Chemistry of Airborne Particles from Metallurgical Processing
by
Neil T. Jenkins
Accepted by the Department of Materials Science and Engineering of Massachusetts Institute of Technology on August 22, 2003, in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Metallurgy
printed copy available in the MIT Science Library
electronic copy of manuscript available through the Digital Library of MIT Theses
(a list of minor errata noticed since August 2003)
Abstract
Airborne particles fall into one of three size ranges.
The nucleation range consists of nanoparticles created from vapor atom collisions. The
decisive parameter for particle size and composition is the supercooling of the vapor.
The accumulation range, which comprises particles less than 2 micrometers, consists of
particles formed from the collision of smaller primary particles from the nucleation range.
The composition of agglomerates and coalesced particles is the same as the bulk vapor
composition.
Coarse particles, the composition of which is determined by a liquid precursor, are greater
than 1 micrometer and solidify from droplets whose sizes are controlled by surface, viscous,
and inertial forces.
The relationship between size and composition of airborne particles could be seen in welding fume, a typical metallurgical aerosol.
This analysis was performed with a cascade impactor and energy dispersive spectrometry
with both scanning electron microscopy (SEM-EDS) and scanning transmission electron
microscopy (STEM-EDS). Other methods for properly characterizing particles were discussed.
In the analysis, less than 10% of the mass of fume particles for various types of gas metal
arc welding (GMAW) were coarse, while one-third of flux cored arc welding (FCAW) fume
particles were coarse. Coarse particles had a composition closer to that of the welding electrode
than did fine particles.
Primary particles were not homogeneous. Particles larger than the mean free path of the
carrier gas had the same composition as that of the vapor, but for particles 20 to 60
nanometers, smaller particles were more enriched in volatile metals than larger particles
were. This was explained by the cooling path along the bubble point line of a binary phase
diagram.
Particles were not necessarily homogenous internally. Because nanoparticles homogenize
quickly, they may form in a metastable state, but will not remain in that state. In this analysis,
the presence of multiple stable immiscible phases explains this internal heterogeneity.
The knowledge contained herein is important for industries that depend on the properties of
nanoparticles, and for manufacturing, where industrial hygiene is important because of
respirable particle by-products, such as high-energy-density metallurgical processing.
Thesis Supervisor: Dr. Thomas W. Eagar, ScD. P.E.
Title: Thomas Lord Professor of Materials Engineering & Materials Systems
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