Effect of Holding Time on Populations of Microparticles in Spheroidal Graphite Irons

Non-metallic microparticles in spheroidal graphite irons are a product of the inoculation and the Mg-treatment of the liquid melt. Besides the influence on the mechanical properties of these iron–carbon–silicon alloys, they are also responsible for the nucleation and the morphology of the graphite phase. The present investigation is undertaken to study holding time effects of a (Ba, Ca, Al)–ferrosilicon (called Ba-inoculant) and (Ca, Al)–ferrosilicon (called Ca-inoculant) inoculants on the overall distribution of microparticles. Using the 2D to 3D conversions method, which is typically used for graphite nodules, the non-metallic microparticles’ statistical parameters, such as size distributions and number densities, are quantified. The total number of particles is similar after Mg-treatment and inoculation for Ca-inoculant but not for Ba-inoculated samples, which lose approximately 25 pct of microparticles after 1 minute of holding time. Iron treated with the Ca-inoculant loses about 37 pct of its nodules after 5 minutes, while the Ba-inoculated melts maintain their performance even after 10 minutes. Based on extrapolating the trend of the undercooling, Ba-inoculated samples would reach the uninoculated undercooling values in 48 minutes, while Ca-inoculated samples in only 11 minutes. By evaluating the size distributions of the non-metallic microparticles, the Ostwald ripening hypothesis or particle aggregation can be verified. The results suggest that sulfides are more critical for graphite nucleation since they can be correlated with the graphite number densities. However, due to the small difference in the microparticle population of the uninoculated sample with Ca-inoculated samples, other aspects of the fading mechanism need to be considered, such as transient metastable states, since the central hypothesis of loss of inclusions cannot alone explain the decrease in the nucleation frequency of graphite.

Development and characterization of ethanol-free spearmint essential oil nanoemulsion for food applications using the low energy technique

Different emulsifiable concentrates containing spearmint essential oil (SEO) were made and evaluated for their potential for giving ethanol-free nanoemulsion spontaneously upon dilution into water. Each one of these formulas had its specific composition regarding the type of excipients, surfactants, surfactant/SEO ratio and surfactant concentration. The results of this evaluation indicated that the chemical composition of SEO has a profound effect on the formation and physical stability of the nanoemulsion. The incorporation of excipients such as long chain triglyceride and propylene glycol into the emulsifiable concentrates at only 1.0% can lead to a stable nanoemulsion that resists Ostwald ripening. A particle size measurement showed that the diameter of SEO in the nanoemulsion was 28.2 nm and its nanostructure was maintained for 3 months. The application of a mixture of binary nonionic food-permitted surfactants enhanced the thermal stability of the nanoemulsion at up to 50 ᵒC. The developed ethanol-free SEO nanoemulsion has promising industrial applications in food and beverage flavoring.

Methanol carbonylation to acetaldehyde on Au particles supported by single-layer MoS2 grown on silica

Homogenous single-layer MoS2 films coated with sub-single layer amounts of gold are found to isolate the reaction of methanol with carbon monoxide, the fundamental step toward higher alcohols, from an array of possible surface reactions. Active surfaces were prepared from homogenous single-layer MoS2 films coated with sub-single layer amounts of gold. These gold atoms formed clusters on the MoS2 surface. A gas mixture of carbon monoxide (CO) and methanol (CH3OH) was partially converted to acetaldehyde (CH3CHO) under mild process conditions (308 kPa and 393 K). This carbonylation of methanol to a C2 species is a critical step toward the formation of higher alcohols. Density functional theory modeling of critical steps of the catalytic process identify a viable reaction pathway. Imaging and spectroscopic methods revealed that the single layer of MoS2 facilitated formation of nanoscale gold islands, which appear to sinter through Ostwald ripening. The formation of acetaldehyde by the catalytic carbonylation of methanol over supported gold clusters is an important step toward realizing controlled production of useful molecules from low carbon-count precursors.

Tracking the Catalyst Layer Depth-Dependent Electrochemical Degradation of a Bimodal Pt/C Fuel Cell Catalyst: A Combined Operando Small- and Wide-Angle X-Ray Scattering Study

The combination of operando small- and wide-angle X-ray scattering (SAXS, WAXS) is here presented to provide insights into the changes in mean particle sizes and phase fractions in fuel cell catalyst layers during accelerated stress tests (ASTs). As fuel cell catalyst, a bimodal Pt/C catalyst was chosen that consists of two distinguishable particle size populations. The presence of the two different sizes should favor and uncover electrochemical Ostwald ripening as degradation mechanism, i.e., the growth of larger particles in the Pt/C catalyst at the expense of the smaller particles via the formation of ionic metal species. However, instead of electrochemical Ostwald ripening, the results point toward classical Ostwald ripening via the local diffusion of metal atoms on the support. Furthermore, the grazing incidence mode provides insights into the catalyst layer depth-dependent degradation. While the larger particles show the same particle size changes close to the electrolyte-catalyst interface and within the catalyst layer, the smaller Pt nanoparticles exhibit a slightly decreased size at the electrolyte-catalyst interface. During the AST, both size populations increase in size, independent of the depth. Their phase fraction, i.e., the ratio of smaller to larger size population, however, exhibits a depth-dependent behavior. While at the electrolyte-catalyst interface the phase fraction of the smaller size population decreases, it increases in the inner catalyst layer. The results of a depth-dependent degradation suggest that employing a depth-dependent catalyst design can be used for future improvement of catalyst stability.

Tracking the Catalyst Layer Depth-Dependent Electrochemical Degradation of a Bimodal Pt/C Fuel Cell Catalyst: A Combined Operando Small- and Wide-Angle X-Ray Scattering Study

The combination of operando small- and wide-angle X-ray scattering (SAXS, WAXS) is here presented to provide insights into the changes in mean particle sizes and phase fractions in fuel cell catalyst layers during accelerated stress tests (ASTs). As fuel cell catalyst, a bimodal Pt/C catalyst was chosen that consists of two distinguishable particle size populations. The presence of the two different sizes should favor and uncover electrochemical Ostwald ripening as degradation mechanism, i.e., the growth of larger particles in the Pt/C catalyst at the expense of the smaller particles via the formation of ionic metal species. However, instead of electrochemical Ostwald ripening, the results point toward classical Ostwald ripening via the local diffusion of metal atoms on the support. Furthermore, the grazing incidence mode provides insights into the catalyst layer depth-dependent degradation. While the larger particles show the same particle size changes close to the electrolyte-catalyst interface and within the catalyst layer, the smaller Pt nanoparticles exhibit a slightly decreased size at the electrolyte-catalyst interface. During the AST, both size populations increase in size, independent of the depth. Their phase fraction, i.e., the ratio of smaller to larger size population, however, exhibits a depth-dependent behavior. While at the electrolyte-catalyst interface the phase fraction of the smaller size population decreases, it increases in the inner catalyst layer. The results of a depth-dependent degradation suggest that employing a depth-dependent catalyst design can be used for future improvement of catalyst stability.

Chemistry-Mediated Ostwald Ripening in Carbon-Rich C/O Systems at Extreme Conditions

There is significant interest in establishing a capability for tailored synthesis of next-generation carbon-based nanomaterials due to their broad range of applications and high degree of tunability. High pressure (e.g. shockwave-driven) synthesis holds promise as an effective discovery method, but experimental challenges preclude elucidating the processes governing nanocarbon production from carbon-rich precursors that could otherwise guide efforts through the prohibitively expansive design space. Here we report findings from large scale atomistically-resolved simulations of carbon condensation from C/O mixtures subjected to extreme pressures and temperatures, made possible by machine-learned reactive interatomic potentials. We find that liquid nanocarbon formation follows classical growth kinetics driven by Ostwald ripening (i.e. growth of large clusters at the expense of shrinking small ones) and obeys dynamical scaling in a process mediated by carbon chemistry in the surrounding reactive fluid. The results provide direct insight into carbon condensation in a representative system and pave the way for its exploration in higher complexity organic materials. They also suggest that simulations using machine-learned interatomic potentials could eventually be employed as in-silico design tools for new nanomaterials.

Formation and Physical Stability of Zanthoxylum bungeanum Essential Oil Based Nanoemulsions Co-Stabilized with Tea Saponin and Synthetic Surfactant

The purpose of this work was to evaluate the possibility of adding tea saponin (TS) to reduce the synthetic surfactant concentration, and maintain or improve the shelf stability of nanoemulsions. The Zanthoxylum bungeanum essential oil (2.5 wt%) loaded oil-in-water nanoemulsions were co-stabilized by Tween 40 (0.5–2.5 wt%) and TS (0.1–5 wt%). A combination of several analytical techniques, such as dynamic laser scattering, interfacial tension, zeta potential, and transmission electron microscope, were used for the characterization of nanoemulsions. Low levels of TS (0.1–0.5 wt%) with Tween 40 had significant effects on the emulsification, and a nanoemulsion with the smallest droplet diameter of 89.63 ± 0.67 nm was obtained. However, in the presence of high TS concentration (0.5–5 wt%), micelles generated by the non-adsorbed surfactants in the aqueous lead to droplets growth. In addition, the combinations of Tween 40 and TS at the high level (>3.5 wt%) exerted a synergistic effect on stabilizing the nanoemulsions and preventing both Ostwald ripening and coalescence. The negative charged TS endowed the droplets with electrostatic repulsion and steric hinderance appeared to prevent flocculation and coalescence. These results would provide a potential application of natural TS in the preparation and stabilization of nanoemulsions containing essential oil.