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Numerous treatments of the diffuse r eflecting properties of scattering media have been
d escribed. Many theories give an adequate account of the refl ectance for a specific set of
conditions for which the model was constructed and the soluti on t ested experimentally.
Only those models which are considered to be fairl y general are considered her e.
It is conveni ent to di vide the theories into those based upon continuum models and
those based upon s tatistical models. The continuum m odels typica ll y describ e the scatterin g
a nd absorbin g properti es of a given m edium in t erm s of two phenomenological constants.
These models may all be regarded as varying levels of approxima t e soluti on to the general
equation of radi ative tra nsfer. This provides a convenient basis for compariso n of the various
theories.
The statistical models a re based upon a summ a tion of transmittances a nd r efl ectances
fr om individual l ayers or parti cles. Thus, ~o m e ass um ptions must be m ade abo ut the n ature
of the fund amenta l units, and the validity of the ultim a te result will depend up on how closely
these assumptions correspond with r eality. Only the statistical models lead to ex pressions
fr om which absolute absorptivities and sca ttering coefficients can be calculat ed and r elated
to the actual particle characteristics.
The relationship between the various models will be discussed and the features which
typify the ab~o rptivity and scatterin g coeffici ent accordin g to each will be compared an d related to the available experimental data. This leads t o a consideration of the charac teristics
of appropri ate model systems and standards.
Key words: Absolute absorptivities; continuum models; diffuse reflectance; r adiative transfer; reflectance spectra; scatt ering coefficients ; statistical models.
radiant intensity
component of source function for selfradiation (equation (5))
scattering function (equation (2))
source func tion (eq ua tion (4))
absorptivity
Kubelka-Munk absorption constant
(equations (16) and (17))
Attenuation constants in Gurevic layer
model (equations (10) and (11))
r.article diameter or layer thickness
'free" path length of Antonov-Romanovsky (equation (58))
Gurevic constant=~K22 _K12
mean number of reflections
transmittance of a particle for a single
pass
radiant flux density
phase function (equation (2))
Legendre polynomial
Rozenberg constant (equation (29))
Rozenberg multiple r eflection constant
(equation (26))
(35) )
H(iJ.)
['
J
S~K (equation
(18))
567
214-427 0 - 76 - 2
r*
!!'"
s
x
y
a
(3
'Y
~
()
K
p
a
T
rP
q,.
Wo
I.
Introduction
It is now recognized that diffuse reflectance spectroscopy is a very useful companion technique to
transmission spectroscopy. Not only can it provide
absorption data in some cases where transmission
measurements fail, but for many industrial and research applications, it may in fact be the preferred
technique.
568
Figures in brackets indicate the literature references at the end of this paper.
dI = -KpIdx+jpdx
j(e, CP)=47r Jo
II.
(1)
Jo
Continuum Theory
J.L,
cp ) - J( T,
J.L,
A.)
'I'
(4)
569
d1i~; )
+~
471"
tt {
("
-Kii j(O, )
(2" p(O, ; 0', ')lj (O', ') sin 0' do' d' }
Jo Jo
+1/(0, cf.
(5)
T/R j
R Hj =R i +1_RR
,
.1
(9)
A model in which the scattering medium is approximated by plane-parallel layers has been used
by numerous workers as a basis for reflectance
theory [7, 8]. We consider a pair of adjacent layers,
with Ri R j and Ti,Tj as the reflectances and transmittanc~s for radiation incident in one direction,
and RI RJ and T I , TJ as the reflectances and transmittan~es for radiation incident in the other
direction.
If the incident beam is of unit intensity, then the
portion Ri is reflected and the portion Ti transmit~ed
by the first layer. At the .second l::yer the portIOn
TiR} is reflected and T/!'j IS transmI~ted. The beam
TiRj strikes the undersIde o~ layer'/, where 'fiRjT/
is transmitted, while T iR jR/ IS reflected. Contmumg
this process indefinitely (see fig. 1) we find that. the
transmittance and reflectance of the combmed
layers are given by
(10)
Similarly we write
T(dx) = 1- K 2dx.
(11 )
(8)
l-R i R j
dR
.. )
K JT 2dx
and
TiTj
T i+ j =I_R/R j
(6)
R
TiT/R j
R i + j= i+l-R/R j
(7)
Integrating this set of coupled di~~rential equations subject to the boundary condItIOns R(O) =0,
T(O) =1 gives
(12)
-Lx
(13)
Xi
R =K2-L=K2-.,JK22_KJ2
KJ
KJ
-.L
(14)
co
~~~~~":":T
while L is given by
(15)
FIGURE
570
--'
to be a special case of the more general KubelkaMunk theory [21], which we will now consider.
B.
(16)
(17)
(18)
we can write
-d1+
Sdx = -a1++L
where R== L /1+. Equation (19) can be easily integrated over the entire thickness x of the scat tering
medium to obtain [5]
l '. '.'
FIGURE
Rozenberg Solutions
~~~=-aL+1+
-----------------------------
(2 1)
00
In this case
e and
(1+,6)1
(23)
X~X
571
(24)
D.
Exact Solutions
p(J,cp;(J'Cp')= wo=-+ .
(25)
IJ'
Q=l+-
r+t
>
1, Rozenberg
f(
r, p.
-2'1 Wo
f +1f ( r,
-1
iJ.
')d'
iJ..
(31)
(32)
and
iJ.]
Pn(iJ.).
(28)
df( r, p.)
dr
The integral occurring in eq (31) may be approximated by a Gaussian quadrature, in which case a
set of coupled linear differential equations is obtained,
(27)
(30)
(34)
572
(36)
~ WI PI (cos
8)
/=0
(1- p.)u
(38)
Statistical Theory
(40)
and
=1'
rl.2.3 . . . . n
+1-t
I
n~
00 ,
2r
2.3.4 .. . n
r lr2.3.4 ... n
we write
where
t2R
R.,=r+ 1
-J.I.
(39)
(41)
_rR
(42)
co
This equation is fundamental to essentially all statistical theories, the only difference being in the
method used to calculate l' and t.
573
A.
d1 +"'(/+);+1-(/+) i
dx
dL",(L);+I-(LL
(IX
l
(K+8) (L);+1-8(1+);
+ (1 -1'oFro5e-6kl+ . ..
(46)
R =(L)I=(L);+1
00
(1+)1
(/+)1+1
R",=
2(8+K-Kl8-K2l/2)
(49)
(50)
8=1'/1
K=(l-1'-t) / I=a/1
ro
(1 )
2
K21
F(R )=-K -K-= a --1 - -a .
8
28
l'
21'
(48)
00
FIGURE
574
chosen for study, but in the gen eral case, Roo is a very
sensitive function of To.
Bauer [43] showed that in some cases the layers
should be considered to have rou gh surfaces where
total internal refiection can take place, and he has
derived expressions analogous to eqs (49) and (50)
for this case.
B.
1+1 .
.J.
241ol6To+STo+ ...
(56)
Johnson [44] h as carried out the summation somewhat differently than B od6, but with quite similar
results (see fig 4). It is assumed that there are p
layers and that the mean number of attenuating
refiections which the rays undergo in the 2p traversals is yp, so that the r efiectance is given by
Rp=To+2ToL::; (1-To)V1' exp ( -2kpl ).
(5 1)
P
Thus y can be regarded as an adjustable parameter
which gives a semi-empirical account of multiple
r efl ections as well as scattering losses. The sum for
an infmite number of layers is
- +2
R ",To
To
(52)
from which y = 2 is seen to be a satisfactory approximation for refr active indices smaller than 1.5. A
smaller value of y is required for larger refractive
indices. Companion and Winslow [43] have used a
model similar to Johnson's, bu t which includes all
multiple reflections. The summation was carried ou t
by compu ter and no explicit expression for the reflectance was given by these workers.
Johnson [441 also suggested that To be equated to
1.5 times the normal Fresnel reflectance. This is
meant to account for the random distribution of
particle surfaces and corresponds with an average
incidence angle of approximately 30. It was shown
[44] that eq (55) yields absorption coefficien ts for
KCl :Tl, KBr :TI, and didymium glass which agree
satisfactorily with those obtained by tr ansmission
measurements of the same materials.
C.
(53)
(54)
(55)
This result could also be obtained directly by in tegration of eq (5 1), which suggests that it may in fact
be a more realistic representation of a real sample
whose particles actually have a range of diameters.
. . . " ...
. . . ' . . , .. .
Antonov-Romanovsky [22] has developed expreswhich. can be used to calculate the true absorptIOn coefficlent from reflectance measurements by
connecting the Kubelka-Munk and B od6 th eories .
Antonov-Romanovsky treats two limiting cases of
r egul arly -shaped sample particles, spher es and parallelepipeds (see fig. 5) .
For spherical particles the radiation impinges on
the surface from within at th e same angle that i t
entered the particle, since the angles which the cord
of a circle makes with respect to th e surface normal
must be the same. Therefore, total in ternal r eflection
is impossible, and l will approximate the p article
diameter, l , actually being somewhat smaller.
In the case of t he parallelepiped, some total
internal reflection is possible, but most radiation
probably exits through an opposite face without
further reflection. In this case also it is obvious that l
s~ons
,'.
T
.
'
. .. . .
. .. ' .
',
,'
"
'
FIGURE
",
....;
",
FIGURE
575
2l
(57)
(l-ro)2-2roF(Roo)
<
(60)
Ao AoR.
AoR.Q
(61)
(62)
FIGURE
(63)
'\
'\
k=2 ln
Titl
D.
(l-ro)2-(1 -ro)F(Roo).
(l-ro)2-2roF(R..,)
'\
'\
(64)
FIGURE
576
Proceedin g in this manner we can write the following expressions for the reflectance and transmit tance
of a layer for radiation from outside (1'1, t l ) and
inside h, tI ) the sample:
1\=2ur e+(1-2ur e)ut
(65)
e+ (l-r e) (l-u)t
(66)
rI =r
(67)
(68)
Uo
E.
(70)
1-(1- 2u o)t
(75)
(76)
F(R)
where
2
(kl)2 [1-(kl+1 ) exp ( -kl)
00
(72)
(78)
r.
('r/2
('0'
odo
(73)
(74)
577
1-t
a=--
1-u,t
(79)
Uu +ud +u s =l.
(84)
~-1+2uo(1-rl)
III
(80)
-~ kl}
cJ>e=(7rl 2/2)
(8 1)
(86)
(7rl 2Me/ 2 )
1"
(87)
rt
2re
(1- r e)2
(83)
,,/2
and
J"
R=[I-(2a-a2)1 /2]/(1-a).
(82)
2uo(1-ri) (1 +re)
(1-re)2
kl=2 'YF(Ra,).
(7I"l2/2)
(85)
where
Jo
r,,/2
(7I"l2/2)
(88)
578
(89)
a= (l-r e)2kl/3
1-r i+2klrd3
l - r e 2kl.
l-r / 3
R= 1
(90)
(92)
(91)
(93)
(94)
IV.
2a
u+a
u+a
S= - - and K = - -
Thus the Kubelka-Munk function may be regarded
as a first approximation to the complete solution for
the equation of rad iative transfer. D etailed comparisons show that the two solutions differ by no more
579
L= (a 2 -1)1/2S=bS
l~dx<Kz
Sx=~
l-r
(96)
(97)
2 zl-r.
-n
-3 l+r.
(98)
580
b
T t (a sinh bSX+b cosh bSX)
J{ l-ro
JC=I+ro'
and
T i = exp (-J{X).
where aI+/aO is the angular distribution of the intensity in the positive x direction. We of course have
an analogous expression for the L componen t. If
we assume that the medium is an ideal diffuser the
intensity is the same in all directions, and the angular
Sc
J{
JC
581
1
n2
3uo (l-r e)
1-r*-~
a-(2ft-1)(1-a)
1+r*+~+(2:j -1)(1- )
l+r*-~
(100)
VI.
where a and it have their previously defined meanings, it being recognized that the factor (2ft- 1)
defines the anisotropy of radiation in the particle
layer. ~ is the effective cross section for holes in the
particle layer, 17* is the mean external reflection
coefficient for side scatter taking account of holes
and back scatter, and If is a parameter which is
related to the mean particle diameter. For a particle
size distribution function of the form
f' is given by
References
[1] Stokes, G. G., Proc. Roy. Soc. (London), 11, 545 (186062).
[2] Ray leigh, Lord, Phil. Mag. 41,107 (1871).
[3] Mie, G., Ann. Physik, 25,377 (1908).
[4] Schuster, A., Astrophys. J. 21, 1 (1905).
[5] Kubelka P ., and Munk, F., Z. tech. Phys . 12,593 (1931) .
[6] Schwarzschild, K, Sitz. ber. Preuss. Akad. Wiss. Berlin
1914, 1183.
[7] Wendlandt, W. W., and H echt, H. G., Reflectance
Spectroscopy (Interscience, 1966).
[8] Kortum, G., Reflexionsspektroskopie, (Springer-Verlag,
1969 ; published also in an English edition).
[9] Frei, R. W., and MacNeil, J. D., Diffuse Re~ectance
Spectroscopy in Environmental Problem-Solvmg (The
Chemical Rubber Co. Press, 1973).
[10] Transactions of the First Conference on the Spectroscopy of Light-Scattering Media, Moscow, 29-30
March 1956 Izvest. Aka d. Nauk. SSSR, Ser. Fiz.,
21(11) 1957' (Columbia Technical Translation, Bull.
Acad. 'Scienc~s SSSR, Physical Series, 21 (11) (1958)) .
582
l
[11] Wendlandt, W. W., Modern Aspects of Rcflectance
Spectroscopy, Proceedings of the American Chemical
Society Symposium on Reflectance Spectroscopy,
Chi cago, 11-12 September 1967 (Plenum Press, 19(8).
[12] Hech t, H. G., The Present Status of Diffuse Refiectance
Theory, in ref. [11], pp. 1- 26.
[13] Rozenberg, G. V., Usp. fiz. Nauk 56, No.2 (1955).
[14] Rozenberg, G. V., Izvest. Akad. Nauk SSSR, Ser. Fiz.
21, 1473 (1957).
[15] Rozenberg, G. V., Usp. fiz. Nauk 69, 57 (1959).
[16] Stepanov, B. 1., Izvest. Akad. Nauk SSSR, Ser. Fiz. 21,
1485 (1957).
[17] Schuster, A., Phi!. Mag. 5, 243 (1903).
[18] King, L. V., Phil. Trans. Roy. Soc. (London), A2 12, 375
(1913).
[19] Kubelka, P., J. Opt. Soc. Am. 44,330 (1954).
[20] Gurevic, M., Phys. Zeits. 31, 753 (1930).
[2 ] ] Kubelka, P., J. Opt. Soc. Am. 38, 448 (1948).
[22] Antonov-Romanovsky, V. V., Zhur. ekspr. i teor. fiz.
26,459 (1954).
[23] Kuznetsov, E. S., Izvest. Akad. Nauk SSSR, Ser. geog.
i geofizika. 5247 (1943).
[24] Ambartsumian, V. A., Dokl. Akad. Nauk Armenian
SSR, 8, 101 (1948); J. Phys. USSR 8, 65 (1944).
[25] Chekalinskaia, 1. 1., Izvest. Akad. Nauk SSSR, Ser.
Fiz. 21 , 1494 (1957).
[26] Il'ina, A. A., and Rozenberg, G. V., Dok!. Akad. Nauk
SSSR 98, 3 (1954).
[27] Rozenberg, G. V., Dok!. Akad. Nauk SSSR 145, 775
(1962) .
[28] Romanova, L. M., Opt. i Spektroskopia 17, 250 (1964).
[29] Romanova, L. M., Opt. i Spektroskopia 13, 429, 819
(1962); 14,262 (1962).
[30] Sagan, C., and Pollack, J. B., J . Geophys. Research
72, 469 (1967).
.
[31] Orchard, S. E., J. Opt. Soc. Am. 59, 1584 (1969).
[32] Reichman, J., Appl. Optics 12, 1811 (1973); Egan, W. G.,
Hilgeman, T., and Reichman, J., ibid., 12, 1816
(1973) .
[33] Chu, C. M., and Churchill, S. W., J. Phys. Chern. 59,
855 (1955); Evans, L. B., Chu, C. 1\1., and Churchill,
S. W., J. Heat Transfer, 87C, 381 (1965); Chu, C. M.,
Churchill, S. W., and Pang, S. C., in Electromagnetic
Scattering, M. Kerker, Ed. (iVIac:i\1illan Company,
New York, 19(3).
[34] Irvine, W. 1\1., Astrophys. J. 152,823 (1968).
[35] Chandrasekhar, S., Radiative Transfer, (Clarendon
Press, 1950) (Reprinted by Dover Publications,
Inc., 19(0).
[36] Giovanelli, R G., Optica Acta 2, 153 (1955).
[37] Pitts, E., Proc . Phys. Soc. B67, 105 (1954).
[38] Blevin, W. R, and Brown, W. J., J. Opt. Soc. Am. 51,
975 (1961) .
[39] Simmons, E . L., App!. Optics 14, 1380 (1975).
583
214 427 0 - 78- 3
(Paper 80A4-902)