Effect of boiling on deposition of metallic colloids

In this study the relationship between heterogeneous nucleate boiling surfaces and deposition of suspended metallic colloidal particles, popularly known as crud or corrosion products in process industries, on those heterogeneous sites is investigated. Various researchers have reported that hematite is a major constituent of crud which makes it the primary material of interest; however the models developed in this work are irrespective of material choice. Qualitative hypotheses on the deposition process under boiling as proposed by previous researchers have been tested, which fail to provide explanations for several physical mechanisms observed and analyzed. In this study a quantitative model of deposition rate has been developed on the basis of bubble dynamics and colloid-surface interaction potential. Boiling from a heating surface aids in aggregation of the metallic particulates viz. nano-particles, crud particulate, etc. suspended in a liquid, which helps in transporting them to heating surfaces. Consequently, clusters of particles deposit onto the heating surfaces due to various interactive forces, resulting in formation of porous or impervious layers. The deposit layer grows or recedes depending upon variations in interparticle and surface forces, fluid shear, fluid chemistry, etc. This deposit layer in turn affects the rate of bubble generation, formation of porous chimneys, critical heat flux (CHF) of surfaces, activation and deactivation of nucleation sites on the heating surfaces. Several problems are posed due to the effect of boiling on colloidal deposition, which range from research initiatives involving nano-fluids as a heat transfer medium to industrial applications such as light water nuclear reactors. In this study, it is attempted to integrate colloid and surface science with vapor bubble dynamics, boiling heat transfer and evaporation rate. Pool boiling experiments with dilute metallic colloids have been conducted to investigate several parameters impacting the system. The experimental data available in the literature is obtained by flow experiments, which do not help in correlating boiling mechanism with the deposition amount or structure. With the help of experimental evidences and analysis, previously proposed hypothesis for particle transport to the contact line due to hydrophobicity has been challenged. The experimental observations suggest that deposition occurs around the bubble surface contact line and extends underneath area of the bubble microlayer as well. During the evaporation the concentration gradient of a non-volatile species is created, which induces osmotic pressure. The osmotic pressure developed inside the microlayer draws more particles inside the microlayer region or towards contact line. The colloidal escape time is slower than the evaporation time, which leads to the aggregation of particles in the evaporating micro-layer. These aggregated particles deposit onto or are removed from the heating surface, depending upon their total interaction potential. Interaction potential has been computed with the help of surface charge and van der Waals potential for the materials in aqueous solutions. Based upon the interaction-force boundary layer thickness, which is governed by debye radius (or ionic concentration and pH), a simplified quantitative model for the attachment kinetics is proposed. This attachment kinetics model gives reasonable results in predicting attachment rate against data reported by previous researchers. The attachment kinetics study has been done for different pH levels and particle sizes for hematite particles. Quantification of colloidal transport under boiling scenarios is done with the help of overall average evaporation rates because generally waiting times for bubbles at the same position is much larger than growth times. In other words, from a larger measurable scale perspective, frequency of bubbles dictates the rate of collection of particles rather than evaporation rate during micro-layer evaporation of one bubble. The combination of attachment kinetics and colloidal transport kinetics has been used to make a consolidated model for prediction of the amount of deposition and is validated with the help of high fidelity experimental data. In an attempt to understand and explain boiling characteristics, high speed visualization of bubble dynamics from a single artificial large cavity and multiple naturally occurring cavities is conducted. A bubble growth and departure dynamics model is developed for artificial active sites and is validated with the experimental data. The variation of bubble departure diameter with wall temperature is analyzed with experimental results and shows coherence with earlier studies. However, deposit traces after boiling experiments show that bubble contact diameter is essential to predict bubble departure dynamics, which has been ignored previously by various researchers. The relationship between porosity of colloid deposits and bubbles under the influence of Jakob number, sub-cooling and particle size has been developed. This also can be further utilized in variational wettability of the surface. Designing porous surfaces can having vast range of applications varying from high wettability, such as high critical heat flux boilers, to low wettability, such as efficient condensers.

Synthesis, characterization and chemical vapor deposition of transition metal di(tert-butyl)amido compounds

Although the transition metal chemistry of many dialkylamido ligands has been well studied, the chemistry of the bulky di(tert-butyl)amido ligand has been largely overlooked. The di(tert-butyl)amido ligand is well suited for synthesizing transition metal compounds with low coordination numbers; such compounds may exhibit interesting structural, physical, and chemical properties. Di(tert-butyl)amido complexes of transition metals are expected to exhibit high volatilities and low decomposition temperatures, thus making them well suited for the chemical vapor deposition of metals and metal nitrides. Treatment of MnBr₂(THF)₂, FeI₂, CoBr₂(DME), or NiBr₂(DME) with two equivalents of LiN(t-Bu)2 in benzene affords the two-coordinate complex M[N(t-Bu)₂]₂, where M is Mn, Fe, Co, or Ni. Crystallographic studies show that the M-N distances decrease across the series: 1.9365 (Mn), 1.8790 (Fe), 1.845 (Co), 1.798 Å (Ni). The N-M- N angles are very close to linear for Mn and Fe (179.30 and 179.45°, respectively), but bent for Co and Ni (159.2 and 160.90°, respectively). As expected, the d⁵ Mn complex has a magnetic moment of 5.53 μΒ that is very close to the spin only value. The EPR spectrum is nearly axial with a low E/D ratio of 0.014. The d⁶ Fe compound has a room temperature magnetic moment of 5.55 μΒ indicative of a large orbital angular momentum contribution. It does not exhibit a Jahn-Teller distortion despite the expected doubly degenerate ground state. Applied field Mössbauer spectroscopy shows that the effective internal hyperfine field is unusually large, Hint = 105 T. The magnetic moments of Co[N(t-Bu)₂]₂ and Ni[N(t-Bu)₂]₂ are 5.24 and 3.02 μΒ respectively. Both are EPR silent at 4.2 K. Treatment of TiCl₄ with three equivalents of LiN(t-Bu)2 in pentane affords the briding imido compound Ti₂[μ-N(t-Bu)]₂Cl₂[N(t-Bu)₂]₂ via a dealkylation reaction. Rotation around the bis(tert-butyl)amido groups is hindered, with activation parameters of ΔH‡ = 12.8 ± 0.6 kcal mol-1 and ΔS‡ = -8 ± 2 cal K-1 ·mol-1, as evidenced by variable temperature 1H NMR spectroscopy. Treatment of TiCl₄ with two equivalents of HN(t-Bu)₂ affords Ti₂Cl₆[N(t-Bu)₂]₂. This complex shows a close-contact of 2.634(3) Å between Ti and the carbon atom of one of the CH₃ substituents on the tert-butyl groups. Theoretical considerations and detailed structural comparisons suggest this interaction is not agostic in nature, but rather is a consequence of interligand repulsions. Treatment of NiI₂(PPh3)₂ and PdCl₂(PPh₃)₂ with LiN(t-Bu)₂in benzene affords Ni[N(t-Bu)₂](PPh₃)I and Pd₃(μ₂-NBut₂)2(μ₂-PPh₂)Ph(PPh₃) respectively. The compound Ni[N(t-Bu)₂](PPh₃)I has distorted T-shape in geometry, whereas Pd₃(μ₂-NBut₂)₂(μ₂-PPh₂)Ph(PPh₃) contains a triangular palladium core. Manganese nitride films were grown from Mn[N(t-Bu)₂]₂ in the presence of anhydrous ammonia. The growth rate was several nanometers per minute even at the remarkably low temperature of 80⁰C. As grown, the films are carbon- and oxygen-free, and have a columnar morphology. The spacings between the columns become smaller and the films become smoother as the growth temperature is increased. The composition of the films is consistent with a stoichiometry of Mn₅N₂.