Impact of Humidity on Silica Nanoparticle Agglomerate Morphology and Size Distribution.

The effect of humidity on flame-made metal oxide agglomerate morphology and size distribution is investigated, for the first time to our knowledge, and compared to that on soot, which has been widely studied. Understanding the impact of humidity on such characteristics is essential for storage, handling, processing, and eventual performance of nanomaterials. More specifically, broadly used agglomerates of flame-made silica nanoparticles are humidified at various saturation ratios, S = 0.2-1.5, and dried before characterization with a differential mobility analyzer (DMA), an aerosol particle mass (APM) analyzer, and transmission electron microscopy. At high humidity, the constituent single and/or aggregated (chemically bonded) primary particles (PPs) rearrange to balance the capillary forces induced by condensation-evaporation of liquid bridges between PPs. Larger agglomerates restructure more than smaller ones, narrowing their mobility size distribution. After humidification at S = 1.5 and drying, agglomerates collapse into compact structures that follow a fractal scaling law with mass-mobility exponent D = 3.02 ± 0.11 and prefactor k = 0.27 ± 0.07. This critical S = 1.5 for silica agglomerates is larger than the 1.26 obtained for soot because of the hydrophilic surface of silica that delays water evaporation. The relative effective density, ρ/ρ, of collapsed agglomerates becomes invariant of mobility diameter, d, similar to that of fluidized and spray-dried granules. The average silica ρ/ρ = 0.28 ± 0.02 is smaller than the 0.36 ± 0.04 measured for the humidified-dried soot because of the larger size of silica aggregates, d/ d, and number of constituent primary particles, n, of diameter d. This is verified by tandem-DMA (TDMA) measurements, yielding maximum d = 3 d or 5 d and n = 13 or 36 for the soot or silica aggregates studied here, in good agreement with those reported from microscopy and high-pressure agglomerate dispersion. A scaling law relating the initial d to d, D, and k after condensation-drying is developed. The mass-mobility relationship of collapsed silica and soot agglomerates obtained by combining this law with fast TDMA measurements is in excellent agreement with that measured by the direct, but tedious, DMA-APM analysis.