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Fire Safety Journal 43 (2008) 3641 www.elsevier.com/locate/resaf

Laboratory evaluation of the effectiveness of nanostructured and conventional particles in clearing smoke in enclosed spaces
R. Yadava, R.G. Maghirangb,, L.E. Ericksona, B. Kakumanua, S.G. Castrob
b

Department of Chemical Engineering, Kansas State University, Manhattan, KS 66506, USA Department of Biological and Agricultural Engineering, Kansas State University, Manhattan, KS 66506, USA Received 28 July 2006; received in revised form 13 February 2007; accepted 14 February 2007 Available online 27 April 2007

Abstract The potential of nanostructured and conventional particulate materials in clearing smoke in enclosed spaces was evaluated. Aggregates of metal oxide nanostructured particles or conventional particles were sprayed into an enclosed experimental chamber (2.4 m 2.4 m 3.6 m) lled with glycol smoke. The times required for the light transmission in the room to reach 10% and 20% served as a measure of the effectiveness of the material in clearing smoke. The effects of material type and deployment pressure were considered. Results indicate the potential of some particles in increasing the rate of smoke dissipation and improving the visibility in the smoke-lled chamber. r 2007 Elsevier Ltd. All rights reserved.
Keywords: Nanoscale particles; Smoke clearing; Smoke dissipation

1. Introduction Military smokes and obscurants are used in combat training and in wartime operations for screening armed forces from view, signaling friendly forces, and identifying enemy targets [1]. Military persons often wish to clear smoke rapidly to counteract such effects. Smoke clearing is also important in rescue operations after res. Smokes and obscurants are composed of many ne particles (i.e., solid and/or liquid) suspended in the air; these particles scatter and absorb different spectra of electromagnetic radiation. Smokes and obscurants, like other aerosols, are unstable in the sense that their concentration and properties change with time. These changes can be a result of external forces or physical and chemical processes that serve to change the size or properties of the particles. Such processes include coagulation, condensation, evaporation, adsorption, absorption, and chemical reaction. Enhancing one or a combination of these processes can enhance the clearing of smoke particles.

Based on such processes, principles for clearing smoke may be categorized into the following:

   

Enhancing coagulation by introducing scavenging particles, electrostatic charging or using intense sound waves. Enhancing condensation by using hygroscopic nuclei. Enhancing evaporation of droplets through heating of the smoke. Dilution of the smoke through mixing with air.

Corresponding author. Tel.: +1 785 532 2908; fax: +1 785 532 5825

E-mail address: rmaghir@ksu.edu (R.G. Maghirang). 0379-7112/$ - see front matter r 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.resaf.2007.02.002

This research investigated the potential of spraying scavenging particles to enhance the rate of smoke dissipation by enhancing coagulation. Coagulation is a process in which particles collide with one another, due to relative motion between them, and adhere to form larger particles [2]. The result of the many collisions between particles is an increase in particle size, decrease in the number concentration, and eventual deposition of the large particles. Aggregates of metal oxide nanostructured particles are potential scavenging particles. These particles have demonstrated effectiveness for the inactivation and destruction of a wide variety of chemical warfare agents, toxic industrial

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R. Yadav et al. / Fire Safety Journal 43 (2008) 3641 37

chemicals, and vegetative cells and bacterial spores [36]. They can be used for mitigation of the hazards posed by aerosols or contaminated surfaces. Furthermore, they have a long shelf life and do not require water (or mixing). And, as Koper et al. [6] noted, the particles are converted to harmless common minerals after several days exposure to the atmosphere. The main objective of this research was to evaluate the potential of nanostructured particles in clearing smoke in enclosed spaces. The overall goal was to rapidly clear the smoke particles in an enclosed space and enable a person to see through the space. The effects of type of material and deployment pressure were determined. The performance of the nanostructured materials was compared with that of conventional particulate materials. 2. Materials and methods 2.1. Description of the chamber and instruments Experiments were conducted in an enclosed experimental chamber measuring 2.4 m 2.4 m 3.6 m. The chamber was equipped with a smoke generator, lter samplers, and a transmissometer (Series 6597, Leeds & Northrup) (Fig. 1). Glycol aerosol was used as a simulant of smoke. It is used in theatrical productions to simulate battle smoke and

Deployment location Filter samplers 2.4 m Transmissometer Mixing fan Smoke generator 3.6 m Elevation view 3.6 m 1.8 m 1.2 m

Filter samplers

res. The glycol aerosol was generated with a commercially available smoke generator (Gummy Industries, Inc.). The generator has a heating element through which the glycol/ water solution is pumped and vaporized. Upon exiting the generator nozzle, the vapor condenses rapidly to form a dense visible aerosol. The glycol/water solution is composed of de-ionized water, propylene glycol, and triethylene glycol. Once generated, the aerosol is dynamic with respect to size and abundance. Immediately after generation of the aerosol, the aerodynamic size distribution was measured by using an eight-stage cascade impactor (Series 290, Andersen Instruments); the resulting aerodynamic geometric mean diameter was 2.7 mm and the geometric standard deviation was 2.6. In a cascade impactor, air is drawn through a series of orices of decreasing size, and the airow is normal to the collecting surfaces on which aerosols are collected by inertial impaction. The particles are separated stepwise by their momentum differences into a number of size ranges and are collected simultaneously. After the last impactor stage, the remaining ne particles are collected by a 34-mmdiameter lter. Impactor cut-point diameters (i.e., largest diameter particles that can pass through a particular stage) range from 21 to 0.5 mm. It was operated at a sampling ow rate of 2 L/min for 12 min. The transmissometer, connected to a datalogger, was employed for measuring changes in light transmission through the chamber. It has a spectral response in the visible portion of the electromagnetic spectrum (400700 nm wavelength). The measurement is achieved by directing a beam of visible light across the room (path length of 3.6 m) onto the light detector, whose output varies with changes in light transmission. A reading of 100% reects complete obscuration (i.e., no transmission of light from the source to the receiver). Particulate mass concentration was measured gravimetrically by using the ltration method. Airborne particles were collected by using three 37-mm-diameter glass-ber lters; each was placed in a cassette holder and air was drawn in by a low-volume pump at a ow rate of 2 L/min. The pump was operated for 1 min immediately after injection of the particles. The lters were weighed, before and after sampling, under controlled temperature and humidity conditions (approximately 25 1C temperature and 50% relative humidity). The mass concentration was obtained from the increase in lter mass and the volume of air sampled. 2.2. Experimental procedure Smoke was generated inside the chamber by using the smoke generator until the opacity reaches 100% (i.e., 0% light transmission). The smoke generator was located on one of the corners of the chamber (Fig. 1). While the smoke was being introduced, two mixing fans inside the chamber were operated for approximately 2 min to disperse the smoke inside the chamber. As soon as the opacity reached

2.4 m 1.2 m

Deployment location

Plan view
Fig. 1. Schematic diagram of the experimental chamber (not drawn to scale).

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38 R. Yadav et al. / Fire Safety Journal 43 (2008) 3641

100%, the fans were turned off. Particles were then immediately deployed into the chamber by using a pressurized canister. The light transmission through the chamber was monitored with the transmissometer. In addition, particulate mass concentration was measured by using the lter samplers. For each of the experiments performed, the percentage deployment and particulate mass concentration were determined. The percentage deployment was calculated as the actual mass of particles deployed divided by the mass of particles placed in the canister. The smoke-clearing effectiveness of a material was evaluated and expressed in terms of the dimensionless parameters, t , and t , which 10 20 are dened as t 10 t 20 t10;p , t10;s t20;p . t20;s (1)

(2)

In Eqs. (1) and (2), the variables t10,s and t20,s are the times to reach 10% and 20% light transmission, respectively, in the chamber, due to natural smoke dissipation. Smoke dissipates naturally because of gravitational settling and evaporation; settling may be enhanced by coagulation of particles. The variables t10,p and t20,p are the times to reach 10% and 20% light transmission, respectively, when scavenging particles are sprayed into the smoke-lled chamber. Small values of t and t indicate effective 10 20 smoke clearing; values greater than 1.0 indicate enhancement of the degree of obscuration in the visible portion of the electromagnetic spectrum. The 10% and 20% levels were chosen in this study because, at these levels, one can begin to see through the smoke. The mean values for t10,s and t20,s in the chamber lled with glycol smoke were 26 and 39 min, respectively. 2.3. Experimental design The type of scavenging particle is expected to inuence smoke dissipation. To identify promising scavenging particles, a preliminary down-selection process was performed to evaluate the effectiveness of selected particles in clearing smoke in a conned space [7]. In this process, a small chamber (0.61 m 0.61 m 1.22 m) was constructed
Table 1 Properties of nanostructured materials Nano-structured material Color Specic surface area (m2/g) Crystallite Average pore size diameter (A)

and instrumented with the glycolsmoke generator and transmissometer. Five types of nanostructured particles (NA TiO2, NA MgO, NA MgO plus, NA Al2O3, NA Al2O3 plus) and ve conventional powders (NaHCO3, CaCO3, Ca(OH)2, MgO, TiO2) were considered. The nanostructured materials were manufactured by NanoScale Corporation, through proprietary processes and were marketed as NanoActiveTM materials, referred to in this paper as NA. Each material was deployed into the small chamber, which was lled with glycol smoke, through a pressurized canister at a pressure of approximately 80 psig. This pressure was selected from preliminary experiments. The light transmission through the chamber was monitored with the transmissometer (path length 1.2 m). The t 10 and t values were obtained from the light transmission 20 data. Results of the small-scale experiments suggested that NA MgO plus, NA MgO, NA TiO2, NaHCO3, and Ca(OH)2 were the most effective (i.e., they have the smallest t and t values). These materials were then 10 20 considered for the large-chamber studies. The properties of the three nanostructured materials (NA MgO plus, NA MgO, and NA TiO2) are presented in Table 1. Many factors could inuence the effectiveness of a scavenging particle in clearing smoke particles in enclosed spaces. In addition to the type of scavenging material, this study considered the mass of material deployed and pressure at which the particles were deployed. Table 2 summarizes the experiments. In conducting each of these experiments, there were either two or three replications. The concentration of particles in the chamber (number and/or mass) will inuence the effectiveness of the material in clearing smoke. As such, the effect of mass of material deployed was also investigated. Particles were sprayed into the experimental chamber by using a pressurized canister at a pressure of 80 psig. Deployment pressure can inuence the distribution of particles in the room and also the degree of agglomeration or de-agglomeration of the nanostructured particles. To determine the effect of deployment pressure, NA MgO plus and NaHCO3 were deployed into the experimental room by using a pressurized canister at three different deployment pressures, ranging from 30 to 100 psig. Measured data were analyzed using SAS (Version 9, SAS Institute, Cary, NC). To determine the effects of the type of material, mass deployed, and deployment pressure on the

Total pore volume Bulk density (cm3/g) (g/cm3)

Particle density (g/cm3)

Mean aggregate size (mm)

NA TiO2 NA MgO NA MgO plus

white 4500 white 4230 white 4600

amorphous 32 8 nm 50 o4 nm 30

40.4 40.2 40.4

0.6 0.6 0.4

3.7 3.2 2.4

5.0 3.3 12

Source: NanoScale Corporation, Manhattan, KS. NA refers to NanoActiveTM, which is a trademark of NanoScale Corporation.

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smoke-clearing effectiveness, the PROC GLM procedure in SAS was used at the 5% level of signicance (i.e., 95% condence). To compare means, the LSMEANS procedure in SAS was used with a 5% level of signicance. 3. Results and discussion 3.1. Effect of type of material on smoke clearing effectiveness Table 3 summarizes the mean deployment percentages and mass concentration of the particles when the deployment pressure was 80 psig. Two types of nanostructured
Table 2 Summary of experiments in the large chamber Experiment Material Nominal mass deployed (g) 25 50 100 40 50 100 40 100 40 50 100 60 50 40 80 100 30 80 100 Deployment pressure (psig) 80

Effect of type of material

NaHCO3

Ca(OH)2

NA TiO2 NA MgO

NA MgO plus Effect of deployment pressure NaHCO3

NA MgO plus

60

The number of replicates for each experiment was 2 or 3.

particles (NA TiO2 and NA MgO) had the smallest deployment percentage while one type (NA MgO plus) had the highest deployment percentage. When handling these materials (e.g., weighing or pouring them from the original container to the canister), it was observed that both NA TiO2 and NA MgO tend to clump together, which could account for difculty in dispersing these materials. NA MgO plus, on the other hand, was observed to be much easier to handle. The deployment percentages of the two conventional particles (NaHCO3 and Ca(OH)2) were signicantly larger than those for NA TiO2 and NA MgO but were signicantly less than that for NA MgO plus. Again, these conventional particles were much easier to handle than NA TiO2 and NA MgO. As expected, the measured mass concentration of particles increased with increasing deployment percentage. NA MgO plus had the highest mean mass concentration of airborne particles. The effectiveness of the materials in clearing smoke, as indicated by the t and t values, is also presented in 10 20 Table 3. The mean t and t values for all types of 10 20 particles were less than 1.0, indicating that they were able to enhance the rate of smoke dissipation or clearing. Note that t and t values greater than 1.0 indicate enhance10 20 ment of the degree of obscuration in the chamber. Dispersing particles into the chamber could have resulted in collisions and coagulation between the deployed particles and smoke. Such collisions would decrease the concentration of smoke particles and, consequently, improve the visibility in the chamber. Comparison of the particles showed that they differed signicantly in the t and t values. NA MgO plus, which 10 20 had the highest mean percentage deployment and highest mean mass concentration of airborne particles, had the smallest values of t and t , indicating that it is the most 10 20 effective in clearing or dissipating the smoke in the chamber. Spraying approximately 60 g of NA MgO plus into the smoke-lled chamber resulted in a mean t of 0.10 10

Table 3 Comparison of different smoke-clearing agents at a deployment pressure of 80 psig Material Mass deployed Nominal (g) NaHCO3 25 50 100 40 100 40 100 40 50 100 60 % Deployment 65 70 78 37 49 36 30 66 77 68 94 Mean % deployment1 71b(4.3) Mass concentration1 mg/m3 662c(121) Smoke clearing effectiveness1 t* 10 0.42c(0.06) t* 20 0.39b(0.05)

NA MgO NA TiO2 Ca(OH)2

43c(5.3) 32c(6.1) 70b(4.0)

549c(148) 377c(171) 1087b(112)

0.38b,c(0.07) 0.76d(0.08) 0.24a,b(0.06)

0.44b(0.07) 0.94c(0.018) 0.23a(0.05)

NA MgO plus
1

94a(6.1)

1932a(171)

0.10a(0.08)

0.11a(0.08)

Column means followed by the same superscript are not signicantly different at the 95% condence level. Values in parentheses represent the standard deviations of the means.

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40 R. Yadav et al. / Fire Safety Journal 43 (2008) 3641 Table 4 Effect of deployment pressure on the effectiveness of NA MgO plus in clearing glycol smoke Deployment pressure (psig) Deployment1 (%) Mass concentration1 (mg/m3) Smoke clearing effectiveness1 t* 10 30 80 100 67b(5.0) 94a(2.6) 74b(3.2) 1570a(514) 1932a(420) 1859a(513) 0.24b(0.03) 0.10a(0.02) 0.11a(0.03) t* 20 0.26b(0.05) 0.11a(0.04) 0.10a(0.05)

1 Column means followed by the same superscript are not signicantly different at the 95% condence level. Values in parentheses represent the standard deviations of the means.

Table 5 Effect of deployment pressure on the effectiveness of NaHCO3 in clearing glycol smoke Deployment pressure (psig) Deployment1 (%) Mass concentration1(mg/m3) Smoke clearing effectiveness1 t* 10 40 80 100 35a(9.7) 70a(9.7) 62a(9.7) 281b(90) 532a(90) 504a(90) 0.52a(0.07) 0.31a(0.07) 0.40a(0.07) t* 20 0.48a(0.06) 0.29a(0.06) 0.42a(0.06)

1 Column means followed by the same superscript are not signicantly different at the 95% condence level. Values in parentheses represent the standard deviations of the means.

and a t of 0.11. As such, light transmissions of 10% and 20 20% through the chamber were achieved in about 2.5 and 4 min, respectively. In contrast, with glycol smoke alone, the corresponding times were 26 and 39 min. The effectiveness of NA MgO plus as a smoke clearing agent could be attributed to the mass concentration and its size relative to the other agents and smoke particles. With the highest mass concentration of airborne particles, the potential for collisions and, consequently, rate of coagulation between the NA MgO plus particles and the smoke particles is expected to be highest for NA MgO plus compared to the other particles. In addition, the NA MgO plus particles are considerably larger than the other particles, including the smoke particles, and would thus settle out faster. 3.2. Effect of deployment pressure on smoke clearing effectiveness Table 4 summarizes the effect of deployment pressure on the performance of NA MgO plus. In general, higher deployment pressures (80 and 100 psig) resulted in signicantly higher mass deployed and mass concentration, and lower values of t and t compared to the lower 10 20 deployment pressure (i.e., 30 psig). In addition, deployment pressures of 80 and 100 psig did not signicantly differ in terms of percentage deployment, mass concentration, and t and t values. The lower t and t values for the 10 10 10 20 higher pressure compared to the lower pressure indicate that NA MgO plus was more effective at higher deployment pressures than at lower pressures. Again, this could be explained by the higher mass concentration of particles for the higher deployment pressures.

Table 5 summarizes the effects of deployment pressure on the performance of NaHCO3. In general, this material exhibited a similar trend as NA MgO plus, that is, higher deployment pressures were better than the low deployment pressure in terms of percentage deployment, mass concentration, and t and t values. However, while 10 20 the values of t and t were smaller for the higher 10 20 pressures (80 and 100 psig), they were not signicantly different (p40.05) from those for the low pressure (i.e., 40 psig). 4. Conclusions The effectiveness of various materials in clearing smoke in an enclosed experimental chamber was investigated. Results showed that spraying particles into the smoke-lled chamber enhanced the rate of smoke dissipation or clearing and improved visibility in the chamber. Of the particles considered in this study, a nanostructured material (i.e., NA MgO plus) was the best smoke-clearing agent, in terms of speed in improving visibility through the smoke-lled room. Also, this material was more effective at higher deployment pressures than at low pressures. Acknowledgments This work was partly funded through the award of a contract from the United States Marine Corps Systems Command to M2 Technologies, Inc. We thank Dr. Larry Glasgow, Dr. Bernardo Predicala, and Edna Razote for their help with experimental aspects of this research. This is Contribution no. 07-6-J from the Kansas Agricultural Experiment Station, Manhattan, Kansas.

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