Accurate Color Measurment

UNIVERSITY OF JOENSUU
DEPARTMENT OF PHYSICS
V
AIS
AL
A LABORATORY
DISSERTATIONS 30
Accurate Color Measurement
Jouni Hiltunen
ACADEMIC DISSERTATION
To be presented, with permission of the Faculty of Science of the Univer-
sity of Joensuu, for public criticism in Auditorium M1 of the University,
Yliopistonkatu 7, Joensuu, on February 8th, 2002, at 12 noon.
JOENSUU 2002
Julkaisija Joensuun yliopisto
Publisher University of Joensuu
Toimittaja Timo J a askelainen, Ph.D., Professor
Editor
Ohjaajat Timo J a askelainen, Ph.D., Professor
Supervisors Department of Physics, University of Joensuu
Jussi Parkkinen, Ph.D., Professor
Department of Computer Science, University of Joensuu
Joensuu, Finland
Esitarkastajat Mauri Aikio, Dr. Tech.
Reviewers VTT Electronics
Oulu, Finland
Erik Vartiainen, Ph.D., Docent
Department of Electrical Engineering,
Lappeenranta University of Technology
Lappeenranta, Finland
Vastav aitt aja Harri Kopola, Dr. Tech., Professor
Opponent VTT Electronics
Oulu, Finland
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ISSN 1458-5332
ISBN 952-458-077-2
Joensuun yliopistopaino 2002
Jouni Hiltunen
; Accurate Color Measurement University of Joensuu, Depart-

ment of Physics, Vais al a Laboratory, Dissertation 30, 2002. - 88 p.
ISBN 952-458-077-2
Keywords: accurate color measurement, tristimulus integration, thermochromism.
Address: Department of Physics, University of Joensuu, P.O. Box 111, FIN-80101,

Joensuu, Finland
Abstract
In this thesis studies on accurate surface color measurements are considered. Errors in
a spectrophotometric measurements are discussed and correction methods introduced.
The wavelength interval in a tristimulus integration is considered next. The ASTM
weighting functions are tested with a large data set of non uorescent colors and shown
to be useless. The thermochromic eect is also discussed in detail and measured. This
thesis shows how thermochromism is based on physical processes. Simple formulas are
derived, and shown to explain the experimental data. In conclusion, this thesis shows
how commercial instruments should be calibrated for precision color measurements, if
one aims at achieving the highest level for measuring accuracy.
iv
Preface
I am deeply indebted to my supervisors Prof. Timo J a askelainen and Prof. Jussi
Parkkinen for their guidance, encouragement and patience during my studies. I am
grateful for the opportunity to work at the Department of Physics.
I want to express my special thanks to all my co-workers during these years, espe-
cially Merja, Kimmo and Jarkko. Furthermore, I wish to express my gratitude to the
colleagues and sta of the department, and the members of the color group.
To my referees, Dr. Mauri Aikio and Docent Erik Vartiainen, I am greatly indepted
for their careful review and constructive comments. For revising the language of the
manuscript I express my gratitude to Dr. Greg Watson.
Finally, I want to express my warmest thanks to my dear parents and to my sister
with her family, and to Liisa for her love and support.
Joensuu January 23, 2002
Jouni Hiltunen
Contents
1 Introduction 1
2 Colorimetry 4
2.1 Background to colorimetry . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.2 CIE Recommendations . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.2.1 Standard physical data . . . . . . . . . . . . . . . . . . . . . . . 7
2.2.2 Standard observer data . . . . . . . . . . . . . . . . . . . . . . . 12
2.2.3 Calculation of tristimulus values and chromaticity coordinates . 12
2.2.4 Uniform color spacing . . . . . . . . . . . . . . . . . . . . . . . 15
2.2.5 Miscellaneous colorimetric practices and formulae . . . . . . . . 17
2.3 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
3 Measurement of surface color 21
3.1 General considerations on color measurement . . . . . . . . . . . . . . . 21
3.2 Intercomparison . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
3.3 Errors in surface color measurements . . . . . . . . . . . . . . . . . . . 24
3.3.1 Errors in absolute scales of diuse reectance and 0/45 radiance
factor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
3.3.2 Errors due to diering properties of white reference standards . 25
3.3.3 Photometric non-linearity . . . . . . . . . . . . . . . . . . . . . 25
3.3.4 Incorrect zero level . . . . . . . . . . . . . . . . . . . . . . . . . 27
3.3.5 Wavelength scale error . . . . . . . . . . . . . . . . . . . . . . . 27
3.3.6 Specular beam exclusion error . . . . . . . . . . . . . . . . . . . 28
3.3.7 Specular beam weighting error . . . . . . . . . . . . . . . . . . . 29
3.3.8 Errors due to non-uniformity of collection of integrating spheres 30
3.3.9 Polarisation errors in the 0/45 geometry . . . . . . . . . . . . . 30
v
vi
3.3.10 Dierences in methods of calculating color data from spectral data 30
3.3.11 Geometry dierences between illumination and collection optics
within the specied limits . . . . . . . . . . . . . . . . . . . . . 31
3.3.12 Errors due to thermochromism in samples . . . . . . . . . . . . 31
3.3.13 Errors due to the dependence of spectral resolution on band-
width, scan speed and integration time . . . . . . . . . . . . . . 31
3.4 Measurements and corrections . . . . . . . . . . . . . . . . . . . . . . . 31
3.5 Intercomparison results . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
3.6 Determination of colorimetric uncertainties . . . . . . . . . . . . . . . . 44
3.7 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
4 Tristimulus integration 54
4.1 The ASTM weighting method . . . . . . . . . . . . . . . . . . . . . . . 55
4.2 Spectral bandpass error . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
4.3 Materials and methods . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
4.4 Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
5 Thermochromism 65
5.1 Background of the study . . . . . . . . . . . . . . . . . . . . . . . . . . 65
5.2 Absorbance, transmittance, and optical density . . . . . . . . . . . . . 66
5.2.1 Transmitting samples . . . . . . . . . . . . . . . . . . . . . . . . 67
5.2.2 Opaque samples . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
5.3 Thermal eects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
5.4 Numerical results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
5.5 Thermochromic measurements . . . . . . . . . . . . . . . . . . . . . . . 76
5.6 Experimental results . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
5.7 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
6 Conclusions 82
References 84
Chapter I
Introduction
Surface color measurement is important for a very wide range of industrial applications
including paint, paper, printing, photography, textiles, plastics [43,45]. Let us consider
an example. A manufacturer wants to produce goods with specic color appearance.
He can design the appearance of the product and he can measure it. After the produc-
tion process the appearance of the product might be changed or it can vary between
manufacturing batches because of noise inherent in the process. Now a manufacturer
would like to know if the actual color is suciently similar to the desired one or whether
the color is so dierent that it is not economically advisable to sell the products be-
cause of fear of consumer complaints. From this point of view, it is very important to
be able to handle measurements and calculations of small color dierences [58].
For demanding color measurement, a spectral approach is denitely needed. Strictly
it is impossible to dene the absolute color values of a sample, that is why we always
work with some kind of approximations, some of us closer than others. The human
eye can perceive color dierences as small as 0.5 CIELAB units and, thus, distinguish
millions of colors. This 0.5 unit dierence should be the goal for precise color measure-
ments. This limit is not a problem if we only want to measure the color dierence of
two samples, but if we want to simultaneously know the exact color coordinate values
accuracy problems arise. The values of two instruments can be astonishingly dierent.
The best accuracy in color measurement could be achieved by use of a spectropho-
tometer. The only geometry for measuring real spectral reectance is normal/diuse
(0/d) geometry where the specimen is illuminated by a beam whose axis at an angle
which does not exceed 10
from the normal to the specimen [5, 60]. The reected ux

should be collected by means of an integrating sphere.
The accuracy of the spectrophotometer used in color measurement may depend
on various errors such as photometric non-linearity, wavelength error, and integrating
sphere dark level error, integrating sphere error in both specular included and specular
excluded modes. Thus, correction formulas should be used to obtain more accurate
1
2 1. Introduction
results. Another question is how many channels i.e. wavelengths were used to measure
a spectrum. It is obvious that the sampling interval should be short enough to gain
more precise results. Furthermore, the result we attain is always a compromise between
measuring time, conditions and cost. Sometimes, one has to use a portable system or
the shape and the size of a sample makes it impossible to be able to use sensitive
equipment.
Regardless of how good an instrument one has, we need to point out that ultimately
color is a sensation produced in the human brain. It is evident that the information
processing system of the human has learned to process, e.g. visual information, in an
ecient way. The human eye is able to distinguish several million colors, and thus color
measuring instruments should accurately match the sensitivity of the eye to be able
to detect small color dierences [18]. The basic sensory system of the eye is known,
but the operation of the process is an open question. The color of any non uorescent
specimen can be matched with a mixture of red, green and blue primaries, because
there are only three types of color sensitive receptor on the retina. Human color vision
shows dierences among people. Thus, some standard observers must be specied.
The CIE 1931 standard observer is dened for a 2
eld of view by two equivalent sets

of color matching functions [5]. The rst set is expressed in terms of spectral stimuli of
wavelengths 700 nm (R), 546.1 nm (G), and 435.8 nm (B). The second set is a linear
transformation of the rst one and remains positive for all wavelengths. The CIE 1964
standard observer has been similarly dened for the 10
eld of view. These sets are

used throughout industry.
As well as standard observers, standard illumination conditions must be dened as
the form of tables of relative spectral power against wavelength. Illuminant A corre-
sponds to the interior illumination by tungsten lament lamps, C represents average
daylight with a correlated color temperature of 6774 K, and the D sources aim to
describe for other phases of daylight. For instance, the most widely used daylight stan-
dard is D
65
, which represents a source whose correlated color temperature is 6504 K.
There are a number of other illuminants which are used, too.
This thesis contains studies on accurate surface color measurements. First, some
basic background is introduced in Chapter II. Errors in a spectrophotometric measure-
ments are discussed and correction methods introduced in Chapter III. This work was
part of the European Union color measurement harmonisation project in 19972000
where 9 laboratories in Europe were involved. The author was responsible for measur-
ing, analysing and reporting the results made in University of Joensuu [15, 20, 43, 44].
In Chapter IV the wavelength interval in a tristimulus integration is considered. The
ASTM weighting functions are tested with a large data set of non uorescent colors
and found to be useless. The results are rst time reported in this thesis and will
be published later. The thermochromic eect is discussed in detail and measured in
Chapter V. The rst idea of this phenomenon comes from the co-authors J a askelainen
3
and Silfsten. However, formulaes introduced here, were derived by the author with co-
authors and entirely calculated numerically by the author [16, 19]. This thesis shows
how thermochromism is based on physical processes. Simple formulas are derived, and
shown to explain the experimental data. Such an explanation has not been published
in literature before.
In conclusion, this thesis shows how commercial instruments should be calibrated
for precision color measurements, if one aims at achieving the highest level for mea-
suring accuracy. In addition, the precise color measuring technique developed during
the preparation of this thesis, has been applied to a number of industrial projects.
Use of spectral data is increasing in a wide range of applications, too. The authors
contribution is shown in [17, 2123, 3032, 37, 38, 4648] but the topic of this thesis was
the rst phase: How to measure spectral data accurately.
Chapter II
Colorimetry
The specication of basic standards used in colorimetry are based on denitions of
the Commission Internationale de lclairage (CIE) by general consent in all countries.
The rst major recommendations regarding colorimetric standards were made by the
CIE in 1931. The original recommendations made in 1931 are reviewed from time
to time by the CIE Colorimetry Committee and changes are made when considered
necessary. In this chapter, the CIE recommendations are briey introduced since they
essentially form the basis of modern color research. The original and more precise
recommendations can be found from [5]. General and historical views of color vision
can be found from [3, 18, 57, 60].
2.1 Background to colorimetry
At the 6th Session of the CIE held at Geneva in 1924 it was decided to set up a Study
Group on Colorimetry (CIE 1924). The reason was the fact that the measurement of
color had become an important factor in industry and scientic laboratories but there
was not color specication system that could be considered satisfactory for general
practice. Later, it was agreed that eorts should be made to reach agreements on
colorimetric nomenclature
a standard daylight for colorimetry
the sensation curves of the average human observer with normal color vision.
At the 8th Session of the CIE held at Cambridge, England, in 1931, the rst major
recommendations were made which laid the basis for modern colorimetry (CIE 1931).
There was a total of ve recommendations. Recommendations 1, 4 and 5 established
the CIE 1931 standard observer and a colorimetric coordinate system, recommendation
4
2.1 Background to colorimetry 5
2 specied three standard sources (A, B and C) and recommendation 3 standardized
the illuminating and viewing conditions for the measurement of reective surfaces and
the standard of reectance in the form of a magnesium-oxide surface.
The CIE 1931 standard colorimetric observer was dened by two dierent but
equivalent sets of color-matching functions based on the photopic luminous eciency
function V (). These were already adopted by the CIE in 1924 and experimental
work was carried out by Guild [13] in 1931 and Wright [59] 19281929. The rst
set of color-matching functions, r(), g(), b(), was expressed in terms of spectral
stimuli of wavelengths 700.0 nm (R), 546.1 nm (G), 435.8 nm (B) (Fig. 2.1), as the
reectance stimuli, with the units adjusted so that the chromaticity coordinates of the
equi-energy spectrum are equal. The equi-energy spectrum is a stimulus whose spectral
concentration of power as a function of wavelength is constant.
400 500 600 700
0.4
0.3
0.2
0.1
0
- 0.1
Wavelength [nm]
T
r
i
s
t
i
m
u
l
u
s
v
a
l
u
e
s
r
g
b
Figure 2.1: Color matching functions r, g and b in terms of spectral stimuli of wave-
lengths 700.0 nm (R), 546.1 nm (G) and 435.8 nm (B), respectively [60].
The second set of color-matching functions, x(), y(), z() (Fig. 2.2), was rec-
ommended for reasons of more convenient application in practical colorimetry. Its
derivation from the rst set was based on a proposal by Judd [24] in 1930 and involved
a linear transformation. The coecients of the transformation were chosen so as to
avoid negative values of x(), y(), z(), at all wavelengths and so that the luminances
L
X
, L
Y
, L
Z
of unit quantities of the stimuli were equal to 0, 1, 0 respectively, result-
ing in a set of color matching functions in which y() is identical to V (). The units
of the new reference stimuli (X), (Y ), (Z) were adjusted to make the chromaticity
coordinates x, y, z also equal for the equi-energy spectrum.
6 2. Colorimetry
400 450 500 550 600 650 700 750
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
Wavelength [nm]
T
r
i
s
t
i
m
u
l
u
s
v
a
l
u
e
s
x
y
z
Figure 2.2: Color matching functions x, y and z [60].
The new color-matching functions, x
10
(), y
10
(), z
10
(), dening the supplemen-
tary standard colorimetric observer (CIE 1959) were ocially adopted in 1964. They
were derived from experimental data supplied by Stiles and Burch [51] in 1959 and
by Speranskaya [49] in 1959. The experimental color-matching data were obtained for
a 10
eld by a direct method which did not involve an appeal to the CIE spectral
luminous eciency function, but depend on the actual measurement of the relative
power distribution of the spectrum studied.
One of the important problems the Colorimetric Committee has dealt with over
several years concerns a coordinate system which would provide a three dimensional
color spacing that would be perceptually more uniform than the XY Z system. Many
dierent proposals have been forwarded over the years. In the 14th Session of the CIE
at Brussels in 1959 the committee considered a number of the systems. The MacAdam
uniform chromaticity scale diagram of 1937 was adopted as a standard UCS diagram.
The proposal was ocially approved by the CIE in 1960, so the diagram is nowadays
known as the CIE 1960 UCS diagram.
At the 18th Session of the CIE in London in 1975 the Colorimetry Committee
approved the adoption of two new color spaces and associated color dierence formulae.
These spaces are known as the CIE 1976 L
color space and the CIE 1976 L
color space. The former was mainly used for TV and illumination industries and the
latter was used for surface color industries.
A lot of work has been done for decades to generate more uniform color spaces such
as CMC(l : c), BFD(l : c), CIE94, since the linearity of the CIE 1976 color spaces is not
satisfactory enough, at least where small color dierences are concerned [4,26,36,41,42].
2.2 CIE Recommendations 7
Among the imaging industry there was still a need for a single color appearance model
that could be used throughout the industry to promote uniformity of practice and
compatibility between various components in a modern imaging system. The CIE was
able to respond these needs. In 1997 CIECAM97s color appearance model was adopted
by the CIE for color imaging applications [2729, 33, 35].
For the color dierence evaluation, a new color dierence formula CIEDE2000 [34]
was developed, which is based on CIELAB space. It includes not only lightness, chroma,
and hue weighting functions but also an interactive term between chroma and hue dif-
ferences for improving the performance for blue colors and a scaling factor for CIELAB
a
scale for improving the performance for grey colors. It has been approved by the
CIE and published as a CIE Technical Report [6].
The present colorimetric recommendations were published in CIE Publication 15.2,
Colorimetry [5], in 1986. The new and up-to-date recommendations will be published
in 2002 as CIE Publication 15.3
1
.
2.2 CIE Recommendations
The terminology of the original recommendations has been altered to be consistent with
modern nomenclature and in some cases the original recommendations have also been
modied in contents to bring them into line with present day thinking and practice.
The recommendations are divided into the following ve groups:
1. Recommendations concerning standard physical data.
2. Recommendations concerning standard observer data.
3. Recommendations concerning the calculation of tristimulus values and chromatic-
ity coordinates.
4. Recommendations concerning uniform color spacing.
5. Recommendations concerning miscellaneous colorimetric practices and formulae.
2.2.1 Standard physical data
Illuminants for colorimetry
Standard illuminants such as Illuminant A, B, C and D
65
are recommended illuminants
for color calculations. Here illuminant refers to a specic spectral power distribution,
1
According to The 9th Congress of the International Colour Association, June 2429, 2001,
Rochester, NY.
8 2. Colorimetry
not necessarily realized by a source which refers to a physical light emitter, such as
a lamp, the sun and the sky. Illuminant A represents light from a full radiator at
absolute temperature 2856 K according to The International Practical Temperature
Scale, 1968. The relative spectral power distribution of illuminant A has been derived
in accordance with Plancks radiation formula.
Illuminant B was intended to represent direct sunlight with a correlated color tem-
perature of approximately 4900 K. Illuminant C was intended to represent average
daylight with a correlated color temperature of about 6800 K. In Fig. 2.3 standard
illuminants A, B and C are shown, where the radiant power has been normalized to the
same value at 550 nm. Illuminant D
65
was intended to represent a phase of daylight
with a correlated color temperature of approximately 6500 K. The illuminant D
65
is
recommended for use whenever possible. Illuminants D
50
, D
55
and D
75
can still be used
to realize a phase of daylight having correlated color temperatures of approximately
5000 K, 5500 K, and 7500 K, respectively. In Fig. 2.4 examples of the standard day-
light illuminants D
55
, D
65
and D
75
are shown. The radiant power has been normalized
to the same value at 550 nm.
400 500 600 700 800
Wavelength [nm]
R
a
d
i
a
n
t
p
o
w
e
r
[
a
.
u
.
]
C
C
B B
A
A
Figure 2.3: Standard illuminants A, B and C. The radiant power has been normalized
to the same value at 550 nm [60].
Sources representing illuminants
It is recommended that the following articial sources are used to realize the illuminants
dened above. Standard illuminant A is to be realized by a gas-lled tungsten lament
400 500 600 700 800
Wavelength [nm]
R
a
d
i
a
n
t
p
o
w
e
r
[
a
.
u
.
]
D
55
D
55
D
65
D
65
D
75
D
75
Figure 2.4: Standard illuminants D
55
, D
65
and D
75
. The radiant power has been
normalized to the same value at 550 nm [60].
lamp operating at a correlated color temperature of 2856 K. A lamp with a fused-
quartz envelope or window is recommended if the spectral power distribution of the
ultraviolet radiation of illuminant A is to be realized more accurately.
Illuminant B and C are to be realized using the source A, combined with a lter
consisting of a layer of agreed solutions. At present, no articial sources have been
recommended to realize illuminant D
65
or any other D illuminants of various correlated
color temperatures.
Standard of the reflectance factor
The perfect reecting diuser is recommended as a reference standard in 1986 in publi-
cation CIE Standard Colorimetric Observers. It is dened as the ideal isotropic diuser
with a reectance equal to unity. Smoked magnesium oxide was superseded from Jan-
uary 1, 1969. A secondary reference standard, such as pressed barium sulphate, must
be calibrated in terms of the perfect reecting diuser.
Illuminating and viewing conditions for a reflecting specimen
CIE recommends the use of one of the following illuminating and viewing conditions:
45
/normal , normal/45
, diuse/normal and normal/diuse. For these conditions the

following symbols are used 45/0, 0/45, d/0 and 0/d, respectively.
In the 45/0 geometry the sample is illuminated by one or more beams whose eective
10 2. Colorimetry
axes are at the angle of 45
from the normal to the sample surface. The viewing

angle from the normal to the sample should be less than 10
. There is also a restriction

in the viewing and illuminating beams: the angle between the axis and ray should not
exceed 8
.
In the 0/45 geometry the illumination is in the direction normal to the sample, and
the viewing angle is 45
from the normal. Now normal illumination is within 2
, and
the angle between the axis and any ray should not exceed 8
. The same restriction

should be observed in the viewing beam. The illuminatig conditions 0/45 and 45/0 are
shown in Fig. 2.5.
0/45 45/0
Figure 2.5: Viewing geometries of 0/45 and 45/0.
If the sample is illuminated diusely by an integrating sphere and the viewing
angle does not exceed 10
from the direction normal to the surface of the sample,

one is referring to the d/0 geometry. The integrating sphere may be of any diameter
provided the total area of the ports do not exceed 10 percent of the internal reecting
sphere area. The angle between the axis and arbitrary ray of the viewing beam should
not exceed 5
.
If the specimen is illuminated by a beam whose axis does not exceed 10
from the
normal to the specimen one is referring to 0/d geometry. The reected ux is collected
by means of an integrating sphere. The angle between the axis and any ray of the
illuminating beam should not exceed 5
.
In Fig. 2.6, a typical setup of 0/d geometry is shown using an integrating sphere.
When integrating spheres are used, they should be equipped with white coated baes
to prevent light passing directly between the sample and the spot of the sphere wall
illuminated or viewed.
sample
beam
detector
gloss trap
or white
sphere cap
sample
reference
beam
reference
baffles
Figure 2.6: Integrating sphere.
In the 0/d and d/0 conditions, specular reection can be excluded or included by
the use of a gloss trap. In the 0/d condition, the sample should not be measured with
a strictly normal axis of illumination if it is required to include the regular component
of reection. Note that only the 0/d geometry provides a spectral reectance. The
other conditions d/0, 0/45 and 45/0 give a specic radiance factor.
Illuminating and viewing conditions for transmitting specimens
It is recommended that the colorimetric specication of transmitting species corre-
spond to one of the following illuminating and viewing conditions: normal/normal,
normal/diuse and diuse/diuse. The following symbols are used 0/0, 0/d and d/d,
respectively.
In the normal/normal (0/0) condition, the specimen is illuminated by a beam whose
eective axis is at a angle not exceeding 5
from the normal to its surface and with the

angle between the axis and any ray of the illuminating beam not exceeding 5
. The
geometric arrangement of the viewing beam is the same as that of the illuminating
beam. The specimen is positioned so that only the regularly transmitted ux reaches
the detector. This condition gives the regular transmittance,
r
.
In the normal/diuse (0/d) condition, the specimen is illuminated by a beam whose
eective axis is at an angle not exceeding 5
from the normal to its surface and with

the angle between the axis and any ray of the illuminating beam not exceeding 5
. The
hemispherical transmitted ux is usually measured with an integrating sphere. The
reectance of the sphere reecting surface or other material at the point of impingement
of the regularly transmitted beam, or at the point of impingement of the illuminating
12 2. Colorimetry
beam in the absence of a specimen, must be identical to the reectance of the remainder
of the internal reecting sphere area. This condition gives the total transmittance, .
If the regularly transmitted ux is excluded, for example by the use of a light trap, it
gives the diuse transmittance,
0/d
. If the positions of the light source and detector
are interchanged, the method gives the equivalent diuse/normal (d/0) quantities.
In the diuse/diuse (d/d) condition, the specimen is illuminated diusely with an
integrating sphere and transmitted ux is collected using a second integrating sphere.
This condition gives the double transmittance,
dd
.
2.2.2 Standard observer data
CIE 1931 standard colorimetric observer
It is recommended that colorimetric specication of color stimuli be based on the
color-matching functions x(), y(), z() given in the CIE Standard on Colorimetric
Observers, whenever correlation with visual color matching of elds of angular subtense
between about 1
and about 4
at the eye of the observer is desired. These color-

matching functions are given in the Standard as values from 360 nm to 830 nm at
1 nm intervals with seven signicant digits, and they dene the CIE 1931 standard
colorimetric observer. The values at 5 nm intervals over the range 380 nm to 780 nm
are consistent with the Standard and are sucient for most applications.
CIE 1964 supplementary standard colorimetric observer
It is recommended that colorimetric specication of color stimuli be based on the color-
matching functions x
10
(), y
10
(), z
10
() given in the CIE Standard on Colorimetric
Observers, whenever correlation with visual color matching of elds of angular subtense
greater than about 4
at the eye of the observer is desired. These color-matching

functions are given in the Standard as values from 360 nm to 830 nm at 1 nm intervals
with six signicant digits, and they dene the CIE 1964 standard colorimetric observer.
2.2.3 Calculation of tristimulus values and chromaticity coordinates
Calculation of tristimulus values
The CIE Standard on Colorimetric Observers recommends that the CIE tristimulus
values of a color stimulus be obtained by multiplying at each wavelength the value of
the color stimulus function
() by that of each of the CIE color matching functions

and integrating each set of products over the wavelength range corresponding to the
entire visible spectrum 360 nm to 830 nm. The integration may be carried out by
numerical summation at wavelength intervals, , equal to 1 nm,
X = k
() x()
Y = k
() y () (2.1)
Z = k
() z () ,
or
X
10
= k
10
() x
10
()
Y
10
= k
10
() y
10
() (2.2)
Z
10
= k
10
() z
10
() ,
where X, Y , Z are tristimulus values, x(), y(), z(), are color-matching functions of
a standard colorimetric observer, and k is a normalizing constant dened below. These
equations may be written without or with the subscript 10 to correspond to the CIE
1931 or 1964 standard colorimetric system, respectively.
For reecting or transmitting object colors, the color stimulus function,
(), is
replaced by the the relative color stimulus function, (), evaluated as
() = R()S()
(2.3)
() = ()S(),
where R() is the spectral reectance factor (or spectral radiance factor or spectral
reectance) of the object color, () is the spectral transmittance of the object color,
and S() is the relative spectral power distribution of the illuminant. In this case, the
constants k and k
10
are chosen so that Y = 100 for objects for which R(), or () = 1
14 2. Colorimetry
for all wavelengths and hence
k =
100
S()y()
(2.4)
k
10
=
100
S()y
10
()
.
For self-luminous objects and illuminants the constants k and k
10
are usually chosen
on the grounds of convenience. However, if in the CIE 1931 standard colorimetric
system the Y value is required to give the absolute value of photometric quantity the
constant k must be equal to K
m
, the maximum spectral luminous ecacy. This value
is equal to 683 lumens per watt and
() must be the spectral concentration of the

radiometric quantity corresponding to the photometric quantity required.
The use of abridged or truncated data
The color stimulus function
() should be known at 5 nm intervals over the wave-

length range from 380 nm to 780 nm. In practical applications, all the required data
may not be available. Data may have been measured at greater intervals than 5 nm or
it may not be equally divided. Many times it is possible to predict unmeasured data.
It is important to use the same wavelength interval and range throughout for any set
of precise color dierence calculations.
Abridgement of the data may lead to errors in the computed tristimulus values.
Data with 10 nm or 20 nm intervals should be used only when it can be demonstrated
that these errors are negligibly small for the intended use of the tristimulus values.
If this is not the case it is recommended to interpolate needed but unmeasured val-
ues. Such a prediction should be made with a polynomial interpolation formula or by
Lagrange interpolation.
In some cases the measurement range is less than the practical range of summation
from 380 nm to 780 nm. Omission of the values at these limits of the measurement
range may lead to errors while computing tristimulus values. Such truncation should
be used only if it can be demonstrated that these errors are negligibly small. If these
errors are not negligibly small adequate extrapolation is recommended. The range
of the summation is an essential part of the tristimulus specication. As a rough
approximation, in the absence of other information, unmeasured values may be set
equal to the nearest measured value of the appropriate quantity in truncation.
Calculation of chromaticity coordinates
The chromaticity coordinates (x, y, z) should be calculated from the tristimulus values
(X, Y, Z) as follows:
x =
X
X + Y + Z
y =
Y
X + Y + Z
(2.5)
z =
Z
X + Y + Z
.
Because of the relation x + y + z = 1, it is sucient to quote x and y only. The
chromaticity coordinates x
10
, y
10
, z
10
are computed similarly from the tristimulus values
X
10
, Y
10
, Z
10
.
2.2.4 Uniform color spacing
The CIE 1976 UCS diagram
The CIE 1976 UCS chromaticity diagram is recommended for use whenever a pro-
jective transformation of the (x, y)-diagram yielding color spacing perceptually more
nearly uniform than that of the (x, y)-diagram is desired. The chromaticity diagram is
produced by plotting u
=
4X
X + 15Y + 3Z
(2.6)
as abscissa and v
=
9Y
X + 15Y + 3Z
(2.7)
as ordinate, in which X, Y, Z are tristimulus values. The third chromaticity coordinate
w
is equal to 1u
. This diagram is intended to apply to comparisons of dierences

between object colors of the same size and shape, viewed in identical white to middle-
grey surroundings, by an observer photopically adapted to a eld of chromaticity not
too dierent from that of average daylight.
16 2. Colorimetry
The CIE 1976 uniform color spaces
The use of the following color spaces is recommended whenever a three-dimensional
spacing perceptually more nearly uniform than that provided by the XY Z system is
desired.
CIE 1976 L
color space or CIELUV color space is dened by quantities

L
, u
, v
= 116
_
Y
Y
n
_
1/3
16 when
_
Y
Y
n
_
> 0.008856 (2.8)
u
= 13L
(u
n
) (2.9)
v
= 13L
(v
n
), (2.10)
where Y, u
, v
describe the color stimulus considered and Y

n
, u
n
, v
n
describe a specied
white object color stimulus. If Y/Y
n
is less than 0.008856, the above equations are
changed as follows
_
Y
Y
n
_
1/3
is replaced by 7.787
_
Y
Y
n
_
+
16
116
.
The CIE 1976 L
color space or CIELAB color space is dened by quantities

L
= 116
_
Y
Y
n
_
1/3
16 (2.11)
a
= 500
_
_
X
X
n
_
1/3
_
Y
Y
n
_
1/3
_
(2.12)
b
= 200
_
_
Y
Y
n
_
1/3
_
Z
Z
n
_
1/3
_
, (2.13)
where X, Y, Z describe the color stimulus considered and X
n
, Y
n
, Z
n
describe a specic
white object color stimulus. If X/X
n
, Y/Y
n
or Z/Z
n
is less than 0.008856, the above
equations are changed as follows
_
X
X
n
_
1/3
_
X
X
n
_
+
16
116
_
Y
Y
n
_
1/3
_
Y
Y
n
_
+
16
116
_
Z
Z
n
_
1/3
_
Z
Z
n
_
+
16
116
.
The dierences E
uv
or E
ab
between two color stimuli are calculated as the
Euclidean distance between the points representing them in the space:
E
uv
=
_
(L
)
2
+ (u
)
2
+ (v
)
2
(2.14)
E
ab
=
_
(L
)
2
+ (a
)
2
+ (b
)
2
. (2.15)
2.2.5 Miscellaneous colorimetric practices and formulae
Dominant wavelength
The dominant wavelength of a color stimulus
d
is a wavelength of the monochromatic
stimulus that matches the color stimulus considered when additively mixed in suit-
able proportions with the specied achromatic stimulus. A monochromatic stimulus
is monochromatic radiant power of given magnitude and wavelength, entering the eye
and producing a sensation of light or color. An achromatic stimulus is the color stim-
ulus chosen because it usually yields a color perception which is devoid of hue under
the desired observing conditions. Complementary wavelength is used instead of dom-
inant wavelength for stimuli whose chromaticities lie between those of the specied
achromatic stimulus and the purple line.
Complementary wavelength
The complementary wavelength of a color stimulus
c
is a wavelength of the monochro-
matic stimulus that matches the specic achromatic stimulus when additively mixed
in suitable proportions with the color stimulus considered.
18 2. Colorimetry
Colorimetric purity
The colorimetric purity p
c
is dened by the relation
p
c
=
L
d
L
n
+ L
d
, (2.16)
where L
d
and L
n
are the luminances of the monochromatic stimulus and of the speci-
ed achromatic stimulus that match the color stimulus considered in an additive mix-
ture, respectively. In the case of stimuli characterized by a complementary wavelength
suitable mixtures of light from the two end of the spectrum are used instead of the
monochromatic stimuli. In the CIE 1931 standard colorimetric system, colorimetric
purity is related to excitation purity p
e
by the equation
p
c
= p
e
y
d
y
, (2.17)
where y
d
and y are the y-chromaticity coordinates of the considered monochromatic
stimulus and the color stimulus, respectively.
Excitation purity
Excitation purity p
e
is dened by the ratio NC/ND of two collinear distances on the
chromaticity diagram of the CIE 1931 or 1964 standard colorimetric system. The rst
distance is that between point C and N which represents the considered color stimulus
and the specied achromatic stimulus, respectively. The second distance is between
point N and point D on the spectrum locus at the considered dominant wavelength of
the color stimulus. The denition leads to the following expressions
p
e
=
y y
n
y
d
y
n
or p
e
=
x x
n
x
d
x
n
, (2.18)
where (x, y), (x
n
, y
n
), (x
d
, y
d
) are the x, y-chromaticity coordinates of the points C, N
and D, respectively.
Special metamerism index
Two specimens having identical tristimulus values for a given reference illuminant and
reference observer are metameric if their spectral radiance distributions dier within
the visible spectrum. It is recommended that two specimens whose corresponding
tristimulus values (X
1
= X
2
, Y
1
= Y
2
, Z
1
= Z
2
) are identical with respect to a reference
illuminant and observer, the metamerism index, M
t
is set to be equal to the index
of color dierence E between the two specimens computed for the test illuminant
t. The preferred reference illuminant is the CIE standard illuminant D
65
. If another
illuminant is used as reference this should be noted.
The evaluation of whiteness
According to CIE recommendations, the formulae W or W
10
for whiteness and T
W
or T
W,10
for tint, given below, are used for comparisons of the whiteness of samples
evaluated for CIE standard illuminant D
65
. The application of the formulae is restricted
to samples that are called white commercially, that do not dier much in color and
uorescence, and that are measured on the same instrument at nearly the same time.
W = Y + 800(x
n
x) + 1700(y
n
y) (2.19)
W
10
= Y
10
+ 800(x
n,10
x
10
) + 1700(y
n,10
y
10
) (2.20)
T
W
= 1000(x
n
x) 650(y
n
y) (2.21)
T
W,10
= 900(x
n,10
x
10
) 650(y
n,10
y
10
), (2.22)
where Y is the Y -stimulus value of the sample, x and y are the x, y chromaticity
coordinates of the sample, and x
n
, y
n
are the chromaticity coordinates of the perfect
diuser, all for the CIE 1931 standard colorimetric observer. Y
10
, x
10
, y
10
, x
n,10
and y
n,10
,
are similar values for the CIE 1964 supplementary standard colorimetric observer. The
higher the value of W or w
10
the greater is the indicated whiteness. The more positive
the value T
W
or T
W,10
the greater is the indicated greenishness. The more negative the
value T
W
or T
W,10
the greater is the indicated reddishness. For perfect diuser W and
W
10
are equal to 100 and T
W
and T
W,10
are equal to zero.
Calculation of correlated color temperature
The correlated color temperature of a given stimulus is the temperature of the Planck-
ian radiator whose perceived color most closely resembles that of the stimulus at the
same brightness and under the same viewing conditions. The recommended method
for calculating the correlated color temperature of a stimulus is to determine on a chro-
maticity diagram the temperature corresponding to the point on the Planckian locus
that is intersected by the agreed isotemperature line containing the point representing
the stimulus.
20 2. Colorimetry
2.3 Summary
The recommendations of the CIE Colorimetry Committee are given for various col-
orimetric practices and formulae such as recommendations for standard illuminants,
for the standard reectance factor, for illuminating and viewing conditions, for the
standard colorimetric observers, for the calculation of tristimulus values, chromaticity
coordinates, and color dierences.
Chapter III
Measurement of surface color
Surface color measurements are of great importance in the production of a very wide
range of manufactured goods in industry. Industry needs to be able to measure surface
color to within the discrimination limits of the human eye of 0.5 E
ab
CIELAB units.
The basic idea is to measure the absolute spectrum as accurately as possible [25].
The spectrum is then used with the stored numerical data to derive desired results.
The algorithms should include the commonly used illuminants together with various
coordinate systems, whiteness formulas, and color dierence formulas.
There are two main classes of color measuring instruments, which are used for
surface color measurements, colorimeters and spectrophotometers. Colorimeters are
trichromatic devices, where the illuminant is simulated by a light source and the color
matching functions are simulated by (interference) colored lters in combination with
a photodetector. These instruments have a simple construction, but they are not
accurate enough for typical quality control tasks in industry.
Spectrophotometers allow accurate measurement, because they measure the spec-
tral reectances of the samples. The disadvantage of traditional scanning spectropho-
tometers is that they are slow. In addition, because of vibration sensitivity and other
environmental requirements they can not be used outside of laboratory conditions.
These disadvantages have recently been avoided by constructing non-scanning spec-
trophotometers, which are based on use of diode array detectors.
3.1 General considerations on color measurement
Internationally accepted illumination and observation angles should be standardised
for use in instruments such as normal/diuse with including or excluding the specular
component, or 0/45. Tolerances on these angles along with the maximum angle of
acceptance are given in CIE Publication 15.2 [5].
If wide spectrum illumination is used (incandescence lamp, xenon lamp, ash lamp),
one should be aware of uorescent samples. The source has to match a CIE standard or
21
22 3. Measurement of surface color
recommended illuminant (A, D
65
, C etc.) as closely as possible to correctly determine
color coordinates. If this is not accomplished, the surface color of a uorescent sample
has to be measured by the double monochromator method [40, 44]. Fluorescence is
present in many objects, even in some white standards.
There are some general principles to follow in order to obtain reliable measurement
results. Color measurement instruments have to be maintained as advised in their
manuals. It is necessary to pay special attention to the handling and maintance of the
instruments calibration standards. The same attention should be paid to integrating
sphere coatings as well. Degradation of this coating produces several errors.
The instruments start up routine should be done as indicated by the manufacturer.
Currently this is automatically done by most spectrophotometers and colorimeters.
The warm-up time should also be followed as indicated in the manual. At the very
least the warm up should be thirty minutes in every case. Samples should be measured
at the same room temperature as the instrument.
Many instruments have their own calibration set, which contains a white standard
and a black standard or zero reectance standard. The low reectance standard is not
as common as the white one. However, it is advisable to use another calibration set to
independently check the instruments performance. Ideally, this set should contain the
following elements: a surface mirror, a wavelength standard, two white standards (one
matt and one glossy), a zero reectance standard and at least one grey standard with
about 50% reectance. The function of these elements is given later in this chapter.
It is good policy to measure a sample a few times and, to calculate the mean
value of those measurements. One can rotate the sample between each measurement
to avoid directional dependency from surface inhomogeneties. For as accurate results
as possible, the performance and potential error sources in the instrument must be
known [7, 8, 15, 20, 43].
3.2 Intercomparison
The human eye can perceive color dierences approximately 0.5 E
ab
in CIELAB
units. The rst European intercomparison stopped in 1993 [45]. This intercomparison
sought to determine the state of the art of measurements of spectral reectance and
color specication of surface colors using spectrophotometry. Four laboratories, each
from a dierent country within the European Community, participated. Sets of four-
teen ceramic color standards were calibrated by each laboratory. The intercomparison
covered the specular excluded, specular included and 0/45 geometries. The result was
that approximately half of the measurements made by the laboratories with respon-
sibility for national standards did not agree on the limit of the human eye. This is
inadequate for industrial requirements.
The second European intercomparison was started in 1997 [43]. The main objective
3.2 Intercomparison 23
in this project was to harmonise color measurements between 8 national laboratories to
achieve a target of 95% agreement within 0.5E
ab
CIELAB units for non-uorescent
colors. This was achieved through the use of a system for determining and correcting
errors, followed by an intercomparison of non-uorescent surface color measurements.
The second objective was to extend the capability for measurement of uorescent safety
colors using the two monochromator method to three countries within the European
Union, and carry out an intercomparison of uorescent colored materials to meet the
metrological requirements of EN471, Specication of High Visibility Warning Cloth-
ing. Partners in this project entitled Harmonisation of National Scales of Surface
Color Measurements, Contract SMT4-CT96-2140, European Commission Standards
Measurements and Testing Programme, were as follows:
National Physical Laboratory (NPL), United Kingdom.
Consejo Superior de Investigatines Cienticas (CSIC), Spain.
Bundesanstalt f ur Materialforchung und-Pr ufung (BAM), Deutchland.
University of Joensuu (UJ), Finland.
Laboratoire National dEssais (LNE), France.
Centro de Ciencias e Technologias Opticas (CETO), Portugal.
Swedish National Testing Research Institute (SP), Sweden.
British Ceramic Researc Ltd (BCRA), United Kingdom.
Danish Electronic Light and Acoustics (DELTA), Denmark.
NPL worked as a co-ordinator of the project. During the rst year, all partners
met at NPL. They agreed upon which errors in the measurements of surface color
that could be determined and corrected, and the principles of the methodology for
achieving this. NPL calibrated and dispatched to partners a set of calibrated artefacts
for determining correcting errors. Partners then determined the errors within their
instruments and reported their result to the co-ordinator. NPL also measured sets of 4
color standards to be used by partners for testing the eectiveness of the methodology
for harmonisation, and to give preliminary results on levels of agreement that might
be achieved for non-uorescent colors.
3.3 Errors in surface color measurements
Spectrophotometric errors are discussed in this section on a qualitative basis. In order
to achieve the target level of agreement of 0.5 E
ab
CIELAB units, it is necessary
to determine and correct errors in the measurement color and to adopt a common
procedure where relevant. The following is a list of the principal errors:
Errors in absolute scales of diuse reectance and 0/45 radiance factor.
Errors due to diering properties of white reference standards.
Non-linearity of the photodetector.
Incorrect zero level.
Wavelength scale error.
Specular beam exclusion error.
Specular beam weighting error.
Errors due to non-uniformity of collection of integrating spheres.
Polarisation errors in the 0/45 geometry.
Dierences in methods for calculating color data from spectral data.
Errors due to thermochromism in samples.
Errors due to the dependence of spectral resolution on bandwidth, scan speed
and integration time.
Geometry dierence between illumination and collection optics within the speci-
ed limits.
At present, there is no method for quantifying the eects of geometry dierences
(last item) and applying corrections. The method used to minimise error due to
non-uniformity of collection by integrating spheres, which is to measure matt sam-
ples against matt masters and glossy samples against glossy masters, has not proved
very eective. Thus, it is now clear that there are signicant undetermined errors
which remain uncorrected, limiting agreement at present.
Integrating sphere errors are due to the fact that the integrating sphere is not an
ideal sphere but a hemispherical sphere. There are also some baes inside the sphere
which prevent straight light from striking the detector.
3.3 Errors in surface color measurements 25
3.3.1 Errors in absolute scales of diuse reectance and 0/45 radiance
factor
The method used for this intercomparison relies on the stability of the white reference
tiles to accurately transfer common absolute scales to all participants with a high degree
of accuracy. All standards were calibrated by NPL, providing a common scale for the
matt and glossy calibrations. These scales contain an inherent uncertainty associated
with the NPL calibration.
3.3.2 Errors due to diering properties of white reference standards
When making measurements of matt samples using spectrophotometers with a inte-
grating sphere accessory, errors may be introduced if the instrument is calibrated using
a glossy standard. The same is also true for glossy measurement against a matt stan-
dard. To minimize these errors a matt standard should be used for matt samples and
a glossy standard for glossy samples.
3.3.3 Photometric non-linearity
A lack of linearity in a detection system causes errors in results. Photometric non-
linearity error assumes that the response of the photodetector is not linear over the
reectance scale from 0% to 100%. Towards the higher end of the signal range, satura-
tion of the detector or electronics may occur. There may also be some additional eects
such as inter-reection between glass surfaces within the instrument and a reduction
in sphere response with dark samples.
The simplest type of relationship between the true value of reectance R and the
instrumental value R
is a quadratic form. That means the dierence is biggest at the

50% reectance level. Now the photometric non-linearity can be corrected by measuring
only one grey tile, about 50% of the reectance. Denition of the non-linearity error
is based on the assumption that the error is zero at 100% and 0%. The 100% level
corresponds to a sample being measured against itself and 0% level errors are classied
as the dark level error and, thus, treated separately.
Assuming the quadratic relationship for the error we arrive at
R = R
+ R
= a + bR
+ cR
2
. (3.1)
By this denition we nd that when R = 0 also R
= 0 and a = 0. In the same way

when R = 100, R
= 100 also. Now we have the equations

100 = 100(b + 100c) (3.2)
b = 1 100c. (3.3)
For a grey tile, we can denote R = r and R
= r
. Thus
r = br
+ cr
2
= (1 100c)r
+ cr
2
= r
100cr
+ cr
2
. (3.4)
For a terms of c and b, we can solve
c =
r
r
100r
r
2
(3.5)
b = 1 100c
= 1
100r
100r
100r
r
2
=
100r + r
2
100r
r
2
. (3.6)
Hence,
R =
_
100r r
2
100r
r
2
_
R
+
_
r
r
100r
r
2
_
R
2
, (3.7)
where r is the certied value for the grey tile, and r
is the corresponding measured

value. Now the linearity corrected spectrum R can be calculated for any color when
the uncorrected spectra R
is measured.
As the tiles used in this intercomparison were calibrated against a white master on
a sphere instrument at NPL, it is possible that the NPLs instruments non-linearity
may have been imposed on all values.
3.3.4 Incorrect zero level
An integrating sphere dark level error is mainly due to light scattered inside the optics
of the spectrophotometer. This eect gives a halo around the main light beam, some
of which falls on the sphere wall. There may also be a component due to an electronic
oset. The error is determined by placing a black glass wedge at the sample port, which
absorbs the light in the main beam and by measuring the variation of reectance reading
with a wavelength. An optical wedge gives a reading
k
. Absolute diuse reectance
of a sample R
a
is
R
a
=

a
k
R
t
=
a
_
1

k
a
_
a
_
1

k
t
_R
t
t
_
1

k
a
__
1 +

k
t
_
R
t
t
_
1

k
a
+

k
t
_
R
t
=

a
t
R
t
+ k
1
_
t
1
_
, (3.8)
where,
k
1
=

k
t
R
t
. (3.9)
a
in Eq. 3.8 is the sample reading,
t
is the white standard reading,
k
is the dark
reading and R
t
is the calibrated value for a white standard.
3.3.5 Wavelength scale error
Wavelength error will lead to color errors, so the instruments wavelength scale should
be checked. Reectance values should be corrected, according to the expression
R() = R
m
() +
R
m
()
, (3.10)
where R() is the correct reectance value, R
m
is the measured reectance value and
is the wavelength scale error, the dierence between the actual and displayed value.
Wavelength error can be determined by using several wavelength standards: spectral
lamps, reection tiles or transmission lters. The user must use the most appropriate
standard for the instrument type.
3.3.6 Specular beam exclusion error
For a glossy sample measured in the specular excluded mode, the specular beam falls
on a gloss trap. Ideally, none of the light entering the trap should be reected back into
the sphere and none of the beam should meet an integrating sphere wall. In practice,
these ideal conditions are not often achieved and, thus, correction is needed. The
simplest method is to use a calibrated front surface mirror to give a strong specular
beam with the white tile used as the diuse reectance standard. A calibrated mirror
of reectance M gives a reading
gm
. In a case where a gloss trap is used to block
specular reectance, a calibrated mirror M will give a reading
g4
=
4
M
gm
. (3.11)
The number 4 is used as a nominal value for the specular reectance of a typical glossy
sample. Absolute diuse reectance R
a
of a sample is
R
a
=

a
g4
g4
R
t
, (3.12)
where , = 0 for a matt surface and , = 1 for a glossy surface. Using the same
approximates as for the dark error correction
R
a

a
t
R
t
+ k
2
_
_
, (3.13)
where,
k
2
=

g4
t
R
t
. (3.14)
Here with the
a
reading of a sample,
t
is read when the white standard is measured,
and R
t
3.3.7 Specular beam weighting error
For a glossy sample measured in the specular included mode, non uniformity of the
integrating sphere may mean that the specular component is not collected with the
same eciency as the diusely reected light. A calibrated mirror of reectance M
placed at the sample port gives a reading
sm
. If there is no specular beam error, the
mirror would give a reading
t
M
R
t
, (3.15)
where
t
is a reading of a calibrated matt white tile R
t
is placed at the sample port.
Thus, the error in the mirror reading e
m
is given by
e
m
=
sm
t
M
R
t
. (3.16)
If we apply the nominal value of 4% specular reectance from a typical glossy sample
we arrive at the error in the specular beam
e
s
=
4
M
_
sm
t
M
R
t
_
. (3.17)
The absolute reectance R
a
of a sample when applying a correction is
R
a
=

a
e
s
t
e
s
R
t
t
_
1
e
s
a
+
e
s
t
_
R
t
=

a
t
R
t
+

a
t
e
s
_
a
_
R
t
, (3.18)
where , = 0 is for a matt surface and , = 1 is for a glossy surface, where the
same approximates are used as before. Substituting e
s
into the above equation we get
R
a
=

a
t
R
t
+

a
t
4
M
_
sm
t
M
R
t
__
a
_
R
t
=

a
t
R
t
+ 4
_
sm
t
1
M

1
R
t
__
_
R
t
=

a
t
R
t
+ 4
_
sm
t
R
t
M
1
__
_
=

a
t
R
t
+ k
3
_
_
, (3.19)
where,
k
3
= 4
_
sm
t
R
t
M
1
_
. (3.20)
In Eqs. 3.19 and 3.20
a
is a sample reading,
sm
is a reading for a calibrated mirror
in a sample port,
t
is a reading for the calibrated white standard, M is the calibrated
value for a mirror and R
t
3.3.8 Errors due to non-uniformity of collection of integrating spheres
The internal reectance of an integrating sphere will usually vary over its surface. In
addition, baes included within the sphere lead to a variation in response to the angle
of reectance. The reectance of samples, particularly materials such as metals and
paper, varies considerably with the direction of view. This, linked with the non-uniform
angular response of the sphere, may lead to errors.
3.3.9 Polarisation errors in the 0/45 geometry
Several researchers have carried out studies on the eects of polarisation. However, no
need for a correction has arisen in typical surface color samples.
3.3.10 Dierences in methods of calculating color data from spectral data
In the calculation of colorimetric values some errors may occur. Usually, the CIE
standard observer data are available at 5 nm intervals. Errors may occur if calculation
is made at dierent intervals.
3.4 Measurements and corrections 31
3.3.11 Geometry dierences between illumination and collection optics
within the specied limits
The tolerances given in the CIE geometry specication are suciently large to result
in a wide range of implementation in instrumental design.
3.3.12 Errors due to thermochromism in samples
In common with all materials, the ceramic tiles used in the intercomparison will change
color with temperature. Thus, samples should be measured at the same temperature.
It was agreed to measure samples in 23 1
C in this comparison. In this thesis,

thermochromism is discussed in more detail in Chapter V.
3.3.13 Errors due to the dependence of spectral resolution on bandwidth,
scan speed and integration time
A fast speed scan with slow integration time will generate a dierent result to a slow
speed, fast integration time scan, particularly in the resolution of slopes. The dierence
between the two resulting spectra might appear as a wavelength shift and particularly
aect the results for the more chromatic tiles. The same is true for an instrument with
a dierently shaped spectral bandwidth. The partners were investigating the eects of
the scan speed and integration time and nally agreed to use same kind of parameters.
3.4 Measurements and corrections
A double beam scanning spectrophotometer, Perkin Elmer -18, was used in reectance
spectra recording. Measurements were performed with a bandwidth of 2 nm and with a
scanning speed of 240 nm/min. The minimum temperature during the measurements
was 22.2
C while the maximum was 23.4
C. All samples were measured 6 times, 3

times in the morning and 3 times in the afternoon after at least a 3 hour interval. No
signicant dierences were noticed between the results. Error correction factors k
1
, k
2
and k
3
were determined as described earlier in Eqs 3.9, 3.14 and 3.20. Quantities of
constants k
i
for a PE-18 instrument are shown in Fig. 3.1 as a function of wavelength.
The correction constants were then used to apply the needed corrections. Wavelength
error was determined by measuring the emission spectrum of a deuterium lamp. This
error was noticeably negligible. The amount of linearity correction was also determined
by measuring the mid-grey calibration sample which was compared to the calibrated
values. The dierence between the calibrated and the measured values was about
0.56%-unit. As a matter of fact, the inuence of the photometric linearity correction
was biggest among all applied corrections in our case. One has to point out that by
using only one grey tile a quadratic relationship is assumed for the linearity error. To
ensure the nature of the behavior of the photodetector, more calibrated grey samples
should be used. One interesting nding during this intercomparison was that a grey
tile and a neutral transmittance lter, at about the same level of 50% refelectance, do
not necessarily have the same amount of non-linearity error. This was conrmed by
measurement between UJ and NPL. Later, in 1998 the co-ordinator received a letter
from Japan as part of the work of a CIE Technical Committee, giving completely
independent results.
350 400 450 500 550 600 650 700 750 800
0
0.01
0.02
0.03
0.04
0.05
0.06
Wavelength [nm]
V
a
l
u
e
Figure 3.1: Error correction factors for the PE-18 spectrophotometer. Solid, dashed,
and dot-dashed lines correspond to the correction factors k
1
, k
2
and k
3
, respectively.
3.5 Intercomparison results
The main objective of the project was to harmonise color measurements between 8
national laboratories within discrimination limits of the human eye. A target was
set to 95% agreement within 0.5 E CIELAB units. Each laboratory measured and
applied corrections for a set of 16 samples, 8 matt samples and 8 glossy samples. All
of the measurements and calculations of Joensuu cite were done by the author. All
the samples were ceramic tiles which are known to be very stable [12]. The matt
samples were measured against a matt white tile and, similarly, glossy tiles against a
glossy white tile. Fig. 3.2 shows the reectance spectra of the 8 matt color samples.
The colors of the tiles were pale grey, mid grey, black, red, bright yellow, green, cyan
and deep blue. These samples were provided and calibrated by the NPL. Partners
did not have a priori knowledge of the spectral data of the samples while making
measurements. Each laboratory tried to measure samples as accurately as they could.
3.5 Intercomparison results 33
Matt samples were measured in specular included geometry and glossy samples were
measured both in specular included and excluded geometry. Some of the laboratories
measured the samples in 0/45 geometry, as well.
400 450 500 550 600 650 700 750
0
10
20
30
40
50
60
70
80
90
100
Wavelength [nm]
R
e
e
c
t
a
n
c
e
[
%
]
Figure 3.2: Reectance spectra of a 8 matt color samples.
Part of the results of the comparison are shown in the Tables 3.13.17. Table 3.1
show the eect of the applied error corrections for the data measured at the University
of Joensuu. In specular included geometry corrections are made in the following order:
dark error correction (R
d
), specular beam error correction (R
s
) and non-linearity cor-
rection (R
nl
). Each correction was added cumulatively to the previous corrections. In
the specular excluded geometry a gloss trap error correction (R
g
) was applied instead
of the specular beam correction.
The colormetric dierences from the NPL-data were calculated for each partner.
The results for the specular included geometry are shown in Tables 3.2 and 3.3 before
and after the corrections, respectively. In Tables 3.4 and 3.5 corresponding results are
shown for the specular excluded geometry. By comparing the results between 3.2 and
3.3 or 3.4 and 3.5 one can see the impact of applied corrections. In most corrections the
results improve. Surprisingly, there are quite large dierences with black, red and deep
blue samples. It is hard to say whether the reason lies in the instrument or if there
is human error in the measurements. Nevertheless, the UJ-results are the only ones
where the impact of error corrections did not change results in the wrong direction, i.e.
in every case better results were achieved after corrections were applied. This indicates
that NPL and us were the best among the participating laboratories. However, we
need to point out that in this kind of experimental investigation the right results do
not exist. It is possible that there may be some error in the NPL-data as well. In that
Table 3.1: CIELAB Colorimetric dierences E for the UJ-data after applied cumu-
lative corrections in the order of dark error (R
d
) correction, specular beam error (R
s
)
or gloss trap error (R
g
) correction and non-linearity error (R
nl
) correction, 10 degree
observer, illuminant D
65
.
Specular Included Specular Excluded
Geometry Geometry
Tile R
d
R
s
R
nl
R
d
R
g
R
nl
Glossy Grey 0.00 0.01 0.23 0.00 0.00 0.25
Glossy Mid Grey 0.01 0.02 0.33 0.01 0.00 0.35
Glossy Black 0.03 0.08 0.20 0.11 0.14 0.21
Glossy Red 0.03 0.02 0.27 0.12 0.26 0.31
Glossy Bright Yellow 0.03 0.02 0.31 0.04 0.14 0.33
Glossy Green 0.01 0.03 0.35 0.02 0.07 0.37
Glossy Cyan 0.01 0.02 0.34 0.01 0.06 0.37
Glossy Deep Blue 0.04 0.15 0.36 0.15 0.90 0.87
Matt Grey 0.00 0.23
Matt Mid Grey 0.01 0.34
Matt Black 0.03 0.25
Matt Red 0.02 0.29
Matt Bright Yellow 0.02 0.29
Matt Green 0.01 0.33
Matt Cyan 0.01 0.32
Matt Deep Blue 0.03 0.27
case there will be some uncertainty in all error corrections. From this aspect one can
not directly conclude that smaller dierences are always better.
First of all, the purpose of this intercomparison was to harmonise measurement
results between all partners. This means that dierences are calculated from the mean
value of all measurements. Tables 3.63.9 show the percentage of the measurements of
each partner below three dierent E limits from the mean. However, there may be
some minor disadvantages in this measure as well, since there are some large dierences
among some colors. This will set the mean value as slightly false and distort the results.
Table 3.2: Partners colorimetric dierences E from NPL for the set of 16 color tiles,
specular included geometry. Uncorrected results, 10 degree observer, illuminant D
65
[43].
Tile UJ LNE BAM CETO CSIC SP BCRA DELTA
Glossy
Pale Grey 0.23 0.31 0.09 0.19 0.15 0.27 0.02 0.21
Mid Grey 0.37 0.41 0.59 0.14 0.28 0.34 0.13 0.59
Black 0.17 0.33 4.06 0.33 1.27 0.32 0.78 1.46
Red 0.73 0.69 4.04 0.68 1.45 0.70 0.92 1.58
Bright Yellow 0.59 0.63 3.25 0.46 1.19 0.66 0.63 1.48
Green 0.34 0.49 1.70 0.33 0.73 0.43 0.63 0.72
Cyan 0.47 0.51 1.37 0.57 0.50 0.49 0.80 0.51
Deep Blue 0.20 0.27 4.47 0.44 1.14 0.29 0.45 1.78
Matt
Grey 0.12 0.11 0.19 0.09 0.22 0.10 0.08 0.26
Mid Grey 0.43 0.20 0.09 0.25 0.06 0.11 0.26 0.37
Black 0.43 0.16 1.76 0.23 0.12 0.35 0.11 0.37
Red 0.71 0.78 1.01 0.56 2.55 0.62 0.79 1.30
Bright Yellow 0.84 0.47 1.56 1.31 0.71 0.76 0.82 0.96
Green 0.49 0.18 0.75 0.40 0.32 0.47 0.47 0.62
Cyan 0.42 0.39 0.70 0.48 0.22 0.40 0.73 0.31
Deep Blue 0.55 0.21 2.16 0.37 0.48 0.46 0.22 0.78
Average
|dierence| 0.44 0.38 1.74 0.43 0.71 0.42 0.49 0.83
Table 3.3: Partners colorimetric dierences E from NPL for the set of 16 color
tiles, specular included geometry. Fully corrected results, 10 degree observer, illuminant
D
65
[43].
Glossy
Pale Grey 0.05 0.31 0.12 0.18 0.20 0.05 0.08 0.24
Mid Grey 0.05 0.41 0.37 0.21 0.24 0.07 0.06 0.40
Black 0.17 0.33 2.72 0.33 0.57 0.17 0.20 0.28
Red 0.72 0.69 2.67 0.42 0.89 0.55 0.82 1.48
Bright Yellow 0.33 0.63 1.91 0.67 0.64 0.34 1.01 1.18
Green 0.26 0.49 1.08 0.50 0.44 0.40 0.55 0.95
Cyan 0.51 0.51 0.97 0.63 0.36 0.52 0.81 0.48
Deep Blue 0.42 0.27 3.06 0.23 0.34 0.14 0.33 0.36
Matt
Pale Grey 0.13 0.11 0.33 0.09 0.13 0.14 0.06 0.20
Mid Grey 0.10 0.20 0.19 0.28 0.10 0.29 0.10 0.47
Black 0.16 0.16 1.64 0.21 0.23 0.05 0.08 0.47
Red 0.57 0.78 1.84 0.46 2.49 0.46 0.80 1.33
Bright Yellow 0.59 0.47 1.34 1.41 0.78 0.47 0.84 1.04
Green 0.33 0.18 0.70 0.46 0.31 0.42 0.43 0.62
Cyan 0.39 0.39 0.75 0.54 0.19 0.39 0.67 0.21
Deep Blue 0.39 0.21 2.17 0.32 0.49 0.27 0.15 0.77
Average
|dierence| 0.32 0.38 1.30 0.43 0.52 0.30 0.44 0.65
Table 3.4: Partners colorimetric dierences E from NPL for the set of 8 color tiles,
specular excluded geometry. Uncorrected results, 10 degree observer, illuminant D
65
[43].
Glossy
Pale Grey 0.24 0.15 0.08 0.20 0.16 0.28 0.02 0.13
Mid Grey 0.51 0.20 0.22 0.22 0.18 0.44 0.06 0.07
Black 0.60 1.17 0.65 1.50 0.66 0.66 0.55 0.51
Red 1.01 1.15 1.78 2.89 0.92 1.24 0.72 2.17
Bright Yellow 0.99 0.48 0.85 0.60 0.59 0.97 0.60 1.08
Green 0.66 0.33 0.53 0.22 0.42 0.68 0.64 0.86
Cyan 0.57 0.45 0.30 0.63 0.58 0.79 1.16 1.13
Deep Blue 1.70 0.98 0.35 0.90 1.48 1.57 0.80 0.90
Average
|dierence| 0.78 0.62 0.60 0.89 0.62 0.83 0.57 0.86
Table 3.5: Partners colorimetric dierences E from NPL for the set of 16 color
tiles, specular excluded geometry. Fully corrected results, 10 degree observer, illuminant
D
65
[43].
Glossy
Pale Grey 0.06 0.15 0.25 0.20 0.26 0.04 0.11 0.12
Mid Grey 0.16 0.20 0.26 0.33 0.31 0.11 0.18 0.06
Black 0.45 1.17 0.53 0.86 0.81 0.26 0.65 0.49
Red 0.44 1.15 0.90 0.73 1.07 0.77 0.86 2.10
Bright Yellow 0.66 0.48 0.47 0.99 0.72 0.72 0.69 1.09
Green 0.54 0.33 0.24 0.64 0.48 0.70 0.64 0.86
Cyan 0.56 0.45 0.27 0.73 0.57 0.93 1.07 1.15
Deep Blue 0.92 0.98 1.37 1.35 1.64 1.11 0.86 0.98
Average
|dierence| 0.47 0.62 0.54 0.73 0.73 0.58 0.63 0.86
Table 3.6: Partners colorimetric dierences E from the mean dierence for the set
of 16 color tiles, specular included geometry. Uncorrected results, 10 degree observer,
illuminant D
65
[43].
UJ LNE BAM CETO CSIC SP BCRA DELTA
Average
|dierence| 0.27 0.32 1.09 0.31 0.22 0.27 0.25 0.20
% within 0.2
E of mean 56.3 43.8 25.0 37.5 75.0 62.5 43.8 62.5
% within 0.5
E of mean 75.0 81.3 43.8 75.0 93.8 81.3 93.8 93.8
% within 0.75
E of mean 87.5 87.5 56.3 93.8 93.8 87.5 100 100
of 16 color tiles, specular included geometry. Fully corrected results, 10 degree observer,
illuminant D
65
[43].
Average
|dierence| 0.22 0.20 0.78 0.21 0.22 0.26 0.18 0.23
% within 0.2
E of mean 43.8 50.0 31.3 62.5 75.0 50.0 56.3 50.0
% within 0.5
E of mean 93.8 100 62.5 81.3 93.8 87.5 100 100
% within 0.75
E of mean 100 100 62.5 100 93.8 100 100 100
of 16 color tiles, specular excluded geometry. Uncorrected results, 10 degree observer,
illuminant D
65
[43].
Average
|dierence| 0.26 0.20 0.22 0.37 0.20 0.20 0.29 0.30
% within 0.2
E of mean 50.0 37.5 62.5 62.5 75.0 62.5 50.0 37.5
% within 0.5
E of mean 87.5 100 87.5 75.0 87.5 100 87.5 87.5
% within 0.75
E of mean 100 100 100 87.5 100 100 87.5 100
of 16 color tiles, specular excluded geometry. Fully corrected results, 10 degree observer,
illuminant D
65
[43].
Average
|dierence| 0.17 0.20 0.20 0.15 0.14 0.15 0.12 0.43
% within 0.2
E of mean 62.5 50.0 50.0 62.5 87.5 62.5 75.0 50.0
% within 0.5
E of mean 87.5 87.5 100 100 100 100 100 87.5
% within 0.75
E of mean 100 100 100 100 100 100 100 87.5
3.6 Determination of colorimetric uncertainties
Generally, the result of a measurement is only a approximation or estimate of the
value of the specic quantity subject to measurement. Because of increasing demands
of measurement accreditation and quality systems there is a need to quote uncertainties
on all certied quantities. The result is complete only when accompanied a quantitative
statement of its uncertainty [8, 53].
The uncertainty of the result of a measurement generally consists of several compo-
nents. These components may be grouped into two categories according to the method
used to estimate their numerical values:
Type A, evaluated by statistical methods.
Type B, evaluated by other means.
The only Type A uncertainty in this intercomparison was the repeatability [43]. The
Type B uncertainties were:
Uncertainty in the level of the absolute scales of diuse reectance and radiance
factor.
Uncertainty in the spectral slope of the scales.
Dark uncertainty.
Linearity uncertainty.
Wavelength scale uncertainty.
Thermochromism uncertainty.
Glossy to matt ratio uncertainty.
Specular beam uncertainty.
Gloss trap uncertainty.
The repeatability was determined by making several measurements. The standard
deviation was then used in the calculation of of the standard uncertainty.
Uncertainty in the level of the absolute scales of diuse reectance or radiance
factor comes from the traceability to the 100% levels. This is taken from a certicate
of calibration for a white standard. Uncertainty in the spectral slope of scales is
connected to absolute scale uncertainty. The scale may have a slope on it within the
uncertainty limits. This eect is assessed using a skew of half the scale uncertainty.
3.6 Determination of colorimetric uncertainties 45
The dark uncertainty is a combination of the electronic oset of the instrument and,
for diuse reectance, an optical oset due to a halo of scattered light surrounding the
sample beam and falling on the integrating sphere. Dark errors can be measured by
placing a gloss trap at the sample port of integrating sphere. Blocking the beam does
not give a true oset reading, because it does not quantify the eects of the halo of
stray light.
Photometric linearity uncertainty is connected to non-linearity of the detector. It
can be assessed from measurements of a white and a grey standards. Non-linearity
error was modelled using a polynomial and was set to zero at 0% and 100%.
Wavelength error cause changes in reectance in regions of spectral slope, where
reectance changes with wavelength. Wavelength error can be measured using a wave-
length standard or a known spectral line of a lamp. Thermochromism causes shift into
spectral data in a similar way as wavelength error.
Errors in the glossy to matt ratio are due to dierences in eciency of collection
of the integrating sphere with angle of reectance. The error can be determined by
measuring glossy samples against matt samples with dierent integrating spheres.
The specularly reected light may not be collected with the same eciency as the
diusely reected light in the specular included geometry. Specular beam uncertainty
can be determined using a mirror and a calibrated matt white standard. In the specular
excluded geometry, the error due to incomplete absorption of the specular beam in the
gloss trap is known as the gloss trap error. This error can also be determined with a
mirror and a calibrated matt white standard.
Each uncertainty is characterised by assessed probability distribution for the un-
certainty. In a case of Gaussian (normal) distribution each component of uncertainty
was rst divided by a coverage factor k, 1 or 2, which refers to condence level of
approximately 65% or 95%, respectively. The total uncertainty was then combined in
quadrature from the components of uncertainty as
u
total
=
_
(u
2
1
+ u
2
2
+ . . . ), (3.21)
which was then multiplied by a coverage factor. In here coverage factor of k = 2 was
used.
The following components of uncertainties were determined for a UJ-data:
repeatability
photometric linearity uncertainty
dark level uncertainty
gloss trap uncertainty
specular beam uncertainty
Uncertainties in the level of the absolute scales and in the spectral slope of the
scales were left to calculate by co-ordinator since they provide partners absolute scales.
The wavelength uncertainty was not determined because of zero wavelength error in
measurement of the emission line of deuterium lamp. Also thermochromism eect was
neglected cause of agreed temperature limit 1
C.
All uncertainty components were calculated using the determined errors. If the error
was corrected for in reectance calculations, the uncertainty was that after correction.
If it was not corrected for, the uncertainty was the error itself.
In Tables 3.103.12 partners colorimetric uncertainties are shown for both specular
included and specular excluded geometries. For the UJ-data the most of the uncertainty
lies in a luminosity coordinate L
. This is due the fact that the photometric linearity

was the biggest error source. In Tables 3.133.14 partners colorimetric uncertainties
combined to give E
ab
for the intercomparison are shown.
Table 3.10: Colorimetric uncertainties for partners tiles for a coverage factor of k = 2,
specular included geometry [43].
Tile UJ LNE BAM CETO CSIC SP BCRA DELTA NPL
Glossy
Pale L
0.23 0.5 0.5 0.01 0.24 0.36 0.26 0.5 0.21

Grey a
0.01 0.5 0.5 0.24 1.44 0.11 0.10 0.2 0.02

b
0.00 0.5 0.5 0.07 0.75 0.34 0.19 0.2 0.02

Mid L
0.35 0.5 0.5 0.00 0.18 0.40 0.29 0.5 0.16

Grey a
0.01 0.5 0.5 0.14 1.10 0.08 0.18 0.2 0.02

b
0.00 0.5 0.5 0.04 0.57 0.26 0.34 0.2 0.02

Black L
0.28 0.5 0.5 0.27 0.12 0.32 0.81 0.5 0.16

a
0.01 0.5 0.5 0.95 0.75 0.55 0.28 0.2 0.02

b
0.00 0.5 0.5 0.98 0.38 0.17 0.79 0.2 0.02

Red L
0.28 0.8 0.5 0.39 0.14 0.39 0.82 0.5 0.16

a
0.02 0.8 0.5 1.45 1.04 0.25 0.38 0.2 0.15

b
0.02 0.8 0.5 1.26 0.41 0.29 1.54 0.2 0.13

Bright L
0.20 0.8 0.5 0.65 0.27 0.38 0.45 0.5 0.21

Yellow a
0.14 0.8 0.5 2.23 1.70 0.32 0.47 0.2 0.11

b
0.18 0.8 0.5 1.76 0.55 0.28 1.13 0.2 0.19

Green L
0.34 0.5 0.5 0.47 0.17 0.39 0.23 0.5 0.15

a
0.00 0.5 0.5 1.56 0.96 0.20 0.65 0.2 0.08

b
0.01 0.5 0.5 1.58 0.46 0.28 1.13 0.2 0.13

Cyan L
0.33 0.5 0.5 0.47 0.17 0.37 0.21 0.5 0.16

a
0.03 0.5 0.5 1.60 0.95 0.32 0.73 0.2 0.13

b
0.01 0.5 0.5 1.86 0.60 0.36 0.52 0.2 0.13

Deep L
0.28 0.8 0.5 0.00 0.17 0.33 1.09 0.5 0.16

Blue a
0.03 0.8 0.5 0.05 0.96 0.32 0.73 0.2 0.06

b
0.05 0.8 0.5 0.02 0.46 0.26 0.64 0.2 0.11

specular included geometry [43].
Matt
Pale L
0.23 0.5 0.5 0.01 0.26 0.43 0.26 0.5 0.21

Grey a
0.01 0.5 0.5 0.24 1.57 0.11 0.10 0.2 0.05

b
0.00 0.5 0.5 0.07 0.82 0.34 0.19 0.2 0.05

Mid L
0.34 0.5 0.5 0.00 0.18 0.40 0.29 0.5 0.16

Grey a
0.00 0.5 0.5 0.14 1.10 0.08 0.18 0.2 0.05

b
0.00 0.5 0.5 0.04 0.57 0.26 0.34 0.2 0.05

Black L
0.27 0.5 0.5 0.00 0.13 0.32 0.81 0.5 0.16

a
0.00 0.5 0.5 0.01 0.77 0.55 0.28 0.2 0.05

b
0.01 0.5 0.5 0.00 0.41 0.17 0.79 0.2 0.05

Red L
0.30 0.8 0.5 0.00 0.15 0.39 0.82 0.5 0.16

a
0.03 0.8 0.5 0.02 1.11 0.25 0.38 0.2 0.15

b
0.03 0.8 0.5 0.01 0.46 0.29 1.54 0.2 0.11

Bright L
0.20 0.8 0.5 0.00 0.29 0.38 0.45 0.5 0.21

Yellow a
0.13 0.8 0.5 0.05 1.82 0.32 0.47 0.2 0.11

b
0.19 0.8 0.5 0.02 0.60 0.28 1.13 0.2 0.19

Green L
0.34 0.5 0.5 0.00 0.19 0.39 0.23 0.5 0.15

a
0.01 0.5 0.5 0.02 1.07 0.20 0.65 0.2 0.08

b
0.00 0.5 0.5 0.01 0.52 0.28 1.13 0.2 0.13

Cyan L
0.33 0.5 0.5 0.00 0.18 0.37 0.21 0.5 0.16

a
0.02 0.5 0.5 0.02 1.03 0.32 0.73 0.2 0.13

b
0.02 0.5 0.5 0.01 0.65 0.36 0.52 0.2 0.13

Deep L
0.28 0.8 0.5 0.00 0.13 0.33 1.09 0.5 0.16

Blue a
0.02 0.8 0.5 0.01 0.78 0.32 0.73 0.2 0.06

b
0.07 0.8 0.5 0.00 0.45 0.26 0.64 0.2 0.11

specular excluded geometry [43].
Glossy
Pale L
0.25 0.5 0.5 0.00 0.23 0.40 0.26 0.5 0.20

Grey a
0.00 0.5 0.5 0.04 1.38 0.10 0.14 0.2 0.02

b
0.00 0.5 0.5 0.02 0.71 0.33 0.17 0.2 0.02

Mid L
0.35 0.5 0.5 0.00 0.16 0.43 0.23 0.5 0.15

Grey a
0.00 0.5 0.5 0.04 0.96 0.08 0.15 0.2 0.02

b
0.00 0.5 0.5 0.01 0.50 0.25 0.22 0.2 0.02

Black L
0.14 0.5 0.5 0.11 0.06 0.39 0.54 0.5 0.41

a
0.04 0.5 0.5 0.36 0.35 0.04 0.26 0.2 0.02

b
0.04 0.5 0.5 0.41 0.17 0.14 0.38 0.2 0.02

Red L
0.22 0.8 0.5 0.13 0.16 0.39 0.74 0.5 0.18

a
0.10 0.8 0.5 0.50 1.12 0.29 0.30 0.2 0.21

b
0.03 0.8 0.5 0.45 0.53 0.44 1.59 0.2 0.47

Bright L
0.21 0.8 0.5 0.00 0.26 0.39 0.37 0.5 0.20

Yellow a
0.15 0.8 0.5 0.04 1.64 0.40 0.66 0.2 0.12

b
0.07 0.8 0.5 0.01 0.56 0.60 0.39 0.2 0.27

Green L
0.33 0.5 0.5 0.00 0.17 0.38 0.23 0.5 0.15

a
0.05 0.5 0.5 0.02 0.93 0.25 0.43 0.2 0.10

b
0.04 0.5 0.5 0.01 0.44 0.32 0.84 0.2 0.15

Cyan L
0.32 0.5 0.5 0.00 0.16 0.37 0.37 0.5 0.16

a
0.06 0.5 0.5 0.02 0.91 0.26 1.03 0.2 0.16

b
0.02 0.5 0.5 0.01 0.56 0.33 0.63 0.2 0.14

Deep L
0.19 0.8 0.5 0.00 0.18 0.32 0.61 0.5 0.39

Blue a
0.05 0.8 0.5 0.02 1.02 0.38 1.01 0.2 0.48

b
0.13 0.8 0.5 0.01 0.47 0.47 0.97 0.2 0.46

Table 3.13: Partners colorimetric uncertainties combined to give a E for the inter-
comparison for a coverage factor of k = 2, specular included geometry [43].
Glossy
Pale Grey 0.31 0.89 0.89 0.33 1.65 0.55 0.40 0.61
Mid Grey 0.39 0.88 0.88 0.22 1.26 0.51 0.51 0.60
Black 0.32 0.88 0.88 1.40 0.86 0.40 1.18 0.60
Red 0.38 1.41 0.90 1.98 1.16 0.60 1.80 0.63
Bright Yellow 0.43 1.42 0.92 2.93 1.83 0.65 1.34 0.65
Green 0.40 0.89 0.89 2.28 1.10 0.56 1.34 0.61
Cyan 0.41 0.90 0.90 2.51 1.16 0.65 0.95 0.62
Deep Blue 0.35 1.40 0.89 0.21 1.10 0.48 1.47 0.61
Matt
Pale Grey 0.32 0.89 0.89 0.21 1.58 0.57 0.40 0.61
Mid Grey 0.38 0.88 0.88 0.15 1.10 0.53 0.38 0.59
Black 0.44 0.96 0.96 0.69 0.57 0.58 0.82 0.71
Red 0.60 1.49 1.02 0.88 1.36 0.85 1.86 0.79
Bright Yellow 0.45 1.43 0.94 0.36 1.79 0.89 0.92 0.68
Green 0.41 0.90 0.90 0.24 1.07 0.60 1.00 0.62
Cyan 0.42 0.91 0.91 0.27 1.11 0.62 1.29 0.63
Deep Blue 0.81 1.59 1.16 0.77 1.37 1.03 1.71 0.96
3.7 Summary 51
Table 3.14: Partners colorimetric uncertainties combined to give a E for the inter-
comparison for a coverage factor of k = 2, specular excluded geometry [43].
Glossy
Pale Grey 0.32 0.89 0.89 0.21 1.58 0.57 0.40 0.61
Mid Grey 0.38 0.88 0.88 0.15 1.10 0.53 0.38 0.59
Black 0.44 0.96 0.88 0.69 0.57 0.58 0.82 0.71
Red 0.60 1.49 1.02 0.88 1.36 0.85 1.86 0.79
Bright Yellow 0.45 1.43 0.94 0.36 1.79 0.89 0.92 0.68
Green 0.41 0.90 0.90 0.24 1.07 0.60 1.00 0.62
Cyan 0.42 0.91 0.91 0.27 1.11 0.62 1.29 0.63
Deep Blue 0.81 1.59 1.16 0.77 1.37 1.03 1.71 0.96
3.7 Summary
Although not all possible errors for the color measurements have been addressed, the
error correction method employed within the project has considerably improved the
agreement regarding measurements carried out by the partners for the 16 color tiles. At
the end of the project, over 92% of the measurements made by all the partners for all
the tiles agreed to within 0.5 E
ab
. This result fell slightly short of the target set at the
outset of the project but is considerably better than those agreements achieved in all
previous intercomparisons. In Tables 3.153.17 summary of percentage of colorimetric
dierences are shown with errors within 0.2, 0.5 and 0.75 E from the mean dierence,
respectively.
Table 3.15: Summary of percentage of Partners colorimetric dierences E from the
mean dierence for the set of 16 color tiles, 10 degree observer, illuminant D
65
. Total
percentage of errors within 0.2 E from the mean dierence [43].
Correction applied geometry geometry
Uncorrected results (R
1
) 51% 55%
R
1
+ Wavelength correction (R
2
) 50% 58%
R
2
+ Sphere error correction (R
3
) 42% 63%
R
3
+ Linearity correction (R
4
) 52% 63%
65
. Total
1
) 80% 89%
R
1
2
) 79% 88%
R
2
3
) 91% 95%
R
3
4
) 90% 95%
3.7 Summary 53
65
. Total
1
) 88% 97%
R
1
2
) 90% 97%
R
2
3
) 94% 98%
R
3
4
) 95% 98%
Chapter IV
Tristimulus integration
The permanent CIE Colorimetry Committee reviews from time to time the original
recommendations and makes those changes considered necessary. The work is done in
dierent working groups which are divided into technical committees. A working group
of USTC-1.3 of the CIE prepared, between 1981 and 1983, new recommendations for
the calculation of CIE tristimulus values. These recommendations state that the stan-
dard method of performing the integration forming the basic denition of tristimulus
values shall be by summation at a wavelength interval of 1 nm over the wavelength
range 360830 nm, but that for most colorimetric purposes the approximation of sum-
mation at a 5nm interval over the range 380780 nm should suce. Recommendations
were also made concerning abridgement, interpolation, extrapolation, truncation and
the calculation of weighting factors, since measured data does not always fulll the
requirements. Weighting factors are used in the calculation of color coordinates with
intervals which are not so dense, such as 10nm or 20 nm. Although tables of weighting
factors were not included in the recommendations to the CIE, they have since been
calculated in cooperation with the Working Group and published by the American
Society for Testing and Materials, ASTM [1].
CIE recommends the use of the method of calculation of weight sets for tristimulus
integration published by the ASTM in its Method E-308-85. In this method, the prepa-
ration of weight sets for any measurement interval or wavelength range by Lagrange
interpolation from standard tables of data at other intervals is described [2, 10, 11, 54].
In this chapter, we show that this recommendation is useless and that it should not be
used. Furthermore, its use may confuse the user and may lead to miscalculation.
54
4.1 The ASTM weighting method 55
4.1 The ASTM weighting method
The tristimulus values are dened by the equations
X = k
_
()S() x()d
Y = k
_
()S() y()d (4.1)
Z = k
_
()S() z()d.
The analytical functions of the three factors in the product are not known, so the
integrals should be evaluated alternatively. CIE recommends this be done by 1 nm
summation. Now the equations for such a summation are of the form
Y = k
()S() y(), (4.2)

where the values have the same meaning as in Eqs. 4.1. In order to solve Eq. 4.2 all
input values of the three functions should also be obtained at 1 nm intervals. Most
colorists will not wish to resort to measurement of the spectral radiance factors at 1
nm interval. In many cases, it would be sucient to measure these functions at 10 nm
or 20 nm intervals. Those unmeasured 9 or 19 unit wavelengths radiance factors can be
interpolated by Lagrange interpolation, method recommended by the Working Group
VIII. The rst and the last missing intervals should be interpolated quadratically using
three measured values and all interior values should be interpolated cubically using four
measured values. Lagrange interpolating coecients may be calculated from
L
j
(r) =
n
i=0
i=j
(r r
i
)
(r
j
r
i
)
for j = 0, 1, . . . n, (4.3)
where n signies the degree of the coecients being calculated. The values of i and r
are the indices denoting the location on the abscissa of the tabular values among which
interpolation is to be carried out.
In the usual case where the measurement interval is uniform across the spectrum
56 4. Tristimulus integration
Eq. 4.3 simplies to
L
0
=
(r 1)(r 2)(r 3)
6
(4.4)
L
1
=
r(r 2)(r 3)
2
(4.5)
L
2
=
r(r 1)(r 3)
2
(4.6)
L
3
=
r(r 1)(r 2)
6
(4.7)
in the cubic case and to
L
0
=
(r 1)(r 2)
2
(4.8)
L
1
=
r(r 2)
1
(4.9)
L
2
=
r(r 1)
2
(4.10)
in the quadratic case. In each of the above equations, indices r are substituted to
generate the necessary set of Lagrange interpolating coecients. Suppose we have 20
nm data and we want to calculate Lagrange coecients for those missing 19 values.
For intermediate intervals indices r now ranges from 1 + 1/20 to 2 1/20 at 1/20
steps. For last interval indices r ranges the same way, but for a rst interval r takes
values from 0 + 1/20 to 1 1/20 again at 1/20 steps. Table 4.1 shows an example of
calculated Lagrange coecients L
0
, L
1
, L
2
, and L
3
in a cubic interpolation for the case
of prediction of 19 values missing.
In Fig. 4.1 calculated Lagrange coecients are shown both for the cubic and the
quadratic cases where data interval was 20 nm. The missing intermediate values may
be predicted from
P(r) =
n
i=0
L
i
m
i
, (4.11)
where P is the value being interpolated, L is the Lagrange interpolation coecient and
m is the measured value corresponding to the indices.
4.1 The ASTM weighting method 57
0 2 4 6 8 10 12 14 16 18 20
0.2
0
0.2
0.4
0.6
0.8
1
1.2
i
c
o
e
c
i
e
n
t
v
a
l
u
e
L
0
L
1
L
2
0 2 4 6 8 10 12 14 16 18 20
0.2
0
0.2
0.4
0.6
0.8
1
i
c
o
e
c
i
e
n
t
v
a
l
u
e
L
0
L
1
L
2
L
3
Figure 4.1: Lagrange coecients for the cubic case and the quadratic case where 19
missing values are interpolated.
Table 4.1: Lagrange coecients L
0
, L
1
, L
2
, and L
3
in a cubic case for 20 nm interval
data where 19 missing values are interpolated.
L
0
L
1
L
2
L
3
-0.0154 0.9726 0.0512 -0.0083
-0.0285 0.9405 0.1045 -0.0165
-0.0393 0.9042 0.1596 -0.0244
-0.0480 0.8640 0.2160 -0.0320
-0.0547 0.8203 0.2734 -0.0391
-0.0595 0.7735 0.3315 -0.0455
-0.0626 0.7239 0.3898 -0.0512
-0.0640 0.6720 0.4480 -0.0560
-0.0639 0.6181 0.5057 -0.0598
-0.0625 0.5625 0.5625 -0.0625
-0.0598 0.5057 0.6181 -0.0639
-0.0560 0.4480 0.6720 -0.0640
-0.0512 0.3898 0.7239 -0.0626
-0.0455 0.3315 0.7735 -0.0595
-0.0391 0.2734 0.8203 -0.0547
-0.0320 0.2160 0.8640 -0.0480
-0.0244 0.1596 0.9042 -0.0393
-0.0165 0.1045 0.9405 -0.0285
-0.0083 0.0512 0.9726 -0.0154
4.2 Spectral bandpass error
Spectral bandpass dependence occurs whenever the width of the passband is other than
innitesimal [50]. The passband must be of sucient width that the power passed to
the detector of the instrument is sucient to lie within the dynamic range of the
detector. The most common situation in industrial equipment is that the bandpass
is both symmetrical and triangular in shape, and that the half-peak width is equal
to the measurement interval. This leads to a result where linear spectral radiance
within bandpass range does not cause any bandpass error. Instead, bandpass error
occurs if the spectral radiance is either concave or convex within the range of bandpass
function. This is because the instrument with a nite bandpass always measures the
4.2 Spectral bandpass error 59
spectral values too high in a concave situation compared to linear a extrapolant. In
a convex case, the situation is exactly opposite. An example of a triangular shape
bandpass and of a concave radiance function is shown in Fig. 4.2.
-9 -5 0 5 9
Figure 4.2: The representation of the triangular bandpass at one nanometer intervals
and its relationship to a concave radiance function. The dashed line represents the linear
extrapolant of the value of the function at the central wavelength.
Stearns has proposed that any wavelength index i can be estimated by
R
c
(i) = kR
m
(i 1) + (1 + 2k)R
m
(i) kR
m
(i + 1), (4.12)
where R
c
is the corrected radiance and the R
m
is the measured radiance [50]. According
to Venable [54] the correct value for coecient k is 0.083 in the case of a symmetrical
bandpass with a half-peak bandwidth equal to measurement interval. When correcting
either the rst or last measured passband the correction is made by
R
c
(i) = (1 + k)R
m
(i) kR
m
(i 1). (4.13)
The ASTM eld test was done by Fairman [11]. In that research, 140 spectra were
used provided by cooperators. Wavelength range was from 380 nm to 780 nm with 10
nm intervals. The spectra were considered to be arbitrarily corrected without regard
to their origin or geometry of measurement. In Table 4.2 summary of the results made
by Fairman are shown.
Table 4.2: Summary of the results of all color dierence E
ab
calculations with and
without the ASTM weighting for 10 nm and 20 nm data [11].
Median 80-percentile
Interval None Weighting None Weighting
10 nm 0.145 0.004 0.253 0.011
20 nm 0.605 0.015 1.053 0.075
4.3 Materials and methods
Two data sets were used to analyze the ASTM weighting sets in the case of non
uorescent color spectra. The rst data set was measured with a Perkin Elmer Lambda
9 UV/VIS/NIR spectrophotometer with an external integrating sphere attached. This
data set consists of 1269 reectance spectra of the matt Munsell chips. The second
data set was measured with a Perkin Elmer Lambda 18 UV/VIS spectrometer with
a Labsphere RSA-PE-18 reectance spectroscopy accessory. In this set, there was a
total of 922 spectra of Pantone colors. Therefore the total number of spectra was 2191.
Both data sets were measured at 1 nm intervals from 380 nm to 780 nm. This data is
considered to be arbitrarily correct and free of bandpass error. Of course, this can be
done if we simply consider the original data to be correct, theoretically.
Let us rst consider the eect of calculating CIELAB color coordinates with dif-
ferent wavelength intervals. In table 4.3, some statistics are shown for the calculated
color dierences E
ab
with dierent wavelength intervals. Data intervals other than
1 nm was achieved by picking data with the appropriate interval from the original
data. The rst value of the wavelength is 380 nm in every case. The last value is not
necessarily 780 nm if the new interval is not evenly divided within the original 400
nm wide wavelength band. Color dierences are then compared with the original 1
nm data. Two dierent illuminants and observers were used which provided a total of
8764 dierences for each interval.
4.3 Materials and methods 61
Table 4.3: Color dierence E
ab
with dierent data intervals, each interval compared
to 1 nm reference data. There were a total of 8764 calculated color dierences in each
interval.
Interval Mean Max Std Median 80-percentile
2 0.006 0.038 0.006 0.003 0.010
3 0.012 0.227 0.017 0.007 0.017
4 0.010 0.096 0.009 0.007 0.015
5 0.002 0.016 0.002 0.001 0.002
6 0.018 0.303 0.020 0.012 0.026
7 0.023 0.336 0.025 0.015 0.036
8 0.024 0.742 0.029 0.015 0.036
9 0.029 0.558 0.032 0.019 0.044
10 0.031 0.433 0.034 0.018 0.046
15 0.074 0.616 0.064 0.054 0.116
20 0.126 1.205 0.103 0.099 0.187
25 0.251 1.671 0.217 0.187 0.388
30 0.397 2.375 0.275 0.331 0.598
35 0.614 3.315 0.495 0.472 0.979
40 0.938 6.264 0.797 0.689 1.502
45 1.302 7.478 1.081 0.959 2.037
50 1.665 9.564 1.331 1.325 2.663
One can see that the mean dierence E
ab
is still less than 0.5 when the wavelength
interval is over 30 nm. If all measurements should go under the limit of the human eye
discrimination, 10 nm data would still be usable. The maximum E
ab
error is 0.433
with a 10 nm interval. The last statistic 80 percentile tells us under what limit 80%
of the data goes. Again the data interval can be almost 30 nm when 20% of the results
are over the 0.5 E
ab
limit value.
Let us now apply the ASTM weighting into the previous sets. Table 4.4 shows the
results with the ASTM weighting. If we now compare the results of Table 4.3 and Table
4.4 one can note only minimal changes. The weighting does not give signicantly better
results. The situation is completely dierent in the results calculated by Fairman [11]
Table 4.2, where the eect of weighting was about tenfold. The reason may be in
the way in which the calculation was made. The starting point was the data of 140
ab
with dierent data intervals with ASTM weighting,
8764 dierences in each interval.
Interval Mean Max Std Median 80-percentile
2 0.006 0.039 0.006 0.003 0.010
4 0.009 0.094 0.009 0.006 0.015
5 0.001 0.016 0.001 0.001 0.001
8 0.023 0.744 0.029 0.013 0.035
10 0.031 0.432 0.034 0.018 0.047
16 0.055 0.942 0.049 0.044 0.080
20 0.122 1.247 0.095 0.104 0.179
25 0.185 1.380 0.159 0.139 0.287
40 1.149 7.984 0.958 0.869 1.791
50 1.925 10.475 1.538 1.451 3.059
spectra with 10 nm intervals. From that data a new data set was formed by Lagrange
interpolation which was then set as the reference data to which the color dierence
calculations were done.
Let us now simulate the calculations of the Fairmans paper. First, 10 nm data is
acquired by picking every tenth reectance value from the original 1 nm interval data
of the 2191 non uorescent color spectra. Then, 1 nm reference data is interpolated
from the former 10 nm data. There is no need for any bandpass weighting if we assume
the original 1 nm data to be free of bandpass errors. Table 4.5 shows the results of the
statistics of the color dierences with the ASTM weighted and unweighted data. Color
dierences are calculated by comparing the 10 nm ASTM weighted and unweighted
data with the 1 nm data which was obtained by interpolation.
If we calculate the same color dierences but use 1 nm original data as the reference
we obtain the results shown in Table 4.6. The dierence between weighted and un-
weighted data is minimal. In fact, weighting has only a minor eect on the 10 nm data.
This is demonstrated in Table 4.7 where E color dierence is calculated between the
10 nm original and 10 nm the ASTM weighted data.
Furthermore, one can notice by comparing Tables 4.5 and 4.6 that the interpolated
1 nm data is much closer to the 10 nm data than to the original 1 nm data. Therefore
interpolation does not lead to the right original data. This can be realized by comparing
color dierences of the original 1 nm data and the interpolated 1 nm data, as shown
4.3 Materials and methods 63
ab
for the ASTM weighted and unweighted data, total
of 8764 dierences. Color dierences were calculated by comparing 10 nm data with 1
nm data which was obtained by interpolation.
Weighting Mean Max Std Median 80-percentile
None 0.0065 0.0793 0.0063 0.0046 0.0022
ASTM 0.0006 0.0028 0.0004 0.0005 0.0003
ab
for the ASTM weighted and unweighted data, 8764
dierences total. Color dierences were calculated by comparing 10 nm data with the
original 1 nm data.
Weighting Mean Max Std Median 80-percentile
None 0.0309 0.4331 0.0342 0.0183 0.0271
ASTM 0.0310 0.4318 0.0342 0.0183 0.0278
ab
for the original 10 nm data compared to the ASTM
weighted 10 nm data, 8764 dierences in total.
Mean Max Std Median 80-percentile
0.0068 0.0805 0.0063 0.0049 0.0025
in Table 4.8.
ab
for the original 1 nm data compared to the 1 nm
interpolated data, 8764 dierences in total.
Mean Max Std Median 80-percentile
0.0308 0.4319 0.0343 0.0180 0.0276
4.4 Results
It was shown that the use of the ASTM weighting functions in the case of non uores-
cent reectance spectra of matt color samples may not greatly aect the accuracy of
tristimulus integration with dierent wavelength intervals. However, the results in the
Fairman paper were shown to depend on the starting point of that research. It can not
be assumed that Lagrange interpolation can reliably accomplish 1 nm reference data
from the original 10 nm data in every case. Even with our instrument, which proved
to perform well in the previous chapter, it is not possible to interpolate correct 1 nm
data from correct 10 nm data. Hence, this becomes even more dicult with the 10 nm
interval instruments.
The error of absolute color coordinates of a given reecting sample is mainly de-
pendent on the instrument that is used in the measurement. If accurate color values
are needed the performance of the instrument must be carefully studied at rst, as
shown in the intercomparison study presented in the previous chapter. This makes the
ASTM standard E-308-85 useless, and we recommend it not be used. Furthermore, in
many quality control tasks where no exact absolute values are needed no weighting is
needed either.
Chapter V
Thermochromism
The color of an object depends on the temperature of the object. This phenomena is
known as the thermochromic eect and it may be already noticed at room tempera-
ture if the temperature varies a few centigrades. Red and orange samples are especially
sensitive to temperature variation and may cause diculties in precise color measure-
ments. This chapter shows, how the phenomenon is based on physical processes and
not only reects the instability of red color pigments. Simple formulas are derived,
which explain the experimental data. We discuss the meaning of thermochromism
for color measurements, measure the magnitude of it and propose the experimental
conditions to avoid this eect [16, 19].
5.1 Background of the study
As pointed out in the previous chapters, accurate color measurements have become
more and more important during the past few decades. This is valid not only in
physical research, but also in industrial production, where the importance of accurate
measurements is mainly due to increased quality requirements set by the customers
of various goods. The development of technology enables more and more accurate
measuring systems. While the accuracy has improved one has noticed, that many un-
expected factors aect the color of an object. One of these factors is the temperature
of the sample. It is known that, for example, the reectance of the ceramic reference
tiles used for calibration of colorimeters and spectrophotometers is temperature de-
pendent. This phenomenon is called thermochromism, which is a reversible change
of color of the sample as a function of temperature. Wyszecki and Stiles state some
general principles of thermochromism in the case of transmitting lters [60]. They
conclude that the spectral transmittance at a given wavelength that increases with in-
creasing wavelength usually decreases with increasing temperature. The more positive
the slope of the spectral transmittance curve, the greater the temperature eects as a
rule. Spectral transmittance that decreases with increasing wavelength is, in general, of
65
66 5. Thermochromism
minor importance, but if it becomes important it often causes a transmittance increase
with increasing temperature. Spectral transmittance curves varying only slightly with
wavelength are usually not sensitive to temperature variations. The data sheets for
SCHOTT colored glass lters give the shift of the half value of maximum transmit-
tance of the rising edge with increasing wavelength towards longer wavelengths in the
units of nm/K [52]. This value gradually increases with increasing wavelength from
0.07 nm at 400 nm to 0.17 nm/K at 700 nm. Malkin et al. have studied reectance
spectra of ceramic color standards as a function of temperature [39]. They reported
that increasing the temperature of a sample caused a fall in reectance which was
concentrated in the steeply rising or falling parts of the spectral reectance. The part
of the spectral curve rising with increasing wavelengths was displaced towards longer
wavelengths, while the part falling with increasing wavelengths was displaced towards
shorter wavelengths on heating. The slope moves typically 0.1 nm/K. It is worth point-
ing out that the reectance usually decreases as the temperature increases. The long
wavelengths reecting e.g. yellow, orange and red samples are found to be aected
most, leading to the largest color dierences in the CIELAB E values. On the other
hand, neutral samples (grey, white, black) do not exhibit thermochrmism. The rea-
son is that the spectral reectance curves of neutral colors have a small or zero slope.
Similar results for color dierences of reectance standards has been earlier reported
by Verrill et. al. [56] and Fairchild and Grum [9]. Instead of the wavelength shift
per nanometer or the color dierence per centigrade, a third measure also exists: the
relative change of the optical density of the sample as a function of wavelength [55].
However, independent of the measure one likes to use, the main point is how much the
observed color depends on temperature.
The aim of this chapter is to derive a simple mathematical model for thermochromism,
and to investigate the magnitude of the eect. The experiments done for this investi-
gation as well as the published data discussed above conrm our model.
5.2 Absorbance, transmittance, and optical density
One knows from the standard literature that the color of an object under a given
illumination depends on the reectance or transmittance spectrum of the sample. Re-
ectance and transmittance are the only quantities which, through absorbance depend
on temperature. In the following, we consider how the spectral properties may depend
on temperature, to see if the long wavelength end of the spectrum is aected more than
the short wavelength end of the spectrum. Luminescent materials might also exhibit
thermochromism, but they are not considered in this thesis. When light reaches a sur-
face of a nonuorescent material, where neither nonlinear nor abnormal polarisation
5.2 Absorbance, transmittance, and optical density 67
eects appear, it holds that
1 = R() +A() +T (), (5.1)
where R() is reectance, A() is absorption and T () is transmittance of the sample.
In the following, we separately consider transmitting and opaque samples.
5.2.1 Transmitting samples
Let us consider external quantities. Light passing through an absorbing material at-
tenuates as
I() = I
0
()e
()d
, (5.2)
where I
0
() is the incoming intensity on the front surface of the sample, I() is the
intensity transmitted through the sample, d is the thickness of the sample and () is
the absorption coecient of the sample at wavelength . Denitely, () is the main
quantity responsible for thermal eect.
We have the following relation between the transmittance and optical density
D = log(T ()) = log
_
I()
I
0
()
_
= ()d log e =
()d
ln 10
. (5.3)
Hence, the changes in the absorption coecient change the optical density, the ab-
sorbance and, thus, the transmittance of the sample.
5.2.2 Opaque samples
In the case of a glossy opaque sample, T () is zero and the changes in absorbance di-
rectly change the reectance. Now, the reected part is comparable to the transmitted
part in transmitting samples and the optical density can be calculated from
D = log
_
I
R
()
I
0
()
_
, (5.4)
where I
R
() is the reected intensity.
On the other hand, the intensity of light falling upon some material attenuates
exponentially and, in the case of opaque materials, the light reected from the material
experiences similar attenuation. Thus, Eq. (5.3) holds for the reected light if d is the
distance the reected light has passed in the material.
For translucent materials, the thickness of the material as well as the background
over which the sample is viewed aect the reectance and the opacity of the material.
For all matt samples, the scattering properties of the material should be taken into
account through the Kubelka-Munk theory, although there is not a requirement for
a specimen to be matt for the Kubelka-Munk theory to hold. However, the simple
formulas given above are enough to investigate the thermochromism of the material.
We conclude that, as a good approximation, investigation of the thermal properties
of absorbance gives correct information on thermochromism for opaque, transmitting,
and translucent samples independent of whether the sample is glossy or matt.
5.3 Thermal eects
The depth from which the reected light is coming is probably not aected by small
changes in temperature, but if () changes as a function of temperature, it also aects
the reected light distribution [14]. The absorption in the visible range is caused
by low level electron transitions, where an absorbed photon excites an electron from
one energy level to another with higher energy. The general case of an undisturbed
absorbing unit leads to two general solutions, which are of a Lorentzian and Gaussian
shape of () and, hence, also of the absorption band. The Lorentzian band appears
at low temperatures and the Gaussian at high temperatures. The absorption peak
is homogeneously broadened if the absorbing units are indistinguishable. This means
that the absorption peak is symmetric in the energy scale, and in the frequency scale,
but not in the wavelength scale. Because the photon energy = h where is the
frequency and h is the Plancks constant, we will get a very simple relation between
energy and wavelength
[eV] =
1239.8
[nm]
. (5.5)
Properties of the absorption band are usually given in electron volts. The Gaussian
shape of the absorption coecient and hence the absorption band is [14] given by
() =
max
exp
_
4 ln 2 (
0
)
2
()
2
_
, (5.6)
5.3 Thermal eects 69
where
0
is the energy of the absorption peak maximum and is the full width at
half maximum absorption (called half width). In Fig. 5.1, an example of the Gaussian
peak is shown as a function of energy. Here
0
=2.5 eV and =0.4 eV. This means
that the left half width point (
1/2
) is at energy 2.3 eV and the right half width
point (
+1/2
) corresponds to the energy 2.7 eV. In Fig. 5.2, the change of equi-energy
1.5 2 2.5 3 3.5
0
0.05
0.1
0.15
0.2
0.25
Energy [eV]
A
b
s
o
r
b
a
n
c
e
1/2

+1/2
Figure 5.1: Example of a Gaussian peak where =2.5 eV and =0.4 eV. The positions
of the left and the right half width points are also shown.
absorbance peaks from the energy scale to the wavelength scale is demonstrated. If
thermal changes appear in the absorption band, they appear so that the integrated
absorption, which is the area of the absorption band, remains constant. In the case of
both line shapes this means that D
max
remains constant. Here, D
max
is the peak
height. Gebhardt and Kuhnert rst reported the change of the absorption bands as
a function of temperature [14]. The general behaviour of at low temperatures
(near room temperature) is found to be proportional to T
1/2
, where T is the absolute
temperature in Kelvin. Thus, the temperature change from 20
C to 40
C (from 293
K to 313 K) causes that of the absorption band becomes 1.034 times broader and
the peak height 1/1.034 = 0.968 times lower. In addition the peak maximum tends to
change towards smaller energies i.e, longer wavelengths as the temperature increases.
This increases the change of rising edge towards longer wavelengths and decreases the
changes of falling edge towards shorter wavelengths. The eect of this phenomenon
is usually small and the change of the position of absorption bands is not taken into
account in this study. The discussion above is valid only to a single absorption line.
Generally, a color spectrum in the energy-absorbance scale might be considered as
1.6 1.8 2 2.2 2.4 2.6 2.8 3 3.2
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
Energy [eV]
A
b
s
o
r
b
a
n
c
e
400 450 500 550 600 650 700 750 800
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
Wavelength [nm]
A
b
s
o
r
b
a
n
c
e
Figure 5.2: Absorbance peaks changed from energy scale to wavelength scale.
a linear combination of Gaussian peaks given by Eq. (5.6). Figs. 5.3 and 5.4 give
examples of two dierent spectra, which are formed from a few Gaussian absorbance
curves.
These gures demonstrate how Gaussian absorption lines form absorbance spectra
in the energy scale, how they convert to the wavelength scale, and nally what the
resulting transmittance is in the wavelength scale. Note, that single absorption lines
are not symmetric in the wavelength scale. The rising and falling edges of a spectrum
1.6 1.8 2 2.2 2.4 2.6 2.8 3 3.2
0
0.5
1
1.5
2
2.5
Energy [eV]
A
b
s
o
r
b
a
n
c
e
400 450 500 550 600 650 700 750 800
0
0.5
1
1.5
2
2.5
Wavelength [nm]
A
b
s
o
r
b
a
n
c
e
400 450 500 550 600 650 700 750 800
0
0.2
0.4
0.6
0.8
1
Wavelength [nm]
T
r
a
n
s
m
i
t
t
a
n
c
e
Figure 5.3: An example on the formation of the absorption and transmittance spectra
from three individual Gaussian Peaks.
1.6 1.8 2 2.2 2.4 2.6 2.8 3 3.2
0
0.5
1
1.5
2
2.5
Energy [eV]
A
b
s
o
r
b
a
n
c
e
400 450 500 550 600 650 700 750 800
0
0.5
1
1.5
2
2.5
Wavelength [nm]
A
b
s
o
r
b
a
n
c
e
400 450 500 550 600 650 700 750 800
0
0.2
0.4
0.6
0.8
1
Wavelength [nm]
T
r
a
n
s
m
i
t
t
a
n
c
e
Figure 5.4: An example on the formation of the absorption and transmittance spectra
from three individual Gaussian Peaks.
may be thought to consist of a single Gaussian peak. Thus, to understand the general
principles of thermochromism it is enough to study the properties of a single Gaussian
absorbance peak instead of a linear combination of them. The peaks forming the edges
have the major inuence on the thermal properties of a spectrum whereas the other
peaks have a minor eect or none at all.
Let us consider in detail the properties of Gaussian absorbance curves. Absorbance
and optical density in the energy scale are
D() = D
max
exp
_
4 ln 2(
0
)
2
()
2
_
(5.7)
where D
max
=
max
d/ ln 10. In the visible range (1.593.3 eV) one can integrate the
absorption peak, and the result is area
A = D
max
_

4 ln 2
. (5.8)
If the temperature changes, A remains constant and = u
T, where u is a constant
and T is given in Kelvins. Let
0
be the halfwidth of the peak at a temperature T
0
.
Then at another temperature T the left and right halfwidth points
1/2
as a function
of temperature are
1/2
(T) =
0
0
_
T
T
0
. (5.9)
Thus, the shift of the halfwidth points is
1/2
(T) =
1/2
(T)
1/2
(T
0
)
=
1
2
0
_
_
T
T
0
1
_

1
4
0
T
T
0
, (5.10)
where T = T
0
+T. The approximation at the last line of Eq. (5.10) is quite valid up
to T = 30 K.
Let us next derive the shift formula in the wavelength scale, where the absorption
bands are not symmetric. Let
1/2
(T) be the wavelengths corresponding to the points
1/2
(T). One can easily conrm that
1
1/2
(T)
=
1
1
2
0
hc
_
T
T
0
, (5.11)
where
0
is the wavelength corresponding to the peak maximum. The shift of the slope
is
1/2
(T) =
1/2
(T) +
1/2
(T
0
)
=
k
_
1/2
(T
0
)
_
2
1 k
1/2
(T
0
)
, (5.12)
where,
k =
1
2
0
hc
_
1
_
T
T
0
_
. (5.13)
Eqs. (5.12) and (5.13) describe exactly the slope shift in the wavelength scale. How-
ever, in many practical situations k is small and one gets from Eq. (5.12) as a rst
approximation
1/2
(T)
=
1
4
T
T
0
0
hc
_
1/2
(T
0
)
_
2
. (5.14)
Let us nally calculate the shift of the transmittance curve by determining the shift
of the 50% transmittance points. For these points
1
2
= exp (ln 10D) . (5.15)
Taking into account that
T
0
D
max
(T
0
) =
TD
max
(T) for two temperatures T
0
and T
one can easily show that the half width point reduces to
1/2
(T) =
0
1
2
0
w(T)
_
T
T
0
, (5.16)
5.4 Numerical results 75
where
w(T) =
1
ln 2
_
ln D
max
+
1
2
ln
T
T
0
+ 1.20055. (5.17)
Thus, one can directly use Eqs. (5.9)(5.13) for transmittance (or reectance) curves
by replacing
0
in these formulas by
0
w(T).
5.4 Numerical results
We have calculated the change of reectance and transmittance curves by generating
Gaussian absorption bands with dierent heights and half widths. We have also modi-
ed absorbance curves so that the integrated absorption remains constant so that half
width and maximum absorbance changes. The position of the peak maximum was
held constant. Modications corresponded to temperature change from 300 K to 400
K. We used 0.2 eV and 0.4 eV as half widths, which are quite typical in solid mate-
rials. Maximum absorbance used was 2.0 and 4.0. This value eects the dynamics of
the transmitting lter. Maximum absorption 4.0 gives four orders of magnitude dy-
namics. Absorption curves were then converted to reectance or transmittance curves
and the change of the rising or falling edge are read from half value of reectance or
transmittance curves.
Fig. 5.5 shows the absolute shift of the halfwidth points of absorbance peaks as
a function of temperature change for three peak widths and two wavelengths. The
solid lines and the dashed lines correspond the shift of the rising and falling parts of
the peaks, respectively. The calculations were done using Eq. 5.12. One notes that
shift in nanometers is much higher for the edges in the red region than for a similar
peak in blue region. One also notes that there is a slight dierence how the fallig and
rising parts of the peaks are moving. The reason is seen from Eq. 5.12. Note that
according to the approximative formula (Eq. 5.14) positive and negative slope exhibit
an equal shift. Figure 5.6 shows the absolute shift of the absorbance half width points
as a function of wavelength. The reference temperature is 300 K, and the peak width
at this temperature was set to 0.4 eV. The curves ae correspond the behavior of the
material when the temperature change is 5010 K. The solid lines and the dashed lines
correspond the shift of the rising and falling parts of the peaks, respectively. Fig. 5.6
shows clearly, that blue samples are not as sensitive as the red samples for temper-
ature changes. Again, exact formulas were used to show the dierence between the
positive and negative slopes. On the other hand, the approximative formulas, which
do not show any dierence between the negative and positive slopes, are valid only on a
limited temperature range. Fig. 5.7 shows the shift of the halfwidth points in nanome-
ters/K. The curves were calculated for a temperature change 10 K when the reference
temperature is 300 K. The eect of the peak height and width is demonstrated, too.
As can be seen, by increasing the half widths of the absorption band or height of the
absorption peak, the changes in rising and falling edges become bigger.
0 10 20 30 40 50 60 70 80 90 100
0
1
2
3
4
5
6
7
8
9
10
Temperature change [K]
S
h
i
f
t
o
f
t
h
e
h
a
l
f
w
i
d
t
h
p
o
i
n
t
s
[
n
m
]
a
b
c
d
e
f
a) = 600 nm, = 0.4 eV
b) = 600 nm, = 0.2 eV
c) = 400 nm, = 0.4 eV
d) = 600 nm, = 0.1 eV
e) = 400 nm, = 0.2 eV
f) = 400 nm, = 0.1 eV
T
0
= 300 K
Figure 5.5: Shift of the halfwidth points as a function of temperature. The solid
and dashed curves correspond to the shift of the rising and falling parts of the spectra,
respectively.
5.5 Thermochromic measurements
Red colored Pantone
paper samples, red, orange, and yellow Labsphere
secondary
standards and cyan, green, yellow and red ceramic tiles were the samples used in this
study. These samples have a common spectral feature: they reect less or about 10
percent for short wavelengths before the steeply rising part of the spectrum. For long
wavelengths these samples reect well over 70 percent. The reectance measurements
at dierent temperatures were made on a Perkin Elmer Lambda 18 spectrophotometer
equipped with a 150 mm integrating sphere. All of the measurements were made in
the 0/d geometry and in the specular included mode. The scanning speed was 480
nm/min, bandwidth 2 nm, and the measuring range 380780 nm.
Before measuring the thermochromic samples, the errors of the spectrophotometer
were carefully investigated and the instrument were calibrated using the NPL stan-
dards. Sample imperfections (size and position of the illuminating beam on the sam-
ple) were investigated but found to be negligible in this study. The purpose of this
calibration procedure was to guarantee that the spectrophotometer is reliable in the
5.5 Thermochromic measurements 77
300 350 400 450 500 550 600 650 700 750 800
0
1
2
3
4
5
6
7
8
9
Wavelength [nm]
S
h
i
f
t
o
f
t
h
e
h
a
l
f
w
i
d
t
h
p
o
i
n
t
s
[
n
m
]
a
b
c
d
e
a) T = 50 K
b) T = 40 K
c) T = 30 K
d) T = 20 K
e) T = 10 K
T
0
= 300 K, = 0.4 eV
Figure 5.6: Shift of the halfwidth points as a function of wavelength. The solid and
dashed curves correspond to the shift of the rising and falling parts of the spectra,
respectively.
300 350 400 450 500 550 600 650 700 750 800
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
Wavelength [nm]
S
h
i
f
t
o
f
t
h
e
h
a
l
f
w
i
d
t
h
p
o
i
n
t
s
[
n
m
/
K
]
a
b
c
d
a) = 0.4 eV, Dmax = 4 eV
b) = 0.4 eV, Dmax = 2 eV
c) = 0.2 eV, Dmax = 4 eV
d) = 0.2 eV, Dmax = 2 eV
T
0
= 300 K, T = 10 K
Figure 5.7: Shift of the halfwidth points in nanometers/Kelvins as a function of wave-
length. The solid and dashed curves correspond to the shift of the rising and falling parts
of the spectra, respectively.
measurements of the thermochromic eect. The measurements at dierent temper-
atures were made as follows. Pantone
samples were heated with a brass cylinder

using an electric resistor. Labsphere SCS standards were heated with another heating
plate and a thermo resistor system was used with the ceramic tiles. The samples were
heated up to 94 centigrades outside the photometer to avoid heating of the instrument.
The temperature of the samples was measured with a calibrated thermopile during the
spectral measurements. The average measurment accuracy of the surface temperature
of the samples was less than one degree in all measurements. The repeatability of our
measurements became excellent after these calibration and temperature checking pro-
cedures. Spectral and colorimetric changes caused by the thermochromic eect were
noticed if the temperature was changed by about two degrees. The corrected spectra
were used to calculate the CIELAB coordinates and the color dierences by standard
means. We need to point out, that although it is well known that CIELAB is not
linear it is generally accepted for the expression of color dierences. In this coordinate
system, an average human eye is able to distinguish E dierences higher than 0.5
units, as pointed out in the beginning of this thesis.
5.6 Experimental results
Table 5.1 shows the results for a typical Pantone
sample (red 032 U). One can note

that all of the CIELAB coordinates decrease while the temperature increases. The
color of this typical paper sample changes 0.093 E units per centigrade. If we dene
the wavelength shift observing the reectance value 50 percent at the steeply growing
part of the spectrum we found that that this part linearly moves towards the longer
wavelengths 0.1 nm/deg, which is of the same order as that for the ceramic tiles.
Tables 5.2 and 5.3 shows the results for two typical Labsphere secondary standards.
One can see decreasing luminance coordinate values with an increase in temperature.
Note, that especially in case of the red sample, the color dierence compared to the
reference temperature increases very rapidly, and in typical living surroundings the
color change of this kind of samples can be noticed by any person with normal color
vision. The average E/deg change of the red and orange samples was 0.107 and 0.088
E/deg, respectively. The color change of our yellow samples was clearly smaller.
The wavelength change of the red, orange, and yellow sample was 0.11, 0.09, and 0.06
nm/deg, respectively. Both the wavelength change and the color dierence change are
linear functions of temperature on the temperature range measured.
In Table 5.4 the results of the thermochromic measurements of the ceramic tiles of
cyan, green, yellow and red are shown. Calculated changes for the wavelength shift for
the rising edge were approximately 0.05, 0.12, 0.18 and 0.15 nm/K, respectively. Fig.
5.8 shows the measured reectance spectra for the red ceramic tile at temperatures
27
C80
C.
5.7 Conclusions 79
Table 5.1: CIELAB values for the Pantone Red 032 U sample at four temperatures
[
C]. Color dierence E was calculated from the lowest temperature curve.
Temperature
[
C] L
E
28 55.75 58.42 27.63
35 55.46 58.17 27.26 0.53
40 55.20 57.98 26.88 1.03
45 55.00 57.78 26.55 1.46
Table 5.2: CIELAB values for the red Labsphere secondary standard SCS-R-010 sample
at six dierent temperatures [
C]. Color dierence E was calculated from the lowest

temperature curve.
Temperature
[
C] L
E
26 47.31 50.38 25.53
30 47.40 49.76 25.04 0.80
35 47.04 49.51 24.75 1.20
40 46.79 49.27 24.43 1.65
45 46.65 48.92 24.11 2.14
50 46.46 48.50 23.68 2.77
5.7 Conclusions
The magnitude of the thermochromic eects of transmitting and reecting materials
has been calculated. If only the change of half width of the absorption curve as a
function of temperature is considered, we will obtain the result that the rising edge with
increasing wavelength shifts towards longer wavelengths and the falling edge towards
shorter wavelengths. The greater the slope (high absorbance) is, the bigger the change
Table 5.3: CIELAB values for the orange Labsphere secondary standard SCS-O-010
sample at six dierent temperatures [
C]. Color dierence E was calculated from the

lowest temperature curve.
Temperature
[
C] L
E
26 65.28 53.60 52.68
30 65.10 53.74 52.55 0.26
35 64.83 53.89 52.20 0.72
40 64.65 53.98 51.63 1.27
45 64.45 54.06 51.28 1.69
50 64.29 54.17 51.02 2.02
Table 5.4: CIELAB E color dierence values for the ceramic tiles at six dierent
temperatures [
C]. Color dierence E was calculated from the lowest temperature.

Cyan Green Yellow Red
T [
C] E T [
C] E T [
C] E T [
C] E
27 28 28 27
38 0.45 40 0.95 40 1.73 39 1.26
48 0.83 50 1.47 50 2.95 52 3.14
62 1.39 60 2.17 60 4.03 60 3.90
72 1.67 70 2.77 70 5.08 68 4.80
82 1.99 83 4.24 80 6.41 80 6.17
is. If we take into account the shift of the peak position this enhances the shift of
the rising edge and diminishes the change of falling edge. In some cases, the eect of
peak a position change towards longer wavelengths can be greater than a shift in the
5.7 Conclusions 81
400 450 500 550 600 650 700 750
0
10
20
30
40
50
60
70
80
90
Wavelength [nm]
R
e
e
c
t
a
n
c
e
[
%
]
600 605 610 615 620 625 630 635 640
40
41
42
43
44
45
46
47
48
49
50
Wavelength [nm]
R
e
e
c
t
a
n
c
e
[
%
]
Figure 5.8: Curves from left to right represent the reectance spectra of a red ceramic
tile measured at temperatures of 27, 39, 52, 60, 68 and 80
C, respectively.
falling edge towards longer wavelengths. This can happen if the slope of the falling
edge is small (low absorption) and total shift can be even towards long wavelengths as
proposed by Wyszecki and Stiles [60]. In the case of a rising edge the shift is always
towards longer wavelengths. The changes become bigger as the wavelength increases.
This means the biggest color dierences occur for yellow, orange and red samples as
found in other studies.
In conclusion the thermal shift of a transmittance or reectance curve edge is di-
rectly proportional to the temperature change and the slope of the spectrum as well as
directly proportional to the square of the wavelength. Because of thermochromism, new
recommendations for color measurements require the temperature during measurement
to be set to a predened temperature e.g. (25 1)
C.
Chapter VI
Conclusions
Surface color measurement is of importance in a very wide range of industrial appli-
cations including paint, paper, printing, photography, textiles and plastics. For de-
manding color measurement the spectral approach is often needed. The most accurate
measurements of non uorescent surface color are made with a spectrophotometer. The
method used internationally for specifying color has been recommended by the CIE.
These recommendations were shortly described and presented in this thesis.
The human eye can perceive color dierence as small as 0.5 CIELAB units and thus
distinguish millions of colors. This 0.5 unit dierence should be a goal for precise color
measurements. By the CIE recommendations the only geometry for reectance mea-
surement is 0/d geometry, other geometries give only values of reectance factors. The
use of a 0/d geometry will require the use of an integrating sphere to collect reected
ux. In practical color measurement situations, an integrating sphere is never ideal
but hemispherical. Thus, absolute reectance can not be collected either, ideally. In
this thesis, methodologies for measuring and correcting errors in color measurements
are discussed. These results are part of the European surface color measurement har-
monisation project. It was shown that it is possible to improve upon the agreement of
color measurement results where 16 samples of the same colors were measured in nine
laboratories of EU countries.
The sampling interval in a tristimulus integration aects the accuracy of a color
coordinate performance. In a publication of the American Society for Testing and
Materials, ASTM, in its method E-308-85 a method for the preparation of weight
sets for any measurement interval or wavelength range by Lagrange interpolation from
standard tables of data at other intervals is described. This method is recommended
by the CIE, although it is not included in CIE recommendations. In this thesis, this
ASTM method is tested with a large set of non uorescent reectance colors from
the Munsell and Pantone basis. The usefulness of this method was found to be quite
minimal and we recommended not to use it.
82
83
The color of an object depends on the temperature of the object. This phenomena
is known as the thermochromic eect and it may be noticed already at room tem-
perature if the temperature varies by a few centigrade. Red and orange samples are
especially sensitive to temperature variation and may cause diculties in precise color
measurements. In this thesis, it has been shown how this phenomenon is based on
physical processes and, that it does not only reect the instability of color pigments.
Simple formulas are derived, which explain the experimental data. The meaning of
thermochromism for color measurements is also discussed, the magnitude of it is mea-
sured and experimental conditions to avoid this eect is proposed to be 1
C.
References
[1] ASTM Standards on Color and Appearance measurement, Standard Test Method
for Computing the Colors of Objects by Using the CIE System, 4th ed., 233259,
(ASTM, Philadelphia, 1994).
[2] J. F. W. Billmeyer and H. S. Fairman, CIE Method for Calculating Tristimulus
Values, Color Research and Application 12, 2736 (1987).
[3] R. M. Boynton, Human Color Vision (Holt, Rinehart & Winston, New York,
1979).
[4] K. M. Braun and M. D. Fairchild, Testing Five Color-Appearance Models for
Changes in Viewing Conditions, Color Research and Application 22, 165173
(1997).
[5] CIE Publication 15.2, Colorimetry, 2nd Edition, Central Bureau of the CIE, (Vi-
enna, 1986).
[6] CIE Publication No 142-2001, CIE Technical Report: Improvement to Industrial
Colour-Dierence Evaluation, Central Bureau of the CIE, (Vienna, 2001).
[7] F. J. J. Clarke and J. A. Compton, Correction methods for integrating-sphere
measurement of hemispherical reectance, Color Research and Application 11,
253262 (1986).
[8] P. J. Clarke, A. R. Hanson, and J. F. Verrill, Determination of colorimetric un-
cerntainties in the spectrophotometric measurement of colour, Analytica Chimica
Acta 380, 363367 (1999).
[9] M. D. Fairchild and M. Grum, Thermochromism of ceramic reectance tiles,
Applied Optics 24, 34323433 (1985).
84
References 85
[10] H. S. Fairman, The Calculation of Weight Factors for Tristimulus Integration,
Color Research and Application 10, 199203 (1985).
[11] H. S. Fairman, Results of the ASTM Field Test of Tristimulus Weighting Func-
tions, Color Research and Application 20, 4449 (1995).
[12] H. S. Fairman and H. Hemmendinger, Stability of Ceramic Color Reectance
Standards, Color Research and Application 23, 408415 (1998).
[13] J. Guild, The colorimetric properties of the spectrum, Philosophical Transac-
tions of the Royal Society A 230, 149187 (1931).
[14] W. Hayes and A. M. Stoneham, Defects and Defect Processes in Nonmetallic
Solids (Wiley & Sons, New York, 1991).
[15] J. Hiltunen, T. Jaaskelainen, and J. P. Parkkinen, Accurate spectral color mea-
surements, Intelligent Robots and Computer Vision XVIII: Algorithms, Tech-
niques, and Active Vision, Proc. SPIE 3837, 202209 (1999).
[16] J. Hiltunen, J. Mutanen, T. Jaaskelainen, and J. Parkkinen, Thermochromism
in color measurement, in Proceedings of the 9th Congress of the International
Colour Association (Rochester, 2001), in press.
[17] J. Hiltunen, R. Silvennoinen, T. Jaaskelainen, K. Nygren, and J. Parkkinen, Re-
ectance spectra of pine grown in polluted environment, in Proceedings of the
XXVIII annual conference of the Finnish physical society, M. Hyvonen-Dabek,
ed. (Helsinki, 1994).
[18] R. W. G. Hunt, Measuring Colour (Ellis Horwood Ltd., Chichester, 1987).
[19] J. Hiltunen, P. Silfsten, T. Jaaskelainen, and J. P. S. Parkkinen, A Qualita-
tive Description of Thermochromism in Color Measurement, Color Research and
Application, in press.
[20] T. Jaaskelainen, J. Hiltunen, H. Laamanen, and J. Parkkinen, Accurate Spec-
tral Measurement and Reconstruction, in Proceedings of the Second Interna-
tional Symposium on Multispectral Imaging and High Accurate Color reproduction
(Chiba, 2000).
[21] T. Jaaskelainen, J. Hiltunen, R. Silvennoinen, K. Nygren, and J. Parkkinen, Spec-
tral forest monitoring on VIS-NIR region, in International Symposium on Meth-
ods and Equipment for Environmental Monitoring (St. Petersburg, 1995).
86 References
[22] T. Jaaskelainen, J. Parkkinen, J. Hiltunen, and M. Hauta-Kasari, Spectral ap-
proach to color and color images, in Proceedings of the ICO Topical Meeting on
Optics for Sustainable Development (Dakar, 2000).
[23] T. Jaaskelainen, R. Silvennoinen, J. Hiltunen, and J. P. S. Parkkinen, Classica-
tion of reectance spectra of pine, spruce and birch, Applied Optics 33, 23562362
(1994).
[24] D. B. Judd, Reduction of data on mixture on color stimuli, Bureau of Standards
Journal of Research 4, 515548 (1930).
[25] S. J. Kishner, Eect of spectrophotometric errors on color dierence, Journal
of the Optical Society of America 67, 772779 (1977).
[26] R. G. Kuehni, Hue Uniformity and the CIELAB Space and Color Dierence
Formula, Color Research and Application 23, 314322 (1998).
[27] R. G. Kuehni, Analysis of Five Sets of Color Dierence Data, Color Research
and Application 26, 141150 (2001).
[28] R. G. Kuehni, Color Space and Its Divisions, Color Research and Application
26, 209222 (2001).
[29] R. G. Kuehni, From Color-Matching Error to Large Color Dierences, Color
Research and Application 26, 384393 (2001).
[30] R. Lenz, M.

Osterberg, J. Hiltunen, T. Jaaskelainen, and J. Parkkinen, Exploring
color spaces with unsupervised lters and gaussian quadrature, in Proc. SSAB
Conference (Linkoping, 1995).
[31] R. Lenz, M.

Osterberg, J. Hiltunen, T. Jaaskelainen, and J. Parkkinen, Unsuper-
vised ltering of color spectra, in Proceedings of the 9th Scandinavian Conference
of Image Analysis (Uppsala, 1995).
[32] R. Lenz, M.

Osterberg, J. Hiltunen, T. Jaaskelainen, and J. Parkkinen, Unsu-
pervised ltering of color spectra, Journal of the Optical Society of America A
13, 13151324 (1996).
[33] C. J. Li, M. R. Luo, and R. W. G. Hunt, A Revision of the CIECAM97s, Color
[34] M. R. Luo, G. Cui, and B. Rigg, The Development of the CIE 2000 Colour-
Dierence Formula: CIEDE2000, Color Research and Application 26, 340350
(2001).
References 87
[35] M. R. Luo and R. W. G. Hunt, The Structure of the CIE 1997 Colour Appearance
Model (CIECAM97s), Color Research and Application 23, 138146 (1998).
[36] M. R. Luo, M.-C. Lo, and W.-G. Kuo, The LLAB(l:c) Colour Model, Color
[37] J. Luostarinen and J. Hiltunen, On-line spectral measurement for grading of
beech parquet blocks, in Proceedings of the Finnish optics days 1998 (Oulu, 1998).
[38] J. Luostarinen, J. Hiltunen, and K. Paukkonen, Use of colour data in grading of
beech parquet blocks, in 3rd International Wood Scanning Seminar (Skelleftea,
1998).
[39] F. Malkin, J. A. Larkin, J. F. Verrill, and R. H. Wardman, The BCRA-NPL
Ceramic Standards, Series II - Master spectral reectance and thermochromism
data, Journal of the Society of Dyers and Colourists 113, 8494 (1997).
[40] H. Minato, M. Nanjo, and Y. Nayatani, Colorimetry and its Accuracy in the Mea-
surement of Fluorescent Materials by the Two-Monochromator Method, Color
[41] Y. Nayatani, Examination of Adaptation Coecients for Incomplete Chromatic
Adaptation, Color Research and Application 22, 156164 (1997).
[42] Y. Nayatani, H. Sobagaki, K. Hashimoto, and T. Yano, Field Trials of a Nonlinear
Color-Appearance Model, Color Research and Application 22, 240258 (1997).
[43] NPL report COEMS33, Harmonisation of National Scales of Surface Colour Mea-
surements, (Luxembourg, 2000).
[44] Project report EUR 19552EN, Good Practice Guide to Surface Colour Measure-
ments, (Luxembourg, 2000).
[45] Report EUR 14982EN, Intercomparison of colour measurements, Synthesis report,
(Luxembourg, 1993).
[46] R. Silvennoinen, T. Jaaskelainen, K. Nygren, J. Hiltunen, and J. Parkkinen, Clas-
sication of Reectance Spectra of Pine, Spruce and Birch, in First Finnish Con-
ference of Environmental Sciences, J. Tuomisto and J. Ruuskanen, eds. (Kuopio,
1993).
[47] R. Silvennoinen, T. Jaaskelainen, K. Nygren, J. Hiltunen, and J. Parkkinen, Re-
ectance spectra of pine, spruce and birch grown in polluted environment, in
Optical Methods in Biomedical and Environmental Sciences, H. Ohzu and S. Ko-
matsu, eds. (Elsevier Science B. V., Tokyo, 1994).
88 References
[48] R. Silvennoinen, T. Jaaskelainen, K. Nygren, J. Hiltunen, and J. P. S. Parkkinen,
Temporal, spatial and environmental classication of pine reectance spectra,
Environmental Science and Technology 29, 14561459 (1995).
[49] N. I. Speranskaya, Determination of spectrum colour coordinates for twenty-
seven normal observers, Optics and Spectroscopy 7, 424428 (1959).
[50] E. I. Stearns and R. E. Stearns, An example of a method for correcting data for
bandpass error, Color Research and Application 13, 257259 (1988).
[51] W. S. Stiles and J. M. Burch, N. P. L. Colour-matching investigation: Final
report, Optica Acta 6, 126 (1959).
[52] URL: http://www.besoptics.com/html/schott color filters.html (valid
15th October 2001).
[53] URL: http://www.ukas.com/pdfs/LAB12.PDF (valid 11th December 2001).
[54] W. H. Venable, Accurate tristimulus values from spectral data, Color Research
and Application 14, 260267 (1989).
[55] J. Verrill, Advances in spectrophotometric transfer standards at NPL, in Spec-
trophotometry, Luminescence and Colour; Science and Compliance, C. Burgess
and D. G. Jones, eds. (Amsterdam, 1995).
[56] J. F. Verrill, J. A. Compton, and F. Malkin, Thermochromism of ceramic color
standards, Applied Optics 25, 3011 (1986).
[57] N. J. Wade, A Natural History of Vision, 2nd ed. (The MIT Press, Cambridge,
1999).
[58] B. A. Wandell, Measurement of Small Color Dirences, Psychological Review
89, 281302 (1982).
[59] W. D. Wright, A re-determination of the trichromatic coecients of the spectral
colours, Transactions of the Optical Society 30, 141164 (1929).
[60] G. Wyszecki and W. S. Stiles, Color Science: Concepts and Methods, Quantitative
Data and Formulae, 2nd ed. (John Wiley & Sons, New York, 1982).

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UNIVERSITY OF JOENSUU

; Accurate Color Measurement University of Joensuu, Depart-

Address: Department of Physics, University of Joensuu, P.O. Box 111, FIN-80101,

from the normal to the specimen [5, 60]. The reected ux

eld of view by two equivalent sets

eld of view. These sets are

color space and the CIE 1976 L

, diuse/normal and normal/diuse. For these conditions the

from the normal to the sample surface. The viewing

. There is also a restriction

from the normal. Now normal illumination is within 2

. The same restriction

from the direction normal to the surface of the sample,

from the normal to its surface and with the

from the normal to its surface and with

at the eye of the observer is desired. These color-

at the eye of the observer is desired. These color-matching

() by that of each of the CIE color matching functions

() must be the spectral concentration of the

() should be known at 5 nm intervals over the wave-

. This diagram is intended to apply to comparisons of dierences

color space or CIELUV color space is dened by quantities

describe the color stimulus considered and Y

color space or CIELAB color space is dened by quantities

is a quadratic form. That means the dierence is biggest at the

= 0 and a = 0. In the same way

= 100 also. Now we have the equations

is the corresponding measured

C in this comparison. In this thesis,

C while the maximum was 23.4

C. All samples were measured 6 times, 3

. This is due the fact that the photometric linearity

0.23 0.5 0.5 0.01 0.24 0.36 0.26 0.5 0.21

0.01 0.5 0.5 0.24 1.44 0.11 0.10 0.2 0.02

0.00 0.5 0.5 0.07 0.75 0.34 0.19 0.2 0.02

0.35 0.5 0.5 0.00 0.18 0.40 0.29 0.5 0.16

0.01 0.5 0.5 0.14 1.10 0.08 0.18 0.2 0.02

0.00 0.5 0.5 0.04 0.57 0.26 0.34 0.2 0.02

0.28 0.5 0.5 0.27 0.12 0.32 0.81 0.5 0.16

0.01 0.5 0.5 0.95 0.75 0.55 0.28 0.2 0.02

0.00 0.5 0.5 0.98 0.38 0.17 0.79 0.2 0.02

0.28 0.8 0.5 0.39 0.14 0.39 0.82 0.5 0.16

0.02 0.8 0.5 1.45 1.04 0.25 0.38 0.2 0.15

0.02 0.8 0.5 1.26 0.41 0.29 1.54 0.2 0.13

0.20 0.8 0.5 0.65 0.27 0.38 0.45 0.5 0.21

0.14 0.8 0.5 2.23 1.70 0.32 0.47 0.2 0.11

0.18 0.8 0.5 1.76 0.55 0.28 1.13 0.2 0.19

0.34 0.5 0.5 0.47 0.17 0.39 0.23 0.5 0.15

0.00 0.5 0.5 1.56 0.96 0.20 0.65 0.2 0.08

0.01 0.5 0.5 1.58 0.46 0.28 1.13 0.2 0.13

0.33 0.5 0.5 0.47 0.17 0.37 0.21 0.5 0.16

0.03 0.5 0.5 1.60 0.95 0.32 0.73 0.2 0.13

0.01 0.5 0.5 1.86 0.60 0.36 0.52 0.2 0.13

0.28 0.8 0.5 0.00 0.17 0.33 1.09 0.5 0.16

0.03 0.8 0.5 0.05 0.96 0.32 0.73 0.2 0.06

0.05 0.8 0.5 0.02 0.46 0.26 0.64 0.2 0.11

0.23 0.5 0.5 0.01 0.26 0.43 0.26 0.5 0.21

0.01 0.5 0.5 0.24 1.57 0.11 0.10 0.2 0.05

0.00 0.5 0.5 0.07 0.82 0.34 0.19 0.2 0.05

0.34 0.5 0.5 0.00 0.18 0.40 0.29 0.5 0.16

0.00 0.5 0.5 0.14 1.10 0.08 0.18 0.2 0.05

0.00 0.5 0.5 0.04 0.57 0.26 0.34 0.2 0.05

0.27 0.5 0.5 0.00 0.13 0.32 0.81 0.5 0.16