloys.

Precipitation in Fe-Cr-Ni-Al-(Cu) model alloys was investigated after ageing for 0.25, 3, 10 and 100h at 798K. Characterization of nanoscale precipitates was performed using three-dimensional atom probe microscopy and transmission electron microscopy. The precipitates are found to be enriched in Ni and Al (Cu) and depleted in Fe and Cr. After 0.25h of ageing the number density of precipitates is approximately 8x10(24)m((-3)), their volume fraction is about 15.5% and they are near-spherical with an average diameter of about 2-3nm. During further ageing the precipitates in the both alloys grow, but the coarsening behaviour is different for both alloys. The precipitates of the Cu-free alloy grow much faster compared with the Cu-containing alloy and their density decreases. Precipitates in Cu-free alloy change to plate shaped even after 10h of ageing, whereas those of Cu-containing alloy remain spherical up to 10h of ageing. The influence of Cu addition on precipitation in these model alloys is discussed with respect to the different coarsening mechanisms.

Coating of meso-porous metallic membranes with oriented channel-like fine pores by pulsed laser deposition.

There is increasing demand to functionalize meso- and nanoporous materials by coating and make the porous substrate biocompatible or environmentally friendly. However, coating on a meso-porous substrate poses great challenges, especially if the pore aspect ratio is high. We adopted the pulsed laser deposition (PLD) method to coat Ni(3)Al-based meso-porous membranes, which were fabricated from a single-crystal Ni-based superalloy by a unique selective phase dissolution technique. These membranes were about 250 µm thick and had channel-like pores (∼200 nm wide) with very high aspect ratio. Two different coating materials, i.e. diamond-like carbon (DLC) and titanium, were used to coat these membranes. High energy C or Ti ions, produced in the plasma plume by the PLD process, penetrated the channel-like pores and deposited coatings on the pore walls deep inside the membrane. The thickness and the quality of coatings on the pore walls were examined using the dual-beam system. The coating thickness, of the order of 50 nm, was adherent to the pore walls and was quite uniform at different depths. The carbon and the Ti deposition behaved quite similarly. The preliminary experiments showed that the PLD is an adequate method for coating fine open cavities of complex geometry. Simulations based on stopping and the range of ions in matter (SRIM) calculations helped in understanding the deposition processes on pore walls at great depths.

Effects of 10 MeV electron irradiation at high temperature of a Ni-Mo-based Hastelloy.

A Hastelloy alloy was irradiated with 10 MeV electrons at 650 degrees C for 700 h to a total dose of 2 x 10(-3) displacements per atom (dpa). The microstructure of irradiated and non-irradiated specimens of this alloy were investigated by transmission electron microscopy (TEM). The non-irradiated specimens were analyzed by 3-D atom probe tomography (APT) in a local-electrode atom-probe (LEAP). TEM analysis before the irradiation detects small precipitates with a mean diameter of 22 nm, which are coherent with the FCC matrix. The number density of these precipitates is approximately 7 x 10(18) m(-3). Electron diffraction patterns from these precipitates exhibit superlattice reflections corresponding to the L1(2) ordered structure. The chemical composition of the precipitates, as measured by APT, is around 75 at% Ni with additions of Al, Ti and Mo. After electron irradiation, small precipitates with an irregular morphology are observed. The number density of these new precipitates about 10(20) m(-3) is greater than that of the L1(2) ordered precipitates before irradiation. The L1(2) superlattice reflections disappear completely, instead diffuse diffraction spots are observed at 1(1/2)0(FCC), which is attributed to compositional short-range order (SRO). The results are discussed with respect to the influence of the electron irradiation on the morphology and structure of the ordered precipitates.

Non-kinkwise field evaporation and kink relaxation on stepped W(112) surface.

Low-temperature field evaporation of the [111] steps on a W(211) surface was investigated by field ion microscopy (FIM). The atoms at the (112)[1;1;1] kink site are anomalously stable against field evaporation. This effect results in non-kinkwise field evaporation near the kink of this type. The non-kinkwise field evaporating steps [211]<111> usually produce the reconstructed atomic chain with double-space arranged adatoms. The experimental results reveal atomic relaxation effects at steps and kinks. The normal to surface differential relaxation of the kink-site atoms was estimated by the geometrical method of indirect magnification and by simulation of the FIM image.

Characterization of nanoscaled heterogeneities in mechanically alloyed and compacted CuFe.

Cu80Fe20 and Cu50Fe50 were mechanically alloyed from the pure elements by ball milling for 36 h. The alloy powder was compacted into tablets at room temperature by applying a pressure of 5 GPa. Characterization of the Cu80Fe20) and Cu50Fe50 alloys was carried out by high-resolution transmission electron microscopy (HREM), atom probe field ion microscopy and three-dimensional atom probe (3DAP). The grain size of the nanocrystalline microstructure of the ball-milled alloys observed with HREM varies between 3 and 50 nm. Atom probe and 3DAP measurements indicate that the as-prepared state is a highly supersaturated alloy, in which the individual nanocrystals have largely varying composition. Fe concentration in Cu was found to range from about 8 to 50 at%. It is concluded that by ball milling and compacting an alloy is produced which on a nanometer scale is heterogeneous with respect to morphology and composition.