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.

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Accelerated Aging Chamber, Part 2

Troubleshooting

Conservation Intern, Associate Conservator, and Project Conservator working to troubleshoot an issue with the water purification system that occurred while this post was written. AMNH/F. Ritchie

Part 1 of our posts on accelerated aging instrumentation introduced the Q-SUN Xe-3 accelerated aging chamber. In this posting we describe some of the challenges we have experienced in installing and operating the machine; challenges which were unexpected and eye-opening. Problem-solving these situations has been such an important learning experience for us, demonstrating what taking on a project of this magnitude really entails.

Modifying the Lab

Our initial challenge was retrofitting the lab to accommodate the needs of the unit. In addition to electrical and plumbing adjustments to provide sufficient voltage, surge protection, purified water, and condensate drainage (all while retaining the ability to move the unit around the lab on its casters as needed), we had to install a ventilation hood over the machine with a fan and ductwork to vent its exhaust directly out of the building. This was necessary to limit the machine’s impact on the environment in the lab and adjacent offices, which otherwise became uncomfortably hot and cold respectively. The improved ventilation also allows the machine to cool itself much more efficiently, reducing both the noise and overall consumption of purified water – saving both our budget and our ears. We learned firsthand how important it is to moderate lab temperature when the HVAC system in the lab randomly failed and the machine was forced to stop because the chamber air rose to an unacceptable temperature. Luckily our maintenance staff provided the troubleshooting for this situation and the test cycle resumed within 24 hours.

Lesson: Make sure to understand completely the needs of a machine and its impact on day-today processes.

IMG_20151104_115246043

Ventilation hood and fan installed above the Q-SUN Xe 3 chamber to extract heat generated from the machine, helping maintain lab temperature. AMNH/F. Ritchie

IMG_20151104_115259244

New ductwork installed to direct exhaust from the Q-SUN out of the lab. AMNH/F. Ritchie

Setting Test Parameters

Our next unexpected hurdle was in setting our testing parameters inside the Q-SUN (i.e. the RH, chamber air temperature, and irradiance). Our previous dye testing was undertaken following the ASTM D4303 (Method C) testing standard in a chamber that did not have the capacity to control for RH. Because our Q-SUN Xe-3 chamber can be run with RH control, we initially chose a different standard ASTM D4303 (Method D). Immediately, to our horror, we found that condensation was forming inside of the machine, dripping onto the carefully prepared samples and making them unusable.

Initial troubleshooting with Q-Lab Corporation (the Q-SUN manufacturer) focused on possible problems with sensors or calibration within the machine, but that did not solve the condensation problem. Ultimately we learned that the D4303 test Method D is outside the capabilities of the Q-SUN Xe-3 (and apparently outside the capabilities of any humidity controlled xenon arc testing chamber). This was not an intuitive conclusion since Method D is specifically written for a Humidity Controlled Xenon Arc Device. As such, we have adjusted our test parameters so that they now lie well within the capabilities of the machine, and more closely replicate the Museum’s diorama conditions that we are chiefly concerned with.

Lesson: Understand that standards are often simply guidelines to follow to provide consistent parameters for comparison. Standards can (and often, should) be adapted to meet necessary requirements.

Dealing with Malfunctions

The most recent wrinkle in our operation of this machine was the spontaneous cracking of one of the UV-blocking filters that we are using for half of the testing rounds. Though this required us to suspend our testing for a few days, Q-Lab Corporation was very quick in providing a replacement, and since then we have been able to run the unit without incident.

cracked filter with arrow

Crack in a portion of the glass UV filter. AMNH/F. Ritchie

Lesson: Be flexible and ready to deal with unforeseen circumstances, and maintain a good relationship with the manufacturer of your equipment.

Budgeting for Consumables

The Q-SUN Xe-3 requires air filters, water purification filters, replacement lamps, sample preparation supplies, and many other expendable items that add cost beyond the initial purchase of the machine. Our grant budget has been adequate to deal with consumable materials, but we have realized that we must be prudent when running the machine and we must stay on top of ordering replacement supplies. There are even differences between test cycles. We are finding that our UV-filtered test cycles use up the lamps and water filters more quickly than the UV-rich test cycles.

Lesson: Pad your budget for expendable supplies and be sure to order the next set of replacements as soon as you install the first set.

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Row of Q-SUN replacement lamps awaiting installation. AMNH/F. Ritchie

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Project Conservator replacing a lamp. AMNH/J. Sybalsky

CONCLUSION

Owning and operating an accelerated aging chamber, at least one as complex as the Q-SUN Xe-3, is more than a plug-and-play operation. We hope that the steepest part of the learning curve is now behind us, but past experiences have taught us to expect that new issues will present themselves as we continue to work with this machine.

Lesson: When using any new tool or taking on any new experimental analysis, be sure to build time into the project timeline for troubleshooting.

Accelerated Aging Chamber, Part 1

Q-Lab Corporation, manufacturer of the Q-SUN Xe-3 accelerated aging chamber, promotes this machine as “the simplest, most reliable, and easiest to use full-sized xenon arc chamber available.” Before purchasing ours in February 2014, we began making upgrades to water and electrical systems in our lab to meet its basic requirements. Perhaps naively, we had planned to install the chamber and begin our testing promptly once those upgrades were complete. Throughout following months, we encountered a series of unexpected challenges in the set up and operation of our new chamber. This is the first in a pair of posts that will introduce the Q-SUN Xe-3, its capabilities and some of the theory behind its use, explore the challenges we have had, and suggest some key issues that you might consider when planning to acquire a large piece of new equipment for your laboratory.

THE Q-SUN ACCELERATED AGING CHAMBER

2014-03-10 15.47.49

Q-SUN Xe3 Accelerated Aging Chamber with Q-Lab training specialist Alan Boerke for size comparison. AMNH/B. Nunan

PART 1: GETTING UP TO SPEED

Much to the disappointment of some of our curious colleagues in other departments who wondered what one does with an accelerated aging chamber, the Q-SUN Xe-3 can not be used to expedite troublesome developmental phases in your toddler, nor be run in reverse to reunite you with your youth. Too bad. Instead, this machine is used to rapidly reproduce the damage to materials that is caused by light, temperature, and humidity in real environments over longer periods of time.

The tester is a bit bigger than a refrigerator, and contains three powerful xenon arc lamps that expose samples to bright, daylight-imitating light inside of a compartment roughly the size of an oven. The spectrum of light produced can be adjusted with the installation of various filters above the sample compartment. Light output is measured in irradiance (W/m2), and can be controlled at either 340nm (ultraviolet) or 420nm (visible) depending on what filters are in use. The tester also maintains set points for relative humidity, chamber air temperature, and the temperature of a black panel placed inside the sample compartment.

2014-03-10 16.06.51

Q-Lab training specialist Alan Boerke discusses the Q-SUN aging chamber with project conservators and other conservation scientists from neighboring NYC institutions. AMNH/B. Nunan

On March 10, 2014 the American Museum of Natural History (AMNH) hosted a training session on accelerated aging and use of our new Q-SUN Xe-3 with Alan Boerke, Technical Sales and Training Specialist at Q-Lab Corporation. The training was attended by selected museum staff and colleagues from Yale’s Institute for the Preservation of Cultural Heritage, the Metropolitan Museum of Art, and the Museum of Modern Art, as well as students from New York University’s Institute of Fine Arts Conservation Center.

Accelerated aging makes use of the principle that exposure to high intensity light for a short time can produce deterioration similar to that caused by low intensity light over a longer time. However, in order to correctly interpret one’s results, one must understand that for many reasons, accelerated aging does not occur in a way that is strictly reciprocal. In part this is due to the inability of any aging chamber to exactly replicate every aspect of real-world exposures: wet/dry, thermal, or light/dark cycling, the spectrum of incident light, and the presence of air pollutants, dust, or adjacent materials may be impossible to simulate. This non-equivalence is also a consequence of thermal chemistry that unfolds simultaneously alongside light damage, but can’t easily be differentiated from it or accelerated proportionally.

Alan emphasized benchmarking as a way of managing this problem. To create a benchmark, materials aged in real-time are used to define the mode and extent of change taking place over a known duration. When a comparable degree of change is observed in the accelerated test, a correlation factor can be identified to be used in calculating an approximate relationship between accelerated and real-time aging. However, benchmarking has some obvious drawbacks, not the least of which is that a material that ages well may take many many years to fail in a real-world exposure environment. If one is conducting accelerated aging on that material, it’s usually because one needs information promptly and can’t afford to wait.

The success of this approach depends on the selection of a standard that exhibits deterioration behavior similar to the samples being tested- both in the real world and accelerated aging environments.  However, since the samples being tested have unknown aging behaviors one standard is usually insufficient.  So instead of choosing a single standard, it is better to select a series of standards that will hopefully bracket the behavior of the samples.  For lightfastness testing, a common set of standards is the Blue Wool scales, wool swatches dyed with eight different dyes that exhibit a range of different lightfasnesses.  By including the Blue Wool scales in our accelerated tests we can determine which of the eight standards our samples behave most similarly to.

Blue Wool card_annotated

Blue Wool scale assembled by the team using blue wool reference standards 1-8 obtained from SDC Enterprises Lmtd and mounted onto card stock. A new Blue Wool reference scale will be used with each test round. AMNH/F. Ritchie

Our training session also included a discussion of other factors that could affect the results of our testing: the color and cleanliness of the sample, whether it is mounted at an angle, or over a backing board, and its height inside the sample compartment; variations in sample handling and measurement technique; breaks in our test cycle for sample measurement; and the age of the xenon lamps. Getting repeatable results hinges on limiting variation in these influences.

We concluded with a tutorial in which Alan showed us all the basics for running and maintaining the machine: how to load and rotate samples, install and calibrate lamps, change light filters, and program the desired parameters.

With all of this new knowledge in hand, we promptly began the process of translating our research plan into an actual method for mounting and testing our dye samples. Very quickly we observed that doing so would not simply be a matter of plugging in the Q-SUN, programming the ASTM D4303 test parameters, and pressing the ON button. Many unanticipated challenges were yet to come…

Calibrating the lamps

Conservation intern Ersang Ma prepares to calibrate the Q-SUN lamps, according to procedures learned during the one-day training session by Q-Lab. AMNH/B. Nunan