Direct atomic scale analysis of the distribution of Cu valence states in Cu/γ-Al2O3 catalysts

In this paper, the microstructure of a 1 wt.% Cu/γ-Al₂O₃ catalyst that was reduced in a 4% hydrogen/argon atmosphere at temperatures of 523, 773 and 1073 K, is studied by Z-contrast imaging and electron energy-loss spectroscopy (EELS) in a scanning transmission electron microscope (STEM). Results show that the copper species are well dispersed when the catalyst is reduced below 523 K. At 773 K, separated Cu(I) and Cu(0) species are found existing as ring-like and bulk-like particles. This appears to indicate that the copper has not been reduced to its metallic form due to the interaction between the copper oxide and the support. Large spherical particles having core-shell structures with Cu(I) in the shells and Cu(0) in the cores are generated when the catalyst is reduced at 1073 K. The formation of partially oxidized copper species upon reduction at 1073 K is attributed to the metallic copper interaction with the alumina support. This study also demonstrates that high-spatial resolution Z-contrast imaging and EELS performed simultaneously can provide unique information on the morphology and chemistry of metal species in supported metal catalysts.     

Maximizing learning without sacrificing the fun: Stealth assessment,adaptivity and learning supports in educational games

In this study, we investigated the validity of a stealth assessment of physics understanding in an educational game, as well as the effectiveness of different game-level delivery methods and various in-game supports on learning. Using a game called Physics Playground, we randomly assigned 263 ninth- to eleventh-grade students into four groups: adaptive, linear, free choice and no-treatment control. Each condition had access to the same in-game learning supports during gameplay. Results showed that: (a) the stealth assessment estimates of physics understanding were valid—significantly correlating with the external physics test scores; (b) there was no significant effect of game-level delivery method on students' learning; and (c) physics animations were the most effective (among eight supports tested) in predicting both learning outcome and in-game performance (e.g. number of game levels solved). We included student enjoyment, gender and ethnicity in our analyses as moderators to further investigate the research questions.     

Selectivities in methanol oxidation over silica supported molybdena

Selectivities in methanol oxidation over silica supported molybdenum oxide catalysts were investigated in relation with the phase distribution. The supported catalysts were prepared by impregnation with ammonium heptamolybdate. In addition to crystalline MoO₃, Mo containing cluster species of 1–2 nm size were observed by STEM even from a used catalyst with 13% catalyst loading. The percentage of Mo present as crystalline MoO₃ increases with the catalyst loading. An ESCA study indicates that part of surface Mo in the supported catalysts is reduced to Mo⁵⁺. The dimethyl ether selectivity increases with the catalyst loading and its formation occurs over the crystalline MoO₃ phase. The Selectivities to CO and methyl formate are greatly enhanced because of the presence of support, and are relatively independent of the catalyst loading and phase distribution. The dependence and independence of the Selectivities of different byproducts on the loading make the silica supported catalysts with high catalyst loadings less selective for the partial oxidation of methanol to formaldehyde.     

Effect of artificial aging on intergranular corrosion of extruded AlMgSi alloy with small Cu content

The effect of artificial aging parameters on the corrosion performance of air cooled AlMgSi(Cu) model alloy extrusions was investigated. Accelerated corrosion test revealed that the extrusions were highly susceptible to intergranular corrosion (IGC) in the naturally aged condition. However, IGC susceptibility was reduced, and finally eliminated, by artificial aging. Overaging introduced slight pitting susceptibility. EDS X-ray mapping in FE-TEM revealed Mg₂Si and Q-phase (Al₄Cu₂Mg₈Si₇) grain boundary precipitates and a continuous Cu-enriched grain boundary film. IGC susceptibility was related to the Cu-enriched grain boundary film. Increased IGC resistance was caused by coarsening of the grain boundary film by aging. Pitting susceptibility by over aging evolved due to coarsening of the Q-phase particles in the grain bodies.     

The influence of aging treatments on sulfide stress corrosion cracking of PH 13-8 Mo steel welds

Slow displacement rate tensile tests were carried out to study sulfide stress corrosion cracking (SSCC) of PH 13-8 Mo stainless steel welds in a saturated H₂S solution. The welds aged in the temperature range of 482-593 °C were susceptible to SSCC; the fracture surfaces revealed mainly quasi-cleavage fractures after notched tensile tests. However, the SSCC susceptibility in terms of the percentage loss of the notched tensile strength (NTS) of the welds was dependent on the aging treatment. The SSCC resistance and the austenite content of the welds increased with the aging temperatures. The presence of greater amounts of austenite, mainly reverted austenite, in the W1100 specimen (the weld aged at 1100 °F or 593 °C) than that in other aged specimens could account for its lower hardness and better SSCC resistance. On the other hand, the AW (as-welded) specimen containing a small amount of retained austenite films in a soft matrix exhibited a slightly improved SSCC resistance than that in the W1100 specimen. The lower hardness of the AW specimen was owing to the absence of fine coherent precipitates, leading to a reduced local stress and an enlarged plastic zone located in front of the notch in the test. With lower hardness, the local stress would also be lower and less likely to exceed some critical stress for failure in the saturated H₂S solution. For the aged specimens, the hardness/strength level and the amount of reverted austenite were the important factors that affect SSCC susceptibility.     

The effect of vacancies on the annular dark field image contrast of grain boundaries: a SrTiO(3) case study

The analysis of grain boundary structure in high resolution electron microscopy is often hindered by contrast variation within the grain boundary region which is not explained by simple models of the grain boundary structure. Recent work suggests that structural disorder along the beam direction and the presence of vacancies contribute significantly to this effect. One might expect a significant reduction in contrast in a Z-contrast image of a grain boundary would imply that vacancies present must result from the absence of heavier elements. Using a [001](210) Σ5 grain boundary in SrTiO₃ as a test case and first principles structure relaxation to calculate stable defect structures, we show that the reduction in the intensity from fully occupied Sr columns due to the structural distortion resulting from a nearby O vacancy can be as great as that due to introducing a Sr vacancy in the column itself. The effect on energy dispersive X-ray spectroscopy signals is also considered, but found to be smaller than that on Z-contrast images.     

Imaging with low-voltage scanning transmission electron microscopy: a quantitative analysis

A dedicated specimen holder has been designed to perform low-voltage scanning transmission electron microscopy in dark field mode. Different test samples, namely InGaAs/GaAs quantum wells, InGaAs nanowires and thick InGaAs layers, have been analysed to test the reliability of the model based on the proportionality to the specimen mass-thickness, generally used for image intensity interpretation of scattering contrast processes. We found that size of the probe, absorption and channelling must be taken into account to give a quantitative interpretation of image intensity. We develop a simple procedure to evaluate the probe-size effect and to obtain a quantitative indication of the absorption coefficient. Possible artefacts induced by channelling are pointed out. With the developed procedure, the low voltage approach can be successfully applied for quantitative compositional analysis. The method is then applied to the estimation of the In content in the core of InGaAs/GaAs core-shell nanowires.     

On the Structure of Amorphous Mesoporous Silica Nanoparticles by Aberration‐Corrected STEM

Mesoporous silica materials have demonstrated a vast spectrum of applications, stimulating an intensive field of study due to their potential use as nanocarriers. Nonetheless, when produced at the nanoscale, their structural characterization is hindered due to the re‐arrangement of the pores. To address this issue, this work combines molecular dynamics simulations with electron microscopy computer simulations and experimental results to provide an insight into the structure of amorphous mesoporous silica nanoparticles. The amorphous silica model is prepared using a simple melt‐quench molecular dynamics method, while the reconstruction of the mesoporous nanoparticles is carried out using a methodology to avoid false symmetry in the final model. Simulated scanning transmission electron microscopy images are compared with experimental images, revealing the existence of structural domains, created by the misalignment of the pores to compensate the surface tension of these spherical nanoparticles.     

TEM Investigations of Fine Niobium Precipitates in HSLA Steel

Commercially produced 0.03 % C, 0.08 % Nb, 0.01 % Ti high strength low alloyed (HSLA) steel in the form of 20 mm thick plates was investigated. The steel was thermomechanically processed and the mechanical properties of the steel were evaluated by tensile testing. Using analytical and high resolution transmission electron microscopy the distribution, morphology, composition, crystal structure and particle size of niobium and titanium carbonitrides were observed and identified in these steels. The distribution of the precipitates was found to be nearly random, with occasional occurrence of precipitation free zones. Complex agglomerates with a cubic TiN seed crystal overgrown by a cubic NbC particle were the most commonly observed precipitates. Further TEM analysis in the accelerated cooled and tempered specimens in 1/4 plate thickness did not reveal any evidence that additional precipitation in the ferrite occurred. Precipitation in ferrite was only detected after subsequent cold deformation and tempering of the same samples. By a combination of EFTEM, STEM, HRTEM in addition to EDX spectroscopy, a large population of strain induced NbC precipitates with fcc crystal structure ranging in size down to 2 nm were identified in the ferrite matrix.     

Applications of medium-voltage STEM for the 3-D study of organelles within very thick sections

Scanning transmission electron microscopy at 300 kV enables the visualization of nucleolar silver-stained structures within thick sections (3–8 μm) of Epon-embedded cells at high tilt angles (–50°; + 50°). Thick sections coated with gold particles were used to determine the best conditions for obtaining images with high contrast and good resolution. For a 6-μm-thick section the values of thinning and shrinkage under the beam are 35 to 10%, respectively. At the electron density used in these experiments (100e^—/Å₂/s) it is estimated that these modifications of the section stabilized in less than 10 min. The broadening of the beam through the section was measured and calculations indicated that the subsequent resolution reached 100 nm for objects localized near the lower side of 4-μm-thick sections with a spot-size of 5·6 nm. Comparing the same biological samples, viewed alternately in CTEM and STEM, demonstrated that images obtained in STEM have a better resolution and contrast for sections thicker than 3 μm. Therefore, the visualization of densely stained structures, observed through very thick sections in the STEM mode, will be very useful in the near future for microtomographic reconstruction of cellular organelles.