Canadian Journal of Basic and Applied Sciences

PEARL publication, 2014

ISSN 2292-3381

CJBAS Vol. 02(01), 25-33, 2014

Spectroscopic Analysis of Archaeological Pottery Excavated from Alagapuri,

Tamilnadu, India
G. Raja Annamalaia, R. Ravisankarb,, K. Rajanc , A.Naseerutheend, V.P.Yatheeskumare ,D.Saravanane
a

Department of Physics, ShriKrishnaa College of Engineering &Technology, Mannadipet,

Puducherry-605501, India.
b
Post Graduate and Research Department of Physics, Government Arts College, Thiruvannamalai606603, Tamilnadu, India.
c
Department of History, Pondicherry University, Kalapet, Puducherry 605014, India.
d
Department of Physics, C.Abdul Hakeem College, Melvisharam-632509, Tamilnadu, India
e
Department of Physics, A.R. Engineering College, Villupuram-605601,Tamilnadu, India.
Keywords:

Abstract

Archaeological Pottery,
Firing temperature,
FT-IR,
XRD,
TG-DTA

The present work is aimed to investigate the ancient pottery from Alagapuri, Sivaganga
District in Tamilnadu in order to study the materials used for firing, the technology of
firing (either controller firing or open firing) and art of controlling the firing using
spectroscopic techniques. The FT-IR and XRD spectrum are recorded in received state
as well as re-fired state of the potsherds to study the thermal transformation of the
minerals in determining the firing temperatures. The constituent of mineral present in
the ancient potteries and also the estimation of firing temperatures are studied by FT-IR
and XRD techniques. Further the TG-DTA was used to study thermal characterization
of the samples. The combined methodology gives a complete spectrum for the
estimation of firing temperatures of potsherds. Spectroscopic results revealed that
ancient pottery was fired to a temperature greater than 750C.

1. Introduction
Ancient Potteries are among the oldest and most significant technological innovations in the history
of human achievement, and were the first truly synthetic material. They are the most common
artifacts found during excavation of archaeological sites; archaeologists are more interested in the
studies of pottery fragments.The analysis of ancient pottery provides active research for gaining a
deep insight of forgone culture [1]. The investigation of the nature of the raw materials and the
technology implemented for the production of potteries e.g. the firing temperature and the nature of
firing atmosphere is important. The mineralogical composition of archaeological potsherds must be
assessed to answer technological issues like the production processes of potteries.
Recently, the spectroscopic techniques (FTIR, XRD and TG-DTA) have been applied for the
investigation of archaeological samples.The mineralogical composition is carried out by Fourier
Transform Infrared (FT-IR) and X-ray diffraction (XRD) due to its non-invasiveness. Many
workers have applied FT-IR spectroscopic techniques in archaeological potteries[2-6].

Corresponding Author (Email: ravisankarphysics@gmail.com, Tel. (Tel: (+91)9840807356))

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The thermal analysis is generally carried out

by TG-DTA to confirm the firing temperature
of the potteries [6].The research work is
focused on two main areas. The first one
refers to the mineralogical composition and
second one concerns firing condition and
firing temperature.This present work is aimed
the examination of archeological potsherds
excavated
from
AlagapuriinSivaganga
District of Tamilnadu, India by spectroscopic
techniques.

small village in TiruppuvanamTaluk in

SivagangaDistrictinTamilnadu, India, by the
Department of History, School of Social
Sciences & International Studies, Pondicherry
University, Puducherry, India. The pottery
shreds of Alagapuri belonging to Iron Age
grave century.Black and Red ware and Black
polished ware were collected in the site. The
visual characteristic of ancient pottery
samples excavated from Alagapuriis shown in
Figure 1. The four samples are labeled as
AP1, AP2,AP3& AP4.After removal of an
area of commercial clay extraction at a depth
30 cm to avoid the layer of surface vegetation,
the pottery shreds were grounded into fine
powder using agate mortar.

2. Materials and Methods.

2.1. Sample Collection
The pottery samples were recently excavated
from
the
site
Alagapuri
(Long:103531N;Lat:775837E) is a

Figure 1.Visual characteristics of ancient pottery samples from Alagapuri.

pellet technique was used by mixing the
powdered samples with KBr in weight
proportion of 1: 20.The spectra were recorded
in the mid region of 4000-400cm-1 in the
received as well as refired state. The precision
of the instrument is 5cm-1. Figure 2 shows
the FT-IR spectrums of as received and
refired potsherds of Alagapuri.

2.2. FT-IR Technique

FT-IR spectra on the pottery samples were
recorded on a BrukerAlpha FT-IR
spectrometer available in department of
chemistry, Government Arts College,
Tiruvannamalai, Tamilnadu, India, using KBr
pellets technique in the wave number range
from 4000 cm-1 to 400 cm-1. The KBr pressed

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Fig- 2.A typical FT-IR spectrums of as received and Refired potsherds of Alagapuri.

data over a 2 range of 10 to 70 were

recorded
by
using
diffractometer.
Mineralogicalcomposition of the studied
samples is determined with the standard
interpretation procedures of XRD. Major
mineral present in the studied sample was
determined asquartz.The XRD spectrum
ofAlagapuri potsherds is shown in Figure 3.

2.3. XRD Analysis

Powder X-ray diffraction data of the
powdered pottery samples was carried out on
a Siemens D500Advance diffractometer using
CuK radiation, equipped with a NaI(Tl)
scintillation detector. The X-ray patterns of
powdered pottery and refiredsamples were
recorded at room temperature. Diffraction

Figure 3.A typical XRD Spectrum of Alagapuri potsherds.

2.4. Thermo gravimetric Analysis (TGDTA):

The thermo gravimetric analysis has gained
wide analytical acceptance in recent years for
thermal analysis, TG-DTA study was carried
out for the samples in SDT Q-600-V.8.3
thermal analyzer. The experiment was carried
out by heating the samples from 30 to 800 C
at 10 C.min-1 with flow of high purity
nitrogen.

3. Results and Discussions.

3.1. Mineral Analysis by FT-IR
Different types of minerals were identified in
the samplessuch as quartz, microcline,
orthoclase, albite, kaolinite, montormorilinte
hematite, magnetite, and organic carbon from
the IR absorption bandsby comparing the
observed frequencies with the available
literature [2-6].The observed IR absorption
band together with mineral identification of
the potsherds is given in the Table-1.
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G. Raja Annamalai et al. - Can. J. Basic Appl. Sci. Vol. 02(01), 25-33, 2014

centered at 695 cm-1 indicates that the

symmetrical bending vibration of Si-O group
in the sample and it is more useful to find
whether it is crystalline or amorphous. In the
amorphous state, 695 cm-1 peak will be
missing. This is a well known fact. As the
695 cm-1 peak is exhibited by the spectra
of the samples AP2-AP4showquartz
mineral isin crystalline form. According to
Elsass and Oliver [7], the presence of the
sharp band at 695 cm-1 indicates thin
particles. In our analysis, the samples AP2AP4 indicates contain quartz of thin particle
size.

Quartz is the major mineral in the pottery

samples. It could be observed from Table 1
that the infrared absorption bands appearing
at1080 ,775, 695 and 460 cm-1 may suggest
the presence of quartz. Out of the four peaks
observed for quartz, the bands at 775780 cm1
may be assigned due to symmetrical
stretching mode and those at 690695 cm-1
and at 455460 cm-1 may be due to
symmetrical bending mode and asymmetrical
bending respectively. This one stretching
mode 775-780 cm-1 and one bending mode,
690695 cm-1 are widely used as the
diagnostic peaks for quartz. The band

Table 1:Observed Absorption of the ancient potteries from Alagapuri together with minerals
identification.

AP1

AP2

AP3

AP4

A
777,460
A
775,695
A
776,695
A1080,775,
696,459

Magnetite

Hematite

Iron Oxide Organic

Mineral
Carbon
Montormorilinte

Kaolinite

Clay
Minerals

Albite

Orthoclase

Microcline

Feldspar Mineral

Quartz

Sample No

Silicate
Mineral

635

6
1030

1439,
1637

539

581

2922

465

4
723

7
1031

1440,
1638

540

580

2925,
2854

466

4
725

7
1033

1439,
1638

540

578

2926,285
5

587

645,5
5
45
-

1035

1440,
1635

538

-2926,
2850

IRabsorption bandat 585-590 cm-1 in the

samples indicates microcline.The presence of
peak at 635-640 and 720-725cm-1 in the
samples indicates the presence of albite.The
absorption peaks of kaolinite occur at
1035cm-1. The band at 3440 cm-1 along with

From the Table 1, the infrared absorption

frequency of the bands at725, 645, 635,585,
and 465 cm-1 may suggest the presence of
feldspar. The peaks at 465470 and 645650
cm-1 are indicating the presence of orthoclase
in the samples.From the Table 1, the
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the weak band at around 1640 cm-1 are due

topresence of montmorillonite[8].
The presence of the peak at 535-540 cm-1 in
the samples assigned to hematite [9].The
presence of hematite indicates the coloring
nature of the samples during the firing
condition of its production.It indicates that
these samples were fired in the open air or
perfectly oxidizing atmosphere at the time of
the manufacture. At the same time, air has
been allowed at high temperature during
cooling which has enabled the oxidation of
iron components formed during reduced
atmosphere, the reason for the red color of the
pottery. It is well established from the red
color of the pottery in the investigation (AP1
& AP4). The presence of magnetite indicates
that the sample fired above 750C [10].From
the table 1, the presence of peak at 575580cm-1 indicates the magnetite. In the case
of block part of the pottery samples,
magnetite may present. In our present
investigation, the presence of magnetite in the
samples AP1, AP2&AP3 supports the above
statement.From the spectra of all the samples
Table-1 a very weak to weak absorption band
present at 2920-2925 and 2850-2855 cm-1
may suggest the presence of organic carbonin
the samples.

all the samples were fired to the temperature

above 500C.
The presence of band around 1035cm-1in the
received state indicates that the samples have
been fired above 600C and made up of
disordered clay [11]. The above statement can
also confirm with the bands at 915 cm-1 and
875cm-1. The peak at 915cm-1 is due to Al
(OH) vibrations in the octahedral sheet
structure which begins to disappear with
increasing temperature and at 500C the
bands disappear completely. In our
analysis,none of the samples taken for the
present study showed the band at 915cm-1 and
it indicates all the samples were fired above
500C.The presence peak at 875cm-1
indicating that the samples were fired above
750C. None of the samples taken for the
present study showed the band at 875cm-1
indicating that all the samples were fired
above 750C[12]. The iron oxide minerals
such as hematite and magnetiteindicate that
the samples were fired above 750C. Table 2
lists the estimation of firing temperature of
the Alagapuri.

3.3. FT-IR Analysis of Refired Samples

The potteries are made of clay minerals and
the common major clay mineral used in
making potteries is kaolinite. The study of
thermal transformations of the clay minerals
can thus help in determining the firing
temperatures of the potteries.The well
knownfactthat once clay is fired at a certain
temperature and then cooled down, it freezes
at a stage which cannot be further altered by
subsequent refiring unless the initial
temperature is exceeded. This peculiar
property of ceramics provides a means of
estimating
the
firing
temperature.By
identifying the mineral trapped in the samples
one can estimate the firing temperature.In this
senses, the samples are heated to temperatures
of 250C, 500C and 750C for one hour using

3.2. Firing Temperature determination

using FT-IR study:
The FTIR spectra of the samples AP1-AP4 in
the received state shows no characteristics
absorption bands for the inner hydroxyl water
bands at 3700 and 3620cm-1 indicating the
firing temperature of the sample might be
more than 450C. The invariably presence of
the bands at 3440 and 1635cm-1 are attributed
to absorbed O-H stretching and H-O-H
bending vibration of absorbed water
molecules. These bands indicate artifacts
during burial under the earth and also
sensitive to temperature effects. The absence
of IR absorption peak at 915 cm1 shows that
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muffle furnace. These spectra are presented in

Figure 2.
Table 2:Estimation of firing temperature of Pottery Shreds excavated at Alagapuri.
Sample Color
Type of the Atmosphere Octahedral Estimation
ID
clay
Prevailed
sheetStruct of
firing
ure
temperature
Black and red Red clay
Oxidizing
Completed
>750C
AP1
ware.
Black polished Red clay
Oxidizing
Completed
>750C
AP2
ware.
Oxidizing

Completed

>750C

AP3

Black polished Red clay

ware.

Black and red White

and Oxidizing
ware
Red clay

Completed

>750C

AP4

The IRspectrum of the received as well as

refiedstatemay help to identify the firing
minerals and their changes are noticed.The
comparison between received and refired IR
spectra
may
reveal
the
appearance/disappearance of new firing
minerals. The detailed discussion is given
below the spectra of the samples show the
absorption bands at 3440 and 1640cm-1are
attributed to absorbed water molecules and
get diminished at 250C to 750C. The
absence of the inner hydroxyl absorption
bands at 3700, 3620cm-1 along with 920cm-1
indicates that all the samples were fired above
450C during the manufacture [7].In the
received state, the presence of the band at 580
and 540cm-1 in AP1and AP4 indicates the
presence of iron oxides. At 250C water
evaporates and become obvious, and the
intensity of the both bands remains the same
up to 750C indicates that they were fired
above 750C under open atmosphere, it is
well established from the red color of the
pottery[13].From the above observations,
these samples were fired under open
atmospheric
conditions
with
firing
temperature of around 750Cwhich is also
reflected from the red color of the pottery.

The presence of quartz in the samples

indicates the coarse materials like sand with
more iron content.
3.4. XRD Analysis
The most direct technique for the
identification of the mineral composition of
pottery is X-ray diffraction technique. The
identification of minerals is carried out by
using JCPDS file [14] with comparing XRD
data of the samples. Quartz, feldspars
(microcline & orthoclase) and magnetite are
identified minerals in received state samples
where as quartz, oligoclase and hematite
noticed in the refired samples.
From the XRD analysis, quartz and feldspar
present in received as well as refired state
indicates that these minerals may indicate a
temperature of at least 750C. It is well
known fact that these two minerals may
persist on firing up to 1000C. Quartz may be
an indigenous mineral in natural clay or may
be an intentionally added temper [2].This
gives a clear indication that all the samples
were fired above 750C. This result also
confirms the firing temperature analysis of
FT-IR study of the refired samples.

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are being destroyed.DTA curve of the pottery

samples show four endothermic peaks at
67C, 332C, 531C, and 660Care observed.
The mass losses of first, second, third and
fourth endothermic peaks are 5.52%, 1.17%,
0.33% and 0.09%[6].At higher temperatures
mass loss are very low. No further weight loss
could be observed above 660C.In the
thermogravimetricanalysiscalcite decomposes
in the temperature range 700-800C[16].The
sample showed no weight loss due to
decomposition of calcite. Theabsence of
thermogravimetric evidence of calcite
between 700 and 800C is supporting the
results of firing temperature of the XRD
andFTIR analysis done in the present
study.This analysis gives an indication of
firing temperature is above 750C.The FT-IR
and XRD results are well agreement with the
TG-DTA results.

3.5. Thermal Analysis:

DTA and TG analysis reveal changes in
samples weight as well as in thermodynamic
properties. DTA and TG curves of the pottery
samples of Alagapuri are given in Fig.4 for
the temperature range 0-800C. The data
obtained for all investigated samples were
similar. The pattern shown by TG curve
suggest mass loss during the burn process
however there is no more mass loss observed
above 660C. Combined TG and DTA data
show two stages of material decomposition
appearing during the burn below 700C. Both
stages are displayed by changes in
thermodynamic properties of investigated
samples appearing during burn process. In
lower temperatures the most probable reason
for mass loss is evaporation of water and in
the temperatures 200660C[15]all the
organic remains originating from ceramic use

Figure 4. A Typical TG-DTA spectrum of Alagapuri potsherds.

potsherds. The results obtained from the
above techniques showed good agreement
with one another. From the analysis, it is
found that the mineral content and firing
temperature of the archeological pottery are
determined. The combined spectroscopic
techniques showed that the potteries of
Alagapuri were fired to a temperature greater
than 750C.

4. Conclusion.
Ancient pottery samples from Alagapuri,
Sivaganga District inTamilnadu were
analyzed by FTIR, XRD and TG-DTA
techniques.
The
mineralogical,
firing
temperature and firing atmosphere conditions
were inferred from the FT-IR analysis. The
result from the T-IR study is confirmed by
XRD technique. Further TG-DTA techniques
are applied for the thermal analysis of the
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Spectroscopic and thermal analysis of red

clay for industrial applications from
Tamilnadu, India. Journal of Molecular
Structure, 1027, 99-103 (2012).
DOI:j.molstruc.2012.05.079

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