Chemical Solution Deposition of Protective Er2O3 and Y2O3 Coatings onto Stainless Steel for Molten Metal Casting using Metal-Nitrate Precursors.

Chemical solution deposition (CSD) methods involving the thermal decomposition of 5.0 M Er(NO3)3·5H2O and Y(NO3)3·6H2O precursor solutions were employed to fabricate protective erbia and yttria coatings onto stainless steel (SS304/SS316) coupons. The two techniques tested were dip and spray coating, which were then compared to a commercial yttria spray (ZYP Coatings). It was determined that solution concentration, solvent choice, injection of Er2O3 and Y2O3 micropowder, and the annealing temperature/ramp profile were critical to the coatings' physical properties. For dip coatings, thicknesses were 1-20 µm after two dipping/annealing cycles, and adhesion strength was ∼1000 psi, increasing up to ∼1300 psi if the SS coupons had preliminary sandblasting. Spray coatings from precursor solutions were reported to have thicknesses of 20-80 µm and adhesion strength less than 500 psi (regardless of the coupon surface finish). Cross-sectional views of the coatings confirmed subsurface porosity, and XRD results indicated that the coatings were polycrystalline, with patterns typical to that of cubic Er2O3 and Y2O3.

Growth and passivation of individual carbon nanoparticles by C2H2 addition at high temperatures: Dependence of growth rate and evolution on material and size.

Absolute kinetics for reactions of C2H2 with a series of ∼60 individual carbon nanoparticles (NPs) from graphite, graphene, graphene oxide, carbon black, diamond, and nano-onion feedstocks were measured for temperatures (TNP) ranging from 1200 to 1700 K. All the NPs were observed to gain mass by carbon addition under conditions that varied with feedstock but with large variations in initial growth rate. Long reaction periods were studied to allow the evolution of growth rates over time to be observed. Diamond NPs were found to passivate against C2H2 addition if heated above ∼1400 K, and the highly variable initial reactivity for carbon nano-onions was found to depend on the presence of non-onion-structure surface carbon. For graphitic and carbon black NPs, three distinct growth modes were observed, correlated with the initial NP mass (Minitial). Smallest graphitic and carbon black NPs, with masses <∼25 MDa, initially grew rapidly but also passivated quickly after adding <4% of Minitial. NPs in the 20-50 MDa range also passivated but only after multiple waves of fast growth separated by periods of low reactivity, with up to ∼11% total mass gain before passivation. The largest carbon black and graphitic NPs, with Minitial >50 MDa, grew rapidly and continuously, adding up to ∼300% of Minitial with no sign of rate slowing as long as C2H2 was present. The efficiencies for C2H2 addition and etching by O2 are strongly correlated, but the correlation changes as the NPs passivate. Growth and passivation mechanisms are discussed.

High-Temperature Oxidation of Single Carbon Nanoparticles: Dependence on the Surface Structure and Probing Real-Time Structural Evolution via Kinetics.

O2 oxidation and sublimation kinetics for >30 individual nanoparticles (NPs) of five different feedstocks (graphite, graphene oxide, carbon black, diamond, and nano-onion) were measured using single-NP mass spectrometry at temperatures (TNP) in the 1100-2900 K range. It was found that oxidation, studied in the 1200-1600 K range, is highly sensitive to the NP surface structure, with etching efficiencies (EEO2) varying by up to 4 orders of magnitude, whereas sublimation rates, significant only for TNP ≥ ∼1700 K, varied by only a factor of ∼3. Its sensitivity to the NP surface structure makes O2 etching a good real-time structure probe, which was used to follow the evolution of the NP surface structures over time as they were either etched or annealed at high TNP. All types of carbon NPs were found to have initial EEO2 values in the range near 10-3 Da/O2 collision, and all eventually evolved to become essentially inert to O2 (EEO2 < 10-6 Da/O2 collision); however, the dependence of EEO2 on time and mass loss was very different for NPs from different feedstocks. For example, diamond NPs evolved rapidly and monotonically toward inertness, and evolution occurred in both oxidizing and inert atmospheres. In contrast, graphite NPs evolved only under oxidizing conditions and were etched with complex time dependence, with multiple waves of fast but non-monotonic etching separated by periods of near-inertness. Possible mechanisms to account for the complex etching behavior are proposed.

Sublimation Kinetics for Individual Graphite and Graphene Nanoparticles (NPs): NP-to-NP Variations and Evolving Structure-Kinetics and Structure-Emissivity Relationships.

A single nanoparticle (NP) mass spectrometry method was used to measure sublimation rates as a function of nanoparticle temperature (TNP) for sets of individual graphite and graphene NPs. Initially, the NP sublimation rates were ∼400 times faster than those for bulk graphite, and there were large NP-to-NP variations. Over time, the rates slowed substantially, though they remained well above the bulk rate. The initial activation energies (Ea values) were correspondingly low and doubled, as a few monolayers worth of material was sublimed from the surfaces. The high initial rates and low Ea values are attributed to large numbers of edge, defect, and other low coordination sites on the NP surfaces, and the changes are attributed to atomic-scale "smoothing" of the surface by preferential sublimation of the less stable sites. The emissivity of the NPs also changed after heating, more frequently increasing. The emissivity and sublimation rates were anticorrelated, leading to the conclusion that high densities of low-coordination sites on the NP surfaces enhance sublimation but suppress emissivity.

Thermal emission spectroscopy for single nanoparticle temperature measurement: optical system design and calibration.

We discuss the design of an optical system that allows measurement of 600-1650 nm emission spectra for individual nanoparticles (NPs), laser-heated in an electrodynamic trap in controlled atmospheres. An approach to calibration of absolute intensity versus wavelength for very low emission intensities is discussed, and examples of NP graphite and carbon black spectra are used to illustrate the methodology.