Color by the Numbers, Part 1: Spectrophotometry vs. Colorimetry

In our lightfastness testing of metal-complex solvent dye solutions, we see some samples that fade a lot and are very easy to qualify as “fast-fading” dyes. (See our previous post for more information on metal-complex solvent dyes and why we’re using them; as well as previous posts that detail our sample set and sample preparation) By visually comparing the test samples to the controls we can see those differences, even after as little as 24 hours in our exposure test-chamber. However, we need to quantify those changes in order to describe them in a more objective way than can be done based on human sight alone. Doing this requires some means for reproducibly recording color and calculating change. But how do we do that?

Answer: we use an instrument called a spectrophotometer to make color measurements, and then use principles of colorimetry to interpret them.

Supplier/Color/Solvent/Substrate: Kremer/Blue GN/acetone

Sample of Kremer Blue GN (CIGN Solvent Blue 67) in acetone, after testing. The A and B test plates (left and middle) were exposed to the accelerated aging chamber, while test plate C (right) was not. There is very little color fade detectable by the naked eye. AMNH/F. Ritchie

Supplier/Color/Solvent/Substrate: Kremer/Yellow 4GN/acetone

Sample of Kremer Yellow 4GN (CIGN Solvent Yellow 146) in acetone, after testing. The A and B test plates (left and middle) were exposed to the accelerated aging chamber, while test plate C (right) was not. The light fading was extreme enough to be detectable by the naked eye. AMNH/F. Ritchie

Background: A Note on the Difference Between Color and Colorants

Before describing the workings of a spectrophotometer and the principles of colorimetry, a refresher on the two different types of color theories – the way humans see color – is necessary.

1.  Subtractive color theory

subtractive color

An illustration of subtractive color theory where colorants (in this example, the pigment from oil pastels) are mixed and absorb light from certain regions of the visible spectrum, thereby subtracting them from the reflectance spectrum that is perceived by the human eye. [Photo source]

This is the type of color-mixing we are taught in grade school: whereby colorants are mixed and then absorb light from certain regions of the visible spectrum, thereby subtracting them from the reflectance spectrum that is perceived by the human eye. Under this theory the primary colors are red, blue, and yellow, and secondary colors are orange, green, and violet. For example, a blue colorant (which absorbs light in the red, orange, and yellow parts of the spectrum) mixed with a yellow colorant (which absorbs light in the red, blue, and violet parts of the spectrum) will produce green (the remaining color in the reflectance spectrum). In modern color printing, cyan, magenta, and yellow are the usual primaries. Black is produced when all colors are present because all wavelengths are absorbed.

2.  Additive color theory

RGB_illumination

An illustration of additive color theory where different light sources are shown onto a wall. Where the lights overlap, another color is perceived because visible wavelengths in the spectrum of light are mixed (or added) together, received by the eye, and interpreted by the brain as color. The white light in the center is the mixture of all three primary additive colors, mixing together to encompass the entire visible spectrum. [Photo source]

This is the type of color perception that we encounter on computer- and television monitors when projected light is combined to make different colors. In additive color theory, visible wavelengths in the spectrum of light are mixed and/or added together, received by the eye, and interpreted by the brain as color. The additive primary colors are red, green, and blue, roughly corresponding to cones in the eye that are sensitive to long, medium, and short wavelengths, respectively. Secondary colors are yellow, cyan, and magenta. For example, a mixture of equal parts red (~650 nm) and green (~510 nm) light stimulates the cones of the eye in a manner that is similar to pure spectral yellow (~570 nm), so the eye does not detect the difference between the two conditions. White light is created when red, green, and blue are all present because they encompass the entire visible spectrum.

Spectrophotometry: Making Color Measurements

Spectrophotometry is a “noninvasive technique that measures the amount of light reflected or transmitted by a material at individual wavelengths of the spectrum” (Johnston-Feller, 2001: p. 1). A spectrophotometer is the instrument that’s used to measure light reflected, or transmitted, by a material. To do this, it relies on a light source, a monochromator that isolates and directs the wavelengths, and a photodetector that detects reflected or transmitted radiation. The measurement is unit-less, or may be given in percent absorbance or transmittance. The reflectance or transmission spectrum of the material describes how a spectrum of light incident on it will be modified upon reflection from, or transmission through, it. That modified spectrum is what we observe and interpret as the material’s color under that particular light.

For this project, we purchased an X-Rite Ci62 handheld spectrophotometer with a tungsten light source, a grating monochromator, and a photodetector consisting of blue-enhanced silicon photodiodes. With this instrument we measure successive reflectance spectra from each sample at intervals during our light exposures. When a sample is measured, the amount of light reflected at each wavelength in the visible spectrum is recorded and plotted along a curve that describes the reflectance of that dye sample. By comparing successive measurements, we can see the spectral-curve change as the dye fades or discolors over time.

MSC solvent red 122 in ethyl acetate

Spectral curves of sample Solvent Red 122 during an accelerated aging test cycle. The initial color reading/spectral curve is in red (the lowest line). During each color reading, the curve flattened as the color faded and there was less to measure. The final measurement is represented by the top line (green).

jig

Top: Spectrophotometer in the jig without quartz plate dye sample. Bottom: Quartz plate dye sample in position for color measurement when spectrophotometer. AMNH/F. Ritchie

Then, from each reflectance spectrum we can calculate parameters that uniquely describe the color we will observe under a particular light and the changes in that perceived color from our exposure test. That translation of light spectrum into color description is done with the tools of colorimetry, the scientific description of color.

Colorimetry: Interpreting Color

Colorimetry is a branch of color science that studies precisely what we need for our research: it is the quantification of color, or, as Ruth Johnston-Feller describes, a way to “describe a color unambiguously and uniquely to distinguish it from all other colors” (Ibid.; p. 15). Most colorimetric systems characterize color in three dimensions because they describe human visual perception, which is a function of the three types of photoreceptors in our eyes. A variety of these systems exist, but most of the descriptors for perceived color are derived from the CIE color system administered by the International Commission on Illumination since 1931, which is itself based on additive color mixture and the visual response to various wavelengths of light that reach our eyes.

CIE 1931 RGB and CIE 1931 XYZ Color Spaces

The 1931 RGB and 1931 XYZ color spaces created by the CIE were the first numerical models linking the wavelength regions of the visible spectrum to human color vision. The CIE system defines a series of standard illuminants (sources) and a standard observer (mathematical representations of average human color vision), since the perception of color requires both a light source to illuminate a material and the human visual response to the light reflected (or transmitted) by that subject. A standard illuminant is characterized in terms of the spectral power distribution that distinguishes a specific light source, including the one most widely used: 6500K daylight (abbreviated D65). A standard observer is defined by a set of three mathematical color-matching functions that describe the average spectral sensitivity of the human eye at each wavelength in the visible spectrum, as derived from experimentally determined response curves for a particular field of view (such as 10 degrees, a wide field suited for viewing rough textured surfaces like fur samples). These color-matching functions are dependent on the selection of a set of three additive primary colors (for example, monochromatic red, green, and blue wavelengths, as in CIE RGB, described below) that together with a reference white point (such as D65) define a unique color space containing the gamut of all possible combinations of those primary color components. The functions are used to convert the reflectance spectrum measured with the spectrophotometer into tristimulus values, which are the relative amounts of each primary color needed to match the color sample measured.

For example, the CIE RGB color space is defined by red (700 nm), green (546.1 nm), and blue (435.8 nm) primary colors, and contains the gamut of colors that can be produced from RGB tristimulus values. A mathematically related color space, CIE XYZ, is derived from CIE RGB by means of a simple conversion, but it is useful because it makes for easier calculations than the RGB space. [For further reading on CIE XYZ, check out other on-line resources.]

CIE 1976 (L*a*b*) Color Space

There have been many developments in color science since 1931, in attempts to describe perceived color in a more straightforward and intuitive way, leading to the development of Lab color space by Richard S. Hunter, in 1945, and later the CIE 1976 (L*a*b*) color space. CIE L*a*b* color space is a mathematical derivative of the CIE XYZ color space, in which the L* parameter captures lightness, and the a* and b* parameters capture the other color dimensions. L* is proportionally related to tristimulus Y, the luminance, with darkest black at 0, and brightest white at 100. Red/green colors are represented along the a* axis, with neutral gray at 0, green at the negative values, and red at positive values. The yellow/blue colors are represented along the b* axis, with neutral gray at 0, blue at negative values, and yellow at positive values.

L*a*b* color is widely used in many industries because it offers a number of advantages over previous RGB and XYZ systems. It more closely approximates the nonlinear response of human vision, and includes a much wider color gamut than its predecessors. And it is more perceptually uniform, meaning that uniform changes in color values produce uniform changes in perceived color. Because of these capabilities, we are using L*a*b* values to describe the appearance of dye samples in our project.

Related to the L*a*b* color system is the color space CIE L*c*h°. In this system the a* and b* parameters are replaced by parameters describing chroma (or relative saturation) and hue. Unlike the L*a*b* system, which uses three-dimensional xyz coordinates to locate a point in color space, L*c*h° uses a polar coordinate system, with h° denoting a hue angle, and c* a radial distance from a central point. This color space is conceptually related to the familiar Munsell notation of color in terms of its hue, value, and chroma. It is also the color description necessary for calculating color differences with certain formulas.

RGB_color_wheel_10

Additive color theory illustration depicting how variations of color are achieved by the different combinations of red, green, and blue light (rgb values). [Photo source]

Putting It All Together

Like many spectrophotometers available today, the X-Rite Ci62 that we are using for this project has integrated software that can quickly execute the complex mathematical calculations needed to translate the measured reflectance spectrum into various colorimetric systems. From each reflectance spectrum, it computes and outputs tristimulus XYZ, L*a*b*, and L*c*h° values based on the standard illuminant (D65) and standard observer (10°) that we have selected. We then use those values to consider the overall amount of perceived color change, as well as changes in individual parameters, such as lightness.

We will go into greater depth about how we are interpreting our color measurements and tracking color changes in the up-coming Part 2 of this blog post.

References/Resources

Billmeyer, Jr., Fred W., and Max Saltzman. 1981. Principles of Color Technology. New York: John Wiley & Sons, Inc.

Christie, R.M. 2001. Colour Chemistry. UK: Royal Society of Chemistry.

Johnston-Feller, Ruth. 2001. Tools for Conservation: Color Science in the Examination of Museum Objects, Nondestructive Procedures. Los Angeles: The Getty Conservation Institute. Available online.

Whitmore, Paul M., Editor. 2002. Contributions to Conservation Science: A Collection of Robert Feller’s Published Studies on Artists’ Paints, Paper, and Varnishes. Pittsburgh, PA: Carnegie Mellon University Press.