X-Ray Fluorescence-Spectroscopy of Artists’ Paints

Tilly Duffy with Rana El Ladki and Ankita Chittiprollu (Group 1)

October 3, 2019
Introduction

The purpose of this experiment is to examine the chemical makeup of various paint samples

using X-Ray fluorescence spectroscopy (XRF) in order to identify which sample contains

cadmium yellow pigment and the identity of a mystery paint mixture. XRF uses x-rays to ionize

electrons close to the nucleus, x-rays are used in this process because they have high energy and

will provide enough energy to remove the core electrons. With the absence of a core electron, the

atom becomes unstable. To fill in the ‘hole’ left by the ionized electron and re-make the atom

stable, an electron from a higher energy level falls down. As this electron falls, it emits energy. If

this energy has a wavelength that corresponds to X-Ray wavelengths, it is detected by the

spectrometer and recorded in a graph much like a spectrum. The various transitions are identified

using K, L, M, N, … to represent the principal quantum number n=1, 2, 3, 4, … respectively.

These letters indicate in which energy level the ‘hole’ is found. Following the capital letters are

lowercase Greek letters that indicate the number of energy levels the falling electron traveled. a

represents a change in one principle quantum number and b represents a change in two principle

quantum numbers. It should also be noted that electrons cannot transition from the same orbital,

so no transitions can occur from 3s to 1s. This creates multiple possibilities for a few specific

transitions where the falling electron can originate from either p1/2 or p3/2, that are denoted as a1

or a2.

Every element has unique energy level transitions and thus emits unique wavelength

combinations when electrons are excited, so a unique graph is made for every element. Items of

unknown makeup are tested with XRF to determine its chemical makeup by comparing the

known XRF spectra of elements with the data collected from the unknown sample. It is also

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helpful to note that XRF is nondamaging to the substances tested and is therefore used frequently

to analyze historical artifacts.

Experimental Methods

In this experiment, XRF was carried out using a Bruker S2 Ranger XRF spectrometer, which can

carry out analysis and detect elements with atomic numbers 11-92, with the exception of C, N,

O, and H in organic compounds containing only those elements. To begin the experiment, each

of three group created a mystery two-paint-mixture from various provided paints. Rana El Ladki,

as a member of group one, prepared a mixture of Cadmium Red Medium and Cerulean Blue

paints by squeezing the two paints onto a mixing palette and using a wooden spatula to mix the

paints together. The mixture was then spread onto the center of a 2.9x2.9 square piece of canva-

paper.

While the mystery samples dried, the second portion of this experiment was carried out. First, a

blank canva-paper sample was placed into the XRF spectrometer to determine the elements that

would present in every sample reading due to the contents of the paper itself, much like a control

test. Then, one yellow paint sample was provided to each of three lab groups and each group

then took turns placing their respective sample paint-side down in the XRF spectrometer and

then analyzing their data using the Spectra EDX software to identify what elements were present

in the sample and the KeV at which each of the emissions were recorded. Once the data was

analyzed, the graphs were placed into a Word document so that other groups could later analyze

each sample to determine which yellow sample contained Cadmium Yellow pigment.

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Following this portion of the experiment and once the mystery samples were dry, those paint

samples were analyzed using the XRF spectrometer and Spectra EDX in the same fashion as the

yellow samples, the elemental makeup of the mystery samples were then compared to the

various paint types in Table 3 to identify the makeup of the paint mixtures. The sample created

by Rana El Ladki was analyzed by members of group 2, Caroline VanDenBrouck and Jared

Bretz. Group one analyzed the mystery sample prepared by group three, with members Michael

Beecher, Amy Thieu, and Ben Nelson.

Results

First, the blank canva-paper and the three yellow paint samples were analyzed using the XRF

spectrometer.

Ca Ka1
6000
5000
4000
3000
2000

Pd La1
Cps

Ca Kb1
1000

Pd Lb1
500
300
200
100
0

0.6 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 32

KeV

Figure 1: Spectrometry data from the blank canva-paper, indicating what elements will be found
in every sample due to the paper and can thus be ignored when determining paint contents.

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 7000
6000
5000
4000

Cl Ka1
3000
2000
Cps
1000
400 600

S Ka1
200

Cl La1 Fe Ka1
0

0.6 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 23 25 27 29 31

KeV
Figure 2: XRF spectroscopy data for Yellow Sample 1, elements from the canva-paper were
excluded (Pd and Ca).
8000

S Ka1
7000
6000
5000
4000

Cd La1
3000

Cd Ka1
Cps
2000

Cd Lb1

Zn Ka2
800 1000
600

Cd Kb1
400

Rh Ka1
Zn Kb1
200

Se La1 Cd Kb2
100
0

0.6 0.8 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32
KeV

Figure 3: XRF spectroscopy data for Yellow Sample 2, elements from the canva-paper were
excluded (Pd and Ca).

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 6000
5000
Bi Ma

Bi La1
4000
3000

Bi Lb1

V Ka1
2000
Cps
800 1000

Zr La1
Zn Ka1
600

Bi Lg1
400

Os Ma V Kb1 Bi Li
200

Bi Lg3
100
0

0.6 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32
KeV

Figure 4: XRF spectroscopy data for Yellow Sample 3, elements from the canva-paper were
excluded (Pd and Ca).

Table 1: Elements Found in Samples of Yellow Paint and Blank Canva-Paper

Sample Elements
Blank Canva-Paper Palladium & Calcium
Yellow Sample 1 Chlorine, Sulfur, & Iron
Yellow Sample 2 Selenium, Cadmium, Sulfur, Zinc, & Rhodium
Yellow Sample 3 Osmium, Zirconium, Bismuth, Vanadium, & Zinc

Using the data about elemental composition of the samples given by the spectra, it can be

determined that Yellow Sample 2 contains the pigment in question: Cadmium Yellow, as it

contains cadmium. All other samples cannot contain Cadmium Yellow, as none of them indicate

that there is any cadmium present in their composition.

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Prior to the experiment, transition energies for Cadmium were calculated using the equation

below, which is based on the Bohr model.

1 1
E = −13.6Z 2 ( 2
− 2)
n f ni
(1)

Where E is energy of the emission, Z is the atomic number, n is the principle quantum number,

and f and i are final and initial states of the falling electron, respectively. This information was

compared to the data collected from the Cd spectrum.

Table 2: Observed vs. Calculated Cadmium XRF Transitions

Calculated Energy Observed Energy
XRF Transition
(KeV) (KeV)
Ka 23.5 23.3
Kb 27.9 26.6
La 4.35 3.14
Lb 5.88 3.31

Next, the unknown paint mixture, made by Group 3, was examined using the XRF Spectrometer

in order to determine the composition of the mixture and help identify the paints used.
11000 12000 13000

Cl Ka1
10000
9000
8000
7000
6000
5000
4000

Fe Kb1
Cps
3000

Cu Ka1
2000

Rh Lb1 Fe Ka2
Cu La1 Rh Li
800 1000

W Ma Cu Kb1 Rh Ka2
600
400

Br Ka2
200
100
0

0.6 0.8 0.9 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32

KeV

Figure 5: XRF spectroscopy data for the unknown paint mixture, elements from the canva-paper
were excluded (Pd and Ca).

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The data was compared to the information in Table 3 to determine which pigments/paints were

used to create the mystery mixture.

Table 3: Acrylic Paints and Their Chemical Makeup1

Based on the data on the prominent elements present in the mixture from Figure 5 and the

information found in Table 3, it can be determined that the mixture contained Phthalocyanine

green (Blue Shade) and Prussian Blue paints. As chlorine, copper, and iron are prominent and all

those can be found in the chemical makeup of the pigments used in Phthalocyanine green (Blue

Shade) and Prussian Blue paint. All other paints in the table contain elements not present in the

spectrum.

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Discussion

The first round of analysis involved the blank canva-paper and the three yellow paint samples in

order to determine which sample contained the Cadmium Yellow pigment. This could be

determined by analyzing the spectra and determining which of the three samples indicated the

presence of cadmium. The blank was taken first in order to determine which elements would be

present in every sample and were not due to the presence of a pigment. The elements from the

blank (Pd and Ca), shown in Figure 1, were removed from the spectra to make them less

cluttered. It was then determined, based on examination of Figures 2-4 and Table 1, that Yellow

Sample 2 was the only sample that contained traces of cadmium, as seen in Figure 3 and

Table 1. Therefore, Yellow Sample 2 must contain the Cadmium Yellow pigment, thus the real

Cadmium Yellow paint, and the other samples did not, as the pigment Cadmium Yellow must

contain traces of cadmium and no cadmium was detected in the other samples as shown by

Figures 2 and 4 and Table 1.

A technique similar to the one used above, was used to determine the identity of the paints used

to make the mystery mixture. Based on the elemental data from the XRF spectrometer in Figure

5, the mixture contains prominent amounts of Chlorine, Copper, Iron, and various other

elements. The presence of Chlorine, Copper, and Iron indicate that the pigment used in the paints

must contain these elements. Based on data from Table 3, it was determined that the mixture

must contain Phthalocyanine green (Blue Shade) and Prussian Blue paints. Phthalocyanine green

(Blue Shade)’s pigments contain chlorinated copper and Prussian Blue’ pigments contain Milori

Blue (Fe4[Fe(CN)6]3). All elements, that are detectable using this spectrometer, from these

pigments were found in the spectrum with prominent peaks and therefore the mixture must

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contain these paints. All other paints contain elements that were not detected by the

spectrometer.

As seen in Table 2, the calculated data for the XRF transitions corresponds with the observed

data fairly closely for transitions in quantum number K where the observed vs. calculated values

are 23.3/23.5 and 26.6/27.9 for alpha and beta, respectively. However, in quantum number L, the

values for the transitions vary much more with observed vs. calculated values measuring

3.14/4.35 and 3.31/5.88 for alpha and beta, respectively. This large variation among calculated

vs. observed values in quantum number L can be attributed to the fact that the equation used

refers specifically to transitions occurring in atoms with one electron, like Hydrogen, as it is

Bohr’s model. As Bohr’s model was used specifically for one electron atoms, it does not account

for the different orbitals in higher energy levels or the way that electrons in the same orbital

effect each other through their spins and other types of repulsions. Therefore, the discrepancies

seen in quantum number L can likely be attributed to the higher energy levels and the presence

of multiple electrons. Values from quantum number K are more similar due to the fact that there

are less electrons present in principle quantum number n=1, so therefore will not impact the

energy of electron transitions as much. It can be predicted that the discrepancies in values will

only increase as the principle quantum number gets larger. This is largely due to the greater

number of electrons present in higher energy levels as there are more orbitals and thus more

space for the electrons (and therefore more factors that impact the binding energy and thus

transition energy). The observation that the discrepancies are smaller the less the electron has to

travel also makes sense, as the less the electron has to travel the less it will interact and incur

interference from other electrons and therefore act more like a one electron atom.

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If the XRF spectrum was to be taken of Ag and compared to the spectrum of Cd, the observed

energies of the electron transitions would be less. There would likely be four prominent emission

lines in Ag’s spectrum, as Ag and Cd have electrons that occupy the same orbital and will likely

experience similar types of transitions, however the lines would emit lower values of energy, as

there is one less electron present which would allow for slightly less interference and therefore

an easier transition for certain electrons. Additionally, thinking about this in terms of Equation

(1), it can be argued that although the equation is not accurate, it can still predict values enough

to compare them across elements. So, by plugging in Z for Ag, which is smaller than Cd by one,

that alone will lower the value for E. This makes sense, as the larger the Z value, the greater the

number of occupied energy levels there are, as it contains more electrons (assuming neutral) to

fill those levels. The more occupied energy levels, the more space there is for an electron to

travel and therefore more energy will be released, additionally, more transitions will occur.

XRF and Atomic Emission Spectroscopy are very similar in that both techniques require energy

to be put into a substance in order to cause an electron to become excited, both techniques then

collect data based on the emission from an electron falling. However, Atomic Emissions only

excites a valence electron and observes the energy emitted as it returns to a ground state, whereas

XRF ionizes a core electron out of the atom and observes the energy emitted as other electrons

fall into the hole created by the ejected electron. Since the electrons being ejected from the core

of the atom are much more tightly bound to the nucleus and are actually ejected, XRF requires

much more energy compared to Atomic Emissions, thus the amount of energy emitted is also

much higher, with detectors used in XRF looking for much smaller wavelengths (X-Rays range

from 0.01-10 nm) than visible light (wavelengths between 300-700 nm) that is observed in

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Atomic Emissions. The number of energy levels passed through with Atomic Emissions varies

based on the atom and the amount of energy used, whereas XRF typically transitions through one

to two energy levels per transition and transitions through orbitals. Perhaps another important

detail to note is that XRF is nondestructive and can be used on samples without damaging them

whereas Atomic Emissions uses up small amounts of the sample when examining the substance.

Conclusion

This experiment was highly successful in terms of obtaining its objective, the sample containing

Cadmium Yellow was easily identified as Sample 2 once the data was collected and examined,

additionally the mystery paint mixture was also easily examined and the contents of the sample

were successfully determined as containing Phthalocyanine green (Blue Shade) and Prussian

Blue using the XRF spectrometer data compared to Table 3. XRF spectroscopy was highly

effective in this experiment, as it explicitly stated the information pertaining to the elemental

composition for all the paints examined and the information was presented in an easy to read

way using the spectral data- this allowed for easy analysis to take place.

Appendix

See attached equation sheet.

Reference

1. Severin, K. Laboratory #3: X-ray Fluorescence Spectroscopy of Artists’ Paints; Michigan

Sate University; CEM 185H; 2019

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