Journal of Molecular Structure 1028 (2012) 16–21

Contents lists available at SciVerse ScienceDirect

Journal of Molecular Structure

journal homepage: www.elsevier.com/locate/molstruc

FT-IR spectroscopy, scanning electron microscopy and porosity measurements

to determine the firing temperature of ancient megalithic period potteries
excavated at Adichanallur in Tamilnadu, South India
G. Velraj a,⇑, R. Ramya a, R. Hemamalini b
a
Department of Physics, Periyar University, Salem 636 011, Tamilnadu, India
b
Department of Physics, Sri Saradha College for Women, Salem 636 016, Tamilnadu, India

h i g h l i g h t s

" We examine archaeological samples for firing temperature.

" Lower limit of firing temperature obtained from FT-IR results.
" Upper limit identified by porosity measurements.
" The ranges of firing temperature narrow down by SEM technique.
" Influence of iron oxides in the sites and artisans technology was exposed.

a r t i c l e i n f o a b s t r a c t

Article history: Scientific examination of archaeological pottery mainly aims to determine the style of production and the
Received 13 April 2012 techniques involved in its manufacture. Technological characterization includes the evaluation of the ori-
Received in revised form 12 June 2012 ginal firing conditions. Maximum firing temperatures may be evaluated by firing clays of compositions
Accepted 12 June 2012
similar to those used for the production of the ancient objects. In the present work, some of the ancient
Available online 19 June 2012
pottery samples were collected from recently excavated site at Adichanallur, Tirunelveli District, Tamiln-
adu, India to estimate the firing temperature of the pottery samples and atmosphere prevailed at the time
Keywords:
of manufacturing those potteries by the ancient artisans. From the Fourier transform infrared spectra of
Archaeological pottery
FT-IR
the samples the lower limit of firing temperature have been determined. The upper limit of firing tem-
Porosimetry perature was evaluated by porosimetry method. The scanning electron microscopic analysis is used to
SEM narrow down the range of firing temperature and the results are consistent with the results obtained
from FT-IR spectroscopic study and porosimetry method.
Ó 2012 Elsevier B.V. All rights reserved.

1. Introduction favorable preservation conditions in the soil or atmosphere. For

Archaeology studies the story of man’s past through his material
remains. It is essentially a method of reconstructing the past from
the surviving traces of former societies. Archaeologists concentrate
their studies on past societies and changes in those societies over ex-
tremely long periods of time. They store the information about the
human past as the archaeological record. The archaeological record
encompasses every area of the world that has been occupied by hu-
mans, as well as of the material remains contained in those areas [1].
Many of the objects left behind by the human societies are not
present in the archaeological record because they have been disin-
tegrated over time. The material remains that still exist after hun-
dreds, thousands or millions of years have survived because of
the most past, potteries are the only things that survive which
are durable items [2].
Clays form the basic material for making bricks and potteries.
Knowledge of the structure of clay mineral goes on a long way in
characterizing quality of such materials. Of the various methods
of analysis, spectroscopic techniques are found to be a potential
tool in investigating the structure of clay minerals. The production
processes of ancient ceramics can be derived jointly with the
changes in the manufacturing techniques. In this respect, firing
temperature, duration of firing and firing atmosphere are impor-
tant factors that help in understanding the transformations [3].
1.1. Adichanallur [8°370 47.600 N; 77°520 34.900 E]

⇑ Corresponding author. Tel.: +91 427 2345766x303; fax: +91 427 2345124. Adichanallur is situated on the right bank of the river Tamirapa-
E-mail address: gvelraj@yahoo.co.uk (G. Velraj). rani which is 24 km from Tirunelveli town in Tamilnadu and about

0022-2860/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.molstruc.2012.06.026
 G. Velraj et al. / Journal of Molecular Structure 1028 (2012) 16–21
680 km from south of Chennai. The burial site is adjacent to a lake
on a huge mound on the southern bank of Tamiraparani. Archaeo-
logical Survey of India (ASI) carried out the excavation at this site.
At the time of excavation, the artifacts discovered are hundreds of
pot shreds with beautiful designs, iron knifes and some organic
materials such as bones, wood or charcoal, with this a piece of
writing has been discovered inside an urn. The urn has a human
skeleton in it along with miniature pots. The script was inscribed
inside the urn after it was baked. The archaeologists discovered
that the script is in ‘‘Tamil Brahmi’’. The term ‘‘Tamil Brahmi’’ is
used when the script is in Brahmi but the language is Tamil. The
Brahmi script was predominantly used from the Mauryan (Asokan)
period.
The Jain and Buddhist monks during the past Asokan period
brought the Brahmi script to the Tamil country in the third century
B.C. The pottery found near the urns date back to the megalithic
period of 1000 B.C. Their date could be fixed using carbon dating
method. In megalithic period (1000B.C–300B.C) man started using
iron for making tools and weapons, unlike in north India, the Iron
Age culture in South India is marked by megalithic burial sites,
which are found in several hundreds of places.
On the basis of some excavations and on the basis of the typol-
ogy monuments, it has been suggested that there was a gradual
spread of the Iron Age sites from the north to south. The megalithic
burials are so called due to their construction using large sized
stones, natural boulders or quarried slabs. The earliest clear evi-
dence of the presence of the megalithic urn burials are those dating
from around 1000B.C, which have been discovered at various
places in Tamilnadu, notably at Adichanallur. The colour photo-
graph of the samples is given in Plate. 3.1.
In this present study some of the scientific techniques on the
samples will tell us the firing methods adopted and firing temper-
ature achieved by the artisans at the time of manufacture.
2. Materials and methods
The potteries from Archaeological site Adichanallur were exam-
ined using FT-IR, Porosimetry and SEM with a view to acquire
information on the techniques employed on the samples to fire
them and to estimate the firing temperature. A good number of
samples were collected from different depths at the recently exca-
vated archaeological site Adichanallur, and the samples were taken
for present study was only dissimilar samples and are named as
ADR 1, ADR 2, ADR 3, ADR 4 and ADR 5.
Plate 3.1. Pottery samples of Adichanallur (ADR).
17
2.1. Fourier transform-infrared spectrometer
The Infrared spectra of the pottery samples were recorded in
the mid region 4000–400 cm1 using Perkin-Elmer Spectrometer
with the ±4 cm1 resolution. The samples were prepared using
KBr pellet technique. The samples were ground to fine powder
using agate mortar and 2 mg of sample mixed with 40 mg of spec-
tra grade KBr. The pellets were prepared at a pressure of 8 atmo-
spheres [4]. The FT-IR spectra were recorded for each sample in
the set mode after attaining consistency in the appearance of the
spectra on the monitor for the consecutive runs.
2.2. Porosity measurement
The porosity values of the pottery samples were determined by
water absorption method as stated by [5] Percentage of porosity is
defined as the ratio between Volume of the pores and Volume of
the sample multiplied with hundred.
2.3. Scanning electron microscope
The microphotographs of the sample were recorded using SEM
JSM 5610LV JEOL make the maximum magnification possible in the
equipment is 3,00,000 times with the resolution of 3 nm. The ele-
mental analyses were done using the OXFORD INCA Energy disper-
sive X-ray fluorescence spectrometer (EDS). The fresh fracture
surface of the potteries at the received state were coated with a
thin layer of gold were examined using SEM, typically setting at
a magnification of x2000 for all the samples of study. The micro-
photographs were recorded with the attached accessories of
high-resolution cathode ray tube and a role film camera. The
microphotographs using SEM are given from Plates. 3.2–3.6.
Plate 3.2. Microphotograph of the sample ADR 1.
Plate 3.3. Microphotograph of the sample ADR 2.
18 G. Velraj et al. / Journal of Molecular Structure 1028 (2012) 16–21
Plate 3.4. Microphotograph of the sample ADR 3.
Plate 3.5. Microphotograph of the sample ADR 4.
Plate 3.6. Microphotograph of the sample ADR 5.
3. Results and discussion
3.1. Identification of lower limit of firing temperature using FT-IR
The production processes of ancient ceramics can be derived
jointly with the changes in the manufacturing techniques. In this
respect, firing temperature, duration of firing and firing atmo-
sphere are important factors that help in understanding the trans-
formations. The FT-IR spectra of the archaeological samples
collected from different depths were recorded and are shown in
Q-Quartz, H-Hematite, M-Magnetite
Fig. 1. FT-IR Spectra of pottery shred excavated in Adichanallur in received state.
Fig.1. The tentative vibrational assignments of IR peaks as received
state of the samples are given in Table 1.
The band at 915 cm1 is due to Al (OH) vibrations in the octahe-
dral sheet structure which starts to disappear with increasing tem-
perature. At 500 °C the band is absent due to the complete
destruction of clay mineral present in the pottery samples. In the
present study, there was no absorption band at 915 cm1, so all
the samples from ADR 1 to ADR 5 might have been fired above
500 °C at the time of manufacture [6–9]. Velraj et al. [6] have stud-
ied the firing temperature of potteries from archaeological sites
Maligaimedu, Thiruverkadu and Palur in Tamilnadu state, India.
The results showed that those potteries might have been fired in
the range 800–900 °C [6].
The red colour of the potteries is due to presence of hematite,
black and gray colours are due to higher amount of magnetite
[10,15] from this, the relative amount of hematite and magnetite
is responsible for the colour of the potteries. The variation in the
amount of these oxides gives important information regarding
the nature of the environment in which the potteries were made
[11]. The amount of Magnetite and Hematite decides the atmo-
sphere whether reducing or oxidizing for firing the artifacts.
In the present study the atmospheric condition of the sample
fired at the time of manufacture is identified by the ratio of iron
oxides (Magnetite and Hematite) present in the sample. If the
amount of magnetite present in the sample is large then it may
be fired at reducing atmosphere. If the amount of hematite is high
it may be fired at oxidizing atmosphere [12–16]. To determine the
concentrations of the Magnetite and Hematite present in the sam-
ple I/I0 method was used. For this method the absorption bands at
580 cm1 and 540 cm1 were used. These two bands have been
attributed to Magnetite and Hematite respectively [17,18]. In this
I/I0 method ‘I’ represents the high value of intensity and I0 repre-
sent the low value of intensity of these two IR bands. The ratio of
Hematite and Magnetite is measured from the ratio of I/I0 value
of band 580 cm1 and 540 cm1 [19]. The atmospheric condition
adopted by the artisans at the time of manufacturing the pottery
samples from ADR 1 to ADR 5 are given in Table 2. The samples
ADR 1, ADR 2 and ADR 4 contains more amount of magnetite
and visually black in colour, which indicates that the reducing
atmosphere was prevailed by the artisans at the time of
 G. Velraj et al. / Journal of Molecular Structure 1028 (2012) 16–21 19

Table 1
FT-IR absorption frequencies (cm1) and relative intensities of ancient pottery samples with tentative vibrational assignment.

ADR1 ADR2 ADR3 ADR4 ADR5 Tentative vibrational assignment

1646 W 1642 W 1646 M 1640 M 1642 W O–H stretching adsorbed water
1457 V.W – 1457 V.W 1457 V.W 1457 V.W Carbonate groups
1397 V.W – 1396 V.W 1397 V.W – Carbonates
1034 V.S 1032 V.S 1035 V.S 1035 V.S 1035 V.S Si–O stretching
777 W 777 V.W 778 W 778 W 778 V.W Si–O quartz
– – – – 694 V.W Quartz
639 V.W – 642 V.W – – Mn–O
585 V.W – – – – Fe–O Fe3O4 (magnetite)
540 V.W 537 M 540 W 538 M 540 M Fe–O Fe2O3 (Hametite)
466 M 467 S – 468 S 467 M Fe–O Fe3O4 (magnetite)
– – 422 S – – Si–O mixed deformation

V.S – very strong; S – strong; M – medium; W – weak; V.W – very weak.

Table 2
Estimation of lower limit of firing temperature of the pottery samples using FT-IR technique.

Sample Colour Ratio of magnetite and hematite Atmosphere Firing temperature

ADR 1 Black ware 5.26 Reducing >500 °C
ADR 2 Black ware 12.1 Reducing >500 °C
ADR 3 Red ware 0.72 Oxidizing >500 °C
ADR 4 Black and red ware 6.28 Reducing >500 °C
ADR 5 Red ware 1.25 Oxidizing >500 °C

manufacture. The samples ADR 3 and ADR 5 have lower amount of calcareous (NC) and calcareous (C) [21]. The clay type of the potter-
magnetite and are red in colour implies that the oxidizing atmo- ies in the present study had been identified with help of EDS spec-
sphere was adopted by the artisans. trum of the samples.
The samples are classified into two groups as lower value of
3.2. Porosimetry study porosity and higher value of porosity in the potteries. The sample
ADR 5 has highest value of porosity 30.81% compared to other sam-
The studies of apparent porosity on archaeological ceramic ples. The difference in the porosity value can be attributed to the
wares and its correlation with colour, particle size and firing tem- nature of the particles present in the specimen. The samples ADR
perature are of recent origin [19] correlated the porosity values of 1 and ADR 2 were fine particles of non-calcareous clay, have the
archaeological materials with firing temperatures. They have lower range of porosity values attributed to the firing temperature
pointed out that the porosity values of potteries generally range less than 900 °C. The sample ADR 3 has the highest porosity value
from 24% to 40%. The pottery samples of non-calcareous clay of fine of calcareous clay fired below 1000 °C. The samples ADR 4 and ADR
particle size subjected to a firing temperature less than 900 °C have 5 are of coarse particles of non-calcareous clay type have the high-
lower range of porosity values. The potteries of fired clay objects er value of porosity might have been fired below 1000 °C [22].
made of coarse particles of both calcareous and non-calcareous The results obtained by FT-IR studies also consistent with this
clays subjected to a firing temperature below 1000 °C have poros- result that the samples from ADR 1 to ADR 5 taken for the present
ity values in the higher range. The porosity values range from 16% study might have been fired above 500 °C [23].
to 48% for archaeological potteries found in the excavation of some
archaeological sites in south India. It concluded that potteries
made of fine clay and fired to lower temperature have lower values Table 4
Elemental concentration of the Archaeological pottery samples.
of porosity. The potteries showing higher values of porosity is due
to the coarse particles present in them, and may be fired at higher Elements Elemental concentration (%)
temperature. If the voids space is larger, the porosity value can be ADR 1 ADR 2 ADR 3 ADR 4 ADR 5
correlated with particle size and pore size distribution in the sam-
Mg 2.97 0.56 2.94 1.20 0.47
ples to estimate the firing temperature [20]. Al 18.02 20.43 20.05 20.93 19.29
The physical appearance such as colour, nature of particle and Si 63.11 53.89 51.44 60.13 61.23
porosity values in percentage and the estimated firing temperature K 4.02 7.09 3.71 6.09 2.64
of the archaeological pottery shreds of the present study are given Ca 2.35 3.44 6.01 5.47 0.49
Ti 0.82 1.85 – 1.45 0.64
in the Table 3. The porosity values for the present study range from Fe 8.72 12.75 15.84 10.02 16.50
17% to 30%. The clays can be divided into two main types as non-

Table 3
Description, porosity values and estimated firing temperature of Archaeological potteries.

Sample Colour Clay particle nature Porosity (%) Clay type Estimated firing temperature
ADR 1 Black ware Fine 22.28 NC <900 °C
ADR 2 Black ware Fine 17.89 NC <900 °C
ADR 3 Red ware Coarse 25.29 C <1000 °C
ADR 4 Black and red ware Coarse 26.96 NC <1000 °C
ADR 5 Red ware Coarse 30.81 NC <1000 °C

NC – non-calcareous; C – calcareous.
20 G. Velraj et al. / Journal of Molecular Structure 1028 (2012) 16–21
Table 5
Estimation of firing temperature-using SEM to the Archaeological potteries.
Sample Colour Atmosphere
ADR 1 Black ware Reducing
ADR 2 Black ware Reducing
ADR 3 Red ware Oxidizing
ADR 4 Black & Red ware Reducing
ADR 5 Red ware Oxidizing
NC – non-calcareous; C – calcareous; NV – no vitrification; IV – initial vitrification.
3.3. Scanning electron microscope with EDS study on archaeological
pottery samples
In the study of ancient pottery it is important to combine geo-
logical, laboratory and technological ideas to achieve good results.
One technique is usually not enough to characterize and define the
mineralogy and firing temperatures because shreds have been bur-
ied and easily exposed to weathering processes.
The examinations of ancient pottery with an analytical SEM is,
therefore, valuable for characterizing and distinguishing between
the traditions in ceramic technology in antiquity because informa-
tion is obtained on both the extent of vitrification and the firing
temperature. The ancient pottery shreds using SEM on similar lines
[24]. The range of firing temperature was estimated from the vitri-
fication stage and atmospheric conditions maintained at the time
of manufacture of the potteries.
The scanning electron microscope is extremely valuable in pro-
viding information on the pore structure and the glassy phase
development used to study systematically the internal morphology
changes occurring when fired at a range of temperatures [25]. The
range of temperature from 600 °C to 1300 °C to which the potteries
were subjected to firing depends upon the type of clay used to
manufacture the products.
According to [26] the development of vitrification also depends
on the atmosphere in which the clay was fired. When non – calcar-
eous clays were fired in a reducing atmosphere it results in the for-
mation of a distinctive with the release of gas after vitrification has
begun. This effect is being particularly pronounced when a fast
heating rate such as 800 °C/h is employed. The elemental concen-
trations of the potteries examined under SEM, along with EDS are
given in Table 4. The effect of reducing atmosphere on calcareous is
less severe. The temperature ranges associated with the various
vitrification stages being similar for both oxidizing and reducing
atmosphere. In the present study the SEM photographs of the pot-
tery shreds ADR 1, ADR 2 and ADR 4 indicates the presence of some
slight buckling and rounding of edges of the clay plates, and iden-
tified that it may be earlier stage in the development of vitrifica-
tion. Such a stage is also known as no vitrification (NV) stage.
The non-calcareous clay fired at temperature below 750 °C will
produce no vitrification. The pottery samples ADR 1, ADR 2 and
ADR 4 are of non-calcareous clay fired in the reducing condition
were subjected to the firing temperature below 750 °C [27].
The vitrification stage of the sample ADR 3 was initial vitrifica-
tion stage of calcareous type and might have been fired in the tem-
perature range 800-8500 C in the oxidizing atmosphere in
accordance with the reports of [28,29]. The sample ADR 5 was in
initial vitrification stage and made of non-calcareous clay. The
sample may be fired in the oxidizing atmosphere between the tem-
perature range 800–850 °C. This result was also conformed by
Porosimetry and FT-IR studies. The type of the clay used, atmo-
sphere prevailed, vitrification stages reached and the range of fir-
ing temperature achieved by ancient artisans at the time of
manufacture of the pottery shreds excavated at Adichanallur is
summarized in the Table 5.
Clay Type Vitrification stage Firing temperature range
NC NV <750 °C
NC NV <750 °C
C IV 800–850 °C
NC NV <750 °C
NC IV 800–850 °C
4. Conclusion
From the FT-IR technique it is focused that all the samples
might have been fired above 500 °C and conformed that the sam-
ples ADR 1, ADR 2 and ADR 4 were fired in the reducing atmo-
sphere. And also the samples ADR 3 and ADR 5 were fired at
oxidizing atmosphere at the time of manufacture. From the poros-
imetry measurements it was inferred that the samples ADR 1 and
ADR 2 were fired below 900 °C and the samples ADR 3, ADR 4 and
ADR 5 might have been fired below 1000 °C at the time of manu-
facture. From the Scanning Electron Microscope and with the
above studies it is concluded that the range of temperature
achieved by the artisans at the time of firing is ADR 1 – 500–
750 °C, ADR 2 – 500–750 °C, ADR 3 – 800–850 °C, ADR 4 – 500–
750 °C, ADR 5 – 800–850 °C. The artisans lived at that time of man-
ufacturing the potteries in the Adichanallur archaeological site
knew the influence of iron oxides and aware of both methods firing
the potteries (open air and closed kiln).
Acknowledgments
The authors acknowledge with thanks to Mr. S. Mathivanan,
Conservation Assistant, Archaeological Survey of India (ASI), Salem
Branch, for his timely help and guidance for the collection of
Archaeological pottery samples. The authors are very thankful to
Prof. Dr. R. Palanivel, Department of Physics, Annamalai University
for his timely help to take SEM photographs in Centralized Instru-
mentation Service Laboratory (CISL), Annamalai University, Anna-
malainagar. Also the authors thankful to Dr. V. Krishnakumar,
Professor and Head, Department of Physics, Periyar University,
Salem for constant encouragement and administrative support
rendered by him.
References
[1] S. Akyuz, T. Akyuz, S. Basaran, C. Bolacal, A. Gulec, J. Mol. Struct. (2007) 150–
153.
[2] D. Barilaro, G. Barone, V. Crupi, M.G. Donato, D. Majolino, G. Messina, R.
Ponterio, J. Mol. Struct. (2005) 744–747;
G.E. De Benedetto, R. Laviano, L. Sabbatini, P.G. Zambonin, J. Cultural Heritage 3
(2002) 177–186.
[3] Y. Maniatis, East Cretan White on Dark Ware, In: P.P. Betan court, University of
Pennsylvania, 1984, pp. 75.
[4] Y. Maniatis, M.S. Tite, Trans. J. British. Ceram. Soc. 74 (1975) 229–232.
[5] Y. Maniatis, M.S. Tite, Ceramic Technology in the Aegan World During the
Bronze Age, Thera and Aegan World I London, 1978, pp. 483.
[6] G. Velraj, K. Janaki, A.M. Mustafa, R. Palanivel, Appl. Clay. Sci. 43 (2009) 303–
307.
[7] F. Elass, D. Oliver, Clay Minerals 43 (13) (1978) 299–308.
[8] Y. Maniatis, A. Simpoulos, A. Kostikas, V. Perdikatsis, J. Am. Ceram. Soc. 66
(1983) 773.
[9] R. Venkatachalapathy, A. Loganathan, C. Manoharan, K. Veeramuthu, Rec. Res.
Sci. Tech. 2 (2010) 51–55.
[10] Piero Mirti, Patrizia Davit, J. Arch. Sci. 31 (2004) 741–751.
[11] P. Mirti, A. Perardi, M. Gulmini, Archaeometry 48 (2006) 31–43.
[12] M. Muresan, Materiaux et Constructions 6 (1973) 203–208.
[13] G. Velraj, A. Mohammed Mustaa, K. Janaki, K. Deenadayalan, N. Basavaiah,
Apply. Clay. Sci. 50 (2010) 148–153.
[14] P. Mirti, P. Davit, J. Archaeol. Sci. 31 (2004) 741–751.
 G. Velraj et al. / Journal of Molecular Structure 1028 (2012) 16–21 21

[15] P. Mirti, A. Perardi, M. Gulmini, Archaeometry 48 (2006) 31–43. [24] S.H. Yariv, E. Mendelovici, Appl. Spectroscopy 33 (1979) 410.
[16] S.H. Yariv, E. Mendelovici, Appl. Spectrosc. 33 (1979) 410–411. [25] P. Sathya, G. Velraj, J. Experiment. Sci. 2 (2011) 04–06.
[17] A.M. Mustafa, K. Janaki, G. Velraj, Microchim. J. 92 (2010) 311–314. [26] G. Velraj, K. Janaki, A. MohammedMustafa, R. Palanivel, Appl. Clay Sci. 43
[18] G. Velraj, K. Janaki, A.M. Mustafa, R. Palanivel, Spec. Chi. Acta A 72 (2009) 730– (2009) 303–307.
733. [27] C.S. Ross, P.E. Kerr, The Kaolin Minerals, US Geological Survey Professional
[19] H. Namduri, S. Nasrazadani, Corros. Sci. 50 (2008) 2493–2497. Paper 165E, 1931, pp. 151–176.
[20] D. Populis, P. Tsolis-Katagas, C. Katagas, Bull. Geol. Soc. Greece XXXVI (2004) [28] J.D. Russell, M.J. Wilson, A Hand Book of Determinative Methods in
474–480. Claymineralogy, Blackie and Son Ltd., Chapman and Hall, New York, 1987. p.
[21] S.R. Bertolino, M. Fabra, Appl. Clay Sci. 24 (2003) 21–34. 133–135.
[22] M.S. Tite, Archaeometry 11 (1969) 134. [29] S.H. Yariv, E. Mendelovici, Appl. Spectrosc. 33 (4) (1979) 410.
[23] M.S. Tite, Y. Maniatis, Trans. J. British Ceram. Soc. 74 (1975) 19–22.