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AD-A283 689 . .. ARMY RESEARCH LABORATORy Midinfrared Optical Properties of Petroleum Oil Aerosols by K. P. Gurton Physical Science Laboratory C. W. Bruce Battlefield Environment Directorate ARL-TR-255 August 1994 IfTI 98ELECTE 2:8 94-27152 Apwudbrpuli rees,• d•stiibulon is

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Page 1: IfTI · 2011. 5. 13. · 7. Relative extinction cross section as a function of radius for fog oil aerosol o . 22 8. Determination of complex index using Mie theory, effective radius,

AD-A283 689 . ..

ARMY RESEARCH LABORATORy

Midinfrared Optical Propertiesof Petroleum Oil Aerosols

by K. P. GurtonPhysical Science Laboratory

C. W. BruceBattlefield Environment Directorate

ARL-TR-255 August 1994

IfTI

98ELECTE 2:8

94-27152 Apwudbrpuli rees,• d•stiibulon is

Page 2: IfTI · 2011. 5. 13. · 7. Relative extinction cross section as a function of radius for fog oil aerosol o . 22 8. Determination of complex index using Mie theory, effective radius,

NOTCICS

The findingin tis report me not to be construed as an official Department ofthe Amy pouitioa, unless so designated by other amiorized documents.

The citation of trade nes amd nsmes of manufacturer in this repo•t is not tobe construed as official Govermment indorsement or approval of commerciallpoducts or services aferenced hereim

Detiem Node*

Whea this document is no longer needed, destroy it by any method that willprevent disclomue of its contents or reconstrucion of the document.

Page 3: IfTI · 2011. 5. 13. · 7. Relative extinction cross section as a function of radius for fog oil aerosol o . 22 8. Determination of complex index using Mie theory, effective radius,

REPORT DOCUMENTATION PAGE OU1&07"8pq~Ig,~sI WAm.IW am Ut- ad~ "1 4" "mniwvug ~ MypM. uid= §W Wim d miwýIwisu.1 g.m m

-. A40C US O LYFeave Nn 2. DATE3 REPORT TYPE ANDODAT SOVEREDI1Au" 4 FinK

AL TITLE AND SUBTITLE S. FUNDING NUMBERS

M~4Op"m Pfopama of Paaambm 01 Awmab

IL AUTHOR(S)

L. P. CIA*=o mi C. W. burn

7. PLV40LMMI ORGANjIZATION NAMWE(S) AND ADDRESS(ES) 8. PERFORMING ORGANIZATIOPhydeaI Sdwe Las K gm~ REPORT NUMBERNow Modoo line UdmvukyLA Cinama, Pw UO

9. SPONSORING /MONITORING AGENCY NAME(S) AND ADDRESS(ES) 10. SPONSORING/ MONITORINGU.S.Ann Romah mbaguyAGENCY REPORT NUMBER

Daddhfisd Nanizumm Disendauwe ARL-TR-WS5AWNl: AMIRL4DB.NWh~lo Smu. M=09~ Rup, NM S80W,=l0

11. SUPPLEMENTARY NOTES

128. DISTREBUTION/AVAILABILITY STATEMENT 12b. DISTRIBUTION CODE

Appuoved for publfic ,uhm; d~rlhdmina - ~imluid. A

13. ABSTRACT (MAximum 200 woirh

Thw tin snvolma d abwqmisla md cmt~imoo asfamia wo monmuWd for fog oil mmmala £3.4 pm wilh a eamsiwand hOtommmaticmid uamiiwmaos£r qmyfu An wiianci qspoul pmofil vu I dmim ovea a imW of Wanfrd (13t) wavalmigft feum 2.7 to 4.0 pmnby an UR momn Ummaniumwdr. 7hU =W s Voctum wa mm inuminad by ufwmoaing it to "h pbftsosamaic partho of theezpuianwA. A couiexmpoaing Mis omloulaiou urn ooo*aMd mad -aqp nd with the above mmsinamta. Agnmma is good for do most

, o ptiodl ooefiauient An cutrpolbion od dds dds to othe imlhr patmulmm pmoducts achma uu. or dimal fuel thot ezabMobidlrw bok abmooption ouchmrtuai urns briWIy exmni

14. SUBJECT TERMS 15. NUMBER OF PAGES35

II~dI~rr~dasmmolpatoleu, - MO~bNI16. PRICE CODE

17. SECURITY CLASSIFICATION 18. SECURITY CLASSIFICATION 19. SECURITY CLASSIFICATION 20. LIMITATION OF ABSTRACTOF REPORT OF THIS PAGE OF ABSTRACT

Uachmiliod Unclmmaifjed Uuclmmified SAR

NSN 7540401-280500 Standard Form 298 (Rev. 2491)Ptegicnb by ANSi Std M-18CM-5102

Page 4: IfTI · 2011. 5. 13. · 7. Relative extinction cross section as a function of radius for fog oil aerosol o . 22 8. Determination of complex index using Mie theory, effective radius,

Acknowledgment

We thank Dr. Gary Eiceman and Mr. Monte Mauldin of the New MexicoState 'U rsity Chemistry Department for their generous support on theresear( ported in this report.

reoession For

NTIS GAM C2 T `f,_ ;

Unav .. "ed 0

ByDistribution/,/

Av'•, :-i1ity CodesAvail rnuidor

Diet spacialfk1 1L..

Page 5: IfTI · 2011. 5. 13. · 7. Relative extinction cross section as a function of radius for fog oil aerosol o . 22 8. Determination of complex index using Mie theory, effective radius,

Acknowledgment . 1

1. Introduction .......................................... 5

2. Approach .... pra......................... 7

3. Environmental Chamber for Measurements at 3.4 pm ............. 9

4. Dosimetry and Size Characterization ........................ 11

5. Photoacoustic Measurements .............................. 13

6. Spectrally Continuous Measurements ........................ 17

7. Effective Radius of Fog Oil Particles ...................... ..... 21

8. Inversion of the Mie Process to Determine Complex Index at 3.39 itm ... 23

9. Chemical and Optical Analysis of Similar Substances .............. 25

10. Comments on the Size Distribution ........................... 27

11. Summary ....... ................................... 29

References .. .......................................... 31

Acronyms and Abbreviations ................................ 33

Distribution .................................... 35

3

Page 6: IfTI · 2011. 5. 13. · 7. Relative extinction cross section as a function of radius for fog oil aerosol o . 22 8. Determination of complex index using Mie theory, effective radius,

1. Typical size distribution for aerosol photoacoustic measurements ........ 122. Gas and aerosol spectrophone/tasmissometer for 0.63,

1.1, or 3.4 #m......................................... .133. Time evolution of extinction and absorption coefficients ................ 144. Fog oil particle size distributions for the two chambers .............. 185. Comparison of calculated (Mie theory) and experimental results ......... 196. Calculated extinction and absorption spectra of fog oil ............... 207. Relative extinction cross section as a function of radius for fog oil aerosol o . 228. Determination of complex index using Mie theory, effective radius,

measured absorption, and total scattering coefficients for fog oil. Mietheory coefficients form an increasing progression as real index increases(for the family of curves) in increments of 0.15 .................... 23

9. Transmissivity (a) and mass spectra (b) of liquid fog oil, kerosene,and diesel fuel ............................ . ............. 26

Tables

1. Fog oil attenuation efficiencies at 3.39 pm for the sizedistribution in figure 1 .................................... 15

2. Complex index using the absorption and scattering efficiencies,effective radius, and Mie theory as compared with thoseof Weng [1J ........................................... 24

4

Page 7: IfTI · 2011. 5. 13. · 7. Relative extinction cross section as a function of radius for fog oil aerosol o . 22 8. Determination of complex index using Mie theory, effective radius,

1. Introduction

A petroleum product called fog oil is the primary substance examined. Fogoil is best characterized as a light oil similar to that used to lubricate smallmachinery. For many years, fog oil has been atomized to produce a fog-like aerosol, most commonly seen in skywriting but also used for manyyears as an Army obscurant, smoke.

The purpose of this study was to determine absorption and scattering ofelectromagnetic radiation by this type of hydrocarbon aerosol in anatmospheric transmission window at wavelengths between 3 and 4 14m.Although interest is shown in describing interaction of fog oil aerosol withhigh-energy laser beams, the optical coefficients are available only inunpublished reports and the values at the wavelengths of interest immenselyvary. In this report, the values of n and k for the midinfrared (IR) regionare shown to be in reasonable agreement with those of the most recentunpublished report.

The measurements of optical properties are made on fog oil aerosolsdispersed and continuously mixed in controlled environmental chambers.Aerosol mass densities and size distributions are determined by usingdosimetry and commercially available techniques. Settling characteristicsof the well-mixed chamber aerosols yield supportive information regardingthe particle size distributions. Mie-theory calculations for the measuredsize distributions are based on values of the complex refractive indicesmeasured by Weng. [1] The study extends to optical properties for othersimilar petroleum products.

5

Page 8: IfTI · 2011. 5. 13. · 7. Relative extinction cross section as a function of radius for fog oil aerosol o . 22 8. Determination of complex index using Mie theory, effective radius,

2. Approach

The approach consisted of two stages:

1. A combination photoacoustical and extinction measurement wasperformed at the single wavelength of 3.39 I&m. Fog oil was nebulizedin a controlled environment (chamber) where the absorption andextinction of the aerosol could be determined in situ. Aerosol densityand size distribution were concurrently measured. From the optical anddosimetry measurements, the mass normalized absorption and totalscattering coefficients were calculated.

2. A relative extinction profile was measured from 2.5 to approximately12,um by an IR scanning transmissometer (IRST). The aerosol densityand size distribution were determined.

The Mie calculations of the extinction efficiencies at 3.39 pm were basedon the previously measured aerosol size distributions and the referencedcomplex indices. Agreement with the photoacoustic portion of theexperiment was good and justified the method of normalizing the relativeextinction profile. The result is a continuous, absolute, extinction profileof the aerosol over the region of interest.

A series of Mie calculations spanning the larger range of 2.5 to 12 pm,using the measured size distribution and referenced indices of fog oil,provide comparison with the IRST results.

7

Page 9: IfTI · 2011. 5. 13. · 7. Relative extinction cross section as a function of radius for fog oil aerosol o . 22 8. Determination of complex index using Mie theory, effective radius,

3. Environmental Chamber for Measurements at 3.4 im

Fog oil was atomized in a small volume (0.07 mn) chamber by a De Vilbispharmaceutical nebulizer. A small fan established and maintained a nearlyuniform distribution of particles throughout the chamber. The stirringensured maintenance of the spatial distribution but was not vigorous enoughto significantly alter the size distribution. rhe photoacoustic systemcontinuously sampled from this plenum.

9

Page 10: IfTI · 2011. 5. 13. · 7. Relative extinction cross section as a function of radius for fog oil aerosol o . 22 8. Determination of complex index using Mie theory, effective radius,

4. Dosimetry and Size Characterization

Dosimetric measurements were made throughout each experiment to recordthe aerosol density as a function of time. A Gelman filter holder and filterwere inserted into a port projecting into the chamber. Gelman typeAE fiberglass filters with a 0.2-pum pore size were used. The volume flowrate (approximately 3 L/min) and the sample time were recorded. The flowrate and sample times were chosen to minimize disturbances and allowcollection of a measurable mass amount. The filters were weighed on aMettler precision balance. Typical mass samples were several milligramswith repeatability of 0.2 mg.

The size distribution for the chamber was characterized in a separate set ofmeasurements. Two types of particle spectrometers were used tocharacterize the distribution: (1) Particle Measuring System (PMS) modelASASP-X (0.07 < radius < 3 pm, with small orifice) and (2) CSASP-100(0.2 < radius < 16 pm). A typical size distribution measured in the fixedfrequency portion of this experiment is shown in figure 1. The numberdensity distribution with radius is very strongly peaked near a radius of0.1 pm, and few particles exceed a radius of 5.0 pm.

11

Page 11: IfTI · 2011. 5. 13. · 7. Relative extinction cross section as a function of radius for fog oil aerosol o . 22 8. Determination of complex index using Mie theory, effective radius,

1.E* 06

1.E* 05-/• t

lEO04EA

S1000.-

AA

U_ 100. A

>- A-J A

10.

A

1. A

A CSASP PROBE

A ASASP-X PROBE0. ....... ........ . ........ ..................

0.00 0.01 0.10 1.00 10.00 100.00

RADIUS (pm)

Figure 1. Typical size distribution for aerosol photoacousdc measurements.

12

Page 12: IfTI · 2011. 5. 13. · 7. Relative extinction cross section as a function of radius for fog oil aerosol o . 22 8. Determination of complex index using Mie theory, effective radius,

5. Photoacoustic Measurements

The photoacoustic and extinction measurements were made with a flow-through photoacoustic unit, described previously by Bruce and Pinnick [2]and Bruce and Richardson, [3] containing a 3.39 pm HeNe laser source,beam positioning optics and a modulator, a cylindrical acoustical cavitywith an isolating array of acoustic filters, and a detector.

The laser beam is directed down the axial center of the cavity by twopositioning mirrors (figure 2). The laser beam is modulated by amechanical tuning fork chopper at the fundamental longitudinal resonantfrequency of the acoustic cavity. The signal from the microphoneembedded centrally in the acoustic cavity wall is amplified with phase-sensitive circuitry. Kreutzer [4] and Trusty [5] show that this signal islinearl, proportional to the amount of energy absorbed by the aerosol. Theconsth., proportionality is repeatedly determined by a calibration gas(isopropyl alcohol for 3.4 ptm), for which the only significant attenuationis due to absorption.

WINDOW/,FLUSH -ACOUSTIC FILTERS ---

W AEROSOL1 RESONANT INNER

OUT CAVITY

DE"ECTOR

/ LASER TUBE

K-CHOPPER AND ELECTRONICS

BEAM TURNAROUND

Figure 2. Gas and aerosol spectrophone/transmissometer for 0.63, 1.1, or 3.4 pm.

The beam intensity is monitored by a detector at the opposite end of thecavity. The attenuation by the aerosol is used to calculate the extinctioncoefficient according to Beer's law, with a forward scattering correctionquantified by Deepak and Box. [6]

13

Page 13: IfTI · 2011. 5. 13. · 7. Relative extinction cross section as a function of radius for fog oil aerosol o . 22 8. Determination of complex index using Mie theory, effective radius,

Aerosol flow through the photoacoustical cavity is regulated and variesfrom 1 to 3 m/s. During measurement, a valve system alternately selectedfresh air and aerosol flow through the spectrophone. This wassystematically performed to monitor the unattenuated laser power andestablish an intensity baseline. After a uniform flow was achieved, thelaser power and spectrophone signal were recorded as a function of time.

From the photoacoustic portion of the experiment the absorption andextinction coefficients as a function of time (figure 3) were measured. Theshaded regions represent the dosimetric sampling time intervals. The logaverages were taken within the intervals to determine an associatedabsorption and extinction coefficient (via the absorption calibrationconstant). An aerosol density was computed for each interval on the basisof the mass samples obtained. Mass normalized efficiencies werecalculated from the absorption and extinction coefficients and the aerosoldensities at specific times. The forward scattering correction for themeasurement geometry and aerosol size distribution of figure 1 is notsignificant.

1000 NN 0 ABSORPTION (11ikm)

ja EXTINCTION (1lkm)

I

L!100 "C.)

U-

U,

0C.).

10. . . . .

0 510 lS20

TIME AFTER DISPERSION (min)

Figure 3. Time evolution of extinction and absorption coefficients.

14

Page 14: IfTI · 2011. 5. 13. · 7. Relative extinction cross section as a function of radius for fog oil aerosol o . 22 8. Determination of complex index using Mie theory, effective radius,

The average measured and calculated efficiencies at 3.39 &m are shown intable 1. The calculated values are obtained using equation (1) and themeasured density distribution.

=l d r r~r 1

JdN 4]w r3P,,dr

whereE = extinction coefficientp = aerosol density(-•) = number of particles per radius increment

ýZi

Qi = Mie coefficientPi = bulk density of the aerosol particle

Table 1. Fog oil attenuation efficiencies at 3.39 jm for the size distribution infigure 1

Measured Calculated

Absorption 0.483 ±0.03 0.401 ±0.06 (mz/g)

Total Scattering 0.887 ±0.05 0.809 ±0.12 (m/g)

The uncertainties given in table 1 are the one-sigma variations. Theuncertainties quoted for the calculated values are solely derived fromvariations in the size distribution. The measured absorption coefficient is17 percent higher than calculated, and the total scattering coefficient is9 percent higher than calculated. Both are within the respective propagateduncertainties, but it is likely (and is illustrated later in this report) that asignificant portion of the error results from an uncertainty in the imaginarycomponent of the index of refraction at 3.39 ptm.

15

Page 15: IfTI · 2011. 5. 13. · 7. Relative extinction cross section as a function of radius for fog oil aerosol o . 22 8. Determination of complex index using Mie theory, effective radius,

6. Spectrally Continuous Measurements

Spectrally continuous measurements were conducted in a larger (cubicmeter) chamber with two large fans (operating at controlled, reduced ratesof rotation) producing an aerosol circulation pattern. Two axial tubes,opposite each other across the center of the chamber, acted as thetransmission windows. Fog oil was nebulized in the same manner as thephotoacoustic measurements in an effort to produce a size distribution closeto that of the 0.07-m3 ch-imber. Three pharmaceutical nebulizers were usedto atomize the fog oil and produced a particle size distribution similar to thephotoacoustic measurement (figure 4). Because the size distributions forboth chambers indicate that nearly all the mass was attributable to particleswith radii above 0.1 pm (as illustrated in figure 7), the measured mass didnot require correction for filter pore size..

A 1000-K glow bar was used as an IR source. Radiation was collimatedand focused through the chamber and onto the IRST.

The IRST utilizes a continuously variable circular filter whose resolutiondepends on the wavelength and the filter quadrant. The wavelengthresolution, generally adequate for aerosol spectra, was just barely adequatefor this study at 1.3 percent of the 3.39-pm wavelength.

The filtered IR radiation was detected by a Mercury-Cadmium-Telluridedetector. The signal was amplified (1000X) and processed by an8085 microprocessor, and noise reduction schemes such as boxcarintegration were applied.

17

Page 16: IfTI · 2011. 5. 13. · 7. Relative extinction cross section as a function of radius for fog oil aerosol o . 22 8. Determination of complex index using Mie theory, effective radius,

A AA.

i.E~O04AA A 4

1000." A A

I~ AA

C~ 100."n- A A

Z

A A4

"-o A10.A

1. A

* PHOTOACOUSTIC MEASUREMENT (small chamber)* IR MEASUREMENT (1 cubic meter chamber)

0. -.... 1 1".. .I.. ........ . .. . - ,- , .0.0 0.1 1.0 10.0

RADIUS (unil

Figmre 4. Fog oil particle size distributions for the two chambers.

A relative extinction curve was computed from 2.5 to 4.0 tm using datameasured by the IRST. The curve was normalized to the measuredabsolute extinction efficiency at 3.39 Im.

Figure 5 shows a comparison of the calculated and measured (massnormalized) extinction coefficients for the large chamber.

18

Page 17: IfTI · 2011. 5. 13. · 7. Relative extinction cross section as a function of radius for fog oil aerosol o . 22 8. Determination of complex index using Mie theory, effective radius,

LUU,

W I,z

•- -.o

w€ --- IIN IMEASURIMFUdNT 1t melq~ u wml =

66

-aw - •CAMLU.AlrION

0 2.4 2.5 2.6 2.7 2.1 2.9 3.6 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.6 1

WAVELENGTH (pjm)

Figure 5. Comparison of calculated (Mi& theory) and experimental results.

The line laser absorption measurement falls within the strong adsorption

band indicated in figure 5. Structurally, this band results primarily fromsymmetric and asymmetric stretch bands of CH3 and Cl-H. Spectrapresented in Szymanski [71 show that the spectra of fog oil arecharacteristic of many hydrocarbons and other substances. The net form

is presumed to be a superposition of the contributions caused by the liquids

of the constituent molecules weighted by their relative occurrence in the

presence of the net liquid. Quantitatively, the problem is even more

complex than a superposition of the constituents.

It is presumed that discrepancies between the calculated and measuredcurves arose from uncertainties in the measured size distribution, noise in

the spectral measurements, uncertainties in the index measurements, andchemical differences between materials affecting the indices. Fog oil is aterm that describes a range of specifications for liquid hydrocarbons

identified in a report by Katz et al.; [8] therefore, actual indices may vary.

The previously discussed Mie calculations were expanded to include the

absorption efficiencies and were extended out to 12 Asm in the plots in

figure 6. The plots show that, for the aerosol size distribution produced(probably typical for fog oil), absorption is a minor contribution to the

19

Page 18: IfTI · 2011. 5. 13. · 7. Relative extinction cross section as a function of radius for fog oil aerosol o . 22 8. Determination of complex index using Mie theory, effective radius,

extinction in the IR, The absorption resonance in the vicinity of 3.4 pm forwhich the absorption is approximaely one-third of the total extinctionprovides the largest contribution.

10.00-- EXTINCTION

iii - ABSORPTION

LU

zC..)

U

ILw

z~.oo 01 - -_

US 0.01!

0

0.001 .... ......... I ......... P 1.... , ........ l ......... ....... ......... 1 ..... , ..... 1 1 .... 1 ......... ,2 3 4 i 6 7 8 9 10 11 12 13 14

WAVELENGTH (pm)}

Figure 6. Cacltdextinction and absorption spectra of fog off.

20

U

Page 19: IfTI · 2011. 5. 13. · 7. Relative extinction cross section as a function of radius for fog oil aerosol o . 22 8. Determination of complex index using Mie theory, effective radius,

7. Effective Radius of Fog Oil Particles

A rather useful and independent calculation was made to corroborate theexperimental results. The calculation involves a method of determining theradii of particles most representative relative to the extinction cross section.The approach is based on an analysis described by Bruce et al. [9] of thesettling properties by the time dependent decay of the extinction coefficient.The method considers the rate at which particles of a given size settle outof a well-mixed medium, which can be related to the aerosol aerodynamiccross section. The result yields the radius with the largest contribution tothe associated cross section (and through the form of time dependence cangive a measure of the size distribution breadth). Settling should not beconfused with diffusion, a much slower process for this size distribution.The effective radius was determined using equation (2).

- -=FxS (2)r

where

S 9 9(h XV)2 ,, x g)

S = slope of the optical coefficient versus timeh = settling height of the chamberV = viscosity of airg = acceleration due to gravity.

This calculation of the most representative radius was made for thephotoacoustic and the IRST measurements (because the size distributionswere slightly different) and the F values for the extinction cross sectionswere found to be 1.58 ±0.2 ;&m (photoacoustic, 0.07-mn chamber) and2.10 ±0.2 pm (IRST, 1.0-m3 chamber).

The f values were compared with the calculated cross sections for eachcase. The calculated radii correspond very well to the respective curvemaxima and further support the integration of the two experiments(figure 7).

21

Page 20: IfTI · 2011. 5. 13. · 7. Relative extinction cross section as a function of radius for fog oil aerosol o . 22 8. Determination of complex index using Mie theory, effective radius,

1.E*04 -

z0

U)U) 1- 1000..0 x dop"Z"0-W

r.4O

Z"C

Z U ioo.4

~o=

X'I

S~---- PHOTOACOUSTIC MEASUREMENT (small chamber)

.. j -.- IR MEASUREMENT (1 cubic meter chamber)uJ 10.- ' i • - •i• • " . . .I

w 0.1 0.5 1.0 S.0 10.0

RADIUS (prn)

Figure 7. Relative extinction cross section as a function of radius for fog oilaerosol.

22

Page 21: IfTI · 2011. 5. 13. · 7. Relative extinction cross section as a function of radius for fog oil aerosol o . 22 8. Determination of complex index using Mie theory, effective radius,

8. Inversion of the Mie Process to Determine ComplexIndex at 3.39 pm

Although the intent was to compare measured values of absorption and totalscattering with calculated values from the size distribution and thepreviously measured complex index, it would perhaps uake more sense toreverse the process and accurately determine the values of n and k by aniterative approach using the Mie theory. The inverse approach has beenused for several aerosols at various wavelengths and found it to stabilize forthe real and imaginary components when a substance exhibits significantabsorption and scattering.

Figure 8 illustrates the character of the inversion process for fog oil at3.39 jm using P as the effective particle radius. Selection of a unique pairof values is apparent for the range of indices. The components determinedare compared with the previously measured values in table 2. Use of thecomplete size distribution provides a more accurate determination, but theexample in table 2 illustrates the uniqueness of the result.

3.0"- , -

75

U 1.7 ---- - --- Scattering>, 1.5- ;

0S

-- .95 -------------------- ---- ----- -- Absorption

0.0 . . . .. •0.00 0.05 0.10 .123 0.15

Imaginary Index

Fiqgure 8. Determination of complex index using Mie theory, effective radius,measured absorption, and total scattering coeffients for fog oil. Mie theoryS oeffcients form an increasing progression as real index increases (for the family ofcurves) in increments of 0.15.

23

Page 22: IfTI · 2011. 5. 13. · 7. Relative extinction cross section as a function of radius for fog oil aerosol o . 22 8. Determination of complex index using Mie theory, effective radius,

Table 2. Complex index using the absorption and scattering efficiencies, effective

radius, and Mie theory as compared with those of Weg. [1]

N K

Calculated 1.425 0.125

Weng [1] 1.450 0.091

24

Page 23: IfTI · 2011. 5. 13. · 7. Relative extinction cross section as a function of radius for fog oil aerosol o . 22 8. Determination of complex index using Mie theory, effective radius,

9. Chemical and Optical Analysis of Similar Substances

Fog oil and several similar petroleum products were analyzed and anattempt was made to relate fog oil optical properties to the opticalproperties of other liquids possessing similar hydrocarbon structures.

A Fourier transform IR spectrometer determined the bulk absorptionprofiles of liquid fog oil, common diesel fuel, and kerosene. The threesubstances exhibited nearly identical absorption structure within the IR(figure 9a).

The chemical analysis of generic petroleum products is complex. Evenrelatively simple oils may be composed of many species. In the presentinvestigation, it was sufficient for comparison to characterize eachsubstance by its overall mass profile. Gas chromatography with massspectroscopy was employed for this procedure. Both the diesel fuel andkerosene had average mass peaks between the C12 and Cl4 hydrocarbons,and the less volatile fog oil processed a heavier average mass peak thatranged from C2 to C24 (figure 9b).

An excellent, thorough chemical characterization was conducted on severaldifferent varieties of fog oil by Katz et al. [8] A brief summary of theirresults follows:

The results show that fog oil consists of nearly pure hydrocarbons, withthe predominant structures being mixtures of aliphatic and aromaticcomponents in almost equal amounts. Also detected were smallamounts of alcohols, organic acids, and esters with very small traces oforganic nitrogen derivatives. The aliphatic hydrocarbons were in theC 12 to C2 range and the aromatics consisted of 1- through 4-memberrings, also within the same range. The results also show that all fogoils contained traces of copper and zinc, with copper near 40 ppb andzinc varying between 20 and 100 ppb. Densities ranged between 0.89and 0.93 g/ml.

A distinctive color change from clear, light yellow to dark brown overa 24-month period was noted.

25

Page 24: IfTI · 2011. 5. 13. · 7. Relative extinction cross section as a function of radius for fog oil aerosol o . 22 8. Determination of complex index using Mie theory, effective radius,

0 WA00

t4ft

0 7ow o

26m

Page 25: IfTI · 2011. 5. 13. · 7. Relative extinction cross section as a function of radius for fog oil aerosol o . 22 8. Determination of complex index using Mie theory, effective radius,

10. Comments on the Size Distribution

Measurements were carefully taken to to ensure that, while the medium waswell mixed, the size distribution was minimally perturbed in the samplingprocess.

The instrumental response function of the PMS light scattering counters tothe radii of the spherical particles is multivalued in the resonance region;therfore, several different sized particles can yield the same response.According to Pinnick and Auvermann, [10] the multivalued response cancreate an artificial ripple structure in the size distribution unless particlesare categorized in radius ranges designed to avoid causing an artificialripple structure. The reduction in resolution resulting from the adjustmentof radius size increments was not severe for the measured distributions offog oil.

27

Page 26: IfTI · 2011. 5. 13. · 7. Relative extinction cross section as a function of radius for fog oil aerosol o . 22 8. Determination of complex index using Mie theory, effective radius,

11. Summary

The absorption and total scattering efficiencies for fog oil aerosol weredetermined and compared with calculated values for given sizedistributions. After various parametric studies and analyses, it isconsidered that most of the uncertainty resides in the size distributions andthe indices (the calculated values).

The optical measurements were extended to a continuous wavelength spanin the vicinity of 3.39 Am by measuring extinction spectra. Absorptionspectra were not measured because available continuous sources do nothave sufficient power to drive the photoacoustical measurement.Normalization of the spectrum using the laser result gains credibilitybecause the calculated values are in reasonable agreement with the form ofthe extinction spectrum and with the absorption and extinction values at thelaser line wavelength.

Indicating similarity of optical properties for related liquid hydrocarbonswas of interest and was investigated here only for the bulk materials, butthe absorption spectra near 3.39 jm were found to be similar for the threesubstances (liquid fog oil, common diesel fuel, and kerosene).

The measured size distribution was, to a degree, substantiated by agreementwith the independent settling theory calculations. The calculation of theeffective radius for an optical coefficient agreed well with the peak radiusfor each distribution and indicated the narrow breadth of the distributionthrough the small curvature of the semilog plot showing decay of the opticalcoefficient with time.

The effective radius and the coefficients provided a basis for an independentand accurate determination of the complex index at the line laserwavelength.

29

Page 27: IfTI · 2011. 5. 13. · 7. Relative extinction cross section as a function of radius for fog oil aerosol o . 22 8. Determination of complex index using Mie theory, effective radius,

References

1. Weng, S., Complex Refractive Indices of Selected Liquids,Master's Thesis, University of Missouri-Kansas City, pp 139-140,1987.

2. Bruce, C. W. and R. G. Pinnick, Appl Opt, 16:1762-1764, 1977.

3. Bruce, C. W. and N. M. Richardson, Appl Opt, 22:1051-1055,1983.

4. Kreutzer, L. B., J. Appl. Phys., 42:2934-2943, 1971.

5. Trusty, G. L., Absorption Measurements of the 10 pjm RegionUsing a C0 2 Laser and a Spectrophone. Ph.D. dissertation,University of Ohio, 1973.

6. Deepak, A. and M. A. Box, Appl Opt, 17:2900-2909, 1978.

7. Szymanski, H. A., I.R. Theory and Practice of InfraredSpectroscopy, Consultants Bureau Enterprises, Inc., New York,NY, 1964.

8. Katz, S., A. Snelson, and R. Butler, Physical and ChemicalCharacterization of Military Smokes (part 2), Report No.A093205, U.S. Army Medical Research and DevelopmentCommand, Fort Detrick, Frederick, MD, 1980.

9. Bruce, C. W.. D. Kalinowski, and D. R. Ashmore, AerosolScience and Technology, 12:1031-1035, 1990.

10. Pinnick, R. G. and H. J. Auvermann, J. Aerosol Sci., 10:55-74,1979.

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Acronyms and Abbreviations

IR infrared

IRST infrared scanning transmissometer

PMS Particle Measuring System

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Record Copy 3

Total. 89

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