S. C. Jennings Vol. 71, No. 8/August 1981/J. Opt. Soc. Am.

923

Attenuated total reflectance measurements of the

complex refractive index
of polystyrene latex at CO2 laser wavelengths

S. G. Jennings

Department of Physics, University College, Galway, Ireland

Received January 24, 1981

Attenuated total reflectance (ATR) measurements of the complex refractive index m of 5, 10,15, 20, and 30% water
suspensions of polystyrene latex are presented for CO2 laser wavelengths (measurements for the 30%suspension
are for X =10.591 ,um only). The use of the Maxwell Garnet mixture rule for the real index and the imaginary index
(at X = 9.305 ,um) and an extrapolation scheme for the remaining values of imaginary index yield the values m =
1.709 - 0.07i (X = 9.305 ,tm); m = 1.887 - 0.06i (X = 9.504 Arm);m = 1.705 - 0.04i (X = 9.694 ,um); m = 1.764 -
0.045i (X = 10.591 ,um). ATR measurements of the complex index of water and water-ammonium sulfate solutions
are in reasonably good agreement with those previously published.

INTRODUCTION DETERMINATION OF COMPLEX REFRACTIVE

The use of the attenuated total reflectance (ATR) technique INDEX FROM ATTENUATED TOTAL
for determining the complex refractive index was first de- REFLECTANCE MEASUREMENTS
scribed by Fahrenfort.1 More detail on the theory, instru- The ATR technique is based on a reflectivity measurement.
2
mentation, and applications of ATR is given by Harrick. Since the intensity of radiation reflected at a surface is a
Early users of the technique include Fahrenfort and Visser,3 function of the real and imaginary indices of refraction n and
who measured the optical constants of liquid benzene in the k, respectively, of the reflecting medium and the incident
9.25-10-ym wavelength band; Hansen, 4 who determined op- angle 6, measurement of the reflectivity at two angles of in-
tical constants of gold film and aqueous solutions of eosin B cidence is sufficient to determine the complex index of re-
dye in the 0.4-0.65-gm spectral region; and Gilby et al., 5' 6 who fraction m, where m = n - ik. A combination of Fresnel's
obtained optical constants of liquid chloroform and carbon reflectivity formula and Snellius's law gives the expression for
tetrachloride in the 12-14.3-gm band and liquid benzene in the ratio of the reflected and incident amplitudes of perpen-
the wavelength regions 8.8-11.5 and 13.6-16.4 gim. dicularly polarized radiation r,
In this work a goniometric ATR arrangement was utilized
that employed a CO 2 laser to determine the optical constants 2
s-(M-Sin
0)1/2 + COS0
of several aerosolconstituents. In this paper the experimental r ( 2
- 2
sin 0)1/2 + COS0
details and alignment procedures are described, and the
performance of the system with air, water, and ammonium
The reflectivity R3, given by Irs 12, is
sulfate solutions used as media is assessed. Then refrac-
tive-index measurements are presented for suspensions (5-
20% by weight) of polystyrene, and use is made of the Maxwell a2 +b2 -2acos0+cos2 0 ,
Mn
Garnet mixture rule and an extrapolation scheme (for three a 2 + b 2 + 2a cos 0 + cos2 0
of the imaginary index values) to derive from the suspension
values the refractive index of polystyrene at CO2 laser wave- where m cos 0 = a - ib. Equation (1) has been explicitly
lengths. solved3 to yield solutions for n and k. The solution requires
It should be pointed out that it is better to use bulk material a measurement of the reflectivity at two angles of incidence,
when it is available to obtain the refractive index directly by one of which must exceed the critical angle. The use of this
either reflection or transmission techniques. The method of analytical solution greatly simplifiesthe determination of the
obtaining refractive-index values from measurements on complex refractive index compared with the use of the
suspensions of particles must be used with extreme caution graphical method first employed by Simon. 7 In this work the
since the inference of index values from measurements on analytical solution was programmed on a HP 9830 desk-top
particles can in general be rather precarious. calculator.

0030-3941/81/080923-05$00.50 © 1981 Optical Society of America

924 J. Opt. Soc. Am./Vol. 71, No. 8/August 1981 S. C. Jennings

The light is refocused at the same distance from the surface

'TER
_SAMPLE
HEMICYLINDER
Fig. 1. Schematic diagram of the attenuated total reflectance ex-
perimental system.
ATTENUATED TOTAL REFLECTANCE SYSTEM
The ATR system is shown schematically in Fig. 1. It consists
of a tunable vertically polarized CO 2 laser source (Sylvania
Model 950) and a sample cell and a ZnSe hemicylinder
mounted on a rotation stage, together with a pyroelectric
detector mounted on a rotatable arm. All apparatus is
mounted on an optical bench for stability. The advantages
of the laser source are its relative ease of alignment and col-
limation and the capability of the user to control and monitor
precisely the radiation wavelength (with the laser spectrum
analyzer). Alignment is accomplished with aluminized mir-
rors M1 and M2 , which are mounted on micrometer-controlled
translational stages. A portion of the CO 2 laser beam is re-
flected by a ZnSe window (positioned at about 780 from the
laser-beam direction in order to minimize the loss of radiation
power) for a laser reference signal. The main beam and ref-
erence detector (Laser Precision Corporation Model RKP-
when it reelierges froii tile hemiicylinder into the pyrocloctric
detector. Collimation within the hemicylinder has the ad-
vantage that the angle of incidence is well defined, which is
particularly important for the measurement of the complex
refractive index.
A schematic and a photograph of the rotatable arm and
hemicylinder mount assemblies are shown in Figs. 2 and 3,
respectively. The arm assembly consists of a rotatable arm
for mounting of the radiation detector, a counterweight, and
a 15-cm-diameter turntable assembly. The turntable as-
sembly possesses a central column that supports an x-y
translational stage giving fine control (displacements
measureable to 0.01 mm) in horizontal positioning.
The sample cell is made from a single solid block of stainless
steel with a protruding central rod that fits snugly into the
lowersupport plate. For measurement of liquids the cell has
a capacity of a few cubic centimeters and has two Luer-Lok
connectors that facilitate filling.
II'll \I IS 'l-l
, XI( TzX
%A,,.
M\151 I 1 SIIA
IIl0

345) has negligible drift (about 10-6 W cm- 2 after warm-up)

I \,>: I(R IJIK
%5 %5111t
\ I

compared with typical radiance levels monitored by the de-

tector (of the order of 0.25 W cm- 2 ).
The internal-reflection element used in this ATR setup is
a precision-machined ZnSe hemicylinder that is transparent
at the wavelengths of interest. The hemicylinder concept was
first used in ATR by Fahrenfort 2 and provides for change in
Fig. 2. Schematic diagram of the goniometric assembly of rotatable
angle without directional changes of the incident or the re- arm, rotation stage, and hemicylinder mount.
flected beam. The sample to be measured is placed in contact
with the flat face of the hemicylinder, and the cylindrical
surface then acts as entrance and exit window. The hemi-
cylinder must of course be carefully aligned so that its axis is
perpendicular to the laser-beam direction. The laser beam
is brought into focus at a distance

Id= r
nc - I
in front of the curved surface (as shown by Fahrenfortl) to
render the light parallel within the hemicylinder. Here r is
the radius of the hemicylinder and n, is the real index of the
hemicylinder material. [Refractive-index values for ZnSe
were derived from the Herzberger dispersion equation

° =no+b + dX2 +eX4

+-0C (3)
X2 - 0.028 (X2 - 0.028)2

Fig. 3. Photograph of the goniometric attenuated total reflectance

with coefficient values 8 since corrected: no = 2.4350823, b system showing the rotatable arm and rotation stage assembly, the
= 5.1567572 X 10-2, c = 2.4901923 X 10-3, d = 2.7245212 X hemicylinder and focusing lens mountings, and the pyroelectric de-
10-4, and e = -9.8541275 X 10-8.] tector.
 S. C. Jennings Vol. 71, No. 8/August 1981/J. Opt. Soc. Am. 925

°00 each of four incident angles 01, 02, 03, 04 and one repeated
measurement of 01 with air as the reference medium, followed
by measurements in reverse order with the sample in the cell,
90O followedby a repeat of the measurements with the empty cell
(which was dried out with a flow of liquid nitrogen). The real
and imaginary indices were then derived by averaging the
,80 values obtained from each set of two angle measurements of
reflectivity. The standard error of this average value was also
evaluated. In some instances (for X = 10.591 Am) more than
-j 70
tLI one sequence of measurements were made for a particular
A:

liquid or solution and then a combined weighted average was

60[ taken. All measurements were carried out at a room tem-
perature of 24 ± 10 C.

50 23 24 25 26 INDEX MEASUREMENTS OF WATER AND

INCIDENCE ANGLE (DEGREES)
Fig. 4. Reflectivity at an air-ZnSe interface at wavelength 10.494
Aim. i, experimental measurements; -theoretical curve.
ATTENUATED TOTAL REFLECTANCE
ALIGNMENT SYSTEM
Since the validity of the complex refractive-index-reflectivity
formula [Eq. (2)] depends on the ATR system's being properly
aligned, considerable effort was made to align the system
precisely and to test its alignment stringently. The longitu-
dinal axis of the hemicylinder and the rotational axis of the
goniometric system were first made to coincide. The align-
ment was facilitated by use of a visible He-Ne laser (shown
schematically in Fig. 1) mounted on a two-axis pitch-and-yaw
support. The infrared beam from a similarly mounted CO2
laser was then positioned relative to the He-Ne beam by
means of a probe having IR-sensitive phosphors.
It turns out that a rather stringent test of the ATR system
alignment can be performed by measurement of reflectivity
with air as the sample medium for angles near the critical
angle. This check for our system is shown in Fig. 4, in which
predicted and measured reflectivities are compared. The
theory predicts a sharp change in reflectivity near the critical
angle (which is 24035' for the ZnSe-air interface at this par-
ticular wavelength, X = 10.494 Am), and this sharp change is
borne out by the measurements. The close agreement
suggests that a high degree of alignment has been obtained.
EXPERIMENTAL PROCEDURE
The ATR method requires at least two measurements of re-
flectivity at different angles for determination of the complex
(real and imaginary parts) index of refraction. In order that
measurement repeatability could be checked, the normal se-
quence consisted of at least two reflectivity measurements at
AMMONIUM SULFATE SOLUTIONS
In order to gain confidence with the ATR system, we made
measurements initially on liquids whose refractive indices
were previously measured by other techniques. Water and
ammonium sulfate solutions were chosen for these checks.
Water used was triply distilled,9 with any ammonia or
carbon dioxide removed, the final sample being stored under
argon. Values for the real and imaginary indices determined
at wavelengths X = 9.603, X = 10.195, and X = 10.494 gm are
shown in Table 1. They compare well (within 1% for the real
part and within 20%for the imaginary part) with interpolated
values from Hale and Querry,' 0 who smoothed data of several
workers.
Ammonium sulfate solutions were prepared from finely
ground ammonium sulfate powder, and their molality was
determined gravimetrically. The ATR-determined optical
constants at wavelengths 9.317 and 9.519 Am are shown in
Table 2. The values are in reasonable agreement (within
about 5% for the real index and within about 35% for the
imaginary index) with values interpolated from Downing et
al. ,1' who employed Kramers-Kronig analysis of reflectance
measurements obtained relative to water at near-normal in-
cidence.
REFRACTIVE INDICES OF POLYSTYRENE
LATEX
Latex particles are becoming widely used for calibration of
optical instruments. However, their usefulness for calibration
of infrared devices is limited because their optical constants
at IR wavelengths have not been measured. In this section
we partially fill this data gap by presenting refractive indices
of polystyrene latex suspensions measured by ATR. These
values are extrapolated to 100% latex by using a suitable
mixture rule.

Table 1. Complex Refractive Index for Water

ATR (Present Work) Interpolated from Hale and Quarrya
Wavelength Real Index Imaginary Index Real Index Imaginary Index
(ym) Incident Angles (n) (k) (n) (k)
9.603 27030', 300, 32030', 350, 40° 1.230 + 0.002 0.054 ± 0.001 1.239 0.045
10.195 27030', 30°, 32030' 1.193 ± 0.008 0.059 ± 0.007 1.202 0.059
10.494 27030', 300, 32030', 350 1.196 + 0.014 0.075 + 0.007 1.185 0.066

a Ref. 10.
926 J. Opt. Soc. Am./Vol. 71, No. 8/August 1981 S. C. Jennings

Table 2. Complex Refraction Index for (NI14 )2SO4 SOlutioS

Interpolated Values from
ATR (Present Work) Downing et al. a
(NH4),S0 4 Wavelength Incident Real Index Imaginary Index Real Index Imaginary Index
Solution (rm) Angles (n) (k) (n) (k)
1.6 M (NH,)2SO 4 9.519 32030', 350, 37°30', 40° 1.411 ± 0.003 0.084 + 0.002 - -
2.4 M (NH 4),S0 4 9.519 42030', 450, 47°30', 50° 1.472 ± 0.003 0.126 i 0.003 1.541 0.153
3.2 M (NH 4 )2 504 9.519 42030', 450, 47°30', 500 1.545 + 0.002 0.129 + 0.002 1.642 0.164
1.6 M (NH 4 )2SO4 9.317 350, 37.30', 42°30' 1.500 + 0.002 0.139 + 0.003 - -
2.4 M (NH 4 )2 S04 9.317 350, 40°, 450, 500 1.560 ± 0.005 0.229 i 0.007 1.543 0.317
3.2 M (NH 4 ) 2 SO4 9.317 40°, 450, 47030', 500 1.605 ± 0.012 0.268 + 0.015 1.65 0.38

a Ref. 11.

Table 3. Complex Refractive Index of Polystyrene Suspensions

Wave- Index of
length Refrac- Percent by Weight Incident
(pm) tiona 30 20 15 10 5 Angles
9.305 n - 1.326 4 0.009 1.311 + 0.009 1.291 i C.003 1.275 + 0.003 25035', 30°
k - 0.041 ± 0.005 0.047± 0.001 0.044 + 0.003 0.037 + 0.001 33024' 350
9.504 n - 1.321 + 0.004 1.320 ± 0.003 1.304 ± 0.001 1.282 ± 0.003 25035', 300
k - 0.038 i 0.004 0.035 I 0.001 0.031 i 0.002 0.033 a 0.002 33024', 350
9.694 n - 1.317 + 0.002 1.296 I 0.003 1.278 + 0.006 1.253 ± 0.004 25035', 300
k - 0.035 + 0.001 0.037 ± 0.002 0.043 + 0.004 0.043 i 0.006 33024', 350
10.591 n 1.326 + 0.004 1.282 + 0.003 (5)b 1.266 ± 0.004 (3 )b 1.228 + 0.003 (4 )b 1.212 ± 0.004 ( 2 }b 220, 26045'
k 0.051 + 0.002 0.048 + 0.001 0.047 + 0.002 0.051 + 0.003 0.051 + 0.009 30°30', 32030', 350

a n, Real index of refraction; k, imaginary index of refraction.

b Number in parentheses indicates the number of different measurement runs.

Latex particles (purchased from Dow Chemical, Midland, Ie21 C Ell JE21
Michigan) with mean diameter 0.091 Azmwere used in sus-
pensions ranging from 5 to 30%by weight. The ATR refrac- E12 C e1l+ 02E2, (5)
tive-index measurements for these suspensions are presented from which it followsthat
in Table 3, together with error estimates and angles of inci-
dence used. The major source of error was that resulting from ;M12 Xb m
1 + 02m 2 , (6)
laser-power fluctuations, despite the fact that the fluctuations where M12 , m1 , and m 2 are the complex refractive indices of
were monitored; errors in reflectivity over a complete run the suspension and its components and
sequence were generally less than 1%. Experimental errors
in reflectivity result in much larger errors in the imaginary 01=f, 02= l - f.
index k than in the real index n. On equating real and imaginary parts, we obtain
Extrapolation of the refractive indices of latex suspensions
to that for pure latex requires a so-called mixture rule. The n12 = nifl + n202, (7a)
more-well-known mixture rules, such as those of Maxwell k12 = k,10 + k 2 02- (7b)
Garnet and Lorentz-Lorenz, have received a fair degree of
attention. Equation (7a) is the Biot-Arago rule, which historically is
Maxwell Garnet'2 derived, on the basis of Maxwell's referred to as being empirical. Use was not made of the Lo-
equations, the following mixture rule for a suspension of rentz-Lorenz mixture rule' 3 later generalized by Debye,14
spheres embedded in a medium, provided that the sphere size since it is correctly applicable only to mixtures of solutions
is small compared with the wavelength: rather than to suspensions.
In this work, we use the Maxwell Garnet mixture rule [Eq.
1 1+ 3/(el - E2) E (4) (4)] to infer the complex index of polystyrene latex from the
El+ 22-f(El OI suspension values. The inferred values are presented in Table
Here, E12, el, and 62 are the dielectric functions of the sus- 4. It was not possible to use the Maxwell Garnet formula to
pension and its components and f is the volume fraction of the obtain the imaginary index for latex at wavelengths 9.504,
material suspended in the medium. 9.694, and 10.591Amsince the particular combination of the
A simplification in the Maxwell Garnet formula [Eq. (4)] large (relative to the measured suspension values) imaginary
follows if index values of the medium (water), coupled with the range
S. C. Jennings
Table 4. Complex Refractive Index of Polystyrene
Latex a Inferred from Suspension Values of Table 3
Measured by Attenuated Total Reflectance
Real Index (n) from Imaginary Index (k) from
Wavelength Use of Maxwell Garnet Use of Maxwell Garnet
(,vm) Mixture Rule [Eq. (4)] Mixture Rule [Eq. (4)]
9.305 1.709 ± 0.017 0.070 i 0.012
9.504 1.887 d 0.017 0.060 0.012b
9.694 1.705 ± 0.011 0.040 i 0 . 00 5 b
10.591 1.764 i 0.021 0.045 i.+19b
a The inferred values of polystyrene latex assume a density of 1.05g cm- 3
for polystyrene latex and neglect the small fraction (0.7%)of emulsifier and
surfactant impurities in the latex suspensions.
b An extrapolation procedure using a least-squares one-degree polynomial
fit was used.
of volume fractions used, yielded negative imaginary index
values for the polystyrene. This can be readily seen by
applying the values in Table 3 to Eq. 7(b)-an approximation
to Eq. (4). This may be interpreted physically, whereby the
latex is less absorbing than the medium (water) at these
wavelengths. An extrapolation procedure to 100%polysty-
rene, using the imaginary index values of the different poly-
styrene suspensions, was carried out using a least-squares
one-degree polynomial fit. A least-squares fit was also ap-
plied to the maximum and minimum values of the mixture
indices, which gives the error bars of the extrapolated values.
Relatively large fractional errors are associated with the
imaginary index values because the suspension' indices possess
fractional standard errors up to about 15%.
We are fully justified in using the Maxwell Garnet formula
here since the particle size is much less than the radiation
wavelength. In addition, the particles are spherical. The
justification for the use of the extrapolation scheme is weaker
and could be regarded with some caution. However, it is
noteworthy that application of the extrapolation scheme to
ATR measurements of ammonium sulfate solutions (see Table
2) does lead to imaginary index values of ammonium sulfate
that are in good agreement (within 6%) with previously mea-
sured values' 5 even in spectral regions of absorption bands.
CONCLUSIONS
An attenuated total reflectance goniometric system has been
applied to measurement of complex refractive indices of
aerosol constituents at CO2 laser wavelengths. The reliability
of the system is demonstrated by the good agreement between
measured refractive indices of water and ammonium sulfate
solutions and previously reported values. Complex refrac-
tive-index measurements are presented for water-polystyrene
latex suspensions, and these measurements are used in a
suitable mixture rule formula to infer index values for poly-
styrene latex. These refractive-index determinations for
polystyrene should facilitate the calibration and performance
evaluation of infrared transmissiometers, spectrophones, and
scattering instruments.
Vol. 71, No. 8/August 1981/J. Opt. Soc. Am. 927
The author is grateful to R. G. Pinnick for his original
suggestion to measure the complex refractive index for poly-
styrene and for a careful critical review of the manuscript.
The author also extends his appreciation to his other sci-
entific colleagues and the managerial personnel at the U.S.
Army Atmospheric Sciences Laboratory, White Sands Missile
Range, New Mexico 88002, for their cooperation and support
throughout all phases of the work at the laboratory.
The supply of raw data of the complex refractive index of
2.4 M and 3.2 M (NH4 )2SO4 solutions by Dudley Williams,
Department of Physics, Kansas State University, Manhattan,
Kansas 66506, is also appreciated.
This work was supported by means of a research contract
with the U.S. government through its European Research
Office, London. The experimental work was performed at
the U.S. Army Atmospheric Sciences Laboratory, White
Sands Missile Range, New Mexico 88002.
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