Spectroscopy Letters

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Variable-Temperature Micro-Raman Spectra of the

Synthetic Artists' Pigments, Chrome Yellow and
Maya Blue: An Undergraduate Research Project

Jacqueline W. Riddle, Emily J. Hopkins & Ian S. Butler

To cite this article: Jacqueline W. Riddle, Emily J. Hopkins & Ian S. Butler (2015) Variable-
Temperature Micro-Raman Spectra of the Synthetic Artists' Pigments, Chrome Yellow and
Maya Blue: An Undergraduate Research Project, Spectroscopy Letters, 48:8, 556-560, DOI:
10.1080/00387010.2014.924529

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Published online: 11 Mar 2015.

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 Spectroscopy Letters, 48: 556–560
Copyright # 2015 Taylor & Francis Group, LLC
ISSN: 0038-7010 print/1532-2289 online
DOI: 10.1080/00387010.2014.924529

Undergraduate Research Article

Variable-Temperature Micro-Raman Spectra of the

Synthetic Artists’ Pigments, Chrome Yellow and
Maya Blue: An Undergraduate Research Project
JACQUELINE W. RIDDLE1, EMILY J. HOPKINS2, and IAN S. BUTLER1
1
Department of Chemistry, McGill University, Montreal, Quebec, Canada
2
Department of Chemistry, University of British Columbia, Vancouver, British Columbia, Canada
Downloaded by [Anelis Plus Consortium 2015] at 00:17 12 January 2016

Received 15 April 2014, Accepted 12 May 2014

As part of an undergraduate summer research project in vibrational spectroscopy, the micro-Raman spectra of synthetic samples of
the famous artists’ pigments, chrome yellow and Maya blue, were investigated at various temperatures to determine their long-term
stability with respect to dramatic changes in temperature. Synthetic chrome yellow was examined from 150 C to 500 C. Synthetic
Maya blue was studied from ambient temperature up to 200 C, when the Raman signals became swamped by the strong fluor-
escence from the sepiolite clay in which the indigo dye was encapsulated. Both pigments proved to be extremely stable with respect
to significant changes in temperature, which presumably accounts in part for their long-term use in artwork.
Keywords: artists’ pigments, chrome yellow, Maya blue, Raman spectroscopy, variable-temperature measurements

Introduction
Chrome yellow (PbCrO4) is a famous yellow pigment that has
been used by artists since the early 1800s, following its initial
discovery in the mineral crocoite by the French chemist Louis
Vauquelin in 1797.[1] This pigment is particularly well known
in North America as the color one associates with school
buses and it can readily be prepared artificially by precipi-
tation from a mixture of aqueous solutions of Pb(NO3)2
and K2CrO4 or K2Cr2O7.[2] Upon exposure to light, however,
the pigment gradually begins to become brown or greenish
and, since it contains the toxic element lead, its use has
greatly diminished lately. On a somewhat historical side note,
Aldous Huxley’s first novel in 1921 was entitled Crome Yel-
low, a satirical story about a house party in Garsington
Manor near Oxford in the village of Crome in England.[3]
Possibly, Huxley was intrigued by the closely related name
of the pigment in providing a title for his book! The degra-
dation process of chrome yellow in Vincent van Gogh paint-
ings has recently been examined by means of an impressive
combination of synchrotron radiation-based X-ray and
vibrational spectromicroscopy techniques, including Raman
microscopy.[4] While the degradation process in these 19th
century paintings is actually quite complex, there is clear
Address correspondence to Ian S. Butler, Department of
Chemistry, McGill University, 801 Sherbrooke St. West, Montreal,
Quebec H3A 2K6, Canada. E-mail: ian.butler@mcgill.ca
evidence for the presence of PbCrO4 and also for the
chemical reduction of Cr(VI) to Cr(III). Chrome yellow is
an excellent Raman scatterer, and the room temperature
spectrum exhibits a strong band at 841 cm1 due to the
symmetric Cr-O stretch of the tetrahedral [CrO4]2 anion,
together with several medium-intense bands at 407, 381 and
361 cm1 due to bending modes of the [CrO4]2 anion.[5]
Because of this situation, it is comparatively easy to identify
the presence of chrome yellow in automotive paint by Raman
spectroscopy.[6] In addition, some interesting Raman work
has been reported on the effect of temperature and humidity
on the chromatic profile of sacral wall paintings, which
involved the artificial (accelerated) aging of 17 pigments,
including chrome yellow.[7] In the aging process, the pigments
were heated at 90 C at 60% humidity for 7 days in a climatic
chamber. In most cases, there was no difference in color of
both the untreated and the aged samples indicating the great
stability of the pigments. The photo-ageing behavior of
chrome yellow on filter papers has been examined in air,
airtight enclosures, and anoxic conditions using UV light.[8]
None of the conditions applied had any effect on the fading
process of chrome yellow.
Maya Blue is the famous azure-colored pigment that
dates back to pre-Columbian Mesoamerica times, that is,
before the arrival of Christopher Columbus in the American
continent.[9] It was used by the ancient Mayans for designs
on pottery, sculptures, and murals and even in ritual human
sacrifices. It has been suggested that objects and human
 Micro-Raman Spectra of Synthetic Artists’ Pigments
sacrifices were painted with the pigment prior to being
thrown into a well at Chichén Itzá in Mexico in an attempt
to ensure rain would return to the area after the dry sea-
son.[10] Maya Blue pigment is resistant to acids, alkalis, sol-
vents, oxidants, reducing agents, moderate heat, and
biocorrosion. The remarkable durability of this vivid blue
pigment has long fascinated scientists and the recipe for its
preparation appears to have been finally deciphered by a
research group at the University of Valencia in Spain.[11,12]
These researchers also succeeded in detecting a small amount
of dehydroindigo (C16H8N2O2), which is yellow, together
with blue indigo (C16H10N2O2) and palygorskite clay
[(Mg,Al)2Si4O10(OH)  4H2O] in authentic Maya Blue sam-
ples. Dehydroindigo was most probably formed by oxidation
of indigo during heating in the manufacture of the Maya Blue
pigment, and its presence apparently contributes to the stab-
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ility of the pigment whereby the dye molecules are trapped in
clay channels. Some of earlier work on the Raman spectra of
Maya Blue comes in part from the same researchers in
Spain[13] who, by using chemometric analyses of normalized
spectra, have reevaluated the Raman literature for indigo,
genuine Maya Blue samples and model specimens obtained
by binding indigo to clays, such as palygorskite and sepiolite
[Mg4Si6O15(OH)2  6H2O]. The latest paper on Maya Blue
describes a vibrational investigation of the indigo–palygorsite
association(s) in a synthetic material.[14] In this study, some
Raman measurements were made as a function of tempera-
ture (130–300 C), using 488.5-nm laser excitation, on a syn-
thetic Maya Blue sample containing 10% indigo. Significant
changes were noted, which involved broadening and shifting
of all the Raman peaks. In addition, new peaks were
observed at 1417, 1138, and 1180 cm1. A structural trans-
formation apparently occurs just above 130 C, which
becomes quantitative at 220 C and the resulting product
is stable up to 300 C. The transformation is fully reversible
upon cooling to ambient temperature in a closed cell, but it
is irreversible if performed under a flow of dry N2. The
authors also pointed out that the transformation was less evi-
dent when using 785 nm laser excitation, strongly suggesting
that a resonance Raman effect plays an important role.
In our own Raman work, using both 514.5- and 785-nm
laser excitation, on synthetic samples of chrome yellow and
Maya Blue, which was being performed at about the same
time as some of that described above, we investigated the
effects of dramatic changes in temperature on these two pig-
ments and report the results here.[15] This study was actually
originally conceived as an undergraduate research project
and is a continuation of a broad examination of the
vibrational spectra of artists’ pigments often under extreme
conditions of temperature and pressure.[16–21]
557
Experimental
Chrome yellow (PbCrO4) was synthesized by combining
aqueous solutions of K2Cr2O7 (0.51 g) and Pb(NO3)2 (0.46 g).
The solution turned red due to the formation of the CrO3
side product, which is soluble in water. The reaction involved
is Pb(NO3)2 þ K2Cr2O7 ! PbCrO4 þ 2KNO3 þ CrO3. The
PbCrO4 pigment that precipitated from the mixture as a micro-
crystalline powder was filtered off by vacuum filtration,
washed four times with cold water and dried in air. Synthetic
Maya Blue (2 wt%) was produced mechanochemically in the
complete absence of solvent from 0.1450 g of sepiolite
clay [Mg4Si6O15(OH)2  6H2O)] and 0.0030 g of indigo
(C16H10N2O2) from Aldrich Chemical Co. (Oakville, Ontario,
Canada). A Retsch MM 400 mixer mill operating at 29.5 Hz
for 30 min was used for the mechanochemical synthesis.
Variable-temperature Raman spectra (five accumulations;
exposure time, 5 s) were recorded on an inVia Renishaw
(Wotton-under-Edge, Gloucestershire, UK) microscope system
using a 514.5-nm argon-ion laser (16 mW, 5% maximum power)
or a 785-nm near-IR laser (500 mW, 20% maximum power
level), a long working length 50 =0.75 objective and a Linkham
(Tadworth, Surrey, UK) model THMS600 thermal stage fitted
with a quartz window. Increasing and decreasing temperature
measurements were made in the range of 150–600 C, usually
at 50 C intervals. The powdered samples were allowed to equi-
librate for 1 min at each temperature before recording the
Raman spectra. Different gratings were used for the two lasers:
2400 grooves=mm (514.5 nm) and 1200 grooves=mm (785 nm).
The spectral data were obtained and manipulated using the
Renishaw wiRe2 proprietary software, and the peak positions
are considered to be accurate to at least 1 cm1.
Results and Discussion
Representative micro-Raman spectra of powdered synthetic
chrome yellow (PbCrO4) at selected temperatures ranging
Fig. 1. Micro-Raman spectra of chrome yellow at selected
temperatures between 150 C and 600 C (785-nm NIR laser
excitation).
 558 J. W. Riddle et al.

from 150 C to 500 C are illustrated in Fig. 1. At 25.1 C,

chrome yellow has a strong peak at 840 cm1 that is assigned
to the n 1 symmetric stretching of the chromate [CrO4]2
ion,[5] with two shoulders indicating overlapping peaks. At
lower temperatures, one of these shoulders becomes clearly
resolved as a second peak located at 856 cm1. The quartet
consisting of peaks at 337, 357, 376, and 399 cm1 is the
result of D2h symmetry correlation-field splitting for the n 2
and n 4 modes of the [CrO4]2 ion similar to that reported
earlier for K2CrO4[22–24] and KMnO4.[25] Above 50 C, the
two groups of peaks exhibit substantial broadening,[26] poss-
ibly indicating the onset of amorphization of the crystal.
This broadening effect is, however, completely reversible
upon cooling. In some cases, such peak broadening has been
attributed to quantum confinement effects as crystals shrink
with increasing temperature (e.g., porous silicon[27]) and
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compressive stress effects (e.g., bismuth thin films[28]). By Fig. 2. Comparison of micro-Raman spectra of indigo and
analogy with the FT-Raman data reported for solid Maya blue (2 wt% indigo–sepiolite) at room temperature
K2CrO4 at 196 C and KMnO4 at 223 C, the proposed (514.5-nm Ar-ion laser excitation).

assignments shown in Table 1 can be made for the peaks

Table 1. Comparison of the Raman spectra (cm1) of samples of observed in our Raman spectra of chrome yellow.
chrome yellow (PbCrO4), K2CrO4 and KMnO4 and proposed The ambient Raman spectra of indigo and our synthetic
vibrational assignments. Maya blue are shown in Fig. 2. The Maya blue spectrum
Chrome has been baseline corrected to remove background fluores-
yellow K2CrO4a K2CrO4b KMnO4c Vib. assign.d cence from the sepiolite clay framework, and the peaks that
are visible in the Maya blue spectrum are due to the defor-
mation of the indigo within the sepiolite framework. The
901 925 gv3þ (ag þb2g) characteristic peak of indigo in the Maya blue pigment at
g 1633 cm1 has increased in intensity, as has the peak at
905 1490 cm1, while the peak at 1380 cm1 has developed a
884 920 gn 3 (ag þb1g þb2g shoulder. These subtle changes in the spectra, when indigo
g þb3g) is encapsulated in the sepiolite clay framework (i.e., in the
881 Maya blue pigment itself) are consistent with previous
877 results published by Sánchez del Rı́o et al.[29] It should be
868 911 n 3 (ag) mentioned that we found no evidence of dehydroindigio in
856 852 856 850 gn 1 (ag þb2g) our Raman spectra, presumably because of the different
g conditions employed in the synthesis of our model Maya
840
399 398 395 408 gn 4 (ag þb2g)
g
397
393 404 n 4 (b3g)
388 388 402 n 4 (b1g)
376 387 389 n 4 (b2g)
352 350 356 gn 2 (b2g þb3g)
g
351
337 348 346 352 gn 2 (ag þb1g)
g
347
a
This work at  150 C using 785-nm NIR laser excitation.
b
From single-crystal Raman measurements at room temperature reported in
ref. [24].
c
From FT-Raman results at 196 C given in ref. [22] (1046-nm NIR laser
excitation).
From FT-Raman results at 223 C given in ref. [23] (1046-nm NIR laser
excitation).
d
These assignments are based on those for the D2h factor group symmetry of Fig. 3. Micro-Raman spectra of Maya blue at selected tem-
K2CrO4 and KMnO4 given in refs. [22] and [25] for the four fundamentals of peratures between 27 C and 200 C (514.5-nm Ar-ion laser
the tetrahedral (Td symmetry) [CrO4]2–and [MnO4]– ions, respectively. excitation).
 Micro-Raman Spectra of Synthetic Artists’ Pigments
blue sample. In addition, the differences between the beha-
vior of the indigo–sepiolite and indigo–palygorskite Maya
blue samples with increasing temperature may reflect the fact
that sepiolite stabilizes the indigo molecules more effectively
than does palygorskite. This is most probably due to the
greater penetration of the indigo molecules into the larger
channels present in sepiolite than those in palygorskite.[30]
With increasing temperatures, ranging from 27 C to
200 C, the micro-Raman spectra of Maya blue shown in
Fig. 3 were obtained. At the higher temperatures, the fluor-
escence from the sepiolite clay becomes overwhelming and
the peaks could no longer be discerned after baseline
correction. No significant changes in the peak positions or
their broadness were seen throughout the temperature range
investigated.
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Conclusions
On the basis of their micro-Raman spectra, the two artists’
pigments, chrome yellow and Maya blue, have been shown
to be remarkably stable with respect to significant changes
in temperature from 150 C to 600 C for chrome yellow
and from around 25 C to 200 C for Maya blue. In addition,
there is no evidence of any structural phase changes in either
case throughout the temperature ranges investigated. Inter-
estingly, most of the pigments for which we have examined
their micro-Raman spectra at different temperatures and
pressures are remarkably stable[20] in line with their contin-
ued long-term usage by artists over the years. One area that
does remain to be examined more thoroughly is the
combined effect of higher temperatures and humidity of
the pigments following the initial work of Raskovska
et al.[7] on quite a wide range of artists’ pigments.
Funding
J.W.R. and E.J.H. gratefully acknowledge undergraduate
research assistantships during the Summer of 2012 from a
NSERC (Canada) Discovery grant (I.S.B.). In addition,
E.J.H. thanks the Inorganic Chemistry Exchange (ICE) pro-
gram in Canada for the award of a scholarship.
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