Characterization of Mural Paintings From Cacaxtla

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J O U R N A L O F M A T E R I A L S S C I E N C E 3 6 (2 0 0 1 ) 2227 – 2236

Characterization of mural paintings from Cacaxtla

M. ORTEGA-AVIL É S, C. M. SAN-GERM ÁN, D. MENDOZA-ANAYA


Instituto Nacional de Investigaciones Nucleares Amsterdam 46-202,
Hipódromo Condesa. 06100 México, D.F. México
E-mail: [email protected]
D. MORALES
Complejo Arqueológico Cacaxtla-Xochitecatl, Tlaxcala, INAH
M. JOS É -YACAM ÁN
Instituto Nacional de Investigaciones Nucleares Amsterdam 46-202, Hipódromo Condesa.
06100 México, D.F. México; Instituto de Fı́sica, Universidad Nacional Autónoma de México,
Apdo. Postal 20-363, Delegación Alvaro Obregón, 01000 México, D.F., México

One of the most remarked customs of ancient mesoamerican cultures was that of record
historical events by painting murals. It was used a rich variety of colours which is still
visible in some mesoamerican buildings. In this work is reported the analysis by SEM, TEM,
XRD, and FTIR, of the materials used to produce mural paintings of the archaeological zone
of Cacaxtla México. The results show needle-like fibers, granular aggregates and large
crystalline areas. The elemental analysis reveal a substantial concentration of O, Ca and C,
followed by Si, Mg, Al, Fe, and K in lower concentration. It was found the main component
in the substrate is calcite. It is also relevant the presence of palygorskite in blue and green
pigments, hematite in red and pink, and calcite in white. It was also possible to identify long
fibers of palygorskite on whose surface there were observed nanoparticles of metallic
oxides attached. ° C 2001 Kluwer Academic Publishers

1. Introduction eral architectural phases; each one elaborated with a


The microstructural analysis performed in archaeolog- great variety of colors [6].
ical studies of pottery, paintings, stuccos and sculptures Electron Microscopy Techniques have gained impor-
provides essential information about the origin of mate- tance in the study and analysis of archaeological mate-
rials used by ancient cultures, and give information on rials and art objects [7, 8]. These techniques have being
their technological development [1–3]. In addition, ar- used to obtain important data about colored materials
chaeological materials normally suffer detriment due to [8–10]. In order to support experimental electron mi-
environmental, biological agents and internal mechan- croscopy results, simulation studies were performed too
ical stresses. It is necessary to understand the physico- [14, 15].
chemical properties of the archaeological materials, in The pigments characterization was performed us-
order to avoid co-lateral effects after the application of ing different analytical techniques such as Scan-
any restoration method [3, 4]. ning Electron Microscopy (SEM), Transmission Elec-
This work presents the results obtained from several tron Microscopy (TEM), Fourier Transform Infrared
samples of mural paintings from the Cacaxtla archaeo- Spectroscopy (FTIR), and X-Ray Diffraction (XRD)
logical site located in Tlaxcala, Mexico. This important [12–14]. A comparison of the structural and chemical
site was occupied by Olmeca-Xicalanca culture during composition among different paintings is included, try-
the Epiclassic period from 700 a.c. to 900 a.c. [5, 6]. ing to establish the origin of the colors.
Distinct cultures like Mayan, Teotihuacans and Olmecs
gave a direct influence. Such influence can be observed
in their buildings, pictorial representations, pottery, and 2. Experimental methods
sculptures. Samples were collected directly in the archaeological
The archaeological site of Cacaxtla has several build- site. Small fragments of paintings, each one of differ-
ings that were decorated with mural paintings, in which, ent color, were selected. In particular blue, red, pink,
war scenes, rulers and warriors such as “eagle and ochre, brown, white and green samples were studied.
jaguar knights” can be observed. Several colors includ- Microstructural analysis was carried out with a Scan-
ing red, blue, ochre, black, brown, white and green were ning Electron Microscope, Phillips XL30 (SEM) fitted
used to perform the murals. Their principal building with an (EDAX) Energy X-ray Dispersive Spectrom-
named The Great Basement, discovered on the 70’s, eter (EDS). The morphology was observed in sec-
was decorated with mural paintings associated to sev- ondary electrons mode and by mixing secondary and

0022–2461 °
C 2001 Kluwer Academic Publishers 2227
backscattered electrons. The beam energy was varied in the thinnest layer. Ca, C and O are distributed uni-
from 10 to 25 KeV. formly in the stucco layer (second layer). Particles with
TEM analysis was performed in a Jeol-2010 micro- high silicon concentration can be seen in different areas
scope with a point resolution of 2.3 Å and with a Jeol corresponding to quartz crystals.
4000-EX with a maximum point resolution of 1.7 Å. SEM analysis of blue pigment showed the pres-
Samples were prepared by removing a small fraction ence of fiber-like structures. These fibers are associ-
of the pigment from the stuccoes. This material was ated to palygorskite clay [16]. In some cases, it can
ground to get a fine powder. The internal structure was be observed clusters of short fibers (Fig. 2a). These
analyzed by using atomic resolution images. fibers have a diameter range from 140 to 200 nm and
A Siemens D-5000 X-ray diffractometer was used to 1.2 µm to 2.8 µm of length (Fig. 2b). It is possi-
identify crystalline phases. The samples were scanned ble to conclude that the artist following the direction
from 5◦ to 70◦ in 2θ degrees, with 0.02◦ intervals at of the fibers applied the paint. The elemental EDS
30 KeV and 25 mA. Finally the identification of organic analysis shows the existence mainly of O, C, Ca, Si,
and inorganic functional groups was done by Fourier Al, Mg, Fe, and K. XRD spectra indicate the pres-
Transform Infrared Spectroscopy (FTIR) with a Nico- ence of two crystalline phases: CaCO3 (calcite) and
lete Magna-IR 550 equipment, the scan was performed ((Mg,Al)2 Si4 O10 (OH)4 H2 O) (palygorskite). High Res-
from 400 to 4000 cm−1 . olution Electron Microscopy (HREM) showed the fiber
lattice planes, as shown in Fig. 3. Planes correspond to
the (110) palygorskite planes (10.036 Å). A few fibers
correspond to sepiolite rather than palygorskite. Be-
3. Experimental results sides, there were observed some nanoparticles in con-
Cross sections studies of the samples showed that the tact with the fiber surface, which correspond to metallic
thinnest paint layer is around 5–10 µm, the stucco layer oxides of Fe, Al and Sn silicates. It is remarkable that the
is between 500 µm and 2.0 mm and the coarse plaster is paint contains palygorskite, which is the main compo-
near to 1.0 cm. Sometimes there is more than one paint nent of the sakalum mineral, which comes from some
layer in pigment samples. A general view of a sam- regions of southern Mexico. It was used in the maya
ple is shown in Fig. 1a. Which corresponds to a green blue pigment elaboration [17, 18, 19], which is very
pigment. The grain size difference among three strati- resistant to the environmental conditions, acid concen-
graphic layers is evident. Some of the elements present trated solutions and bacterian action [9].
were mapped in cross section as shown in Fig. 1b. A In the case of the Red pigment SEM images show
major concentration of Fe, Mg, Si and O was found granular aggregates sizing between 350 nm and 850 nm;

(a)

Figure 1 a) Cross section SEM image of a typical paint showing the different component plaster, stucco and pigment. b) Elemental mapping of the
cross section of a typical paint; the Fe, Si, Mg, Ca, and C are observed. (Continued)

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(b)

Figure 1 (Continued).

these structures are uniformly distributed. According Sr, which also could contribute to this color, as a com-
to EDS analysis, these paintings are mainly constituted ponent of CaCO3 . This hypothesis agrees with XRD
by C, O, Si, Fe, Ca, Al, Mg, and K. The red pigments results. A typical electron micrograph of this paint can
showed an important amount of iron ∼19% (atomic per- be seen in Fig. 5.
cent). XRD analysis showed that α-Fe2 O3 (hematite) The ochre painting morphology is characterized by
was the main crystalline phase in the red pigment. Cal- a compact surface constituted by flake-like particles of
cite was present in the stucco. Opaque iron nanoparti- 5 to 20 µm and massive granular particles. Two dis-
cles were found by TEM (Fig. 4). EDS analysis indicate tinct kinds of agglomerates were found; the first one
the presence of Fe and O and minor amounts of C, Si and is around 16 µm in diameter formed by particles of
Al. The atomic ratio between Fe and O, which is 2 : 3, 600 nm approximately (Fig. 6a). The second ones are
confirms that this particle correspond to the hematite compact agglomerates in a range size from 30 nm to
crystalline phase (α-Fe2 O3 ). This phase is a very stable 3 µm. The sample presents small areas with fiber like
mineral obtained from dehydration of hydrated iron ox- structures, similar to the observed in the blue paint layer.
ides such as limonite (hydrous Fe oxides), lepidocrocite The observed fibers in the ochre paint correspond to a
(FeO(OH)), and goethite (FeO(OH)). blue paint layer, and the ochre paint was applied over the
A physical mixture of α-Fe2 O3 and CaCO3 was blue paint layer. We found long fibers, grouped in bun-
found in the pink pigment. SEM images agglomerates dles of 3 µm to 5 µm in length (Fig. 6b). The elemen-
of α-Fe2 O3 , CaCO3 , and quartz crystals. By EDS, it tal composition in ochre painting is mainly conformed
was possible the identification of a low percentage of by C, O, Si, Ca and Fe; however, Al, and Mg were

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Figure 2 SEM images from palygorskite fibers observed in blue pigments, a) section shows short size clustered fiber. b) Section showing clustered
fibers.

Figure 3 High Resolution TEM image of a palygorskite fiber which also contains a α-Fe2 O3 particle. The fiber shows a d = 10.036 Å interplanar
distance corresponding to (1 1 0) planes of palygorskite.

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Figure 4 Bright field TEM image the inset shows the electron diffraction pattern of α-Fe2 O3 (hematite). The zone axis is h2̄4 2̄3i.

Figure 5 SEM image from pink pigment shows hematite crystals and agglomerates from calcite, which form this pigment.

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Figure 6 SEM image from ochre pigment. a) Agglomerates of calcite. b) Fibers of palygorskite forming bundles.

also identified in fewer proportions. In this pigment, the crystalline phases present in the brown pigment.
we also found the crystalline phases CaCO3 , SiO2 , It is important to mention that all these compounds
CaMg(CO3 )2 and NaAlSi3 O8 . There were identified could turn into a brownish color by the presence
nanoparticles with high concentration of Ca and some of impurities or by cationic exchange [9]. The in-
silicates by electron diffraction in TEM. Bands in the frared spectrum is shown in Fig. 7, could be identi-
infrared spectrum corresponding to calcite, quartz and fied typical bands corresponding to calcite, quartz and
H2 O molecules were identified by FTIR (Fig. 7). It was H2 O molecules. Some bands are associated to organic
also possible to appreciate some bands associated to or- compounds, as the band at 1798 cm−1 correspond-
ganic compounds, such as the band at 1798 cm−1 which ing to aromatic compounds, bands at 2920 cm−1 and
corresponds to aromatic rings; the bands at 2920 cm−1 2852 cm−1 belong to CH2 groups, also we could ob-
and 2852 cm−1 belong to CH2 groups; it is interesting serve that the infrared spectrums of white and ochre
to notice that the absorption band at 1728 cm−1 which pigments are very similar, a small difference in bands
corresponds to C=O bond, appears only in the ochre intensity is observable and we can observe a little
pigment. shift towards a short wave numbers respect to ochre
Needle-like fibers were observed in Green pigment spectrum.
with diameters smaller than 150 nm and 3 µm of length, White pigment shows a morphology of compact ag-
very similar to those observed in the blue painting glomerates made by granular particles (Fig. 10), EDS
(Fig. 8a). Moreover, it was observed agglomerates of analysis shows large amounts of Ca, C, and O. XRD
particles with in a diameter range of 200 nm to 600 nm, analysis showed the CaCO3 , SiO2 and NaAlSi3 O8
which are distributed uniformly above the entire surface as crystalline phases. FTIR presents typical bands
(Fig. 8b). In all cases it can be observed agglomerates of corresponding to CO3 groups, Si-O bonds and H2 O
fibers with a diameter of 30 µm approximately, form- molecules were identified. It was possible to appreciate
ing a large grain. According to the EDS analysis, those some bands associated to organic compounds, like the
agglomerates of particles present O, Ca, C, and in lesser band at 1798 cm−1 belonging to aromatic overtones,
proportion Si; in the fibers area C, O, Si, Ca, Mg, Al, 2920 cm−1 and 2852 cm−1 correspond to CH2 groups
Fe, and K were identified. In this particular case, it was as shown in Fig. 7. In Fig. 11, we report the observed
not possible to use other characterization techniques, variation in atomic percent of some typical elements
due to the small amount of sample (this color was the (Mg, Al, Si, Ca, Fe) from minerals, found in different
less frequently used). samples.
Brown pigment morphology is constituted mainly In Table I we present a summary of the elemental
by a large amount of granular particles with a size composition in atomic percent of the analyzed paint-
∼170 nm, these particles form aggregates of 1.2 µm ings, while Table II is a summary of the crystalline
in diameter as shown in Fig. 9. All these particles are phases identified in the samples. Furthermore, it is in-
supported on a flat surface. Elements like C, O, Ca, Si, teresting to notice the presence of the needle-like fibers
Al, Mg, Fe, K, and P were identified by EDS analysis associated to palygorskite clay in other pigments, such
as main components. Calcite (Ca CO3 ), quartz (SiO2 ), as green and ochre. In a previous work [19] about
dolomite (CaMg(CO3 )2 ), and albite (NaAlSi3 O8 ) are Maya paintings, it was reported that the palygorskite

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Figure 7 FTIR spectrums of ochre, brown and white pigments, show characteristic bands from calcite, C=O groups, CH2 groups and overtones from
aromatic compounds.

Figure 8 Micrograph of green paint, a) region containing fibers in non agglomerated state. b) Region shown agglomerates of little crystals.

fibers were found in blue pigments. In the present work from a mural (known as The warriors battle) which
we found that this colorant is also observed in green had a previous layer of blue pigment. Therefore, it is
and ochre pigments. Palygorskite was also found in the possible that the palygorskite fibers observed in the
green pigment from Maya sites, but not in the ochre, sample were the result of contamination from the blue
and this is because used samples of ochre pigment came layer.

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Figure 9 Low vacuum SEM image from brown pigment, we can observe agglomerates with porous appearance, similar to calcite in ochre and white
pigments.

Figure 10 Low vacuum SEM micrograph from white pigment constituted by calcite mainly.

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Figure 11 Variation on the atomic percent of some elements identified in the samples of different color.

4. Discussion and conclusions do not bleach out in fresco technique. XRD results in-
According to the SEM and TEM results, fibrous and dicate that the plaster was made using feldspars rich
granular shapes with nanometric size are the dom- in Sodium, calcite and quartz. HREM results of ochre
inant structures in the blue paintings, while gran- pigments indicate that the main particles are rich in
ular agglomerates are present in red, pink, brown, calcium, in its carbonate form. It was possible to iden-
white, and ochre paintings. CaCO3 , SiO2 , NaAlSi3 O8 tify opaque particles of iron oxide in the red pigment
and (Ca, Na)(Si, Al)4 O8 are the main components and calcium particles too. The metallic nanoparticles
of the samples that could be associated to the sub- play an important roll in the materials color, some of
strates or stuccoes; other crystalline phases such as these particles such as iron and aluminum oxides could
(Mg8 (H2 O)4 (OH)4 Si12 O30 , αFe2 O3 and CaMg(CO3 )2 be identified and characterized by HREM. On the other
were identified, the last mineral is associated to paly- hand, traces of elements identified by EDS, such as Bar-
gorskite growths in nature. Palygorskite was also asso- ium in the structure of calcite could be turned to pink,
ciated to blue and green pigments, while hematite was and iron could be turned to yellow or brown according
associated to red pigment. Dolomite, calcite, and albite to the literature. These elements are in the crystalline
were associated with ochre painting. structure by cationic exchange with other minerals.
Atomic percent variation of some elements showed FTIR analysis provides evidence of organic com-
that Mg, and Al have a linear tendency as it can be pounds in the paintings. In the range of 1500–
observed in Fig. 11; their percentage is between 0.5 and 2700 cm−1 of the IR spectrum, there are not
3% (atomic percent). Green and blue pigments have the characteristic bands from minerals. Therefore, bands
highest amounts of Mg and Al, due to the palygorskite which correspond to organic functional groups, such as
structure (octahedral site). Red pigment contains the 1798 cm−1 band (aromatic compounds); 2920 cm−1
largest percentage of Fe, followed by the brown, ochre, and 2852 cm−1 (CH2 groups); absorption band at
green, pink, and blue pigments. Silicon has a similar 1728 cm−1 which belongs to C=O bond. The last one
tendency as the iron variation, except for the brown appears only in the ochre pigment, and all these bands
pigment, and all the samples contain around of 15% must belong to vegetable gums used as binder in pig-
(atomic percent) of Ca. The lowest amount of calcium ment applications over the wall.
was found in ochre and brown pigments. The Olmeca-Xicalanca culture used a technique for
Calcite was used as a substrate for the pigments, this elaborating their wall paintings similar to the Maya
is an indicative of the painting technique used, in this technique. The blue pigment is like the maya blue paint
case it was fresco or a mixed technique of fresco and used by the Maya culture and the green pigment is also
tempera. Calcite mineral was used to have better ad- like the maya green, which was elaborated using paly-
hesion between the pigment and the substrate. A curi- gorskite may be maya blue combined with any ochre
ous fact is that plaster has a high alkali concentration, pigment to obtain green color. This last pigment is a
which has a tendency to bleach out pigments. How- physical mixture of two pigments: blue and ochre. SEM
ever, the mineral pigments identified in the samples confirmed this fact.

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Colorant materials are basically minerals with the 5. M . F O N C E R R A D A D E M O L I N A , “Cacaxtla La Iconografı́a
exception of the blue paint, which is a combination of a de los Olmeca-Xicalanca” (UNAM, 1983).
6. K . D . M A G A L O N I , “Metodologı́a para el análisis de la
palygorskite matrix and indigo dye, in maya blue FTIR
técnica pictórica mural prehispánica: El templo rojo de Cacaxtla”
spectrum was possible to identify characteristic bands (Colección cientı́fica INAH, 1994).
of the mineral clay palygorskite. A curious fact is that 7. M . S . T I T E , “Methods of Physical Examination in Archaeology”
was not possible to separate the indigo dye and the clay (Seminar Press, London and New York, 1972).
as was claimed by Cabrera [19]. To our knowledge no 8. M . J O S É - Y A C A M Á N , L . R E N D Ó N , J . A R E N A S and M . C .
S E R R A P U C H E , Science 273 (1996) 223.
other group has also reproduced the Cabrera Claim.
9. D . MENDOZA-ANAYA, V. R O D R ı́ G U E Z - L U G O ,
It should be concluded that the technology used by G . M A R T ı́ N E Z - C O R N E J O and M . J O S É - Y A C A M A N , in
the Olmeca-Xicalanca culture in their paintings was Proceedings of the ICEM 14 (Cancun, Mexico, 1998) Vol. 3, p. 253.
totally equivalent to the Maya culture. This suggests a 10. V . R O D R Í G U E Z - L U G O , L . O R T Í Z - V E L Á Z Q U E Z ,
very strong contact between these two cultures. In fact J . M I R A N D A , M . O R T Í Z - R O J A S and V . M . C A S T A Ñ O ,
Journal of Radionalitical and Nuclear Chemistry 240 (1999) No. 2.
the dating of the paints suggest that the maya blue was
11. M . J . W I L S O N , “Clay Mineralogy” (Chapman & Hall, 1980).
developed in a larger region of Mesoamerica. There- 12. P . K . H A R O L D and L . E . A L E X A N D E R , “X-Ray Diffrac-
fore, the original description of the blue colorant as tion Procedures for Polycrystalline and Amorphous Materials” (John
maya blue might not be totally correct. Wiley and Sons, 1974).
13. D . M . M O O R E and R . C . R E Y N O L D S , J R . , “X-Ray Diffrac-
tion and the Identification and Analysis of Clay Minerals” (Oxford
University Press, 1997).
Acknowledgements 14. M . M E N D O Z A S E R R A N O , Master Thesis, “Procesamiento dig-
The authors are indebted to L. Rendón, S. Tehuacanero ital de Imagnes y vision aplicado a materiales nanoestructurados”
and T. Santamaria for technical support. This work was (ININ-ITT, 1999).
supported by CONACYT through the grant “Coloides 15. M . O R T E G A , J . A . A S C E N C I O , C . M . S A N - G E R M A N ,
M . E . F E R N A N D E Z , L . L O P E Z - L U J A N and M . J O S E -
Cuánticos,” puntos cuánticos y nanopartı́culas. We
Y A C A M A N , J. Mater. Sci., in press.
thank The “Consejo de Arqueologı́a del INAH” for per- 16. M . E . F E R N Á N D E Z , J . A . A S C E N C I O , D . M E N D O Z A -
mission to the study of pigments from Cacaxtla archae- A N A Y A , D . V . R O D R ı́ G U E Z - L U G O and M . J O S É -
ological site. Y A C A M Á N , ibid. (1999).
17. M . J O S É - Y A C A M Á N , L . R E N D Ó N and M . C . S E R R A
P U C H E , in Proceedings of the Material Research Society Sym-
posium (1995) Vol. 352, p. 3.
References 18. L . T O R R E S - M O N T E S , in Proceedings of the Material Research
1. R . G I O V A N O L I , Archaeometry 11 (1969) 53. Society Symposium (1998) Vol. 123, p. 123.
2. K . D . M A G A L O N I , M . A G U I L A R and V . C A S T A Ñ O , Pro- 19. J . M . C A B R E R A G A R R I D O , “Informes y Trabajos del Instituto
ceedings of the Material Research Society Symposium 185 (1991) de Conservación y Restauración de Obras de Arte, Arqueologı́a y
145. Etnologı́a” (Artes Gráficas Soler, 1969) Vol. 8, p. 1.
3. M . J O S É - Y A C A M Á N and J . A . A S C E N C I O , “Modern Meth-
ods In Art And Archeology” (John Wiley and Sons, 1999).
4. M . A . F E R R E R , “La pintura mural, su soporte, conservación,
restauración y las técnicas modernas” (Universidad de Sevilla, Received 11 April
1995). and accepted 15 September 2000

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