Colorimetry

Silja Holopainen
29.3.2006
 Outline
• Introduction to colorimetry
• Colorimetry in general
• Measuring diffuse reflectance
• Measuring fluorescence
• Measuring transmittance
• Measurement geometry and special cases
• Conclusion
 Introduction
• Color has always
been important in art,
religion and clothing
• At present color is
also used for signs,
safety cloths, paper
whitening etc.
• It is often important to
be able to measure
color accurately
 What is color?
• Electromagnetic radiation
between 380-780 nm
• Color is one aspect of
appearance
• Color = light source +
object properties + eye +
brain
• The human eye is most
sensitive at 555 nm
 The three dimensions of color
White
• Hue distinguishes blue
Lightness
from green from yellow
Chroma
etc.
• Lightness distinguishes Hue
light colors from dark
colors Black

• Chroma describes how

different a color is from
grey
Hue Lightness Chroma
 Colorimetry
• Two objects may appear the same
when viewed under one light source,
but different under another =
metamerism
• Metamerism is one of the major
industrial problems in color matching
• Colorimetry attempts to quantify the
perception of color
• CIE is a voluntary organization giving
recommendations concerning
modern colorimetry
 Sources and illuminants
• Source = physical
entity that produces
radiation
• Illuminant = table of
values of spectral
power distribution
• Illuminant D65
represents average
daylight. D50
represents typical
indoor light
 Color perception
• 92 % of men and 99,5 %
of women have “normal”
color vision
• The retina comprises rod
cells (night vision) and
cone cells (color vision)
• Majority of the cells are
rod cells
• There are three types of
cone cells: one has peak
sensitivity to blue light,
one to green light and
one to red light
 Tristimulus values
• All colors can be matched by varying amounts of
red, green and blue lights (X, Y and Z)
• The amounts of X, Y and Z that must be mixed
to match a color are called the tristimulus values
• The tristimulus values depend on the reflectance
or transmittance of the object, the illuminant and
the observer
• Pairs of objects are said to match when their
tristimulus values are the same
 The CIE Standard Observers
• In the CIE experiment one
half of a circular field is
illuminated with spectrum
color and the other with a
mixture of red, green and Test Side Matching
blue Side

• The observer adjusts the Spectral Red +

red, green and blue until it Light Green +
Blue
matches the spectrum color
• The result is a set of color
matching functions used to
calculate the tristimulus
values
 Color difference
• Color measurements are mostly made to
determine quantitatively whether or not the color
of two objects are the same
• The total color difference ∆E and its coponents:
lightness ∆L, chroma ∆C and hue ∆H can be
numerically calculated
• The color difference is calculated using the
tristimulus values
• Numerical color differences may be used for
setting tolerances for quality control
 Objects
• Objects are characterized by the
amount of light they emit and
reflect or transmit at each Incident
wavelength of interest Light

• When light is incident on an

object a part of it is absorbed, a
part is reflected and a part may Reflected
be trasmitted Light Absorbed
Light
• The object may also emit light Transmitted
• All these characteristics Light

contribute to the observed color

 Reflectance
• Specular (regular)
reflectance = mirror like Specular
reflectance
• Diffuse reflectance =
reflectance in all Diffuse
directions
• Gloss = combination of
specular and diffuse Glossy
reflectance
 Definitions
• Reflectance ρ is the ratio of the total radiant flux
reflected by the surface to the flux incident on
the surface
• Reflectance factor R is the radiant flux reflected
in the direction delimited by a given cone to that
reflected in the same direction by a perfectly
reflecting diffuser identically irradiated
• If the solid angle of the cone approaches a limit
of 0 or 2π sr, reflectance factor R approaches
radiance factor β or reflectance ρ
 Spectrophotometers and
colorimeters
• Spectrophotometers are used to measure an
object’s reflection characteristics
• Colorimeters measure directly tristimulus values
or related color coordinates
• Colorimeters are less expensive and simple to
use but less accurate for determining tristimulus
values
• Colorimeters determine the color difference
between two samples better than tristimulus
values
• Colorimeters can not determine metamerism
 Measuring diffuse reflectance
• Instruments measuring the color of reflecting
objects consist of an illuminator, a sample
holder, and a receiver
• The CIE recommends four illuminating and
viewing geometries for making reflectance
measurements: 45/0, 0/45, d/0, and 0/d
• The most common instrument for measuring
diffuse reflectance is the integrating sphere
• Another type of technique, which is getting more
popular, is the angular integration of
gonioreflectometric measurement results
 Integrating sphere-based
techniques
• An integrating sphere is
coated from the inside with
uniformly diffusing material
• It has openings for the
sample, light source and
the receiver
• The idea is to either create
a diffuse geometry of
illumination or to collect
light scattered diffusely by
the sample
 d/0 geometry
• The light is incident on
Photometer
the sphere wall and is
reflected in all directions
Specular port
• As the result of multiple
reflections the sample is
illuminated from all
directions
Light
• The sample is viewed in a source
near normal angle
• The specular reflection is
directed back to the
source and is not Sample
measured
 0/d geometry
• The light is incident
Photometer
on the sample
• The sample scatters Baffle
the light and after
multiple reflections it
Light
illuminates the Sample
source
detector from all
directions
• The 0/d geometry is
equivalent to the d/0
geometry
Absolute and relative measurement
methods
• Relative measurement methods produce values
that are relative to reference standards
• Absolute measurement methods relate the
reflectance values of a standard to that of the
perfect reflecting diffuser
• The relative methods are commonly used in
industry, whereas the absolute methods are
commonly realized in national standards
laboratories
 Example of relative method
• Signals are measured
from the sample, the Sample
reference, and the light Holder
trap (light incident on the
trap)
• The light trap gives the
dark signal which is Reference Reference
subtracted from the Entrance Holder
results
• The sample and Light Sample
reference readings are Trap Entrance
compared and corrected
by the known values of
the reference
 Example of absolute method
• Taylor’s method: Detector
readings when the C
sample port is not
covered (a), it is covered
with sphere material (b), A Light
and it is covered by the B
source
sample (c)
• Increase from a to b is
proportional to the
reflectance of the sphere Sample, Cap
or Light trap
• The reflectance of the
sample is calculated from
the ratio of a and c
 Goniometric techniques
• Gonia = angle
• The idea is to illuminate the sample in a certain
angle and measure reflectance on the surface of
a hemisphere around the sample (or vice versa)
• In practice this can be realized with a two-axis
goniometer or with a one-axis goniometer by
integrating over the polar angles
• Enables bidirectional measurements
 Gonioreflectometer at TKK
• One-axis goniometer
• The idea is to illuminate Rotation

the sample in one Detector

Translation
Source and input optics Meas.
direction and measure enclosure MD
BS
position
θ
L

SPM
reflectance over the QTH
M
P Iris Sample Reference

OSF
GT2 position
semiarch GT1
A
OPM

• Total diffuse reflectance is Light-tight enclosure

Double monochromator
obtained by integrating
the measured values over
the whole hemisphere
 Things to be considered
• The major source of Detector
Rotation

uncertainty in the system

Translation
Source and input optics Meas.
enclosure L
is isochromatic stray light SPM
MD
DP
position
θ
M2
• The biggest contribution QTH M1
Iris Sample Reference

OSF
GT2 OPM position
is light scattered about GT1
A
SPM
the main beam Light-tight enclosure
• To compensate the effect Double monochromator

a significant correction
factor must be used
• In our previous system
the correction factor was
much greater than today
due to the more
complicated optics
 Gonio vs. sphere
• Goniometric technique provides bidirectional
measurements which are not possible with a
sphere
• The scattering of light about the main beam is
clearly a problem for the gonio but not for the
sphere
• Systematic deviations have been reported
earlier between goniometric and sphere-based
techniques
• The scattering of light about the main beam is a
strong candidate for causing these
discrepancies
 Fluorescence
• A fluorescent material
absorbs some of the light
incident on it and emits it
on higher wavelengths
• Part of the energy of the
incident photon is lost in
internal vibrations and
heat
• Fluorescence is used e.g.
in paper whitening, safety
signs and textiles
 Commercial fluorescent colorants
• Inorganic fluorophors: stable but toxic, used in
security markings and fluorescent lamps
• Optical whiteners: organic compounds, with
excitation at 340-400 nm and emission at 430-
460 nm, used heavily in textile, paper and plastic
industries to whiten materials
• Daylight fluorescent materials: organic
compounds, emission and excitation in the
visible part of the spectrum, used to color papers
and plastics and especially in safety applications
 Measuring fluorescence
• Polychromatic illumination → appearance and
color
• Monochromatic illumination → fluorescence
separated from reflectance
• Often we want to measure fluorescence
quantum yield of a material
• Fluorescence quantum yield = the number of
emitted photons relative to the number of
absorbed photons
• Quantum yield measurements require
monochromatic illumination and viewing
Reference spectrofluorimeter at
NRC
Gonio-fluorometer at TKK
 The principle of a CCD
• CCD = charge-coupled
device
• The CCD comprises a
two-dimensional array of
pixels
• Every pixel gathers
radiation from a different
spatial position → large
area of spectrum (~200
nm) measured in one
picture
 Problems related to fluorescence
• Stability of the fluorescent standards
• No universally recognized method for
characterization of fluorescent instruments
• Different instruments give different results
• Even the same instrument can give different
results over time
• Comparing different fluorescent samples is
difficult even with the same device
 Transmittance measurements
• Similarly to reflectance,
Regular
we can have regular,
diffuse or glossy
transmittance
• Transmittance is utilized
Diffuse
e.g. in interference filters
and glass filters
• The most common
measurement geometry
Glossy
is 0/0
 Fabry-Perot filter and interference
filters
• The cavity length
determines the passed Fabry-Perot
wavelength cavity
• MDI filter: thin partially
transmitting metal layers Transmitted
Input
waves add
• ADI filters: alternating signal
In phase
layers of substances with Reflections
differing refractive indices
• Sensitive to temperature
and angle
 A double-beam transfer standard
spectrometer at TKK
• Used to calibrate
filters
• The idea is to Light
Source
measure similar Reference
beams through the
filter and through air MC Detector
Sample Unit
• Detector readings
from both sample and
reference are
compared to yield
transmittance
 A single-beam reference
spectrometer at TKK
• Detector readings are
taken through the filter,
Light
through air and dark Source
reading
• The filter and light trap
can be moved into the MC
beam by a linear Averaging
translator A Sphere
Detector
• The measurement
system can be modified OPM
to measure e.g. diffuse Filter-holder
transmittance Unit
 Choosing measurement geometry
• Bidirectional illuminating and viewing geometries
can be very sensitive to surface texture and
polarization
• Bidirectional geometries are similar to the way a
person evaluates color visually
• Diffuse geometries minimize the effect of a
sample’s texture and gloss
 Special cases
• Metallic and
pearlescent samples
• Retroreflecting
samples
• Lamps, light sources
and displays
 Conclusion
• Color and appearance are important quantities
in several branches of industry e.g. paper, textile
and plastic industry
• The color and appearance of a material are
effected by the light source, observer and
spectral properties of the material
• Reflectance, transmittance and fluorescence
measurements all require special instruments
• Fluorescence measurements still present severe
problems due to the instability of standards and
lack of universal calibration methods of
instruments