Impact of humidity on silica nanoparticle

Swiss Federal Institute of

Technology Zürich
agglomerate morphology and size distribution
G.A. Kelesidis, F.M. Furrer, K. Wegner and S.E. Pratsinis
Particle Technology Laboratory, ETH Zürich, CH-8092 Zürich, Switzerland
gkelesidis@ptl.mavt.ethz.ch www.ptl.ethz.ch

Motivation
In the presence of humidity, agglomerates of single primary particles (PPs) and/or chemically-bonded ones (aggregates) restructure, forming smaller
and more compact structures.1,2 This is known to affect the fluidization3 and spray drying4 of soot. Here, the evolution of silica morphology and mobility
size distribution processed under humid conditions is monitored for the first time and compared to humidified soot nanoparticles.

Water Processing
Processing of SiO2 Agglomerates
of SiO2 Agglomerates with Water Vapor Agglomerate Restructuring
Characterization
by by
Capillary
ScalingForces
Laws
Condensation & Evaporation
𝒅𝒎 < 𝒅𝒎,𝒐
𝑭

Capillary Forces1,2
𝒅𝒎,𝒐 𝒅𝒎,𝒐
2.22
𝒅𝒎 𝑫𝒇𝒎
𝒏𝒑 = 𝒏𝒑 = 𝒌𝒎
𝒅𝒑 [5] 𝒅𝒑
Agglomerates restructure due to capillary forces, F, during condensation/evaporation of a solvent. 1,2
(𝑛𝑝 , 𝑑𝑝 : PP number and diameter; 𝐷𝑓𝑚 , 𝑘𝑚 : mass-mobility exponent and prefactor)

Drastic Change of Agglomerate Morphology by Humidity

0.5
Data, S: Agglomeration Theory:5
Relative Effective Density, 𝜌𝑒𝑓𝑓 /𝜌

Silica agglomerates are sampled above the flame, diluted and mixed with humid air with varying
-0.78
temperature to achieve saturation ratios, S, from 0.2 to 1.5. The diluted sample is directed
through two diffusion dryers to a differential mobility analyzer (DMA) and then to an aerosol
1.5 𝝆𝒆𝒇𝒇 𝒅𝒎
=
particle mass analyzer (APM), a condensation particle counter (CPC) or collected for
0.9 𝝆 𝒅𝒑
transmission electron microscopy (TEM). During tandem-DMA (TDMA) measurements, dry
agglomerates with mobility diameter, 𝑑𝑚,𝑜 , are selected by TDMA before mixing with humid air.
0.4
Shrinking of Agglomerate Mobility Size 50 nm Soot6: 0.36 ± 0.04
ഥ 𝒎 = 99.6 nm
𝒅
S
d𝑁/𝑑𝑙𝑜𝑔(𝑑𝑚 )/𝑁𝑡𝑜𝑡

𝝈𝒈,𝒎 = 1.55
1 0.2 0.3 100 nm
100 nm

0.9
1.5 Silica: 0.28 ± 0.02
ഥ 𝒎 = 91.4 nm
𝒅 ഥ 𝒎 = 99.7 nm
𝒅
0.1 𝝈𝒈,𝒎 = 1.45 0.2
𝝈𝒈,𝒎 = 1.56
10 % smaller agglomerates
with narrower distribution
by humidity 50 nm

0.01 0.1
0 10 20 30 0 5 10 15
Normalized Mobility Diameter, 𝑑𝑚 /𝑑𝑝 Normalized Mobility Diameter, 𝑑𝑚 /𝑑𝑝
Mobility size distribution, mean mobility diameter, 𝑑ҧ𝑚 , and geometric standard Relative effective density, 𝜌𝑒𝑓𝑓 /𝜌, of silica agglomerates exposed to different S (symbols) compared to soot
deviation, 𝜎𝑔,𝑚 , of silica agglomerates after exposure to different saturation ratio, S. agglomerates6 with smaller PP standard deviation, 𝜎𝑔,𝑝 ,(dot broken line) and agglomeration theory5 (solid line).

Mass-mobility Relationship of Restructured Agglomerates measured by TDMA [7]

15 600
Number of Primary Particles, 𝑛𝑝

Maximum
Silica APM: TDMA: Deviation: 8 %
Soot2 2
Soot
10 𝑫𝒇𝒎 = 3.02
100 nm
400
Silica
𝑑𝑚 /𝑑𝑝

Silica
100 nmforms larger aggregates

than Soot 𝒌𝒎 = 0.27

50 nm

5 𝑫𝒇𝒎
Agglomerates: 𝒅𝒎
𝟏 𝟐. 𝟐𝟐 200 𝒏𝒑 = 𝒌𝒎
𝒅𝒎 −
𝑫 𝒅𝒎,𝒐 𝑫𝒇𝒎 𝒅𝒑
𝑫𝒇𝒎 = 2.74 = 𝒌𝒎 𝒇𝒎
𝒅𝒑 𝒅𝒑
𝒌𝒎 = 0.68
0 50 nm

0 5 10 15 0
𝑑𝑚,𝑜 /𝑑𝑝 0 5 10 15
Restructured silica (green) and soot2 agglomerate 𝑑𝑚 /𝑑𝑝 (red) Normalized Mobility Diameter, 𝑑𝑚 /𝑑𝑝
as function of their 𝑑𝑚,𝑜 /𝑑𝑝 measured by TDMA (filled symbols) and fitted to a scaling law (broken lines). Mass-mobility relationships measured here by TDMA (lines) are validated against APM (symbols).

References
[1] Kütz S, Schmidt-Ott A. (1992) J Aerosol Sci. 23, S357.
[2] Ma XF, Zangmeister CD, Gigault J, Mulholland GW, Zachariah MR. (2013) J.
Aerosol Sci. 66, 209.
[3] van Ommen J. (2012) J. Nanopart. Res. 14, 737.
[4] Lee SY, Chang H, Ogi T, Iskandar F, Okuyama K. (2011) Carbon 49, 2163.
[5] Kelesidis GA, Goudeli E, Pratsinis SE. (2017) Carbon 121, 527.
[6] Zangmeister CD, Radney JG, Dockery LT, Young JT, Ma XF, You RA, Zachariah
MR. (2014) PNAS 111, 9037.
[7] Kelesidis GA, Furrer FM, Wegner K, Pratsinis SE. (2018) Langmuir 34, 8532.
Conclusions
1. At S = 0.9, the 𝜌𝑒𝑓𝑓 /𝜌 of ramified silica agglomerates decreases with 𝑑𝑚 /𝑑𝑝 , following closely the agglomeration theory.5
2. At S = 1.5, silica PPs restructure into spherical agglomerates with 10 % smaller 𝑑ҧ𝑚 and 𝜌𝑒𝑓𝑓 /𝜌 = 0.28 ± 0.02 invariant of 𝑑𝑚 /𝑑𝑝 .
3. Silica agglomerates consist of larger aggregates compared to those of soot due to their flame synthesis conditions. This
results in less compact agglomerates with smaller 𝜌𝑒𝑓𝑓 /𝜌 and 𝑘𝑚 after water condensation and evaporation.
4. TDMA measurements can be coupled with the scaling law derived here to measure the restructured agglomerate mass-mobility
relationship as an alternative to the tedious APM.