HEIN & AL.

: GREAT POTS ON FIRE: THERMAL PROPERTIES OF ARCHAEOLOGICAL COOKING WARE

GREAT POTS ON FIRE: THERMAL PROPERTIES OF ARCHAEOLOGICAL COOKING WARE

1
1

A. Hein 1,2N.S. Mller 1V. Kilikoglou

Institute of Materials Science, N.C.S.R. Demokritos, 15310 Aghia Paraskevi, Athens, Greece Department of Archaeology, University of Sheffield, Northgate House, West Street, Sheffield S1 4ET, UK

Abstract: In the past, experimental studies of the functionality of archaeological cooking pots were focussed mainly on thermal shock resistance. Other properties, such as the thermal conductivity, and their relation with specific ceramic fabrics were discussed rather generally without being directly investigated. In the present study a modified Lees disk setup was used in order to determine the thermal conductivity of a series of experimental ceramic disks. The effect of production parameters on the thermal conductivity was assessed by examining mixtures of two different base clays, one non-calcareous and one calcareous, which were tempered with different amounts of granite or phyllite and fired at three specific temperatures: 550C, 850C and 1050C. The selection of the examined ceramic fabrics was based on archaeological evidence from the Aegean Bronze Age. The most important parameters emerged to be degree of vitrification and porosity of the ceramic matrix. Keywords: cooking pots, thermal conductivity, heat capacity, temper

INTRODUCTION Among the most significant advantages of ceramic materials are their remarkable thermal properties. Ceramics are heat resistant, i.e. they remain inert up to considerably high temperatures and they present relatively high thermal shock resistance and heat capacity. For these reasons they were the most common materials for various applications involving the use of heat: ranging from daily life, such as cooking, to specialised technical processes, as for example metallurgy or glass making. Depending on the application, however, different properties were required regarding the heat capacity and particularly the thermal conductivity. It can be argued that in the case of cooking pots, for example, ceramics with comparably high thermal conductivity were required, in order to provide optimum heat transfer. But also mechanical properties such as strength and toughness had to be suitable (Tite et al. 2001, Mller et al. this volume). The physicochemical properties of ceramics depend on the nature of the raw materials, on the clay paste processing and on the firing technology. Indeed, various approaches can be observed in ancient functional ceramics, towards achieving suitable material properties. As for the thermal properties of cooking pots, most of the discussion so far was focused on thermal shock resistance, with the thermal conductivity referred to only in side notes as being controllable trough wall thickness (Tite & Kilikoglou 2002; Broeksman et al. 2004). The development towards thinner walls, which enhanced the heat transfer, was explained also with changes in nutrition patterns (Braun 1983). An actual approach to quantify heat transfer in cooking pots was the definition of 'heating effectiveness' as a parameter, which describes the rate at which the temperature of a pots content is raised

Fig. 1 Schematic model of a ceramic microstructure as multiphase composite: In this example the phases are the clay body, the voids (black) and two different kinds of nonplastic inclusions (white and light grey). The individual phases affect the heat transfer in the ceramics differently. when applying an external heat source (Skibo et al. 1989; Schiffer 1990). During simulated cooking tests, water was heated in replicate miniature vessels over an open flame under sufficiently controlled conditions. Nevertheless, 'heating efficiency' is a rather arbitrary parameter being a complex product of heat conductivity, heat flux, heat capacity, permeability and shape of the vessels. Therefore, it does not provide thorough information about principles that control these properties. Another approach to assess the thermal properties of ceramics is the use of computer simulations (Hein & Kilikoglou 2007). Here, the ceramic microstructure is regarded as a multiphase composite, with the clay body, the voids and the particular inclusions being the different phases, all of them having specific thermal properties (Fig. 1). The voids for example act as heat barriers.

15

EMAC'07 BUDAPEST - VESSELS: INSIDE AND OUTSIDE

Table 1 Clay mixtures used for the experimental ceramic disks: The base clays came from Pikermi and Kalami (both in Greece) and they were tempered with different amounts of granite and phyllite material. In the last columns the total porosities of the ceramic disks fired at different temperatures are listed. base clay PIK -UT PIK-G10 PIK-G40 PIK-P10 PIK-P40 KAL-UT KAL-G10 KAL-G40 KAL-P10 KAL-P40 calcareous calcareous calcareous calcareous calcareous non-calcareous non-calcareous non-calcareous non-calcareous non-calcareous temper non-tempered 10% granite 40% granite 10% phyllite 40% phyllite non-tempered 10% granite 40% granite 10% phyllite 40% phyllite 550 C 32 30 29 30 30 34 32 31 33 32 porosity in % 850 C 1050 C 32 33 31 32 31 32 31 33 33 34 33 11 31 13 30 22 34 12 32 19

particular ceramics can be developed. These models can then be tested for their simulated performance during use, in terms of heat transfer and thermal stress. The results demonstrate the importance of parameters controlled by ceramic technology and constituting the thermal performance of the final products. In order to verify results from computer simulations, the thermal properties of test ceramics with controlled microstructures were measured in laboratory experiments, which will be presented in this paper. Furthermore, the determined data will provide the basis for further, more complex simulations which consider also the shape of cooking vessels, following an approach applied in a recent study on smelting furnaces used in metallurgy (Hein & Kilikoglou 2007). It is hoped that the data provided by this work will provide a further parameter in the discussion of cooking ware ceramic technology and the choice of particular raw materials. EXPERIMENTAL In order to study the thermal conductivity of typical cooking ware pottery experimental ceramic disks were prepared from ten different clay mixtures, with noncalcareous or calcareous base clays and different amounts of granite or phyllitic temper materials, each fired at three different temperatures (Table 1) (Mller et al. this volume). For the determination of their thermal conductivity a modified Lees' disk setup was used (Fig. 2). The examined sample in the shape of a flat disk is in contact with a heat source at one side and with a heat conductor at the opposite side. The temperature of the heat source is controlled and stabilized during the measurement.

Fig. 2 Principle of the measurement of thermal conductivity with a Lees disk setup: The ceramic disk to be measured is placed between a heat source with controlled and regulated temperature and a heat conductor which transfers heat to the ambient air. The heat loss of the heat conductor in relation to its temperature is known. Therefore the thermal conductivity of the test disk can be determined from the temperature difference between heat source and heat conductor after steady state is reached. However, while some properties as e.g. the effective heat capacity of the composite can be estimated in a straightforward way as the sum of the heat capacities of the individual phases weighted by their volume fraction, the effective thermal conductivity is affected also by the spatial distribution and the shape of the individual phases. Therefore, based on observations multiphase models of ceramic structures are developed and tested with computer simulations for their effective thermal properties. If the properties of the base material components are known, computer models of

16

HEIN & AL.: GREAT POTS ON FIRE: THERMAL PROPERTIES OF ARCHAEOLOGICAL COOKING WARE

Fig. 3 Thermal conductivity of the disks from the non-tempered clays at specific temperatures: Presented are the measured values for the non-calcareous Kalami clay (left) and the calcareous Pikermi clay (right). The symbols correspond to the firing temperatures: - 550C, - 850C and - 1050C. Beforehand, the heat loss of the heat conductor into the & environment depending on the temperature qloss (T ) is estimated. The heat loss from the rim of the sample disk can be neglected provided that its thickness is small compared to its diameter. In this way the heat flux through the sample can be determined. When steady state is reached, the temperature difference between heat source and ceramic surface in contact with the heat conductor, dT = T0 Tsurf , provides the thermal conductivity of the ceramic, taking into account the area A and the thickness x of the sample: (1) thermal conductivity of the ceramics manufactured from the calcareous clay is actually slightly higher than one of the ceramics produced from the non-calcareous clay. However, when fired at 1050C, the thermal conductivity of the non-calcareous ceramics was approximately twice as high as the value of the calcareous ceramics. One explanation for this is the clearly lower porosity of the high-fired non-calcareous ceramics (Table 1). The effect of porosity, however, as it can be estimated, is too small to explain the entire difference. Another explanation is provided by the difference in the development of the ceramics microstructure during firing. In the case of the calcareous clay a fairly continuous development of the microstructure, reflected in the degree of vitrification at different firing temperatures, is observed. In contrast to this, the non-calcareous clay experiences only small changes in its microstructure at firing temperatures of 550C and 850C, but when fired at 1050C a high degree of vitrification with extensive areas of solid glass is observed. Effect of tempering According to Table 1, only in the case of high-fired ceramics produced from clay mixtures with the noncalcareous base clay the total porosity was significantly different from all other ceramic disks, i.e. clearly smaller. Therefore, the absolute amount of porosity cannot be the only reason for differences of the effective thermal conductivity. It remains to be discussed up to which extent observed differences in pore shape or crack development at different firing temperatures and with different tempering materials (Mller et al. this volume), affect the effective thermal conductivity. However, the measurements indicated a difference between granitic and phyllitic temper. For ceramics fired to 550C and 850C, moderate granite tempering appeared to increase the thermal

& k (T ) = qloss (T )

x A dT

The heat loss of the brass disk was determined by heating it up to a temperature of 400C and afterwards leaving it for cooling down while recording its temperature. During cooling the surface, which is in contact with the sample during a normal measurement, was placed on a thermal insulator. Therefore, the measured temperature decay allows for the & determination of the heat flux qloss (T ) from the brass disk to the environment at specific temperatures. RESULTS AND DISCUSSION Effect of clay type and firing temperature As for the non-tempered ceramics, both clay types show increased thermal conductivity with increasing firing temperature (Fig. 3). In the case of the noncalcareous clay a significant increase in thermal conductivity was observed between 850C and 1050C. For firing temperatures at 550C and 850C, the

17

EMAC'07 BUDAPEST - VESSELS: INSIDE AND OUTSIDE

conductivity, while tempering with phyllite appeared rather to decrease the effective thermal conductivity. An explanation might have been the different nature of the tempering materials: granite as a plutonic rock with low porosity has a higher thermal conductivity than the base clay, while phyllite possesses an anisotropic thermal conductivity. Due to the production process of the disks, the platy phyllite particles are oriented parallel to the surfaces, perpendicular to the heat transfer direction, resulting in decrease of thermal conductivity. An exception of these observations was the case of the high-fired ceramics. Here, the effective thermal conductivity decreased with both tempers, particularly using the non-calcareous base clay. This behaviour is probably due to the development of cracks that act as heat barriers. Moreover, it must be considered that the non-calcareous base clay presents a comparably high thermal conductivity presumably in the same range as the thermal conductivity of the granite temper. In summary, for low to intermediate firing temperatures, moderate tempering with a material that has higher thermal conductivity than the base clay indeed seems to increase the effective thermal conductivity of the ceramics, at high firing temperatures this effect seems to be disturbed by crack development due to thermal expansion. Increased amounts of temper appear to diminish the effective thermal conductivity, probably due to the presence of manufacture induced macro-pores resulting in a microstructure in which the ceramic matrix is less connected. Heat capacity Heat capacity affects, together with thermal conductivity and density, the rate of the temperature increase during heat transfer under transient conditions, i.e. when the temperature of the material is not in equilibrium. This relation is expressed by the parameter thermal diffusivity , which is the quotient between the thermal conductivity k and the heat capacity per unit volume cp. The slope of the heating curve and particularly the time after which steady state is reached depend on the thermal diffusivity of the ceramics. The higher the thermal diffusivity, the faster the temperature increases and equilibrium is reached. Therefore, the measurements with the modified Lees disk in principle also provide information about thermal diffusivity or the heat capacity, respectively. This, however, is still subject to further examination. In the present study the effect of heat capacity might be neglected due to rather small variations of the heat capacity of the particular clays and temper materials. As for the examined clay mixes, thermal conductivity and density are expected to affect the thermal diffusivity to a greater extent. After all, the

optimum heating rate also depended on the supposed use of the cooking vessel. Thermal stress Thermal shock resistance is a complex parameter affected by heat transfer, thermal expansion, strength and toughness. Furthermore, it depends on the vessel shape. After determining the basic materials properties (Mller et al. this volume) all these parameters can be considered and evaluated in computer models of the vessels, the simulated use of which can be examined for example with the Finite Element Method (FEM) (Hein and Kilikoglou 2007). CONCLUSIONS The present work demonstrates the role of raw materials (base clay and temper), manufacturing process and firing temperatures in the thermal conductivity of the ceramic products. At the same time it became evident that the thermal performance of the ceramic material is not in a straightforward relationship with each of the above parameters, but the effect is complex and sometimes the effect of one of them obscures the effect of another. Therefore, when explaining archaeological ceramic technology and choice of materials in view of thermal performance one should consider all the parameters collectively and furthermore availability of materials but also existing traditions. The next step after the determination of the basic material parameters will be their employment in computer models in order to simulate the use of the cooking vessels and their behaviour under thermal stress. ACKNOWLEDGEMENTS This study was partly funded by the Institute for Aegean Prehistory (INSTAP).The support of N.S.M. through an IKY (Greek State Scholarship Foundation) scholarship is gratefully acknowledged, as is an ORSAS Scholarship awarded by Universities UK. REFERENCES
BRAUN, D. (1983): Pots as tools, in Archaeological hammers and theories (eds J.A. Moore and A.S. Keene), 107-134, Academic Press, New York. BROEKSMAN, T., ADRIAENS, A.. & PANTOS, E. (2004): Analytical investigations of cooking pottery from Tell Beydar (NE-Syria), Nuclear Instruments and Methods in Physics Section B, 226 (1-2) 92-97.

18

HEIN & AL.: GREAT POTS ON FIRE: THERMAL PROPERTIES OF ARCHAEOLOGICAL COOKING WARE

HEIN, A. & KILIKOGLOU, V. (2007): Modeling of Thermal Behavior of Ancient Metallurgical Ceramics, Journal of the American Ceramic Society 90, 3, 878 884. MLLER, N.S., KILIKOGLOU, V., DAY, P.M., VEKINIS, G & HEIN, A.: The influence of temper on performance characteristics of cooking ware ceramics, this volume. SCHIFFER, M.B. (1990): The influence of surface treatment on heating effectiveness of ceramic vessels, Journal of Archaeological Science, 17, 373-381.

SKIBO, J.M., SCHIFFER, M.B. & REID, K.C. (1989): Organic-tempered pottery: an experimental study, American Antiquity, 54 (1), 122-146. TITE, M. S., KILIKIOGLOU, V. & VEKINIS, G. (2001): Strength, toughness and thermal shock resistance of ancient ceramics, and their influence on technological choice. Archaeometry 43 (3):301-324. TITE, M. S. & KILIKOGLOU, V. (2002): Do we understand cooking pots and is there an ideal cooking pot?, in Modern trends in scientific studies on ancient ceramics (eds. V. Kilikoglou, A. Hein and Y. Maniatis), 18, BAR International Series 1011, Archaeopress, Oxford.

19

EMAC'07 BUDAPEST - VESSELS: INSIDE AND OUTSIDE

20