
rough surfaces
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INSTITUTE OF PHYSICS PUBLISHING JOURNAL OF PHYSICS D: APPLIED PHYSICS
J. Phys. D: Appl. Phys. 39 (2006) 3571–3581 doi:10.1088/00223727/39/16/008
Modiﬁed Kubelka–Munk model for
calculation of the reﬂectance of coatings
with opticallyrough surfaces
A B Murphy
CSIRO Industrial Physics, PO Box 218, Lindﬁeld NSW 2070, Australia and CSIRO Energy
Transformed National Research Flagship, Australia
Email: tony.murphy@csiro.au
Received 16 June 2006, in ﬁnal form 3 July 2006
Published 4 August 2006
Online at stacks.iop.org/JPhysD/39/3571
Abstract
The Kubelka–Munk twoﬂux radiative transfer model is strictly applicable
only to the case of diffuse illumination but is often applied in the case of
collimated illumination. Here, the application of the Kubelka–Munk
twoﬂux model to the collimated illumination of opticallyrough surfaces is
investigated. Expressions for the reﬂectance from such surfaces are
obtained. A relatively simple treatment of reﬂection from surfaces of
arbitrary roughness is developed that takes into account the characteristics of
the spectrophotometer used to measure reﬂectance. The modiﬁed
Kubelka–Munk model is tested in the case of an opticallyrough rutile
titanium dioxide coating on a titanium substrate and found to give good
agreement with experiment, even for negligible scattering within the
coating. It
is expected that if the surface is sufﬁciently rough to ensure that the light
transmitted into the coating is diffuse, the modiﬁed Kubelka–Munk model
will be applicable irrespective of the magnitude of the absorption and
scattering coefﬁcients of the coating material.
(Some ﬁgures in this article are in colour only in the electronic version)
1. Introduction
The propagation of light in layered media is well understood
and relatively easily treated mathematically as long as
each layer is homogeneous and the interfaces between
media are smooth (e.g. [1]). However, when the layers
are inhomogeneous, or the interfaces are opticallyrough,
treatment becomes more difﬁcult. Analytical treatments of
propagation of light in inhomogeneous media are typically
complex, and for this reason transport theories are often
used. Such theories treat the transport of radiative energy
through the medium directly, using effective absorption and
scattering coefﬁcients. While the development of transport
theories is less rigorous than that of analytical treatments,
they are nonetheless very useful, and have been applied
to a wide range of problems. The Kubelka–Munk model
[2, 3] is by far the most widely used transport theory, having
been applied to examine materials as diverse as paints [4],
pigmented plastics [5], decorative and protective coatings [6],
solarabsorbing pigments and paints [7], human tissue [8],
leaves [9], crystalline materials [10], melting of solids [11],
powders [12] and ﬁbres and wool [13]. In this model, it is
assumed that the optical properties of the coating are described
by two constants, the absorption and scattering coefﬁcients.
Kubelka and Munk’s original treatment [2,3] took into account
only transport within a layer; Saunderson [5, 14] extended the
treatment to allow reﬂection from the front and back surfaces
of the layer to be considered.
In the Kubelka–Munk model, it is assumed that the light
is diffuse within the layer. Strictly, this can only occur
when the incident light is diffuse; however, the model is
frequently used for collimated illumination [15–18]. Vargas
and Niklasson [19] have examined the case of collimated
illumination and shown that the Kubelka–Munk model, with
the Saunderson extension, is of very limited applicability,
being accurate only for weaklyabsorbing coatings containing
highlyscattering particles whose sizes are larger than a
wavelength. They developed a slightly modiﬁed method, in
00223727/06/163571+11$30.00 © 2006 IOP Publishing Ltd Printed in the UK 3571
A B Murphy
which the reﬂection coefﬁcient from the front of the coating
was the Fresnel coefﬁcient (i.e. the reﬂection coefﬁcient for
collimated reﬂection of collimated light) and found it to have
a wider range of applicability. While it was rigorously correct
only for opticallythick weakly or nonabsorbing coatings,
useful results were also obtained for absorbing coatings whose
reﬂectance is very weak and for coatings containing highly
scattering particles whose sizes are larger than a wavelength.
The Kubelka–Munk model is a twoﬂux model; the two
ﬂuxes are diffuse light travelling in the forward and reverse
directions. The differential equations treat absorption and
scattering of the light. In cases where it is not reasonable
to assume that the light is diffuse, fourﬂux models (in which
the ﬂuxes are both collimated and diffuse light travelling in
forward and reverse directions) may be used [20–22].
The reﬂection coefﬁcients used in the Saunderson
extension were for diffuse reﬂection of diffuse light. As
noted above, Vargas and Niklasson [19] also used reﬂection
coefﬁcients for collimated reﬂection of collimated light.
However, when collimated illumination is used, it is possible,
depending on the optical roughness of the surface, for the
reﬂected light to be collimated, diffuse or partially collimated
and partially diffuse. In the case of opticallyrough surfaces,
the reﬂected light is mainly diffuse. The transmitted light is
also mainly diffuse. This means treatment by the twoﬂux
method is likely to be valid under collimated illumination for
a wider range of coating parameters than is the case for an
opticallysmooth surface.
Treatment of collimated illumination of a general surface
requires expressions for reﬂection coefﬁcients valid for
both opticallysmooth and opticallyrough surfaces, and in
particular the separation of these reﬂection coefﬁcients into
specular (collimated) and diffuse components. In keeping
with the simplicity of the twoﬂux model, it is appropriate
to use relatively simple expressions for these reﬂection
coefﬁcients. It is important, in comparing predictions of the
model with experiment, to take into account the properties
of the measurement apparatus (e.g. a spectrophotometer with
integrating sphere attachment), in particular the means by
which the apparatus separates the reﬂected light into diffuse
and specular components. Note that reﬂection from optically
rough surfaces is often referred to as scattering. Here the term
reﬂectionis usedfor bothopticallyroughandopticallysmooth
surfaces, and the term scattering is reserved for the description
of scattering of light within the coating.
In this paper, I derive a slightlymodiﬁed twoﬂux model
for the case of collimated illumination of a coating on an
opaque substrate that allows general surfaces to be treated.
This extends previous studies that examined only optically
smooth surfaces. Further, I obtain simple expressions for
reﬂection coefﬁcients at surfaces of arbitrary roughness that
allow the characteristics of the measurement apparatus to be
taken into account. This is done by developing expressions,
using a physical optics approach, for reﬂection coefﬁcients
from a general surface that depend on the acceptance cone of
the measurement apparatus.
The range of surface characteristics for which the modiﬁed
twoﬂux model will be valid is then investigated. The model is
tested for the case of collimated illumination of an optically
rough rutile TiO
2
coating on a titanium substrate. This
Figure 1. Schematic of measurement geometry of the diffuse
reﬂectance attachment of the Cary 5 spectrophotometer. The
diagram on the left represents the geometry for diffuse reﬂectance
measurements (‘D’ position), and that on the right shows the
geometry for total reﬂectance measurements (‘S’ position). In each
case, the sample is represented by the rectangle on the right of the
integrating sphere.
provides a good test of the model, since scattering within
the coating is weak, and absorption can be either strong or
weak, depending on the wavelength. Rutile TiO
2
coatings on
titanium substrates can be produced, for example, by ﬂame
oxidation or ovenoxidation of titanium and have been applied
in the photocatalytic splitting of water into hydrogen and
oxygen [23–25]. Application of the modiﬁed Kubelka–Munk
model developed here allows the interpretation of reﬂectance
measurements of these coatings, and inversion of the equations
derived allows the absorption coefﬁcient and refractive index
to be determined from the measured reﬂectance [26]. The
bandgap of the coating can then be determined from the
wavelengthdependence of the absorption coefﬁcient using
standard methods [27]; reduction of the bandgap of rutile
TiO
2
is imperative to improve its efﬁciency in photocatalytic
watersplitting [23].
In section 2, the measurement of reﬂectance using a
spectrophotometer with an integrating sphere is described.
This systemis used for the measurements, which are presented
and discussed in section 5. The modiﬁed Kubelka–Munk
model is derived in section 3 and the reﬂection coefﬁcients
for a general surface are derived and analysed in section 4.
Conclusions are given in section 6.
2. Reﬂectance measurements
Measurements of reﬂectance are typically performed using a
spectrophotometer with an integrating sphere attachment. For
example, the measurements to be presented in section 5 were
performed using the diffuse reﬂectance attachment of a Cary 5
UVvisible spectrophotometer. Aschematic of the geometry is
given in ﬁgure 1. The incident light is collimated, and reﬂected
light is captured by an integrating sphere.
The diffuse reﬂectance attachment has two settings. In the
‘D’ position, the sample is oriented so that the incident light is
normal to the surface of the sample. Light reﬂected specularly,
i.e. normal to the surface, is not captured by the integrating
sphere, so only diffusely reﬂected light is measured. In the
‘S’ position, the sample is oriented so that the incident light
is at a small angle to the normal to the surface. In this case,
both specularly and diffuselyreﬂected light are captured by
the integrating sphere.
The sample measured in the experiment described in
section 5 was smaller than the approximately 8 by 12 mm
3572
Modiﬁed Kubelka–Munk model for calculation of the reﬂectance
Figure 2. Geometry, showing boundary conditions at z = 0 and
z = h. Collimated light is denoted by solid arrows and diffuse light
by dotted arrows.
aperture at the back of the integrating sphere. A matt black
plate with a small (3 mm diameter) aperture is placed between
the sphere and the sample. Hence a 3 mm diameter spot on
the sample was illuminated. The entrance aperture of the
integrating sphere is oval in shape and 11.04 mm vertically
by 13.44 mm horizontally. The inner diameter of the sphere is
110 mm. Hence, in the ‘D’ position, light reﬂected from the
centre of the sample at an angle greater than 2.87
◦
vertically
and 3.50
◦
horizontally is captured. Taking into account the fact
that a 3 mm diameter circular region is illuminated, it can be
calculated that light reﬂected at angles greater than 2.9 ±0.8
◦
vertically and 3.5 ± 0.8
◦
horizontally is captured in the ‘D’
position.
In the calculations of reﬂectance froma rough surface that
are presented in this paper, diffuse reﬂectance corresponds
to measurements made in the ‘D’ position and collimated
reﬂectance to the difference between measurements made in
the ‘S’ and ‘D’ positions. A matt Teﬂon reference was used to
provide a nominal 100% reﬂectance measurement.
3. Modiﬁed Kubelka–Munk model
Figure 2 shows the geometry considered, which is appropriate
to a coating on an opaque substrate. The coating lies between
the front plane at z = 0 and the back plane at z = h.
The coating rests on an inﬁnite substrate starting at z = h.
The incident light travels in the positive z direction and is
collimated.
I assume that the light within the coating is diffuse, as is
required to apply a twoﬂux model. This is a reasonable a
priori assumption in the case of an opticallyrough surface at
the aircoating interface. I allow the light reﬂected from the
front surface of the coating to have both collimated and diffuse
components. While at ﬁrst glance this may seem inconsistent
with the previous assumption, it allows the validity of that
assumption to be checked. Further, there are cases in which the
reﬂectedlight maybe partiallycollimatedwhile the light within
the coating is diffuse, for example coatings with an optically
smooth front surface that are strongly scattering. Finally, since
the spectrophotometer allows both the collimated and diffuse
components of the reﬂectance to be measured, it is useful to
calculate both components.
I distinguish between reﬂectance, which refers to the
reﬂection of light from the coating–substrate system, and
reﬂection coefﬁcients, which refer to reﬂection from a single
surface. Both are dimensionless ratios. I will use R to
denote reﬂectance and r to denote a reﬂection coefﬁcient. The
following reﬂection coefﬁcients have to be considered:
• r
i
cc
: reﬂection of collimated light as collimated light,
• r
i
cd
: reﬂection of collimated light as diffuse light,
• r
i
dd
: reﬂection of a diffuse light as diffuse light.
Superscript i represents the surface from which reﬂection
occurs as follows:
• i = f represents reﬂection from the front surface of the
coating (at z = 0),
• i = b represents reﬂection from the back surface of the
coating (at z = 0),
• i = s represents reﬂection from the front surface of the
substrate (at z = h).
Since the incident light is collimated, but the light within the
coating is diffuse, the following reﬂection coefﬁcients have to
be calculated: r
f
cc
, r
f
cd
, r
b
dd
and r
s
dd
.
Let the incident collimated light intensity be denoted
by I
c0
, and the forward and backwarddirected diffuse light
intensities in the coating by I
d
(z) and J
d
(z), respectively. The
boundary conditions at z = 0 and z = h are, respectively,
I
d
(0) = (1 −r
f
cc
−r
f
cd
)I
c0
+ r
b
dd
J
d
(0) (1)
and
J
d
(h) = r
s
dd
I
d
(h). (2)
The Kubelka–Munk model uses an effective scattering
coefﬁcient S and an effective absorption coefﬁcient K
to describe the optical properties of the coating. The
effective scattering coefﬁcient is related to the usual scattering
coefﬁcient s by S = 2(1 −ζ )s, where the forward scattering
ratio ζ is deﬁned as the ratio of the energy scattered by a
particle in the forward hemisphere to the total scattered energy.
For Rayleigh scattering, ζ = 1/2, while for Mie scattering,
1/2 < ζ < 1. The effective absorption coefﬁcient is related
to the usual absorption coefﬁcient k by K = εk, where the
average crossing parameter ε is deﬁned such that the average
path length travelled by diffuse light crossing a length dz is
εdz. For collimated light, ε = 1, while for semiisotropic
(i.e. isotropic in the direction of propagation) diffuse light,
ε = 2 [28]. It is usual in applying the Kubelka–Munk model
to write ζ = 1/2 and ε = 2, so that S = s and K = 2k.
The differential equations describing the energy balance
between diffuse light in the forward (positive z) and backward
(negative z) directions are
dI
d
dz
= −(S + K)I
d
+ SJ
d
, (3)
dJ
d
dz
= (S + K)J
d
−SI
d
. (4)
3573
A B Murphy
The general solution to these equations is
I
d
(z) = C
1
exp(−Sbz) + C
2
exp(Sbz), (5)
J
d
(z) = (a −b)C
1
exp(−Sbz) + (a + b)C
2
exp(Sbz), (6)
where a = (S + K)/S and b =
√
a
2
−1 and C
1
and C
2
are
constants. Using boundary conditions (1) and (2) gives
I
d
(z) = {(1 −r
f
cc
−r
f
cd
)I
c0
[b cosh(Sbh −Sbz)
+(a −r
s
dd
) sinh(Sbh −Sbz)]]{b(1 −r
b
dd
r
s
dd
) cosh(Sbh)
+(a −r
b
dd
−r
s
dd
+ ar
b
dd
r
s
dd
) sinh(Sbh)]
−1
, (7)
J
d
(z) = {(1 −r
f
cc
−r
f
cd
)I
c0
[br
s
dd
cosh(Sbh −Sbz)
+(1 −ar
s
dd
) sinh(Sbh −Sbz)]]{b(1 −r
b
dd
r
s
dd
) cosh(Sbh)
+(a −r
b
dd
−r
s
dd
+ ar
b
dd
r
s
dd
) sinh(Sbh)]
−1
. (8)
From (8), we obtain
J
d
(0) =
(1 −r
f
cc
−r
f
cd
)R
KM
I
c0
1 −r
b
dd
R
KM
, (9)
where
R
KM
=
1 −r
s
dd
[a −b coth(bSh)]
a + b coth(bSh) −r
s
dd
. (10)
The collimated reﬂectance from the coating and substrate
system is just the collimated reﬂected component of the
incident radiative ﬂux normalized to the incident radiative ﬂux
R
cc
= r
f
cc
. (11)
The diffuse reﬂectance from the coating and substrate system
is the sum of the diffuse reﬂected component of the incident
radiative ﬂux and the transmitted diffuse backward ﬂux at
z = 0, normalized to the incident radiative ﬂux
R
cd
=
r
f
cd
I
c0
+ (1 −r
b
dd
)J
d
(0)
I
c0
. (12)
Using (9) gives
R
cd
= r
f
cd
+
(1 −r
f
cd
−r
f
cc
)(1 −r
b
dd
)R
KM
1 −r
b
dd
R
KM
, (13)
with R
KM
given by (10). This result is similar to that ﬁrst
obtained by Saunderson [5, 14] for diffuse reﬂectance in the
case of diffuse illumination
R
dd
= r
f
dd
+
(1 −r
f
dd
)(1 −r
b
dd
)R
KM
1 −r
b
dd
R
KM
. (14)
4. Reﬂection coefﬁcients
4.1. Reﬂection of collimated incident light from an
opticallyrough surface
In this section, I consider the calculation of reﬂection
coefﬁcients for collimated light incident on a surface that
may be opticallyrough or opticallysmooth, or intermediate.
The derivation of reﬂection coefﬁcients for collimated light
incident on an opticallysmooth surface, i.e. the Fresnel
coefﬁcients, is treated in standard optics textbooks (e.g.
[29, 30]). Expressions for Fresnel coefﬁcients are given in
appendix A. Opticallyrough surfaces are usually deﬁned by
the Rayleigh criterion, which states that surfaces can be treated
as opticallysmooth if the heights of surface irregularities are
less than λ/(8 cos θ
i
), where θ
i
is the angle of incidence. The
factor 8 is sometimes replaced by 16 or 32 [31].
Before continuing, it is useful to consider nomenclature.
Reﬂection fromrough surfaces is often described as scattering,
since a proportion of the reﬂected light is scattered at angles
of reﬂection other than that equal to the angle of incidence.
Here I use the term reﬂection to include such ‘scattering’,
i.e. to describe reﬂection at any angle. I deﬁne the reﬂection
coefﬁcient as the ratio of the intensity of the reﬂected light to
the intensity of the incident light. (The reﬂection coefﬁcient is
sometimes deﬁned in terms of the electric ﬁeld amplitude.)
Further, in this section, I only consider reﬂection from
the initial interaction of the incident light with the surface.
Reﬂection arising fromscattering fromdiscontinuities beneath
the surface or reﬂections from subsurface interfaces is taken
into account using the Kubelka–Munk model that was derived
in section 3.
Two important approaches to the calculation of reﬂection
properties of rough surfaces are that based on physical
optics (the Beckmann–Spizzichino model) and that based
on geometrical optics (the Torrance–Sparrow model). The
geometrical optics approach is mathematically simpler but is
only valid when the wavelength of the incident light is much
smaller than the dimensions of the surface irregularities. Since
this is not always the case for the surfaces of interest, I follow
the more general physical optics approach.
Beckmann and Spizzichino [31] derived expressions
describing the reﬂection of light from rough surfaces.
However, they gave results for only one polarization, and
did not consider shadowing effects. I use the results of
He et al [32], who gave expressions for the bidirectional
reﬂectance distribution function (BRDF) for incident light of
both polarizations and for unpolarized light and also took into
account shadowing. The assumptions made in the derivation
are:
• The height distribution on the surface is assumed to be
Gaussian and spatially isotropic. Under such conditions,
the probability that a point on the surface falls within the
height range z to z + dz is p(z)dz, where
p(z) =
1
√
2πσ
0
exp(−z
2
/2σ
2
0
). (15)
The mean height is z = 0 and σ
0
is the rms roughness
of the surface. To specify the surface fully, a horizontal
length measure is also required. The measure used is the
autocorrelation length τ, which is a measure of the spacing
between surface peaks. The rms slope of the surface is
proportional to σ
0
/τ.
• The electric ﬁeld at a given point on the surface is set to
the value that would exist if the surface were replaced by
its local tangent plane (the ‘tangent plane’ or ‘Kirchoff’
approximation). Thorsos showed that this approximation
is accurate for τ/λ 1 when an appropriate shadowing
treatment is used [33].
• The assumption is made, in evaluating an integral that
arises in the derivation, that the surface is either optically
3574
Modiﬁed Kubelka–Munk model for calculation of the reﬂectance
very rough (i.e. (2πσ/λ)
2
¸ 1, where σ is an effective
surface roughness, deﬁned below) or that the surface has
gentle slopes (i.e. σ/τ _1).
• Multiple reﬂections from the surface are ignored. This
contribution is negligible for a surface with gentle slopes.
He et al [32] gave expressions for the BRDF as the sum
of a specular component, a ‘directional diffuse’ component,
and a ‘uniform diffuse’ component. The latter corresponds to
the subsurface scattering and multiple subsurface reﬂections
described by the Kubelka–Munk model. These have been
accounted for in section 3 and are ignored here. The
‘directional diffuse’ component corresponds to what is here
called diffuse reﬂection. The BRDF for unpolarized light is
given by
ρ = ρ
s
+ ρ
d
, (16)
where the specular component is
ρ
s
=
r
F
_
θ
/
_
exp(−g)Z
cos θ
i
dω
i
, (17)
and the diffuse component is
ρ
d
=
r
F
(θ
/
)GZD
π cos θ
i
cos θ
r
. (18)
Here r
F
(θ
/
) is the Fresnel reﬂection coefﬁcient evaluated at the
bisecting angle
θ
/
= cos
−1
([
ˆ
k
˜
r
−
ˆ
k
˜
i
[/2), (19)
where
ˆ
k
˜
i
and
ˆ
k
˜
r
are, respectively, the unit vectors in the
direction of the incident and reﬂected light, is a delta
function that is unity in the cone of specular reﬂection and
zero elsewhere, θ
i
and θ
r
are, respectively, the polar angles
of incidence and reﬂection and φ
r
is the azimuthal angle of
reﬂection. It is assumed that the azimuthal angle of incidence
is φ
i
= 0. The geometric factor G is given by
G =
4(1 + cos θ
i
cos θ
r
−sin θ
i
sin θ
r
cos φ
r
)
2
(cos θ
i
+ cos θ
r
)
2
. (20)
The surface roughness function g is given by
g = [(2πσ/λ)(cos θ
i
+ cos θ
r
)]
2
. (21)
The distribution function D is given by
D =
π
2
τ
2
4λ
2
∞
m=1
g
m
exp(−g)
m!m
exp
_
−v
2
xy
τ
2
4m
_
, (22)
where
v
xy
=
2π
λ
_
sin
2
θ
i
−2 sin θ
i
sin θ
r
cos φ
r
+ sin
2
θ
r
_
1/2
. (23)
Calculation of D can cause numerical problems because of the
large numbers involved for large values of m. Nayar et al [34]
give useful approximate expressions for D. For g _ 1 (i.e. a
smooth surface)
D
∼
=
π
2
τ
2
4λ
2
exp(−g)g exp
_
−v
2
xy
τ
2
4
_
, (24)
and for g ¸1 (i.e. a rough surface)
D
∼
=
π
2
τ
2
4λ
2
1
g
exp
_
−v
2
xy
τ
2
4g
_
. (25)
The effective roughness σ was introduced by He et al to
allow averaging to occur over only the illuminated (non
shadowed) parts of the surface. Particularly for grazing angles
of incidence or reﬂection, it can be considerably smaller than
the rms roughness σ
0
. They are related by
σ = σ
0
(1 + z
2
0
/σ
2
0
)
−1/2
, (26)
where z
0
is the root of the equation
_
π
2
z =
σ
0
4
(K
i
+ K
r
) exp
_
−
z
2
2σ
2
0
_
, (27)
and
K
i
= tan θ
i
erfc(τ cot θ
i
/2σ
0
), (28)
K
r
= tan θ
r
erfc(τ cot θ
r
/2σ
0
). (29)
The shadowing function Z is given by
Z = Z
i
(θ
i
)Z
r
(θ
r
), (30)
where
Z
i
(θ
i
) =
_
1 −
1
2
erfc(τ cot θ
i
/2σ
0
)
_
(cot θ
i
) + 1
, (31)
Z
r
(θ
r
) =
[1 −
1
2
erfc(τcotθ
r
/2σ
0
)]
(cot θ
r
) + 1
, (32)
(cot θ) =
1
2
_
2σ
0
√
πτ cot θ
−erfc
_
τ cot θ
2σ
0
__
. (33)
The BRDF expressions (17) and (18) are now fully deﬁned.
These expressions, together with the expression for the
reﬂection coefﬁcient r in terms of the BRDF
r =
_
π
−π
_
π/2
0
ρ cos θ
i
cos θ
r
sin θ
r
dθ
r
dφ
r
(34)
obtained in appendix B, can be used to obtain expressions for
the collimated–collimated and collimated–diffuse reﬂection
coefﬁcients, r
f
cc
and r
f
cd
, respectively, from a rough surface.
The total reﬂection coefﬁcient is split into specular and diffuse
components
r = r
s
+ r
d
. (35)
Using (16), (18) and (34), the diffuse component of r is given
by
r
d
=
_
π
−π
_
π/2
0
ρ
d
cos θ
i
cos θ
r
sin θ
r
dθ
r
dφ
r
. (36)
For specular reﬂection, θ
r
= θ
i
and φ
r
= π, which imply
that θ
/
= θ
i
. Further, for a perfectlyreﬂecting mirrorlike
surface, we expect r
F
(0) = 1 and r
s
= 1. In calculating the
specular component of the BRDF for rough surfaces, r
F
(θ
/
) is
multiplied by exp(−g)Z, so the specular reﬂection coefﬁcient
is modiﬁed accordingly to give
r
s
= r
F
(θ
i
) exp(−g)Z. (37)
3575
A B Murphy
0.01 0.1 1 10
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
R
e
f
l
e
c
t
i
o
n
c
o
e
f
f
i
c
i
e
n
t
s
r
,
r
s
,
r
d
Wavelengthnormalised rms roughness σ
0
/ λ
τ/σ
0
= 5: diffuse, total
τ/σ
0
= 10: diffuse, total
τ/σ
0
= 20: diffuse, total
specular (all values of τ/σ
0
)
Figure 3. Dependence of total, specular and diffuse reﬂection
coefﬁcients r, r
s
and r
d
, respectively, at normal incidence on rms
roughness normalized to wavelength. Results are given for different
values of inverse rms surface slope. The Fresnel reﬂection
coefﬁcient at normal incidence is assumed to be 100%. The regions
in which the total and diffuse reﬂection coefﬁcients may be
inaccurate are indicated by crosshatching. The specular reﬂection
coefﬁcient is independent of rms surface slope.
Figure 3 shows the reﬂection coefﬁcients r
d
, r
s
and r as
a function of wavelengthnormalized surface roughness σ
0
/λ
for θ
i
= 0, for different values of the inverse rms surface
slope τ/σ
0
. It is assumed that the Fresnel reﬂection coefﬁcient
for normal incidence r
F
(0) is 100% for the purposes of the
ﬁgure, to allow the effect of surface roughness to be shown
more clearly. Note that the specular reﬂection coefﬁcient
r
s
is independent of τ/σ
0
. The diffuse reﬂection coefﬁcient
is lower for smaller values of τ/σ
0
; this is because of two
effects. The ﬁrst is that on the scale of the surface roughness
the average angle of incidence increases as the surface slope
increases, decreasing the average reﬂection coefﬁcient. The
second is a result of shadowing of the diffuselyreﬂected light;
i.e. Z < 1. Note that the equation for calculation of diffuse
reﬂection coefﬁcient is only accurate for τ/λ > 1; hence for
lowτ/σ
0
, the results are not reliable for lowσ
0
/λ. The regions
that may therefore be inaccurate are marked on the graph by
crosshatching.
Figure 4 shows the angular dependence of the integrand
(1/π)r
F
(θ
/
)GZDsin θ
r
in expression (36) for diffuse
reﬂection coefﬁcient r
d
, for the case of θ
i
= 0. The value of the
integrand depends strongly on τ/σ
0
and relatively weakly on
σ
0
; in particular, for σ
0
1 µm, the integrand is independent
of σ
0
. While the integrand is zero for θ
r
= 0, since reﬂection
at this angle is classed as specular, a signiﬁcant fraction of the
diffuselyreﬂected light is reﬂected within a few degrees of
θ
r
= 0
◦
, particularly for larger values of τ/σ
0
.
In the measurement of reﬂectance using a spectropho
tometer withanintegratingsphere, the incident collimatedlight
has angle of incidence θ
i
= 0, and reﬂected light within an
acceptance cone centred around θ
r
= 0 is measured as specu
larly reﬂected light (see section 2). If this acceptance cone has
halfangular width ψ, then the reﬂection coefﬁcients required
in the modifed Kubelka–Munk model ((11) and (13)) are
r
f
cc
= r
s
+ r
d
[
θ
r
ψ
(38)
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
(
1
/
π
)
r
F
(
θ
'
)
G
Z
D
s
i
n
θ
r
Angle of reflection θ
r
(degrees)
λ = 500 nm
σ
0
= 1 µm, τ / σ
0
= 2
σ
0
= 1 µm, τ / σ
0
= 5
σ
0
= 1 µm, τ / σ
0
= 10
σ
0
= 1 µm, τ / σ
0
= 20
σ
0
= 1 µm, τ / σ
0
= 50
σ
0
= 50 nm, τ / σ
0
= 10
σ
0
= 100 nm, τ / σ
0
= 10
Figure 4. Dependence of integrand in diffuse coefﬁcient expression
on the angle of reﬂection, for different values of rms roughness and
inverse rms surface slope, for normal incidence. The Fresnel
reﬂection coefﬁcient at normal incidence is assumed to be 100%.
The wavelength is 500 nm. Values for rms roughness greater than
1 µm are equal to the 1 µm values shown.
and
r
f
cd
= r
d
[
θ
r
>ψ
. (39)
Using (36) and (37), we obtain (noting that the following
apply for normal incidence: r
F
(θ
i
) = r
F
(0), the BRDF is
independent of azimuthal angle φ
r
, and Z = 1 for specular
reﬂection)
r
f
cc
= r
F
(0) exp(−g) +
1
π
_
ψ
0
r
F
(θ
r
/2)GZDsin θ
r
dθ
r
(40)
and
r
f
cd
=
1
π
_
π/2
ψ
r
F
(θ
r
/2)GZDsin θ
r
dθ
r
. (41)
In calculating r(0) and r(θ
r
/2) with (A.4), the refractive index
N
1
is that of air, and the refractive index N
2
is that of the
coating.
The total reﬂection coefﬁcient at θ
i
= 0 is given by
r(0) = r
s
+ r
d
= r
f
cc
+ r
f
cd
= r
F
(0) exp(−g)
+
1
π
_
π/2
0
r
F
(θ
r
/2)GZDsin θ
r
dθ
r
. (42)
Figure 5 shows the total reﬂection coefﬁcient r and its
components r
f
cc
and r
f
cd
for halfangular width ψ = 3.2
◦
, which
is the average value for the diffuse reﬂectance attachment of
the Cary 5 spectrophotometer. For opticallyrough surfaces
(e.g. σ
0
= 1 µm), the diffuse component r
f
cd
dominates. For
opticallysmooth surfaces (e.g. σ
0
= 10 nm), the specular
component r
f
cc
dominates. For surfaces of intermediate
roughness, both components are important.
4.2. Comparison with other expressions
It is common (e.g. [35–37]) when dealing with the reﬂection
fromopticallyrough surfaces to use just the specular reﬂection
coefﬁcient
r
s
= r
F
(0) exp
_
−
_
4πσ
0
cos θ
i
λ
_
2
_
, (43)
3576
Modiﬁed Kubelka–Munk model for calculation of the reﬂectance
300 400 500 600 700 800
0.001
0.010
0.100
1.000
(b) τ/σ
0
= 20
σ
0
= 10 nm: r & r
f
cc
, r
f
cd
σ
0
= 100 nm: r, r
f
cc
, r
f
cd
σ
0
= 1 µm: r & r
f
cd
(r
f
cc
~ 0)
Wavelength (nm)
0.001
0.010
0.100
1.000
R
e
f
l
e
c
t
i
o
n
c
o
e
f
f
i
c
i
e
n
t
s
r
,
r
f
c
c
,
r
f
c
d
(a) τ/σ
0
= 10
Figure 5. Reﬂection coefﬁcient r and its specular and diffuse
components r
f
cc
and r
f
cd
, respectively, for three different rms surface
roughnesses and for two values of inverse rms surface slope, for
normal incidence. The Fresnel reﬂection coefﬁcient at normal
incidence is assumed to be 100%.
which is equivalent to (37) for the case of normal incidence.
Boithias [38] suggested a modiﬁcation to
r
s
= r
F
(0) exp
_
−
_
4πσ
0
cos θ
i
λ
_
2
_
_
I
0
_
1
2
_
4πσ
0
cos θ
i
λ
_
2
__
2
, (44)
where I
0
is the modiﬁed Bessel function of order zero; this
expression has also been used by, for example, Landron et al
[39]. Miller et al [40] derived this modiﬁcation, and claimed
that it gave a better ﬁt to experimental results of Beard [41]
for ‘coherent’ reﬂection from sea waves. However, Hristov
and Friehe [42] have recently claimed that the Bessel function
factor is unnecessary.
Presumably in these cases it is assumed that light that is not
reﬂected specularly is reﬂected diffusely, so the total reﬂection
coefﬁcient is r(0). Hence, if r
s
is given by (43), we have
r
d
= r(0)
_
1 −exp
_
−
_
4πσ
0
cos θ
i
λ
_
2
__
. (45)
There are a number of shortcomings inherent in using (43)
and (45), compared with using the expressions (40) and (41)
derived here for r
f
cc
and r
f
cd
, respectively. First, the division of
the reﬂected light into specular and diffuse components does
not take into account the component of the diffuse reﬂection
that is reﬂected at or close to the specular angle of reﬂection
(θ
r
≈ θ
i
, φ
r
= φ
i
+ π). Further, shadowing is neglected,
and the effective angle of incidence on the scale of the surface
roughness increases when the average surface slope increases;
these affect the calculation of the total reﬂection coefﬁcient.
Finally, deviations of σ from σ
0
are neglected.
Figure 6 compares expressions (43) and (44) for the
specular reﬂectance with the value of r
f
cc
given by (40), for
halfangular width ψ = 3.2
◦
, which is the average value for the
0.001
0.010
0.100
1.000
S
p
e
c
u
l
a
r
r
e
f
l
e
c
t
i
o
n
c
o
e
f
f
i
c
i
e
n
t
Wavelengthnormalised rms roughness σ
0
/λ
r
f
cc
, τ/σ
0
= 5
r
f
cc
, τ/σ
0
= 10
r
f
cc
, τ/σ
0
= 20
r
f
cc
, τ/σ
0
= 50
r
s
, equation (43)
r
s
, equation (44)
Figure 6. Comparison of reﬂection coefﬁcient r
f
cc
for
spectrophotometer of halfangular width ψ = 3.2
◦
, with specular
reﬂection coefﬁcient r
s
calculated by expressions (43) and (44), as a
function of rms roughness normalized to the wavelength and for
different values of inverse rms surface slope.
diffuse reﬂectance attachment of the Cary5spectrophotometer.
Expression (43) is a good approximation in the case of τ/σ
0
10. For τ/σ
0
10, signiﬁcant deviations occur for σ/λ 0.1,
due to the signiﬁcant proportion of the diffuse component that
is reﬂected into the acceptance cone of the spectrophotometer,
and therefore measured as specular reﬂection.
Figure 6 also shows that expression (44) is a better
approximation than (43) for a limited range of parameters
(τ/σ
0
≈ 10 and σ
0
/λ ≈ 0.1) but is worse for other parameters;
this may explain the controversy about its accuracy relative
to (43).
4.3. Reﬂection of diffuse incident light from an
opticallyrough surface
The diffuse–diffuse reﬂection coefﬁcient is calculated using
an angular average over all angles of incidence of the Fresnel
reﬂection coefﬁcient r
F
(θ
i
), where θ
i
is the angle of incidence
of the light [43]:
r
dd
=
2
π
_
π/2
0
r
F
(θ
i
)dθ
i
. (46)
We use the same values of diffuse–diffuse reﬂection coefﬁcient
for reﬂection from a rough surface and a smooth surface. This
is because in both cases the reﬂection coefﬁcient is an average
value over all angles of incidence, and the total reﬂected light
is equal to a good approximation if multiple surface reﬂections
at a rough surface are neglected. For the case of a coating on
a substrate,
r
b
dd
= r
dd
(N
1
= N
c
, N
2
= N
air
), (47)
r
s
dd
= r
dd
(N
1
= N
c
, N
2
= N
s
), (48)
where N
c
, N
s
and N
air
are the complex refractive indices of the
coating, substrate and air, respectively. Note that the complex
refractive index is N = n + iκ, where n is the refractive index
and κ = kλ/4π is the extinction coefﬁcient.
3577
A B Murphy
300 400 500 600 700 800
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
R
e
f
r
a
c
t
i
v
e
i
n
d
e
x
Wavelength (nm)
n(TiO
2
)
κ(TiO
2
)
n(Ti)
κ(Ti)
Figure 7. Real and imaginary parts of the refractive indices of rutile
and titanium.
It is worth noting that the expressions (40), (41), (47)
and (48) for r
f
cc
, r
f
cd
, r
b
dd
and r
s
dd
, respectively, are required
in fourﬂux models as well as twoﬂux models. The other
reﬂection coefﬁcients that are required in fourﬂux models, r
b
cc
,
r
b
cd
, r
s
cc
, r
s
cd
, and for diffuse illumination, r
f
dd
, (the notation used
is deﬁned in section 3) are easily calculated using analogous
expressions.
5. Experiment and discussion
A rutile titanium dioxide coating was formed by oxidizing a
piece of titanium sheet in oxygen at 1 bar at a temperature
of 850
◦
C for 10 min. The titanium sheet was etched in
Kroll’s solution for 10 s, prior to oxidation, to provide a rough
substrate. Suchoxide semiconductor coatings ontitaniumhave
been used to investigate the photocatalytic splitting of water
into hydrogen and oxygen [23, 24]. The thickness of the rutile
coating is estimated to be 2000 ±200 nm using the oxidation
rate data given by Dechamps and Lehr [44]. Using an atomic
force microscope to measure the surface proﬁle and standard
analysis methods [45], the rms roughness σ
0
of the surface was
measured to be 571 nm and the autocorrelation length τ to be
6.48 µm, given an inverse rms surface slope of τ/σ
0
= 11.3.
(For the substrate, σ
0
was 520 nm and τ was 9.71 µm; these
data are not required by the model.)
The reﬂection coefﬁcients r
f
cc
and r
f
cd
were calculated
using (40) and (41) for acceptance cone halfangular width
ψ = 3.2
◦
, which is the average value for the geometry of the
Cary 5 diffuse reﬂectance attachment, as discussed in section 2.
The complex refractive indices N = n + iκ of TiO
2
and Ti
used in the calculation are shown in ﬁgure 7; κ is known
as the extinction coefﬁcient. The real part of the refractive
index of rutile was taken from Cardona and Harbeke [46] and
Devore [47], as reported by Ribarsky [48] and the imaginary
part fromthe work of Eagles [49]. The Ti data were taken from
Ribarsky [48].
Figure 8 shows calculated values of the reﬂection
coefﬁcients r
f
cc
, r
f
cd
, r
s
dd
and r
b
dd
. As expected for the relatively
rough surface, r
f
cd
¸ r
f
cc
. This indicates that the transmitted
light will be predominately diffuse, so the modiﬁed Kubelka–
Munk model should be applicable.
300 400 500 600 700 800
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
R
e
f
l
e
c
t
i
o
n
c
o
e
f
f
i
c
i
e
n
t
Wavelength (nm)
r
f
cd
r
f
cc
r
b
dd
r
s
dd
Figure 8. Reﬂection coefﬁcients for a rutile TiO
2
coating on a Ti
substrate, with σ
0
= 570 nm and τ = 6.5 µm, and for ψ = 3.2
◦
.
300 400 500 600 700 800
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
D
i
f
f
u
s
e
r
e
f
l
e
c
t
a
n
c
e
R
c
d
Wavelength (nm)
Calculated ( N
c
+ 10%, N
c
 10%)
Measured
Figure 9. Measured and calculated value of the diffuse reﬂectance
from the rutile TiO
2
coating on a Ti substrate, with thickness
2000 nm, negligible scattering coefﬁcient, absorption coefﬁcient
calculated from the data shown in ﬁgure 7 and other parameters as
for ﬁgure 8. The dashed and dotted line, respectively, show the
effect of increasing and decreasing the refractive index by 10%.
Figure 9 shows measured values of the reﬂectance R
cd
and the values calculated using the modiﬁed Kubelka–Munk
model. The scattering coefﬁcient S is set to a negligible value
(to avoid dividing by zero, it has to be nonzero). The inﬂuence
on the calculated reﬂectance of altering the real and imaginary
components of the refractive index by ±10% is shown in the
graph. The literature values of refractive index vary by at
least 10%, so this is a useful estimate of the uncertainty in
the calculated value. The inﬂuence of altering the coating
thickness by the same percentage is smaller.
The agreement between the measured and calculated
values is good for wavelengths above about 300 nm. The
reﬂectance curve has the same form as the refractive index
of rutile TiO
2
, except for a pronounced dip at around 400 nm.
This dip corresponds to the rapid decrease of the absorption
coefﬁcient K = 2k = 8πκ/λ at the bandgap wavelength of
rutile TiO
2
. The absorption coefﬁcient is greater than 10
7
m
−1
for wavelengths below350 nm, decreasingtoless than100 m
−1
for wavelengths above 450 nm. Clearly, the Kubelka–Munk
3578
Modiﬁed Kubelka–Munk model for calculation of the reﬂectance
model is able to calculate the reﬂectance accurately in the
case of collimated illumination of a rough surface, even for
a coating with negligible scattering coefﬁcient S and for a very
wide range of absorption coefﬁcient K. At wavelengths below
300 nm, the agreement between the measured and calculated
reﬂectance is not as good; agreement can be obtained if the
real and imaginary parts of the refractive index are increased
by about 25%. At these wavelengths at which absorption is
strong, measurement of the refractive index is difﬁcult, and the
literature values differ by up to 50% [46], so the discrepancy
between the prediction of the model and measurement is likely
to be related to uncertainties in the refractive index data.
The main requirement for the Kubelka–Munk model to
be valid is that the light ﬂuxes within the coating are diffuse.
This will of course be the case if illumination is diffuse. If
illumination is collimated, then there has to be a mechanism
for the light ﬂux to become diffuse. One way this can be
provided is by strong scattering within the coating. The
mechanism considered here is that provided by an optically
rough surface; the roughness of the surface means that the
incident light is ‘scattered’, so that both the reﬂected and
transmitted light are diffuse. The angular distribution of the
reﬂected light provides an indication of the diffuseness of the
transmitted light. Figure 4 indicates the reﬂected and hence
transmitted light will be mainly diffuse for opticallyrough
surfaces (σ
0
λ/8) with inverse surface slope τ/σ
0
10.
In the current case, σ
0
∼ λ and τ/σ
0
∼ 10, so the coating
is near the edge of the range of applicability of the modiﬁed
Kubelka–Munk model. Nevertheless, the model predicts the
reﬂectance of the coating and substrate well.
For opticallyrough surfaces r
f
cc
_ r
f
cd
, and thus can be
neglected in expression (13) for the reﬂectance. However,
it remains important to use (41) for the diffuse reﬂection
coefﬁcient r
f
cd
, rather than simply the Fresnel coefﬁcient r
F
.
This is apparent from ﬁgure 3; for τ/σ
0
10 and σ
0
/λ 0.1,
the diffuse reﬂection coefﬁcient is signiﬁcantly smaller than
the Fresnel coefﬁcient (which was assumed to be 100% for the
purposes of the ﬁgure).
It should be noted that it is possible for both the surface of
the coating and the interface between the coating and substrate
to be opticallyrough, but for the reﬂected light to exhibit
interference effects. This can occur when the coating is of
approximately constant thickness and follows the contours
of the substrate and when scattering and absorption within
the coating are weak. This did not occur for the current
coating; the surface of the substrate had an autocorrelation
length about 50% greater than that of the coating and had a
very different appearance on the scale of the surface roughness.
However, it can occur in thin coatings (of the order of 200 nm
or less) formed by oxidation of the substrate or by deposition
techniques. Transport models such as the Kubelka–Munk
model do not take into account optical phase and are therefore
not applicable when interference fringes occur.
6. Conclusions
The Kubelka–Munk twoﬂux model is strictly only applicable
to the case of diffuse illumination. However, it has frequently
been used, as extended by Saunderson to allow treatment of
reﬂection from interfaces, to calculate diffuse reﬂectance of
coatings under collimated illumination. Previous work has
shown that useful results can be obtained for only speciﬁc
cases: opticallythick weakly or nonabsorbing coatings,
absorbing coatings whose reﬂectance is very weak and for
coatings containing highlyscattering particles whose sizes
are larger than a wavelength. The inﬂuence of the surface
morphology of the coating has not been considered.
I have extended the Kubelka–Munk model to the case
of collimated illumination of opticallyrough surfaces, by
modifying the Saunderson extension to allow treatment of
reﬂection of collimated light from opticallyrough, optically
smooth and intermediate surfaces. Further, I have introduced
an expression for the reﬂection coefﬁcient that allows the
separation of reﬂectance into diffuse and collimated (specular)
components, taking into account the characteristics of the
integrating sphere used to measure the reﬂectance. The
expression for the reﬂectance has been compared with other
simple treatments, which have been found to be inaccurate
for some classes of rough surfaces, including those for which
the modiﬁed Kubelka–Munk model is applicable. Analysis
of the angular distribution of the reﬂected radiation indicates
that the light in the coating will be diffuse, and hence the
modiﬁed Kubelka–Munk model is applicable, for optically
rough surfaces with inverse surface slope τ/σ
0
10.
The modiﬁed Kubelka–Munk model has been tested in
the case of an opticallyrough rutile titanium dioxide coating
on a titanium substrate and found to give good agreement with
measurements for wavelength ranges in which absorption of
the coating is both strong and weak, even with neglibible
scattering. Hence, the modiﬁcations extend the range in
which the Kubelka–Munk model can be applied to collimated
illumination to a wide range of opticallyrough coatings. It is
expected that if the surface is sufﬁciently rough to ensure that
the light transmitted into the coating is diffuse, the modiﬁed
Kubelka–Munk model will be applicable irrespective of the
magnitude of the absorption and scattering coefﬁcients of the
coating.
Acknowledgments
I thank Dr Piers Barnes for measuring the rms roughness
and autocorrelation length of the rutile TiO
2
coating and the
titanium substrate and Dr Ian Plumb and Dr Barnes for helpful
comments.
Appendix A. Fresnel reﬂection coefﬁcients
The Fresnel reﬂection coefﬁcient for unpolarized light is given
by r
F
(θ
i
) =
1
2
[r

(θ
i
) + r
⊥
(θ
i
)], where r

(θ
i
) and r
⊥
(θ
i
)
are, respectively, the reﬂection coefﬁcients of light polarized
with electric ﬁeld parallel and perpendicular to the plane of
incidence, and θ
i
is the angle of incidence of the light [29, 30].
We consider light passing from medium 1 to medium 2, where
the complex refractive index of medium l is
N
l
= n
l
+ iκ
l
, (A.1)
where n
l
is the real part of the refractive index (usually referred
to as the refractive index) and κ
l
is the extinction coefﬁcient.
3579
A B Murphy
It can be shown that [29]
r
⊥
(θ
i
) =
cos
2
θ
i
+ u −v cos θ
i
cos
2
θ
i
+ u + v cos θ
i
, (A.2)
r

(θ
i
) = r
⊥
(θ
i
)
u −v sin θ
i
tan θ
i
+ sin
2
θ
i
tan
2
θ
i
u + v sin θ
i
tan θ
i
+ sin
2
θ
i
tan
2
θ
i
. (A.3)
We then obtain the Fresnel reﬂection coefﬁcient by averaging
(A.2) and (A.3):
r
F
(θ
i
) =
1
2
[r

(θ
i
) + r
⊥
(θ
i
)]
= r
⊥
(θ
i
)
u + sin
2
θ
i
tan
2
θ
i
u + v sin θ
i
tan θ
i
+ sin
2
θ
i
tan
2
θ
i
, (A.4)
where
u =
_
{n
2
1
(n
2
2
−κ
2
2
) −[(n
2
2
−κ
2
2
)
2
+ 4n
2
2
κ
2
2
] sin
2
θ
i
]
2
+ 4(n
2
κ
2
n
2
1
)
2
_ 1
2
_
(n
2
2
−κ
2
2
)
2
+ 4n
2
2
κ
2
2
_
−1
, (A.5)
v =
_
2
_
n
2
1
(n
2
2
−κ
2
2
) −[(n
2
2
−κ
2
2
)
2
+ 4n
2
2
κ
2
2
] sin
2
θ
i
+ ({n
2
1
(n
2
2
−κ
2
2
) −[(n
2
2
−κ
2
2
)
2
+ 4n
2
2
κ
2
2
] sin
2
θ
i
]
2
+ 4(n
2
κ
2
n
2
1
)
2
)
1/2
__
(n
2
2
−κ
2
2
)
2
+ 4n
2
2
κ
2
2
_
−1
_
1/2
. (A.6)
Appendix B. Calculation of reﬂection coefﬁcients
from BRDF
The geometry of the reﬂectance problem was discussed in
detail by Horn and Sjoberg [50]. I present some of the relevant
deﬁnitions and results and combine these with the results of
He et al [32] to obtain expressions for the reﬂection coefﬁcient
r. Here θ represents the polar angle (relative to the surface
normal), and φ represents the azimuthal angle, of a direction.
The subscript i denotes quantities associated with the incident
radiant ﬂux, and the subscript r denotes quantities associated
with the reﬂected radiant ﬂux.
The irradiance I
i
is the incident ﬂux density, while the
radiant exitance M
r
is the reﬂected ﬂux density. The incident
radiance L
i
is the incident ﬂux per unit surface area per unit
projected solid angle, and the reﬂected radiance L
r
is the ﬂux
reﬂected per unit surface area per unit projected solid angle.
The projected solid angle is related to the actual solid angle
ω by
= ωcos θ. (B.1)
The irradiance and the incident radiance are related by
I
i
=
_
ω
i
L
i
dω
i
. (B.2)
Similarly, the radiant exitance andreﬂectedradiance are related
by
M
r
=
_
r
L
r
d
r
. (B.3)
We will make use of the geometric relations
_
Xd =
_
π
−π
_
π/2
0
Xcos θ sin θdθdφ (B.4)
and
_
ω
Xdω =
_
π
−π
_
π/2
0
Xsin θdθdφ. (B.5)
The reﬂection properties of a rough surface are usually
speciﬁed using the BRDF, deﬁned as
ρ(θ
i
, φ
i
, θ
r
, φ
r
) =
dL
r
(θ
i
, φ
i
, θ
r
, φ
r
)
dI
i
(θ
i
, φ
i
)
. (B.6)
The BRDF gives information about how bright a surface will
appear viewed from a given direction when illuminated from
another given direction. We do not require such directional
information; rather we require the reﬂection coefﬁcient, given
by
r = M
r
/I
i
. (B.7)
We therefore need to obtain an expression for r in terms of the
BRDF. Using (B.3) and (B.4),
M
r
=
_
r
L
r
d
r
=
_
π
−π
_
π/2
0
L
r
cos θ
r
sin θ
r
dθ
r
dφ
r
.
(B.8)
From the deﬁnition of the BRDF (B.6), and (B.4),
L
r
=
_
i
ρL
i
d
i
=
_
π
−π
_
π/2
0
ρL
i
cos θ
i
sin θ
i
dθ
i
dφ
i
. (B.9)
We use a collimated source; the irradiance for such a source
in the direction (θ
0
, φ
0
) will be proportional to the product of
the delta functions δ(θ
i
−θ
0
)δ(φ
i
−φ
0
). It must also satisfy
(using (B.2) and (B.5))
I
i
=
_
ω
i
L
i
dω
i
=
_
π
−π
_
π/2
0
L
i
sin θ
i
dθ
i
dφ
i
. (B.10)
This can be accomplished if
L
i
= I
i
δ(θ
i
−θ
0
)δ(φ
i
−φ
0
)/ sin θ
0
. (B.11)
Substituting (B.11) into (B.9) gives
L
r
=
_
π
−π
_
π/2
0
ρI
i
δ(θ
i
−θ
0
)δ(φ
i
−φ
0
)
sin θ
0
cos θ
i
sin θ
i
dθ
i
dφ
i
= ρI
i
cos θ
i
. (B.12)
Substituting this expression into (B.8) gives
M
r
= I
i
_
π
−π
_
π/2
0
ρ cos θ
i
cos θ
r
sin θ
r
dθ
r
dφ
r
. (B.13)
Using (B.7), we obtain the required expression for the
reﬂection coefﬁcient in terms of the BRDF for a collimated
source
r =
_
π
−π
_
π/2
0
ρ cos θ
i
cos θ
r
sin θ
r
dθ
r
dφ
r
. (B.14)
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Analytical treatments of propagation of light in inhomogeneous media are typically complex. melting of solids [11]. this can only occur when the incident light is diffuse. the modiﬁed Kubelka–Munk model will be applicable irrespective of the magnitude of the absorption and scattering coefﬁcients of the coating material. with the Saunderson extension. 39 (2006) 3571–3581 JOURNAL OF PHYSICS D: APPLIED PHYSICS doi:10.1088/00223727/39/16/008 Modiﬁed Kubelka–Munk model for calculation of the reﬂectance of coatings with opticallyrough surfaces A B Murphy CSIRO Industrial Physics. Here. 00223727/06/163571+11$30. Saunderson [5.INSTITUTE OF PHYSICS PUBLISHING J. leaves [9].au Received 16 June 2006. it is assumed that the light is diffuse within the layer. Vargas and Niklasson [19] have examined the case of collimated illumination and shown that the Kubelka–Munk model. even for negligible scattering within the coating. While the development of transport theories is less rigorous than that of analytical treatments. Kubelka and Munk’s original treatment [2. Expressions for the reﬂectance from such surfaces are obtained. Australia Email: tony. 3] is by far the most widely used transport theory. The modiﬁed Kubelka–Munk model is tested in the case of an opticallyrough rutile titanium dioxide coating on a titanium substrate and found to give good agreement with experiment. crystalline materials [10].00 © 2006 IOP Publishing Ltd solarabsorbing pigments and paints [7]. and for this reason transport theories are often used. pigmented plastics [5]. Phys. decorative and protective coatings [6]. in 3571 Printed in the UK .murphy@csiro. or the interfaces are opticallyrough. They developed a slightly modiﬁed method. D: Appl. 14] extended the treatment to allow reﬂection from the front and back surfaces of the layer to be considered. in ﬁnal form 3 July 2006 Published 4 August 2006 Online at stacks. they are nonetheless very useful. and have been applied to a wide range of problems. is of very limited applicability. (Some ﬁgures in this article are in colour only in the electronic version) 1. Australia and CSIRO Energy Transformed National Research Flagship. however.org/JPhysD/39/3571 Abstract The Kubelka–Munk twoﬂux radiative transfer model is strictly applicable only to the case of diffuse illumination but is often applied in the case of collimated illumination.3] took into account only transport within a layer. A relatively simple treatment of reﬂection from surfaces of arbitrary roughness is developed that takes into account the characteristics of the spectrophotometer used to measure reﬂectance. having been applied to examine materials as diverse as paints [4]. The Kubelka–Munk model [2. Strictly. the application of the Kubelka–Munk twoﬂux model to the collimated illumination of opticallyrough surfaces is investigated. It is expected that if the surface is sufﬁciently rough to ensure that the light transmitted into the coating is diffuse. Such theories treat the transport of radiative energy through the medium directly. Lindﬁeld NSW 2070. using effective absorption and scattering coefﬁcients.iop. PO Box 218. when the layers are inhomogeneous. the absorption and scattering coefﬁcients. being accurate only for weaklyabsorbing coatings containing highlyscattering particles whose sizes are larger than a wavelength.g. In this model. human tissue [8]. However. In the Kubelka–Munk model. [1]). the model is frequently used for collimated illumination [15–18]. Introduction The propagation of light in layered media is well understood and relatively easily treated mathematically as long as each layer is homogeneous and the interfaces between media are smooth (e. treatment becomes more difﬁcult. powders [12] and ﬁbres and wool [13]. Phys. it is assumed that the optical properties of the coating are described by two constants.
Here the term reﬂection is used for both opticallyrough and opticallysmooth surfaces. Application of the modiﬁed Kubelka–Munk model developed here allows the interpretation of reﬂectance measurements of these coatings. I derive a slightlymodiﬁed twoﬂux model for the case of collimated illumination of a coating on an opaque substrate that allows general surfaces to be treated. The bandgap of the coating can then be determined from the wavelengthdependence of the absorption coefﬁcient using standard methods [27]. Further. In cases where it is not reasonable to assume that the light is diffuse. Conclusions are given in section 6. Reﬂectance measurements Measurements of reﬂectance are typically performed using a spectrophotometer with an integrating sphere attachment. The sample measured in the experiment described in section 5 was smaller than the approximately 8 by 12 mm . For example. However. The diffuse reﬂectance attachment has two settings. the measurement of reﬂectance using a spectrophotometer with an integrating sphere is described. and that on the right shows the geometry for total reﬂectance measurements (‘S’ position). 2. the sample is oriented so that the incident light is at a small angle to the normal to the surface.or nonabsorbing coatings. using a physical optics approach. Light reﬂected specularly. the measurements to be presented in section 5 were performed using the diffuse reﬂectance attachment of a Cary 5 UVvisible spectrophotometer. the reﬂected light is mainly diffuse. i. This 3572 Figure 1. and inversion of the equations derived allows the absorption coefﬁcient and refractive index to be determined from the measured reﬂectance [26]. depending on the wavelength. useful results were also obtained for absorbing coatings whose reﬂectance is very weak and for coatings containing highlyscattering particles whose sizes are larger than a wavelength. by ﬂameoxidation or ovenoxidation of titanium and have been applied in the photocatalytic splitting of water into hydrogen and oxygen [23–25].e. The differential equations treat absorption and scattering of the light.g. Vargas and Niklasson [19] also used reﬂection coefﬁcients for collimated reﬂection of collimated light. The incident light is collimated. the sample is oriented so that the incident light is normal to the surface of the sample. for reﬂection coefﬁcients from a general surface that depend on the acceptance cone of the measurement apparatus. Rutile TiO2 coatings on titanium substrates can be produced.e.A B Murphy which the reﬂection coefﬁcient from the front of the coating was the Fresnel coefﬁcient (i. and reﬂected light is captured by an integrating sphere. provides a good test of the model. In the ‘D’ position. In section 2. for the reﬂected light to be collimated. so only diffusely reﬂected light is measured. The modiﬁed Kubelka–Munk model is derived in section 3 and the reﬂection coefﬁcients for a general surface are derived and analysed in section 4. The range of surface characteristics for which the modiﬁed twoﬂux model will be valid is then investigated. In this paper. The diagram on the left represents the geometry for diffuse reﬂectance measurements (‘D’ position). normal to the surface. for example. The model is tested for the case of collimated illumination of an opticallyrough rutile TiO2 coating on a titanium substrate. in particular the means by which the apparatus separates the reﬂected light into diffuse and specular components. The Kubelka–Munk model is a twoﬂux model. It is important. and in particular the separation of these reﬂection coefﬁcients into specular (collimated) and diffuse components. In this case. The reﬂection coefﬁcients used in the Saunderson extension were for diffuse reﬂection of diffuse light. In the case of opticallyrough surfaces. This is done by developing expressions. Treatment of collimated illumination of a general surface requires expressions for reﬂection coefﬁcients valid for both opticallysmooth and opticallyrough surfaces. Schematic of measurement geometry of the diffuse reﬂectance attachment of the Cary 5 spectrophotometer. a spectrophotometer with integrating sphere attachment). A schematic of the geometry is given in ﬁgure 1. the reﬂection coefﬁcient for collimated reﬂection of collimated light) and found it to have a wider range of applicability. it is appropriate to use relatively simple expressions for these reﬂection coefﬁcients. This extends previous studies that examined only opticallysmooth surfaces. depending on the optical roughness of the surface. fourﬂux models (in which the ﬂuxes are both collimated and diffuse light travelling in forward and reverse directions) may be used [20–22]. both specularly. the two ﬂuxes are diffuse light travelling in the forward and reverse directions. in comparing predictions of the model with experiment. is not captured by the integrating sphere. which are presented and discussed in section 5. The transmitted light is also mainly diffuse. and the term scattering is reserved for the description of scattering of light within the coating. In each case. reduction of the bandgap of rutile TiO2 is imperative to improve its efﬁciency in photocatalytic watersplitting [23]. In keeping with the simplicity of the twoﬂux model. Note that reﬂection from opticallyrough surfaces is often referred to as scattering. and absorption can be either strong or weak.and diffuselyreﬂected light are captured by the integrating sphere. As noted above. diffuse or partially collimated and partially diffuse. I obtain simple expressions for reﬂection coefﬁcients at surfaces of arbitrary roughness that allow the characteristics of the measurement apparatus to be taken into account. While it was rigorously correct only for opticallythick weakly. the sample is represented by the rectangle on the right of the integrating sphere. This system is used for the measurements. In the ‘S’ position. it is possible. since scattering within the coating is weak. when collimated illumination is used. to take into account the properties of the measurement apparatus (e. This means treatment by the twoﬂux method is likely to be valid under collimated illumination for a wider range of coating parameters than is the case for an opticallysmooth surface.
This is a reasonable a priori assumption in the case of an opticallyrough surface at the aircoating interface. Taking into account the fact that a 3 mm diameter circular region is illuminated. I distinguish between reﬂectance. Superscript i represents the surface from which reﬂection occurs as follows: Figure 2. showing boundary conditions at z = 0 and z = h. The coating lies between the front plane at z = 0 and the back plane at z = h. It is usual in applying the Kubelka–Munk model to write ζ = 1/2 and ε = 2. respectively. While at ﬁrst glance this may seem inconsistent with the previous assumption. Both are dimensionless ratios. which refers to the reﬂection of light from the coating–substrate system. while for Mie scattering. In the calculations of reﬂectance from a rough surface that are presented in this paper. The incident light travels in the positive z direction and is collimated. A matt Teﬂon reference was used to provide a nominal 100% reﬂectance measurement. i • rdd : reﬂection of a diffuse light as diffuse light. Modiﬁed Kubelka–Munk model Figure 2 shows the geometry considered. I will use R to denote reﬂectance and r to denote a reﬂection coefﬁcient. since the spectrophotometer allows both the collimated and diffuse The Kubelka–Munk model uses an effective scattering coefﬁcient S and an effective absorption coefﬁcient K to describe the optical properties of the coating. ε = 2 [28]. which is appropriate to a coating on an opaque substrate. it allows the validity of that assumption to be checked. The effective absorption coefﬁcient is related to the usual absorption coefﬁcient k by K = εk. so that S = s and K = 2k. where the forward scattering ratio ζ is deﬁned as the ratio of the energy scattered by a particle in the forward hemisphere to the total scattered energy. and reﬂection coefﬁcients. dz dJd = (S + K)Jd − SId . and the forward. in the ‘D’ position. 1/2 < ζ < 1.04 mm vertically by 13. I allow the light reﬂected from the front surface of the coating to have both collimated and diffuse components. where the average crossing parameter ε is deﬁned such that the average path length travelled by diffuse light crossing a length dz is εdz. there are cases in which the reﬂected light may be partially collimated while the light within the coating is diffuse. light reﬂected from the centre of the sample at an angle greater than 2. f b Id (0) = (1 − rcc − rcd )Ic0 + rdd Jd (0) f (1) and s Jd (h) = rdd Id (h). Since the incident light is collimated. but the light within the coating is diffuse.8◦ vertically and 3. for example coatings with an opticallysmooth front surface that are strongly scattering.and backwarddirected diffuse light intensities in the coating by Id (z) and Jd (z). The entrance aperture of the integrating sphere is oval in shape and 11.Modiﬁed Kubelka–Munk model for calculation of the reﬂectance components of the reﬂectance to be measured. dz (3) (4) 3573 . while for semiisotropic (i.e. the following reﬂection coefﬁcients have to f f b s be calculated: rcc . • i = b represents reﬂection from the back surface of the coating (at z = 0). The effective scattering coefﬁcient is related to the usual scattering coefﬁcient s by S = 2(1 − ζ )s. diffuse reﬂectance corresponds to measurements made in the ‘D’ position and collimated reﬂectance to the difference between measurements made in the ‘S’ and ‘D’ positions. as is required to apply a twoﬂux model. The coating rests on an inﬁnite substrate starting at z = h. it can be calculated that light reﬂected at angles greater than 2. The differential equations describing the energy balance between diffuse light in the forward (positive z) and backward (negative z) directions are dId = −(S + K)Id + SJd . Hence. isotropic in the direction of propagation) diffuse light. • i = f represents reﬂection from the front surface of the coating (at z = 0). Hence a 3 mm diameter spot on the sample was illuminated. respectively. ζ = 1/2.44 mm horizontally. Let the incident collimated light intensity be denoted by Ic0 . it is useful to calculate both components. which refer to reﬂection from a single surface. Finally. (2) 3.9 ± 0. Geometry. The boundary conditions at z = 0 and z = h are. The following reﬂection coefﬁcients have to be considered: i • rcc : reﬂection of collimated light as collimated light. Collimated light is denoted by solid arrows and diffuse light by dotted arrows. The inner diameter of the sphere is 110 mm.87◦ vertically and 3. aperture at the back of the integrating sphere. rdd and rdd . ε = 1. rcd . A matt black plate with a small (3 mm diameter) aperture is placed between the sphere and the sample. i • rcd : reﬂection of collimated light as diffuse light. For collimated light.50◦ horizontally is captured. I assume that the light within the coating is diffuse. For Rayleigh scattering. Further. • i = s represents reﬂection from the front surface of the substrate (at z = h).5 ± 0.8◦ horizontally is captured in the ‘D’ position.
I deﬁne the reﬂection coefﬁcient as the ratio of the intensity of the reﬂected light to the intensity of the incident light. Beckmann and Spizzichino [31] derived expressions describing the reﬂection of light from rough surfaces. 30]). Reﬂection of collimated incident light from an opticallyrough surface In this section. To specify the surface fully. or intermediate.e. The measure used is the autocorrelation length τ . s a + b coth(bSh) − rdd (10) The collimated reﬂectance from the coating and substrate system is just the collimated reﬂected component of the incident radiative ﬂux normalized to the incident radiative ﬂux f Rcc = rcc . Thorsos showed that this approximation is accurate for τ/λ 1 when an appropriate shadowing treatment is used [33]. I only consider reﬂection from the initial interaction of the incident light with the surface. Reﬂection arising from scattering from discontinuities beneath the surface or reﬂections from subsurface interfaces is taken into account using the Kubelka–Munk model that was derived in section 3. I consider the calculation of reﬂection coefﬁcients for collimated light incident on a surface that may be opticallyrough or opticallysmooth. Expressions for Fresnel coefﬁcients are given in 3574 The mean height is z = 0 and σ0 is the rms roughness of the surface. the Fresnel coefﬁcients. 14] for diffuse reﬂectance in the case of diffuse illumination Rdd = rdd + f (15) (1 − f b rdd )(1 − rdd )RKM . in this section. b 1 − rdd RKM f f b rcd Ic0 + (1 − rdd )Jd (0) . (13) with RKM given by (10). is treated in standard optics textbooks (e. (5) Jd (z) = (a − b)C1 exp(−Sbz) + (a + b)C2 exp(Sbz). Ic0 f (12) appendix A. Using boundary conditions (1) and (2) gives f Id (z) = {(1 − rcc − rcd )Ic0 [b cosh(Sbh − Sbz) s b s +(a − rdd ) sinh(Sbh − Sbz)]}{b(1 − rdd rdd ) cosh(Sbh) b s b s +(a − rdd − rdd + ardd rdd ) sinh(Sbh)}−1 . in evaluating an integral that arises in the derivation. Reﬂection coefﬁcients 4. (The reﬂection coefﬁcient is sometimes deﬁned in terms of the electric ﬁeld amplitude. the probability that a point on the surface falls within the height range z to z + dz is p(z)dz. normalized to the incident radiative ﬂux Rcd = Using (9) gives Rcd = rcd + f b (1 − rcd − rcc )(1 − rdd )RKM . who gave expressions for the bidirectional reﬂectance distribution function (BRDF) for incident light of both polarizations and for unpolarized light and also took into account shadowing.1. and did not consider shadowing effects. that the surface is either optically . where θi is the angle of incidence. i. to describe reﬂection at any angle. (11) The diffuse reﬂectance from the coating and substrate system is the sum of the diffuse reﬂected component of the incident radiative ﬂux and the transmitted diffuse backward ﬂux at z = 0.g. The factor 8 is sometimes replaced by 16 or 32 [31]. Here I use the term reﬂection to include such ‘scattering’. I follow the more general physical optics approach. Since this is not always the case for the surfaces of interest. The geometrical optics approach is mathematically simpler but is only valid when the wavelength of the incident light is much smaller than the dimensions of the surface irregularities. it is useful to consider nomenclature. which is a measure of the spacing between surface peaks. since a proportion of the reﬂected light is scattered at angles of reﬂection other than that equal to the angle of incidence. where p(z) = √ 1 2π σ0 2 exp(−z2 /2σ0 ).) Further. The rms slope of the surface is proportional to σ0 /τ . a horizontal length measure is also required.A B Murphy The general solution to these equations is Id (z) = C1 exp(−Sbz) + C2 exp(Sbz). we obtain Jd (0) = where RKM = (1 − rcc − rcd )RKM Ic0 . Under such conditions. Before continuing. Opticallyrough surfaces are usually deﬁned by the Rayleigh criterion.e. i. I use the results of He et al [32]. (7) f s Jd (z) = {(1 − rcc − rcd )Ic0 [brdd cosh(Sbh − Sbz) s b s +(1 − ardd ) sinh(Sbh − Sbz)]}{b(1 − rdd rdd ) cosh(Sbh) b s b s −1 (8) +(a − rdd − rdd + ardd rdd ) sinh(Sbh)} . This result is similar to that ﬁrst obtained by Saunderson [5. [29. which states that surfaces can be treated as opticallysmooth if the heights of surface irregularities are less than λ/(8 cos θi ). (6) √ where a = (S + K)/S and b = a 2 − 1 and C1 and C2 are constants. However. Reﬂection from rough surfaces is often described as scattering. • The assumption is made. The derivation of reﬂection coefﬁcients for collimated light incident on an opticallysmooth surface. The assumptions made in the derivation are: • The height distribution on the surface is assumed to be Gaussian and spatially isotropic. Two important approaches to the calculation of reﬂection properties of rough surfaces are that based on physical optics (the Beckmann–Spizzichino model) and that based on geometrical optics (the Torrance–Sparrow model). • The electric ﬁeld at a given point on the surface is set to the value that would exist if the surface were replaced by its local tangent plane (the ‘tangent plane’ or ‘Kirchoff’ approximation). b 1 − rdd RKM (14) 4. b 1 − rdd RKM f f (9) s 1 − rdd [a − b coth(bSh)] . they gave results for only one polarization. f f From (8).
The geometric factor G is given by G= 4(1 + cos θi cos θr − sin θi sin θr cos φr )2 . (cot θr ) + 1 (30) Here rF (θ ) is the Fresnel reﬂection coefﬁcient evaluated at the bisecting angle ˆ ˆ θ = cos−1 (k r − k i /2). The shadowing function Z is given by . for a perfectlyreﬂecting mirrorlike surface. it can be considerably smaller than the rms roughness σ0 . The BRDF for unpolarized light is given by (16) ρ = ρs + ρd . is a delta function that is unity in the cone of specular reﬂection and zero elsewhere. In calculating the specular component of the BRDF for rough surfaces. These have been accounted for in section 3 and are ignored here. the polar angles of incidence and reﬂection and φr is the azimuthal angle of reﬂection. Particularly for grazing angles of incidence or reﬂection. a ‘directional diffuse’ component. (22) obtained in appendix B. It is assumed that the azimuthal angle of incidence is φi = 0. (24) . θi and θr are.Modiﬁed Kubelka–Munk model for calculation of the reﬂectance very rough (i. which imply that θ = θi . and a ‘uniform diffuse’ component.e. where the specular component is ρs = rF θ exp(−g)Z cos θi dωi 2 and for g 1 (i. rcc and rcd . from a rough surface. together with the expression for the reﬂection coefﬁcient r in terms of the BRDF r= π −π 0 π/2 ρ cos θi cos θr sin θr dθr dφr (34) The surface roughness function g is given by g = [(2πσ/λ)(cos θi + cos θr )] . (cos θi + cos θr )2 (20) 1 2σ0 τ cot θ − erfc √ 2σ0 2 π τ cot θ The BRDF expressions (17) and (18) are now fully deﬁned. • Multiple reﬂections from the surface are ignored. (26) where z0 is the root of the equation σ0 π z2 z = (Ki + Kr ) exp − 2 2 4 2σ0 and Ki = tan θi erfc(τ cot θi /2σ0 ). These expressions. so the specular reﬂection coefﬁcient is modiﬁed accordingly to give rs = rF (θi ) exp(−g)Z. rF (θ ) is multiplied by exp(−g)Z. (25) The effective roughness σ was introduced by He et al to allow averaging to occur over only the illuminated (nonshadowed) parts of the surface. 2 (21) The distribution function D is given by D= where vxy = 2π sin2 θi − 2 sin θi sin θr cos φr + sin2 θr λ 1/2 π 2τ 2 4λ2 2 −vxy τ 2 g m exp(−g) exp m!m 4m m=1 ∞ . They are related by 2 2 σ = σ0 (1 + z0 /σ0 )−1/2 . respectively. The latter corresponds to the subsurface scattering and multiple subsurface reﬂections described by the Kubelka–Munk model. θr = θi and φr = π . (36) . (35) Using (16). Kr = tan θr erfc(τ cot θr /2σ0 ). Further. we expect rF (0) = 1 and rs = 1. (27) . a rough surface) 2 −vxy τ 2 π 2τ 2 1 exp D∼ = 4λ2 g 4g . This contribution is negligible for a surface with gentle slopes. (18) and (34). the unit vectors in the ˜ ˜ direction of the incident and reﬂected light.e. respectively.e. (2πσ/λ) 1. the diffuse component of r is given by rd = π −π 0 π/2 ρd cos θi cos θr sin θr dθr dφr . Nayar et al [34] give useful approximate expressions for D.e. σ/τ 1). deﬁned below) or that the surface has gentle slopes (i. can be used to obtain expressions for the collimated–collimated and collimated–diffuse reﬂection f f coefﬁcients. where σ is an effective surface roughness. (17) (28) (29) and the diffuse component is ρd = rF (θ )GZD . (37) 3575 . 1 1 − 2 erfc(τ cot θi /2σ0 ) . respectively. He et al [32] gave expressions for the BRDF as the sum of a specular component. For g 1 (i. ˜ ˜ (19) Zi (θi ) = Zr (θr ) = (cot θ ) = (31) (32) . The total reﬂection coefﬁcient is split into specular and diffuse components r = rs + rd . (33) ˆ ˆ where k i and k r are. a smooth surface) 2 2 2 −vxy τ 2 ∼ π τ exp(−g)g exp D= 4λ2 4 For specular reﬂection. The ‘directional diffuse’ component corresponds to what is here called diffuse reﬂection. (23) Calculation of D can cause numerical problems because of the large numbers involved for large values of m. π cos θi cos θr (18) where Z = Zi (θi )Zr (θr ). (cot θi ) + 1 1 [1 − 2 erfc(τ cotθr /2σ0 )] .
decreasing the average reﬂection coefﬁcient. i. for different values of the inverse rms surface slope τ/σ0 .8 0. for the case of θi = 0. The Fresnel reﬂection coefﬁcient at normal incidence is assumed to be 100%. In the measurement of reﬂectance using a spectrophotometer with an integrating sphere. diffuse. the refractive index N1 is that of air.0 0. Figure 4 shows the angular dependence of the integrand (1/π)rF (θ )GZD sin θr in expression (36) for diffuse reﬂection coefﬁcient rd .1 0. The regions that may therefore be inaccurate are marked on the graph by crosshatching. a signiﬁcant fraction of the diffuselyreﬂected light is reﬂected within a few degrees of θr = 0◦ . + 4.01 0.6 1.0 0. this is because of two effects. The ﬁrst is that on the scale of the surface roughness the average angle of incidence increases as the surface slope increases.e. The specular reﬂection coefﬁcient is independent of rms surface slope. and rcd = rd θr >ψ .8 0.6 0. respectively. then the reﬂection coefﬁcients required in the modifed Kubelka–Munk model ((11) and (13)) are f rcc = rs + rd θr ψ Using (36) and (37).g. Note that the equation for calculation of diffuse reﬂection coefﬁcient is only accurate for τ/λ > 1. Z < 1. Figure 4. The wavelength is 500 nm. For opticallyrough surfaces f (e. specular and diffuse reﬂection coefﬁcients r. the diffuse component rcd dominates. which is the average value for the diffuse reﬂectance attachment of the Cary 5 spectrophotometer. total total total specular (all values of τ/σ 0) 0.5 0.g. for normal incidence. For opticallysmooth surfaces (e.7 0. rs and rd . τ / σ 0 = 2 σ 0 = 1 µ m. (43) (38) 3576 . σ0 = 10 nm). τ / σ 0 = 10 Reflection coefficients r. The total reﬂection coefﬁcient at θi = 0 is given by f r(0) = rs + rd = rcc + rcd = rF (0) exp(−g) f 1 π/2 rF (θr /2)GZD sin θr dθr .0 0. the specular f component rcc dominates. we obtain (noting that the following apply for normal incidence: rF (θi ) = rF (0).g. the results are not reliable for low σ0 /λ. the incident collimated light has angle of incidence θi = 0.9 1.4 λ = 500 nm σ 0 = 1 µ m. The value of the integrand depends strongly on τ/σ0 and relatively weakly on σ0 . and reﬂected light within an acceptance cone centred around θr = 0 is measured as specularly reﬂected light (see section 2). τ / σ 0 = 5 σ 0 = 1 µ m.0 0. Dependence of total. both components are important. τ / σ 0 = 10 σ 0 = 100 nm. Results are given for different values of inverse rms surface slope. The second is a result of shadowing of the diffuselyreﬂected light.A B Murphy 1. Values for rms roughness greater than 1 µm are equal to the 1 µm values shown.4).2. to allow the effect of surface roughness to be shown more clearly. The diffuse reﬂection coefﬁcient is lower for smaller values of τ/σ0 .4 0. particularly for larger values of τ/σ0 . for different values of rms roughness and inverse rms surface slope.2 τ/σ 0 = 5: τ/σ 0 = 10: τ/σ 0 = 20: (1/π ) rF (θ') GZD sin θr 1. The Fresnel reﬂection coefﬁcient at normal incidence is assumed to be 100%. and the refractive index N2 is that of the coating. rs and r as a function of wavelengthnormalized surface roughness σ0 /λ for θi = 0.3 0. While the integrand is zero for θr = 0. in particular.2 diffuse. Dependence of integrand in diffuse coefﬁcient expression on the angle of reﬂection. If this acceptance cone has halfangular width ψ. τ / σ 0 = 20 σ 0 = 1 µ m. diffuse. the integrand is independent of σ0 .8 1. For surfaces of intermediate roughness.1 1 10 Wavelengthnormalised rms roughness σ 0 / λ Angle of reflection θ r (degrees) Figure 3.2 1. for σ0 1 µm. rd 0. τ / σ 0 = 50 σ 0 = 50 nm. Comparison with other expressions It is common (e.6 0. rs. (42) π 0 Figure 5 shows the total reﬂection coefﬁcient r and its f f components rcc and rcd for halfangular width ψ = 3. f (39) Figure 3 shows the reﬂection coefﬁcients rd . hence for low τ/σ0 . since reﬂection at this angle is classed as specular. and Z = 1 for specular reﬂection) f rcc = rF (0) exp(−g) + 1 π ψ rF (θr /2)GZD sin θr dθr (40) 0 and rcd = f 1 π π/2 rF (θr /2)GZD sin θr dθr . σ0 = 1 µm). [35–37]) when dealing with the reﬂection from opticallyrough surfaces to use just the specular reﬂection coefﬁcient rs = rF (0) exp − 4π σ0 cos θi λ 2 . ψ (41) In calculating r(0) and r(θr /2) with (A. It is assumed that the Fresnel reﬂection coefﬁcient for normal incidence rF (0) is 100% for the purposes of the ﬁgure.4 0. Note that the specular reﬂection coefﬁcient rs is independent of τ/σ0 . the BRDF is independent of azimuthal angle φr . The regions in which the total and diffuse reﬂection coefﬁcients may be inaccurate are indicated by crosshatching. at normal incidence on rms roughness normalized to wavelength.2◦ . τ / σ 0 = 10 σ 0 = 1 µ m.
for normal incidence. this may explain the controversy about its accuracy relative to (43). (45) There are a number of shortcomings inherent in using (43) and (45). for ◦ halfangular width ψ = 3. The Fresnel reﬂection coefﬁcient at normal incidence is assumed to be 100%.100 0. so the total reﬂection coefﬁcient is r(0). N2 = Nair ).010 f f f (b) τ/σ 0 = 20 0.100 r cc. Reﬂection coefﬁcient r and its specular and diffuse f f components rcc and rcd . τ/σ0 = 10 0. Comparison of reﬂection coefﬁcient rcc for spectrophotometer of halfangular width ψ = 3. τ/σ0 = 5 f Reflection coefficients r. 4. deviations of σ from σ0 are neglected. Hristov and Friehe [42] have recently claimed that the Bessel function factor is unnecessary. where θi is the angle of incidence of the light [43]: rdd = 2 π π/2 rF (θi )dθi .2 . and the total reﬂected light is equal to a good approximation if multiple surface reﬂections at a rough surface are neglected. and the effective angle of incidence on the scale of the surface roughness increases when the average surface slope increases. substrate and air.010 Specular reflection coefficient 0. Landron et al [39]. f f f 0. respectively. this expression has also been used by.100 r cc. these affect the calculation of the total reﬂection coefﬁcient. signiﬁcant deviations occur for σ/λ 0. and therefore measured as specular reﬂection. Boithias [38] suggested a modiﬁcation to rs = rF (0) exp − × I0 1 2 4πσ0 cos θi λ 2 2 4πσ0 cos θi λ 2 .3. for three different rms surface roughnesses and for two values of inverse rms surface slope. Presumably in these cases it is assumed that light that is not reﬂected specularly is reﬂected diffusely. as a function of rms roughness normalized to the wavelength and for different values of inverse rms surface slope. Note that the complex refractive index is N = n + iκ. Figure 6 compares expressions (43) and (44) for the f specular reﬂectance with the value of rcc given by (40). τ/σ0 = 20 r cc. τ/σ0 = 50 rs.010 0. First. the division of the reﬂected light into specular and diffuse components does not take into account the component of the diffuse reﬂection that is reﬂected at or close to the specular angle of reﬂection (θr ≈ θi .000 1. Figure 6 also shows that expression (44) is a better approximation than (43) for a limited range of parameters (τ/σ0 ≈ 10 and σ0 /λ ≈ 0. φr = φi + π).001 Wavelengthnormalised rms roughness σ0/λ 300 400 500 600 700 800 Wavelength (nm) Figure 5. (44) where I0 is the modiﬁed Bessel function of order zero. Reﬂection of diffuse incident light from an opticallyrough surface The diffuse–diffuse reﬂection coefﬁcient is calculated using an angular average over all angles of incidence of the Fresnel reﬂection coefﬁcient rF (θi ).2◦ . Further. r. r cc. which is the average value for the We use the same values of diffuse–diffuse reﬂection coefﬁcient for reﬂection from a rough surface and a smooth surface.1) but is worse for other parameters.000 σ 0 = 100 nm: σ 0 = 1 µ m: r cd f f r & r cd (r cc ~ 0) r cc. with specular reﬂection coefﬁcient rs calculated by expressions (43) and (44).001 0. if rs is given by (43). we have 4πσ0 cos θi rd = r(0) 1 − exp − λ 2 diffuse reﬂectance attachment of the Cary 5 spectrophotometer. f f f r cd r cc. For the case of a coating on a substrate. However. Miller et al [40] derived this modiﬁcation. equation (43) rs. respectively.Modiﬁed Kubelka–Munk model for calculation of the reﬂectance 1.000 (a) τ/σ 0 = 10 0.1. f Figure 6. r cd σ 0 = 10 nm: r & r cc. For τ/σ0 10. N2 = Ns ). (47) (48) where Nc .001 1. Finally. compared with using the expressions (40) and (41) f f derived here for rcc and rcd . Ns and Nair are the complex refractive indices of the coating. equation (44) 0. Hence. This is because in both cases the reﬂection coefﬁcient is an average value over all angles of incidence. respectively. 0 (46) . shadowing is neglected. due to the signiﬁcant proportion of the diffuse component that is reﬂected into the acceptance cone of the spectrophotometer. and claimed that it gave a better ﬁt to experimental results of Beard [41] for ‘coherent’ reﬂection from sea waves. where n is the refractive index and κ = kλ/4π is the extinction coefﬁcient. b rdd = rdd (N1 = Nc . Expression (43) is a good approximation in the case of τ/σ0 10. for example. 3577 . s rdd = rdd (N1 = Nc . which is equivalent to (37) for the case of normal incidence.
35 0. negligible scattering coefﬁcient. show the effect of increasing and decreasing the refractive index by 10%. (the notation used is deﬁned in section 3) are easily calculated using analogous expressions. rcd . decreasing to less than 100 m−1 for wavelengths above 450 nm. The complex refractive indices N = n + iκ of TiO2 and Ti used in the calculation are shown in ﬁgure 7. it has to be nonzero). Figure 8.2◦ .40 0. and for ψ = 3.5 2.0 0. to provide a rough substrate.5 4.3 0. rcd . rdd .10%) Wavelength (nm) Figure 9. The dashed and dotted line.05 0. the Kubelka–Munk .5 0. σ0 was 520 nm and τ was 9. The thickness of the rutile coating is estimated to be 2000 ± 200 nm using the oxidation rate data given by Dechamps and Lehr [44]. respectively. Clearly. Using an atomicforce microscope to measure the surface proﬁle and standard analysis methods [45]. The other b reﬂection coefﬁcients that are required in fourﬂux models.20 0. respectively.2 0. Figure 8 shows calculated values of the reﬂection f f s b coefﬁcients rcc . prior to oxidation. as reported by Ribarsky [48] and the imaginary part from the work of Eagles [49]. (For the substrate.2◦ . these data are not required by the model.45 Diffuse reflectance Rcd It is worth noting that the expressions (40).50 0. Real and imaginary parts of the refractive indices of rutile and titanium. absorption coefﬁcient calculated from the data shown in ﬁgure 7 and other parameters as for ﬁgure 8. The inﬂuence of altering the coating thickness by the same percentage is smaller.0 1.0 300 400 500 600 700 rcd rcc rdd rdd s b f f n(TiO 2) κ (TiO 2) n(Ti) κ (Ti) Wavelength (nm) 800 Wavelength (nm) Figure 7. which is the average value for the geometry of the Cary 5 diffuse reﬂectance attachment.48 µm.00 300 400 500 600 700 800 5.A B Murphy 5. Nc . This dip corresponds to the rapid decrease of the absorption coefﬁcient K = 2k = 8π κ/λ at the bandgap wavelength of rutile TiO2 . rcd . rdd and rdd .9 0. rcc .0 2. Experiment and discussion A rutile titanium dioxide coating was formed by oxidizing a piece of titanium sheet in oxygen at 1 bar at a temperature of 850 ◦ C for 10 min. the rms roughness σ0 of the surface was measured to be 571 nm and the autocorrelation length τ to be 6. rcc .5 0. The real part of the refractive index of rutile was taken from Cardona and Harbeke [46] and Devore [47]. so this is a useful estimate of the uncertainty in the calculated value.0 4. with σ0 = 570 nm and τ = 6. as discussed in section 2.7 0. 0.6 0. rdd and rdd .0 0.1 0. and for diffuse illumination.5 3. given an inverse rms surface slope of τ/σ0 = 11.10 0. 0. The titanium sheet was etched in Kroll’s solution for 10 s.5 1. (41). Measured and calculated value of the diffuse reﬂectance from the rutile TiO2 coating on a Ti substrate. κ is known as the extinction coefﬁcient. with thickness 2000 nm. As expected for the relatively f f rcc . except for a pronounced dip at around 400 nm.4 0. (47) f f b s and (48) for rcc .) f f The reﬂection coefﬁcients rcc and rcd were calculated using (40) and (41) for acceptance cone halfangular width ψ = 3. The inﬂuence on the calculated reﬂectance of altering the real and imaginary components of the refractive index by ±10% is shown in the graph.0 1.8 Refractive index 3. Figure 9 shows measured values of the reﬂectance Rcd and the values calculated using the modiﬁed Kubelka–Munk model.30 0. 24]. 3578 Calculated ( Measured Nc + 10%. The scattering coefﬁcient S is set to a negligible value (to avoid dividing by zero.3. The reﬂectance curve has the same form as the refractive index of rutile TiO2 . The literature values of refractive index vary by at least 10%.71 µm.15 0. rcd light will be predominately diffuse. The absorption coefﬁcient is greater than 107 m−1 for wavelengths below 350 nm. are required in fourﬂux models as well as twoﬂux models. so the modiﬁed Kubelka– Munk model should be applicable. The Ti data were taken from Ribarsky [48]. f b s s rcd . Reﬂection coefﬁcients for a rutile TiO2 coating on a Ti substrate. The agreement between the measured and calculated values is good for wavelengths above about 300 nm.25 0.0 300 400 500 600 700 800 Reflection coefficient 0.5 µm. Such oxide semiconductor coatings on titanium have been used to investigate the photocatalytic splitting of water into hydrogen and oxygen [23. This indicates that the transmitted rough surface.
and hence the modiﬁed Kubelka–Munk model is applicable. coatings under collimated illumination. where the complex refractive index of medium l is Nl = nl + iκl . Analysis of the angular distribution of the reﬂected radiation indicates that the light in the coating will be diffuse. for τ/σ0 10 and σ0 /λ 0. Conclusions The Kubelka–Munk twoﬂux model is strictly only applicable to the case of diffuse illumination. it has frequently been used. and thus can be For opticallyrough surfaces rcc neglected in expression (13) for the reﬂectance. the modiﬁcations extend the range in which the Kubelka–Munk model can be applied to collimated illumination to a wide range of opticallyrough coatings. Further. If illumination is collimated. Acknowledgments I thank Dr Piers Barnes for measuring the rms roughness and autocorrelation length of the rutile TiO2 coating and the titanium substrate and Dr Ian Plumb and Dr Barnes for helpful comments. The inﬂuence of the surface morphology of the coating has not been considered. the roughness of the surface means that the incident light is ‘scattered’. surfaces (σ0 In the current case. taking into account the characteristics of the integrating sphere used to measure the reﬂectance. the modiﬁed Kubelka–Munk model will be applicable irrespective of the magnitude of the absorption and scattering coefﬁcients of the coating. One way this can be provided is by strong scattering within the coating. Figure 4 indicates the reﬂected and hence transmitted light will be mainly diffuse for opticallyrough λ/8) with inverse surface slope τ/σ0 10. the reﬂection coefﬁcients of light polarized with electric ﬁeld parallel and perpendicular to the plane of incidence. This will of course be the case if illumination is diffuse. respectively. I have introduced an expression for the reﬂection coefﬁcient that allows the separation of reﬂectance into diffuse and collimated (specular) components. f f rcd . where r (θi ) and r ⊥ (θi ) are. Transport models such as the Kubelka–Munk model do not take into account optical phase and are therefore not applicable when interference fringes occur. I have extended the Kubelka–Munk model to the case of collimated illumination of opticallyrough surfaces.1) 6. opticallysmooth and intermediate surfaces. This is apparent from ﬁgure 3.or nonabsorbing coatings. agreement can be obtained if the real and imaginary parts of the refractive index are increased by about 25%. so that both the reﬂected and transmitted light are diffuse. then there has to be a mechanism for the light ﬂux to become diffuse. Fresnel reﬂection coefﬁcients The Fresnel reﬂection coefﬁcient for unpolarized light is given 1 by rF (θi ) = 2 [r (θi ) + r ⊥ (θi )]. The expression for the reﬂectance has been compared with other simple treatments. the diffuse reﬂection coefﬁcient is signiﬁcantly smaller than the Fresnel coefﬁcient (which was assumed to be 100% for the purposes of the ﬁgure). Appendix A. it remains important to use (41) for the diffuse reﬂection f coefﬁcient rcd . even for a coating with negligible scattering coefﬁcient S and for a very wide range of absorption coefﬁcient K. (A. The angular distribution of the reﬂected light provides an indication of the diffuseness of the transmitted light. it can occur in thin coatings (of the order of 200 nm or less) formed by oxidation of the substrate or by deposition techniques. as extended by Saunderson to allow treatment of reﬂection from interfaces. by modifying the Saunderson extension to allow treatment of reﬂection of collimated light from opticallyrough. which have been found to be inaccurate for some classes of rough surfaces. the model predicts the reﬂectance of the coating and substrate well. At wavelengths below 300 nm. Previous work has shown that useful results can be obtained for only speciﬁc cases: opticallythick weakly. σ0 ∼ λ and τ/σ0 ∼ 10. Hence. Nevertheless. It should be noted that it is possible for both the surface of the coating and the interface between the coating and substrate to be opticallyrough. the surface of the substrate had an autocorrelation length about 50% greater than that of the coating and had a very different appearance on the scale of the surface roughness. However. to calculate diffuse reﬂectance of where nl is the real part of the refractive index (usually referred to as the refractive index) and κl is the extinction coefﬁcient. even with neglibible scattering. This can occur when the coating is of approximately constant thickness and follows the contours of the substrate and when scattering and absorption within the coating are weak. The modiﬁed Kubelka–Munk model has been tested in the case of an opticallyrough rutile titanium dioxide coating on a titanium substrate and found to give good agreement with measurements for wavelength ranges in which absorption of the coating is both strong and weak. 3579 . However. so the coating is near the edge of the range of applicability of the modiﬁed Kubelka–Munk model.Modiﬁed Kubelka–Munk model for calculation of the reﬂectance model is able to calculate the reﬂectance accurately in the case of collimated illumination of a rough surface. the agreement between the measured and calculated reﬂectance is not as good. 30]. We consider light passing from medium 1 to medium 2. and θi is the angle of incidence of the light [29. measurement of the refractive index is difﬁcult. However. The mechanism considered here is that provided by an opticallyrough surface. so the discrepancy between the prediction of the model and measurement is likely to be related to uncertainties in the refractive index data. but for the reﬂected light to exhibit interference effects. At these wavelengths at which absorption is strong. The main requirement for the Kubelka–Munk model to be valid is that the light ﬂuxes within the coating are diffuse. absorbing coatings whose reﬂectance is very weak and for coatings containing highlyscattering particles whose sizes are larger than a wavelength. for opticallyrough surfaces with inverse surface slope τ/σ0 10. This did not occur for the current coating. rather than simply the Fresnel coefﬁcient rF . and the literature values differ by up to 50% [46].1. It is expected that if the surface is sufﬁciently rough to ensure that the light transmitted into the coating is diffuse. including those for which the modiﬁed Kubelka–Munk model is applicable.
2) and (B. Opt. 38 448 [4] Krewinghaus A B 1969 Infrared reﬂectance of paints Appl. 12 593 [3] Kubelka P 1948 New contributions to the optics of intensely lightscattering materials.3): 1 rF (θi ) = 2 [r (θi ) + r ⊥ (θi )] = where r ⊥ (θi ) u + sin2 θi tan2 θi u + v sin θi tan θi + sin2 θi tan2 θi The BRDF gives information about how bright a surface will appear viewed from a given direction when illuminated from another given direction.2) and (A.3) We then obtain the Fresnel reﬂection coefﬁcient by averaging (A. We do not require such directional information. dIi (θi . cos2 θi + u + v cos θi 2 2 The reﬂection properties of a rough surface are usually speciﬁed using the BRDF.4) π/2 X sin θdθdφ. (B. Lr = (A. Part I J. (B.4). Substituting (B. and the subscript r denotes quantities associated with the reﬂected radiant ﬂux.A B Murphy It can be shown that [29] r ⊥ (θi ) = r (θi ) = r ⊥ (θi ) cos2 θi + u − v cos θi .7). φi . φi ) (B. (B. 8 807 We will make use of the geometric relations Xd and Xdω = ω = π −π π −π 0 π/2 X cos θ sin θ dθdφ (B.6). I present some of the relevant deﬁnitions and results and combine these with the results of He et al [32] to obtain expressions for the reﬂection coefﬁcient r. We therefore need to obtain an expression for r in terms of the BRDF.13) Li dωi . The irradiance Ii is the incident ﬂux density. (B. the irradiance for such a source in the direction (θ0 . The projected solid angle is related to the actual solid angle ω by = ω cos θ. (B. θr . Soc.3) References [1] Heavens O S 1955 Optical Properties of Thin Solid Films (London: Butterworths) [2] Kubelka P and Munk F 1931 Ein Beitrag zur Optik der Farbanstriche Z.3) and (B.6) i ρLi d i = π −π 0 π/2 ρLi cos θi sin θi dθi dφi . Here θ represents the polar angle (relative to the surface normal).11) into (B. (B. of a direction. (A.2) Using (B. and φ represents the azimuthal angle. rather we require the reﬂection coefﬁcient. Phys. (A.12) Substituting this expression into (B. deﬁned as (A. Tech. while the radiant exitance Mr is the reﬂected ﬂux density. the radiant exitance and reﬂected radiance are related by Mr = r ρ cos θi cos θr sin θr dθr dφr .5) 2 2 2 v = 2 n2 (n2 − κ2 ) − [(n2 − κ2 )2 + 4n2 κ2 ] sin2 θi 1 2 2 2 2 2 2 + ({n2 (n2 − κ2 ) − [(n2 − κ2 )2 + 4n2 κ2 ] sin2 θi }2 1 2 2 2 2 2 + 4(n2 κ2 n2 )2 )1/2 (n2 − κ2 )2 + 4n2 κ2 1 2 2 −1 1/2 From the deﬁnition of the BRDF (B. δ(θi − θ0 )δ(φi − φ0 ) cos θi sin θi dθi dφi sin θ0 (B. Am. φi . we obtain the required expression for the reﬂection coefﬁcient in terms of the BRDF for a collimated source r= π −π 0 π/2 Similarly.8) gives Mr = Ii π −π 0 π/2 ρ cos θi cos θr sin θr dθr dφr .8) + 4(n2 κ2 n2 )2 1 1 2 (n2 2 − 2 κ 2 )2 + 2 −1 4n2 κ2 .9) gives Lr = π −π 0 π/2 (B. φr ) = dLr (θi .5)) Ii = ωi Li dωi = π −π 0 π/2 Li sin θi dθi dφi . given by (B.5) 3580 . (B.6) u − v sin θi tan θi + sin θi tan θi u + v sin θi tan θi + sin2 θi tan2 θi . Calculation of reﬂection coefﬁcients from BRDF The geometry of the reﬂectance problem was discussed in detail by Horn and Sjoberg [50]. Appendix B.10) This can be accomplished if Li = Ii δ(θi − θ0 )δ(φi − φ0 )/ sin θ0 . Mr = Lr d r . The subscript i denotes quantities associated with the incident radiant ﬂux. Opt. (B. 2 (A.1) The irradiance and the incident radiance are related by Ii = ωi We use a collimated source. and the reﬂected radiance Lr is the ﬂux reﬂected per unit surface area per unit projected solid angle. 0 (B.7) r = Mr /Ii . and (B.4). The incident radiance Li is the incident ﬂux per unit surface area per unit projected solid angle.11) ρIi = ρIi cos θi .2) ρ(θi . φr ) . Using (B.9) .14) Lr d r. θr . φ0 ) will be proportional to the product of the delta functions δ(θi − θ0 )δ(φi − φ0 ).4) 2 2 2 u = {n2 (n2 − κ2 ) − [(n2 − κ2 )2 + 4n2 κ2 ] sin2 θi }2 1 2 2 2 r = π −π 0 π/2 Lr cos θr sin θr dθr dφr . It must also satisfy (using (B.
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