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Modified Kubelka–Munk model for calculation of the reflectance of coatings with optically

-
rough surfaces
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2006 J. Phys. D: Appl. Phys. 39 3571
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INSTITUTE OF PHYSICS PUBLISHING JOURNAL OF PHYSICS D: APPLIED PHYSICS
J. Phys. D: Appl. Phys. 39 (2006) 3571–3581 doi:10.1088/0022-3727/39/16/008
Modified Kubelka–Munk model for
calculation of the reflectance of coatings
with optically-rough surfaces
A B Murphy
CSIRO Industrial Physics, PO Box 218, Lindfield NSW 2070, Australia and CSIRO Energy
Transformed National Research Flagship, Australia
E-mail: 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 two-flux 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
two-flux model to the collimated illumination of optically-rough 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 optically-rough 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 optically-rough,
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],
solar-absorbing 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 weakly-absorbing coatings containing
highly-scattering particles whose sizes are larger than a
wavelength. They developed a slightly modified method, in
0022-3727/06/163571+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 optically-thick weakly- or non-absorbing 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 two-flux 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, four-flux 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 optically-rough surfaces,
the reflected light is mainly diffuse. The transmitted light is
also mainly diffuse. This means treatment by the two-flux
method is likely to be valid under collimated illumination for
a wider range of coating parameters than is the case for an
optically-smooth surface.
Treatment of collimated illumination of a general surface
requires expressions for reflection coefficients valid for
both optically-smooth and optically-rough surfaces, and in
particular the separation of these reflection coefficients into
specular (collimated) and diffuse components. In keeping
with the simplicity of the two-flux 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 bothoptically-roughandoptically-smooth
surfaces, and the term scattering is reserved for the description
of scattering of light within the coating.
In this paper, I derive a slightly-modified two-flux 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
two-flux 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 oven-oxidation 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
band-gap of the coating can then be determined from the
wavelength-dependence of the absorption coefficient using
standard methods [27]; reduction of the band-gap of rutile
TiO
2
is imperative to improve its efficiency in photocatalytic
water-splitting [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
UV-visible 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 diffusely-reflected 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
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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 two-flux model. This is a reasonable a
priori assumption in the case of an optically-rough surface at
the air-coating 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 backward-directed 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 semi-isotropic
(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
optically-rough surface
In this section, I consider the calculation of reflection
coefficients for collimated light incident on a surface that
may be optically-rough or optically-smooth, or intermediate.
The derivation of reflection coefficients for collimated light
incident on an optically-smooth surface, i.e. the Fresnel
coefficients, is treated in standard optics text-books (e.g.
[29, 30]). Expressions for Fresnel coefficients are given in
appendix A. Optically-rough surfaces are usually defined by
the Rayleigh criterion, which states that surfaces can be treated
as optically-smooth 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

i
, (17)
and the diffuse component is
ρ
d
=
r
F

/
)GZD
π cos θ
i
cos θ
r
. (18)
Here r
F

/
) 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

2

m=1
g
m
exp(−g)
m!m
exp
_
−v
2
xy
τ
2
4m
_
, (22)
where
v
xy
=

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

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

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

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

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

i
)Z
r

r
), (30)
where
Z
i

i
) =
_
1 −
1
2
erfc(τ cot θ
i
/2σ
0
)
_
(cot θ
i
) + 1
, (31)
Z
r

r
) =
[1 −
1
2
erfc(τcotθ
r
/2σ
0
)]
(cot θ
r
) + 1
, (32)
(cot θ) =
1
2
_

0

πτ cot θ
−erfc
_
τ cot θ

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

r

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

r

r
. (36)
For specular reflection, θ
r
= θ
i
and φ
r
= π, which imply
that θ
/
= θ
i
. Further, for a perfectly-reflecting mirror-like
surface, we expect r
F
(0) = 1 and r
s
= 1. In calculating the
specular component of the BRDF for rough surfaces, r
F

/
) is
multiplied by exp(−g)Z, so the specular reflection coefficient
is modified accordingly to give
r
s
= r
F

i
) exp(−g)Z. (37)
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A B Murphy
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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
Wavelength-normalised 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 cross-hatching. 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 wavelength-normalized surface roughness σ
0

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 diffusely-reflected 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
cross-hatching.
Figure 4 shows the angular dependence of the integrand
(1/π)r
F

/
)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
diffusely-reflected 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
half-angular 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

. (39)
Using (36) and (37), we obtain (noting that the following
apply for normal incidence: r
F

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

r
/2)GZDsin θ
r

r
(40)
and
r
f
cd
=
1
π
_
π/2
ψ
r
F

r
/2)GZDsin θ
r

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

r
/2)GZDsin θ
r

r
. (42)
Figure 5 shows the total reflection coefficient r and its
components r
f
cc
and r
f
cd
for half-angular width ψ = 3.2

, which
is the average value for the diffuse reflectance attachment of
the Cary 5 spectrophotometer. For optically-rough surfaces
(e.g. σ
0
= 1 µm), the diffuse component r
f
cd
dominates. For
optically-smooth 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
fromoptically-rough 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

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
half-angular 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
Wavelength-normalised rms roughness σ
0

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 half-angular 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
optically-rough surface
The diffuse–diffuse reflection coefficient is calculated using
an angular average over all angles of incidence of the Fresnel
reflection coefficient r
F

i
), where θ
i
is the angle of incidence
of the light [43]:
r
dd
=
2
π
_
π/2
0
r
F

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 four-flux models as well as two-flux models. The other
reflection coefficients that are required in four-flux 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 half-angular 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 non-zero). 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 band-gap 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 optically-rough
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 optically-rough 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 optically-rough, 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 two-flux 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: optically-thick weakly- or non-absorbing coatings,
absorbing coatings whose reflectance is very weak and for
coatings containing highly-scattering 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 optically-rough surfaces, by
modifying the Saunderson extension to allow treatment of
reflection of collimated light from optically-rough, 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 optically-rough 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 optically-rough 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

i
) =
1
2
[r
|

i
) + r


i
)], where r
|

i
) and r


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


i
) =
cos
2
θ
i
+ u −v cos θ
i
cos
2
θ
i
+ u + v cos θ
i
, (A.2)
r
|

i
) = r


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

i
) =
1
2
[r
|

i
) + r


i
)]
= r


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

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

i
, φ
i
, θ
r
, φ
r
)
dI
i

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

r

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

i

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

i
=
_
π
−π
_
π/2
0
L
i
sin θ
i

i

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

i

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

r

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

r

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:10.1088/0022-3727/39/16/008 Modified Kubelka–Munk model for calculation of the reflectance of coatings with optically-rough surfaces A B Murphy CSIRO Industrial Physics. Here. 0022-3727/06/163571+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 E-mail: tony. 3] is by far the most widely used transport theory. The modified Kubelka–Munk model is tested in the case of an optically-rough rutile titanium dioxide coating on a titanium substrate and found to give good agreement with experiment. crystalline materials [10].00 © 2006 IOP Publishing Ltd solar-absorbing 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 optically-rough. 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 two-flux 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 two-flux model to the collimated illumination of optically-rough 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 weakly-absorbing coatings containing highly-scattering 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 optically-rough and optically-smooth surfaces. Application of the modified Kubelka–Munk model developed here allows the interpretation of reflectance measurements of these coatings. I derive a slightly-modified two-flux model for the case of collimated illumination of a coating on an opaque substrate that allows general surfaces to be treated. The band-gap of the coating can then be determined from the wavelength-dependence 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 non-absorbing 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 UV-visible 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 oven-oxidation 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 two-flux 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 two-flux 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 optically-rough surfaces. This is done by developing expressions. Treatment of collimated illumination of a general surface requires expressions for reflection coefficients valid for both optically-smooth and optically-rough 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. four-flux 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 band-gap of rutile TiO2 is imperative to improve its efficiency in photocatalytic water-splitting [23]. In keeping with the simplicity of the two-flux model. Note that reflection from opticallyrough surfaces is often referred to as scattering. and absorption can be either strong or weak.and diffusely-reflected 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 optically-thick 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 two-flux method is likely to be valid under collimated illumination for a wider range of coating parameters than is the case for an optically-smooth surface.

This is a reasonable a priori assumption in the case of an optically-rough surface at the air-coating 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 backward-directed 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 semi-isotropic (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 two-flux 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 optically-rough 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 optically-rough or optically-smooth. 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 text-books (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. Optically-rough 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 optically-smooth 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 optically-smooth 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 perfectly-reflecting mirror-like 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 cross-hatching. a significant fraction of the diffusely-reflected 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 optically-rough 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 optically-smooth 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 diffusely-reflected 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 wavelength-normalized 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 half-angular 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 Wavelength-normalised 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 half-angular 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 optically-rough 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 cross-hatching. 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 ◦ half-angular 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 half-angular 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 Wavelength-normalised 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 optically-rough 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 non-zero). 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 four-flux 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 band-gap 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 half-angular 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 four-flux models as well as two-flux 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 two-flux model is strictly only applicable to the case of diffuse illumination. it has frequently been used. and thus can be For optically-rough 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 optically-rough 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 optically-rough 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 optically-rough surfaces.1) 6. opticallysmooth and intermediate surfaces. This is apparent from figure 3.or non-absorbing 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 optically-rough. 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: optically-thick 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 optically-rough. 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 optically-rough 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 highly-scattering 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 light-scattering 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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