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Aerosol Science and Technology

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A Generator for Homogeneous Liquid Aerosols

M. Suresh , R. A. Mackay & C. Acquista
a a a b

Department of Chemistry, Drexel University, Philadelphia, PA, 19104

b

Department of Physics, Drexel University, Philadelphia, PA, 19104 Published online: 05 Jun 2007.

To cite this article: M. Suresh , R. A. Mackay & C. Acquista (1982): A Generator for Homogeneous Liquid Aerosols, Aerosol Science and Technology, 1:4, 441-447 To link to this article: http://dx.doi.org/10.1080/02786828208958607

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A Generator for Homogeneous Liquid Aerosols

M. Suresh, R. A. Mackay, Department o f Chemistry
and C . Acquista
Department o f Physics, Drexel University, Philadelphia, PA 19104

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A generator of the evaporation-condensation type for the production of monodisperse aerosols has been designed and tested. Dibutyl phthalate aerosols in the submicron range and of narrow size distribution were generated with excellent reproducibilitywhen nucleated with NaCI. The particle size was determined from light scattering data using the polarization ratio method, and with a light

microscope. The generator is capable of maintaining a stable output of aerosol over a long period of time. The effects of the flow rate of the carrier gas, the nuclei concentration, the temperature of the furnace used for making the NaCl nuclei, and the heating temperature on the aerosol output are reported.

INTRODUCTION

Since the work of Sinclair and La Mer (1949), a number of generators have been reported for the laboratory preparation of relatively monodisperse liquid aerosols with radii in the 0.1-1-pm range. The generators function by the evaporation of a high-boiling point liquid, followed by condensation on foreign nuclei (1966).A variety of modifications designed to improve the stability and reproducibility of the Sinclair-La Mer generator have been reported (Nicolaon et al., 1970; Nicolaon et al., 1971; Davis and Nicolaon, 1971). These modified generators use externally produced salt nuclei and are quite versatile in terms of size range and number density. However, they do require long warm-up times and rather large volumes of liquid, which must either be recirculated or wicked. This can be inconvenient if corrosive or reactive fluids are involved. The Rapaport-Weinstock generator (Rapaport and Weinstock, 1955) employs a nebulizer to generate a plydisperse aerosol, which subsequently enters an evaporationcondensation column. Impurities in the liquid were used as nuclei. A similar generator was recently reported by Mulholland and Liu (1980).
Aerosol Science and Technology 1:441-l47 (1982) @ 1982 Elsevier Science Publishing Co., Inc.

Here, anthracene is added to a solution of the high-boiling-point liquid in a volatile solvent to act as a source of nuclei. A syringe and pump is used to feed the solution into the atomizer. We have designed a similar generator, which employs externally produced salt nuclei, and report here a systematic study of its operating characteristics using dibutyl phthalate (DBP) aerosols.

EXPERIMENT

Aerosol Generator

A schematic of the apparatus is shown in Figure 1. Helium carrier gas produces NaCl nuclei in the furnace (B), and this gas stream is then used to atomize the liquid in the nebulizer (E). The concentration of nuclei can be controlled by both the flow rate and the length of tubing between the furnace and nebulizer. The syringe pump is adjusted to maintain a constant level of liquid in the nebulizer, thus providing a constant output rate. The total amount of liquid in the nebulizer is about 10 ml, and a syringe of any convenient size may be employed (e.g., 10-100 ml). In this study, pure liquid DBP was em-

Suresh, Mackay and Acquista

Light Scattering Measurements A Brice-Phoenix series 2000 light scattering photometer was employed for measuring the scattered light intensity. The aerosol was made to flow through a cell similar to that described by Matijevic et al. (1964).The only modification was the addition of a sheathing gas (nitrogen) flow of 2.1 literlmin around the inlet tube to improve the collimation and stability of the aerosol stream. The standard slit in front of the photomultiplier was replaced by a circular aperture of 1 mm diameter in order to minimize the solid angle subtended by the photomultiplier. The internal surfaces of the cell were painted black to reduce reflections and stray light. Signals corresponding to the intensities of the vertically and horizontally polarized components of the scattered light were measured at 20 intervals between 50" and 130". The 436- and 546-nm lines of the mercury lamp were employed for all of the measurements. A background correction, taken with no aerosol flowing, was applied to the scattering measurements. After a set of background and sample intensities was obtained as a function of angle, the set was repeated to ensure constancy of the aerosol concentration and flow pattern. No polarization of the mercury light source was detected at any scattering angle.

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FIGURE 1. Schematic of aerosol generator, showing gas supply (A), furnace (B), boat containing salt (C), flow meter (D), nebulizer (E), syringe and pump (F), entrance chamber ( G ) , heating tape wrapped evaporator (H), voltage control (I), air-cooled chirnney.(J), water-cooled condenser (K), and aerosol outlet (L).

ployed. Typically, 10 ml of liquid will provide about 2 hr of continuous operation. The polydisperse aerosol entering the heated zone (H) is vaporized, and part of this vapor is recondensed on the salt nuclei in the air- and water-cooled chimney sections (J and K). The homogeneous (monodisperse) aerosol emerges from the outlet (L). If the furnace and evaporator are at their respective operating temperatures, the colors of higher-order Tyndall spectra (HOTS) are observed within a few minutes of turning on the carrier gas supply (maintained at 20 psi gauge). The output is stable within 10 min. The entrance chamber (G) is 2 cm inside diameter (i.d.)and 14 cm long. The tube from the nebulizer enters about midpoint. This tube connects by means of 24/40 standard taper to the evaporator (H) and air-cooled chimney (J), which is a single tube of 1.5 cm i.d. and 35 cm long. A length of 25 cm wrapped with heating tape is the evaporator section (H). The watercooled condenser (K) is 20 cm long with a 1.2 cm i.d. and connects to (J) by means of a 24/40 joint. The outlet (L) is a standard taper that necks down within 3 cm to a 0.5-cm i.d. tube from which the aerosol emerges.

Microscope Measurements

The aerosol was diluted by a factor of about 8500 and allowed to impinge on a cleaned glass microscope slide from a tube of 0.7 crn i.d The tube was held perpendicular to the slide, and 2-3 cm above it. The slide was examined under a Reichert Light Microscope Model number 324882 at a magnification of 1300 x , a photograph of which is shown in Figure 2. The drops are somewhat distorted from collision with the slide. However, measuring both the major and minor axis of each drop yields a mean radius (T) of 0.65 pm, which may be compared with a modal radius (rm)of 0.63 pm from the light scattering measurements. The contact angle of the DBP on the

A Generator for Homogeneous Liquid Aerosols

ing the nebulizer operating by itself. The flow rates were measured by means of ACE Glass Incorporated, Vineland, N.J., model 7481 rotameters using No. 36 glass floats.

RESULTS AND DISCUSSION

Ophcal Sizing Measurements

For fairly monodisperse aerosols it is possible to measure the mean aerosol radius and the standard deviation of the size distribution function photometrically by the polarization ratio method (Kerker, 1969, 1972). In this method a beam of unpolarized monochromatic light is scattered by the aerosol jet, and measurements of the scattered intensity polarized parallel (I,) and perpendicular (I,)to the scatteringplane are made as a function of scattering angle 8. To remove calibration effects, the polarization ratio I,/I, is recorded and compared against the theoretical Mie calculations (Van de Hulst, 1957).The polarization ratio curve for a monodisperse aerosol contains a number of peaks of varying heights due to interference effects within individual aerosol droplets. As the droplet radius increases, more peaks appear, and the peaks become sharper. For a polydisperse aerosol, the situation is more complicated. If the aerosol size distribution is unimodal and fairly monodisperse, it can be parameterized in terms of a zero-order log normal distribution function

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FIGURE 2. Dibutyl phthalate droplets on a glass

slide (see the text). The reference mark is 10 pm.

slides employed was greater than 9CP, and the microscope was focused to read the actual drop diameter. Therefore, the measured radius is expected to be slightly greater than the actual radius of the airborne aerosol drop (Liu et al., 1980).

'

Mass Concentrations
The mass concentrations reported here were all obtained by allowing the aerosol stream to pass through 0.5-pm Milipore filters, 1 in. in diameter, in teflon holders. The aerosol was collected for 15 min, and the filter assemblies were weighed on a five place mettler balance, model H18. The nebulizer rate was obtained by weigh' ~ n equation for microscopic drop size determination for contact angles (0) <9O0 has been given by Liu et al. Here 0 = 130". and the ntio of the actual D to measured (maximum)diameterD' is given by (DID')3 = I - 1/4(sin 9)?(2 + sin 9). where $ = 0 - n/2. Thus, 0.97, and a measured value of 0.65 pm gives a corrected DID' valueof 0.63 pm. For a0 = 0.03, r = r,.

where x is the Mie size parameter 27tr/i., x, is the modal value of x, and a, measures the width of . are the the distribution. The quantities r and 1 droplet radius and wavelength of the scattered light, respectively. As ooincreases from zero and the distribution function becomes less monodisperse, the peaks in the polarization ratio curve decrease in height and increase in width as the internal droplet interferences get washed out. In practical terms, one determines the modal aerosol radius r, from the positions and relative heights of the peaks, the width of the distribution

Suresh, Mackay and Acquista

function a, from absolute heights and widths of the peaks. The intensity measurements were carried out at two different wavelengths, 0.5463 pm (green) and 0.4367 pm (blue). Polarization ratios were measured for scattering angles SO'< O < 1300 for approximately 50 different DBP aerosols, using the previously described generator under different conditions. The modal radius of each aerosol sample was obtained by comparing the positions and heights of the measured peaks against monodisperse (a, =0) calculations of the theoretical ratio. For each aerosol sample both the blue and green measurements individually matched only one monodisperse radius, and this radius was the same for both wavelengths. The radius was determined by matching (quantitatively) the absolute angular position of all peaks, as well as (qualitatively) the relative peak heights. As expected, absolute peak heights and peak widths for these monodisperse calculations differed significantlyfrom our observed values. Attempts to estimate the width a, of the actual polydispersion were less successful. The theoretical polydisperse ratio curve (computed by forming a weighted average over the monodisperse I, and I, curves separately) was substantially different from our observations. By varying a, and r , we were unable to match both the widths and heights of the peaks in our polarization ratio measurements. We attribute this diserepancy to several experimental problems, including scattering cell design, sensitivity, and angular resolu-

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tion, and are currently redesigning the photometer to overcome these problems. We confirmed our values of r , by measuring aerosol droplets deposited on a glass slide under a microscope. After measuring about a hundred droplets, we found that the corrected modal radius measured microscopically agreed exactly with the one inferred from the polarization ratio measurements [see the experimental methods section and Liu et al. (1982)l.The mean radius F is expected to be slightly larger than r , approaching it as a, approaches zero. Estimates of the upper bound on a,, based on microscopic measurements and on observations of the higher order Tyndall spectrum suggest that a, <0.1. We have also determined an upper bound on a, by comparing the peak widths in the polarization ratio versus 0 plots with computed values. For the data shown in Figures 3 and 4, the best match at both wavelengths is for ao=0.03. For F=0.63 pm, the standard deviation of the size distribution is about 0.02 (273, corresponding to a fairly monodisperse aerosol.
Aerosol Generator

The nebulizer output increases slightly with increasing flow rate, here 3-5 liter /min. The mass concentration was approximately conglliter. Over 75% of this stant at 2.5 f0.1 x is lost in the entrance chamber. The polydisperse aerosol entering the heated zone is completely vaporized at 125OC as evidenced by the lack of both wall condensate and any visible aerosol for

2 Ia
[r

II 6 10 4

P I a

09
Oe

N I L a

2 07 0 40 06 140

FIGURE 3. Polarization ratio p versus scattering angle 8 for a DBP aerosol using X = 546 nm. The open circles are experimental points (right-hand ordinate) and the solid line is the theoretical curve for o,, = 0.03 and r , = 0.35 1 pm (left-hand ordioate).

60

80

100

120

ANGLE IN DEGREE

(8)

A Generator for Homogeneous Liquid Aerosols

FIGURE 4. Polarization ratio p versus scattering angle 0 for a DBP aerosol using X = 436 mm. The

open circles are experimental points (right-hand ordinate) and the solid line is the theoretical curve for oo = 0.03 and r , = 0.35 1 pm (left-hand ordinate).
0.5 140

40

60

80

100

120

ANGLE IN DEGREE (8)

about 2-3 cm above the heating tape. Most of the remaining 25% represented by this vapor is lost by condensing on the walls of the cooling chimney, and only about 1% emerges as homogeneous aerosol. The evaporation temperature does not apear to be too important as long as it is above some critical value. For example, at a flow rate and furnace temperature of 3.3 literlmin and 59032, respectively, essentially the same polarization ratio curves were obtained for evaporator temperatures of 100,125, and 150C. However, at 75OC, appreciable polydispersity was evident. A number of experiments were carried out under a fixed set of conditions in order to test the stability and reproducibility of the generator. By stability is meant the uniformity of the particle radius as measured over a given period of steady operation of the generator, usually from several hours up to a day. The stability is illustrated by the results in Table 1, obtained over a period of 3 hr. These have been selected from among scores of similar results as being typical of the perform.ance of the generator. The mean radius is 0.628 pm with a relative standard deviation of 0.4%. By reproducibility is meant uniformity of particle size under the same operating conditions on different days or on the same day, with an intervening period when the generator was either shut down or operated under different conditions. The data in Table 2, taken over a four-month period, have a mean of 0.628 pm and a relative standard deviation of 1.5%.

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TABLE 1. Aerosol Generator Stability Under continuous Operation.

Run
Time (rnin)
Radius (prn)

OThe furnace temperature was 5 9 W , evaporator temperature 125C. and He flow rate 3.3 literlmin. The radii were determined fmm light scattering measurernens by the polarization ratio method at two wavelengths.

TABLE 2. Aerosol Generator Reproducibi1it)P

Run
5

Time
30 min 3h 6h 10h 2 days 8 days 20 days
2 months

Radius (pm)

9
16 25 26 34 35 48 49 60 61 72

73
85 86
0

4 months

0.620 0.630 0.615 0.635 0.650 0.619 0.628 0.638 0.630 0.640 0.630 0.610 0.619 0.634 0.628

Same conditions as in Table I .

446

Suresh, Mackay and Acquista

The effect of flow rate on radius number concentration is shown in Figures 5 and 6. The radius decreases with increasii~g oven temperature and increasing flow rate, owing to an increase in nuclei concentration and possibly a bit less mass transfer in the evaporator and a bit more condensation loss in the chimney. This type of behavior has been observed in other generators (Kerker, 1972). Since the number
FIGURE 5. Radius as a function of flow rate at various furnace temperatures; 590C (open, 725C (closed), and 790C (half-filled).

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concentration increases linearly with flow rate and the mass concentration does not vary greatly (1.5-2.5 x glliter), the nuclei concentration is roughly proportional to the flow rate. That the particle radius in this generator does in fact depend on the external nuclei concentration is shown by the data in Table 3. Varying lengths of Tygon tubing were inserted between the furnace and the nebulizer to remove the nuclei by diffusion to the wall thus decreasing their concentration. As expected, the droplet radius increases. It should be mentioned that we have also successfully generated monodisperse aerosols of sulfuric acid and chlorosulfonic acid in this generator. All the components were of glass, and the only change made was the replacement of Tygon with flexible Teflon tubing.

SUMMARY

FLOW RATE (I/min)

We have tested a liquid aerosol generator of the evaporation-condensation type. This generator is easy to construct, rugged, and fairly inexpensive. Homogeneous aerosols of DBP in the 0.350.65-pm radius range at number densities of 38 x lo5 cm-3 have been generated. This output
TABLE 3. Effect of Decreasing Nuclei Concentra(Increasing Tubing Length) on Particle Radiusa
-

FIGURE 6. Number concentration as a function of flow rate at various furnace temperature; 590C (open, 725C (closed), and 790C (half-filled).

Radius of particle Run

10.0

Length (rn) 2.00 2.00 2.00 2.00 7.50 7.50 7.50 15.00 15.00 15.00 30.00 30.00 30.00

(m)

0
Z

120 121 122 123 130 131 132 135 136 137 140 141 142
2.0
4.0

0.504 0.500 0.506 0.501 0.547 0.545 0.540 0.630 0.636 0.628 0.704 0.710 0.707

6.0

8.0

10.0

FLOW RATE (I/min)

"The furnace temperature was 725C. evaporator temperature 125C. and the tlowrate 3.3 literlmin.

A Generator for Homogeneous Liquid Aerosols

447

is both stable and reproducible, and the generator can be used with corrosive or reactive liquids.
The authors wish to acknowledge the support of the Chemical System Laboratory, Aberdeen Proving Ground, under contract DAAK 11-80-C-0051.

REFERENCES
Davis, E. J., and Nicolaon, G. (1971). J. ColloidInterface Sci. 37:76&-778. Fuchs. N. A., and Sutugin, A. G. ( 1966). Aerosol Science (C. N. Davis, ed.), New York, Ch. 1, p. I. Kerker, M. (1969). The Scattering of Light and Other ElectromagneticRadiation, Academic Press, New York. Kerker, M. (1972). J . ColloidInt. Sci., 39:2-24.

Liu, B. Y. H., Pui, D. Y. H., and Wang, Xran-Quing. (1982). Atmospheric Environment 16:563-567. Matijevic, E., Kitani, S., and Kerker, M. (1964). J . Colloid Interface Sci. l9:223-237. Mulholland, G. W., and Liu, B. Y. H. (1980). J . Research N.B.S. 85:223-238. G. Nicolaon et al. (1970). J . Colloid Interface Sci. 34:534544. G. Nicolaon et al. (1971). J. Colloid InterfaceSci. 35:490501. Rapaport, E., and Weinstock, S. E. (1955). Experientia. 11:363-364. Shahrian, S., Samiento, A. N., andGmdrich, F. C. (1972). J. Colloid Interface Sci. 39:305-377. Sinclair, D., and LaMer, V. K. (1949). Chem. Rev. (44: 245-267. Van de Hulst, H. C. (1957). Light Scattering by Small Particles, Wiley, New York. Received 1 January 1982; accepted 12 July 1982

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