Atom probe microscopy of self-assembled monolayers : preliminary results

We have achieved three-dimensional imaging of decanethiol self-assembled monolayers (SAMs) on metal surfaces by atom probe tomography (APT). The present Letter provides preliminary results on Ni [001] and Au [111], shows the analytical potential of APT analysis of SAMs, and details developments in specimen preparation and in data-treatment methodologies. Importantly, the investigation of the mass spectra from analysis of the SAMs revealed no combination of sulfur and hydrogen at the interface between the metal substrates and the organic materials, potentially providing insight about the bonding of the thiols on the substrate.

Mining information from atom probe data

Whilst atom probe tomography (APT) is a powerful technique with the capacity to gather information containing hundreds of millions of atoms from a single specimen, the ability to effectively use this information creates significant challenges. The main technological bottleneck lies in handling the extremely large amounts of data on spatial-chemical correlations, as well as developing new quantitative computational foundations for image reconstruction that target critical and transformative problems in materials science. The power to explore materials at the atomic scale with the extraordinary level of sensitivity of detection offered by atom probe tomography has not been not fully harnessed due to the challenges of dealing with missing, sparse and often noisy data. Hence there is a profound need to couple the analytical tools to deal with the data challenges with the experimental issues associated with this instrument. In this paper we provide a summary of some key issues associated with the challenges, and solutions to extract or "mine" fundamental materials science information from that data.

Characterization of nano-scale particles in hot-rolled, high strength low alloy steels (HSLA)

The contribution of nano-scale particles observed using Atom Probe Tomography in an increase of yield strength of conventional and advanced HSLA steels was studied. The advanced HSLA steel showed higher yield strength than conventional HSLA steel. There were two types of carbides, which primarily contribute to an increase in yield strength of conventional HSLA steel: (i) coarse TiC with average size of 25±5nm and (ii) fine TiC with average radius of 3±1.2nm. The presence of two types of carbides was found in the microstructure of advanced HSLA steel: (i)
nano-scale Ti0.98Mo0.02C0.6 carbides with average radius of 2.2±0.5nm, and (ii) C19Cr7Mo24 particles with an average radius of 1.5±0.3nm. The contribution of precipitation hardening in the yield strength of advanced HSLA steel due to the nano-scale particles was 174MPa, while this value in the conventional HSLA steel was 128MPa.

A study of the strengthening mechanism in the thermomechanically processed TRIP/TWIP steel

The strengthening mechanism responsible for the unique combination of ultimate tensile strength and elongation in a multiphase Fe-0.2C-1.5Mn-1.2Si-0.3Mo-0.6Al-0.02Nb (wt%) steel was studied. The microstructures with different volume fraction of polygonal fenite, bainite and retained austenite were simulated by controlled thermomechanical processing. The interupted tensile test was used to study the bainitic ferrite, retained austenite and polygonal ferrite behavior as a function of plastic strain. X-ray analysis was used to characterize the volume fraction and carbon content of retained austenite. TEM and heat-tinting were utilized to analyze the effect of bainitic fenite morphology on the strain induced transformation of retained austenite and retained austenite twinning as a function of strain in the bulk material. The study has shown that the austenite twinning mechanism is more preferable than the transformation induced plasticity mechanism during the early stages of deformation for a microstructure containing I5% polygonal ferrite, while the transformation induced plasticity effect is the main mechanism in when there is 50% of polygonal ferrite in the microstructure. The baillitic fenite morphology affects the deformation mode of retained austenite during straining. The polygonal fenite behavior during straining depends on dislocation substructure tonned due to the deformation and the additional mobile dislocations caused by the TRIP effect. TRIP and TWIP effects depend not only on the chemical and mechanical stability of retained austenite, but also on the interaction of the phases during straining.

Microstructure and mechanical properties of thermomechanically processed TRIP steel

The strengthening mechanism responsible for the unique combination of ultimate tensile strength and elongation in a multiphase Fe-0.2C-1.5Mn-1.2Si-0.3Mo-0.6Al-0.02Nb (wt%) steel was studied. The microstructures with different volume fractions of polygonal ferrite, bainite and retained austenite were simulated by controlled thermomechanical processing. The interrupted tensile test was used to study the bainitic ferrite, retained austenite and polygonal ferrite behaviour as a function of plastic strain. X-ray analysis was used to characterise the volume fraction and carbon content of retained austenite. Transmission electron microscopy was utilised to analyse the effect of bainitic ferrite morphology on the strain induced transformation of retained austenite and retained austenite twinning as a function of strain in the bulk material. The study has shown that the austenite twinning mechanism is more preferable than the transformation induced plasticity (TRIP) mechanism during the early stages of deformation for a microstructure containing 15% polygonal ferrite, while the transformation induced plasticity effect is the main mechanism when there is 50% of polygonal ferrite in the microstructure. The bainitic ferrite morphology affects the deformation mode of retained austenite during straining. The polygonal ferrite behaviour during straining depends on dislocation substructure formed due to the deformation and the additional mobile dislocations caused by the TRIP effect. Operation of TRIP or twinning mechanisms depends not only on the chemical and mechanical stability of retained austenite, but also on the interaction of the phases during straining.

Effect of bake-hardening on the structure-property relationship of multiphase steels for the automotive industry

The effect of a bake-hardening (BH) treatment on the microstructure and mechanical properties has been studied in C-Mn-Si TRansformation Induced Plasticity (TRIP) and Dual Phase (DP) steels after: (i) thermomechanical processing (TMP) and (ii) intercritical annealing (IA). The steels were characterized using X-ray diffraction, transmission electron microscopy (TEM) and three-dimensional atom probe tomography (APT). All steels showed high BH response. however, the DP and trip steels after IA/BH showed the appearance of upper and lower yield points, while the stress-strain behavior of the trip steel after TMP/BH was still continuous. This was due to the higher volume fraction of bainite and more stable retained austenite in the TMP/BH steel, the formation of plastic deformation zones with high dislocation density around the "as-quenched” martensite and “TRIP” martensite in the IA/BH DP steel and IA/BH TRIP steel, respectively.

Characterization of the bake-hardening behavior of transformation induced plasticity and dual-phase steels using advanced analytical techniques

The bake-hardening (BH) behavior of TRansformation Induced Plasticity (TRIP) and Dual-Phase (DP) steels after intercritical annealing (IA) has been studied using transmission electron microscopy, X-ray diffraction and three dimensional atom probe tomography. It was found for the DP steel that carbon can segregate to dislocations in the ferrite plastic deformation zones where there is a high dislocation density around the "asquenched" martensite. The carbon pinning of these dislocations, in turn, increases the yield strength after aging. It was shown that bake-hardening also leads to rearrangement of carbon in the martensite leading to the formation of rod-like low temperature carbides in the DP steel. Segregation of carbon to microtwins in retained austenite of the TRIP steel was also evident. These factors, in combination with the dislocation rearrangement in ferrite through the formation of cells and microbands in the TRIP steel after pre-straining, lead to the different bake-hardening responses of the two steels.

Nano-scale analysis of nano-bainite formed in advanced high strength steels

The effect of composition and processing schedule on the microstructure of C-Mn-Si-Mo-(Al)-(Nb) steels containing nano-bainite was studied using transmission electron microscopy (TEM) and atom probe tomography (APT). The major phase formed in all steels was nano-bainite. However, the steels with lower carbon and alloying addition content subjected to TMP had better mechanical properties than high alloyed steel after isothermal treatment. The presence of ferrite in the microstructure can improve not only ductility but lead to the formation of retained austenite with optimum chemical stability.

Application of advanced analytical techniques to study structure-property relationship of hot rolled high strength low alloy steel

The microstructure-property relationship in conventional high strength low alloy (HSLA) steel was evaluated using data obtained from transmission electron microscopy (TEM) and atom probe tomography (APT). Atom probe tomography allowed the characterisation of fine TiC particles with average radius of 3±1·2 nm that were not observed by TEM. The increase in the yield strength of steel due to the presence of fine precipitates was calculated to be 128 MPa.

Solute segregation and texture modification in an extruded magnesium alloy containing gadolinium

The alloy Mg-1.5Gd has been extruded at different temperatures to produce two significantly different textures. At lower extrusion temperatures there was significant solute clustering in the matrix, coupled with segregation of solute to the grain boundaries. At higher temperatures these two phenomena were both less pronounced. It is suggested here that segregation of solute to the grain boundaries plays a significant role in the texture modification effect that rare earth elements have in magnesium alloys.

Understanding of the bainite transformation in a nano-structured bainitic steel

A 0.79C-1.5Si-1.98Mn-0.98Cr-0.24Mo-1.06Al-1.58Co (wt%) steel was isothermally heat treated at 200°C for 10 days to form a nano-scale bainitic microstructure consisting of nanobainitic ferrite laths with high dislocation density and retained austenite films. The crystallographic analysis using TEM and EBSD revealed that the bainitic ferrite laths are close to the Nishiyama-Wassermann orientation relationship with the parent austenite. There was only one type of packet identified in a given transformed austenite grain. Each packet consisted of two different blocks having variants with the same habit plane, but different crystallographic orientations. The presence of fine C-rich clusters and Fe-C carbides with a wide range of compositions in bainitic ferrite was revealed by Three-dimensional Atom Probe Tomography (APT). The high carbon content of bainitic ferrite compared to the para-equilibrium level of carbon in ferrite, absence of segregation of carbon to the austenite/bainitic ferrite interface and absence of partitioning of substitutional elements between the retained austenite and bainitic ferrite were also found using APT.

Application of advanced experimental techniques for the microstructural characterization of nanobainitic steels

A 0.79C-1.5Si-1.98Mn-0.98Cr-0.24Mo-1.06Al-1.58Co (wt%) steel was isothermally heat treated at 350°C bainitic transformation temperature for 1 day to form fully bainitic structure with nano-layers of bainitic ferrite and retained austenite, while a 0.26C-1.96Si-2Mn-0.31Mo (wt%) steel was subjected to a successive isothermal heat treatment at 700°C for 300 min followed by 350°C for 120 min to form a hybrid microstructure consisting of ductile ferrite and fine scale bainite. The dislocation density and morphology of bainitic ferrite, and retained austenite characteristics such as size, and volume fraction were studied using Transmission Electron Microscopy. It was found that bainitic ferrite has high dislocation density for both steels. The retained austenite characteristics and bainite morphology were affected by composition of steels. Atom Probe Tomography (APT) has the high spatial resolution required for accurate determination of the carbon content of the bainitic ferrite and retained austenite, the solute distribution between these phases and calculation of the local composition of fine clusters and particles that allows to provide detailed insight into the bainite transformation of the steels. The carbon content of bainitic ferrite in both steels was found to be higher compared to the para-equilibrium level of carbon in ferrite. APT also revealed the presence of fine C-rich clusters and Fe-C carbides in bainitic ferrite of both steels.