Homogeneity in Copper Artifacts from

Petra, Jordan – Project Proposal

Nick Sinnott-Armstrong and Max Mankin

The microstructure and mechanical properties of metals can allow archaeologists to determine
the conditions under which they were forged. Microstructure refers to crystal (grain) sizes,
atomic structures, shapes, and distributions, as well as inclusions such as slag. Mechanical
properties include stress and strain: that is, how the metal responds to forces. Such properties
are largely determined by the metal’s composition, defects, and microstructure. It is possible to
infer forging conditions from observations of microstructure and mechanical properties of
metals. Forging conditions are significant because they can provide an idea of the control that
the smiths had over the production process. An understanding of the degree of control
available to craftspeople could lead to information about past resource management, what the
craftsperson’s priorities were, and the level of technical understanding of the manufacturing
process that the craftsperson had. In order to gain an understanding of these underlying factors
presented through forging microstructure, we plan to examine artifacts using a number of
microscientific tools. In particular, we plan to study several copper artifacts excavated at Petra,
Jordan to determine the control that Roman period smiths had over their copper working
forges.

Petra
Petra is located in Jordan about 80 kilometers south of the Dead Sea. The site is most famous
for two impressive facades and buildings sculpted out of sandstone cliffs known as the
“Treasury” and the “Monastery.” Of course, there are remains of less striking buildings
scattered throughout the site, as the city consisted of more than two large buildings in a cliff
face. Occupation of Petra may have begun as early as ~1200BCE. In 64 CE, the area was
conquered by the Roman general Pompey, thus beginning the Roman period. Despite Roman
control, the region remained mostly independent, even while being heavily taxed. In 106, the
region was absorbed by the Roman Empire and Petra became the capital of the Empire
province (Nabataea) that contained Jordan. Over the next 200 years, the city flourished. With
Egypt and the Mediterranean Sea to the west, the Red Sea and Arabia to the South, Asia to the
east, and the Aegean, Europe, and the Black Sea to the north, Petra was a bustling crossroads.
Even after the split of the Roman Empire and a devastating earthquake in the fourth century,
Petra maintained itself as a trade center and prominent city in the Byzantine Empire. By the
sixth century, trade routes had shifted out of the way of Petra, causing its slow decline. Another
earthquake in 551 devastated the city, ensuring its decline to a small settlement.

The Artifacts
Due to the trade center nature of Petra, the artifacts we will be studying may or may not have
been manufactured at Petra itself. It is more than likely that they were forged elsewhere and
brought to Petra. This aspect has negative and positive consequences. On one hand, artifacts
with scattered provenance make it difficult to determine trends in forging control over time at a
single site of production. In other words, it might be interesting to know how one family, line of
craftsmen, or people at a particular site changed their production process – for better or worse
- over time. But, it would be impossible to use data from our artifacts to assert anything about
production at Petra itself. On the contrary, having a relatively random sampling of artifacts
from around the Roman Empire and beyond can give a good indication of the general state of
copper forging in the Mediterranean region.

We will primarily use two copper nails, each measuring about 10cm in length. One of the nails is
bent (Sample 1); the other is still straight (Sample 2). Each has a layer of corrosion products
(Copper oxides, sulfates, and sulfides) on the surface. Nails are ideal for this type of variability
testing because they are long and thin. As such, they spanned several inches of the forge and
could potentially display varying properties along their length depending on the homogeneity
of the furnace conditions. We plan to cut the nails perpendicularly to their length into four
small disks to expose the bulk metal underneath. The samples we will examine will be
distributed throughout the inner ~six centimeters of the nail, rather than the two centimeters
on either end. In this way, we will hopefully keep hammering conditions constant. This is a
concern because the head of the nail and the tip were hammered and annealed differently
during production. Thus, we will compare sections with similar production techniques rather
than sections which underwent different processes.

Techniques
We will use several techniques to determine the grain structure, grain size, composition, and
mechanical properties of the copper-based nails.

The two techniques which give the best approximation of microstructure stability, consistency,
and durability are scanning electron microscope (SEM) imagery and nanoindentation. The SEM
images can provide a wealth of information related to the large scale microstructures present in
samples by showing images of the components. These larger structures, such as grains, are very
important to the overall stability and strength of the resulting artifacts. Large, consistent grains
are representative of annealing at high temperatures, whereas less advanced technologies
produce less consistent grain sizes and more variation in structural properties. The shape of the
grains themselves is also indicative of processing, though it does not have as large an effect as
size itself on the properties of materials. Grains with long, straight edges have been either
hammered into alignment or annealed in a controlled environment, whereas more erratic
structures are representative of less technological sophistication.

Another important microstructural application of SEM technology is a direct indication of the

consistency and distribution of material in a sample. While most of an iron artifact is in fact
refined iron, there are small pockets of impurities in any manufactured product. This is
primarily slag, a product of smelting which contains leftover metallic impurities from the
original ore, but can also be a number of other inclusions (such as gases). Any impurity in the
iron structure leads to discontinuous strength properties. With the SEM, individual impurities
can be measured and tested, as an indication of the stages of production used on a particular
artifact. The relative size and distribution of impurities can also give a good indication of the
homogeneity of an artifact, which provides valuable information as to the precision of the
technology employed during production.

The second is nanoindentation, which will be used to measure the mechanical properties of the
artifacts. Nanoindentation is a technique in which a hard (diamond, sapphire, silicon, or
tungsten carbide) probe is pushed several hundred nanometers into a substance with unknown
mechanical properties. The tip, usually a three-sided Berkovich Tip, has a known hardness.
Based on the resistance experienced by the indenter as it is pushed into the specimen, the
unknown material’s hardness and ability to respond to forces can be measured. Given that the
indenter tip is usually less than 5μm wide, a good resolution can be achieved, allowing for a
good idea of how localities in the metal structure behave. This is especially important in
archaeological artifacts; Smith (1981) gives the example of a brass fish-hook, where the tip and
barb are both over twice as hardened as the rest of the hook, due to a disparate construction
process. Because of this variability, nanoindentation at a number of locations along the body of
the artifact can provide important clues as to the construction technologies and sophistication
of ancient cultures.

Another important analytical technique which we plan to use is x-ray diffraction (XRD). This
consists of shooting an x-ray beam at a sample at a glancing angle and measuring the signal
returned along a large angle so that the diffractive properties, and therefore the crystalline
structure, of the samples can be determined. Each crystalline structure has different structural
properties and it is critical that these be properly grouped in order to correctly interpret
nanoindentation data.

Using the combination of these techniques, we will evaluate several points on each artifact to
determine the homogeneity of single artifacts along their lengths, giving us an idea of the
continuity of the conditions in the forge. Therefore, we can infer the control that the forger had
over his furnace. We will then compare the homogeneity of several artifacts in order to
evaluate the general forging practices of the Roman period.

To prepare samples for SEM, they must be cut, polished, mounted, and etched. This process
takes about 3-4 hours per sample. The mounted SEM samples can simply be placed in the
nanoindenter setup as long as they do not exceed 1.5 cm in height and 10cm in width and
height. Similarly, the SEM mounts can be placed directly in the XRD. One challenge may be
focusing the XRD x-ray beam onto the small sample. However, provided that the XRD machine
is working properly, this can be done to reliably shoot the exposed metal surface rather than
the corrosion layer or the resin block.
Timeline
We plan to approach the analysis on a week-by-week basis. This is due predominantly to two
factors: variation in actual sample preparation and analysis time, and the actual schedule
variability for the tools necessary to collect our data. A preliminary schedule is shown below.
Week of 3/7: Identify samples and determine locations of interest. Also, use XRF to gain a
general idea of their composition.
Week of 3/14: Mount and etch samples for SEM+EDS.
Week of 3/21: Image samples in SEM, do XRD on mounted samples.
Week of 4/4: Perform nanoindentation on samples.
Week of 4/11: Analyse results and determine conclusions.

Conclusions
Artifacts from Roman Petra came from a number of different sources through elaborate trade
networks across the Mediterranean. As a bustling metropolis, Petra had artifact production
centers within its walls as well. These different sources of artifacts, while all made at similar
times and using processes which differed only slightly, are potentially very different in their
structural properties. This could lead to a change in relative value and also a good measure of
actual prowess of the individual craftsmen. As such, we plan to investigate the properties of a
number of Petra artifacts to gain a deeper insight into how ancient processes were controlled
and how consistent manufacture in the ancient world really was.

Bibliography
General Copper Production and Analysis
Rothenberg, B. 1990. Ancient Metallurgy of Copper: archaeology-experiment-theory. London: University of
London Press.

S. La Niece, D. Hook and P. Craddock, Editors. Metals and Mines. Studies in Archaeometallurgy, The British
Museum, London (2007).

R. F. Tylecote, H. A. Ghaznavi, P. J. Boydell. Partitioning of trace elements between the ores, fluxes, slags and
metal during the smelting of copper. Journal of Archaeological Science, 4, 1977, 305-333.

Scott, D. A. Copper and Bronze in Art, Getty Publications, 2002.

Roman Era Copper

Roman Copper Alloys: Analysis of Artefacts from Northern Britain. Journal of Archaeological Science, 24, (1997)
901-910.
Chris O. Hunt, David D. Gilbertson, Hwedi A. El-Rishi. An 8000-year history of landscape, climate,
and copper exploitation in the Middle East: the Wadi Faynan and the Wadi Dana National Reserve in southern
Jordan. Journal of Archaeological Science, 34, 2007, 1306-1338.

J.P. Grattan, D.D. Gilbertson, C.O. Hunt. The local and global dimensions of metalliferous pollution derived from a
reconstruction of an eight thousand year record of copper smelting and mining at a desert-mountain frontier in
southern Jordan. Journal of Archaeological Science, 34, 2007, 83-110.
F. B. Pyatt, G. Gilmore, J. P. Grattan, C. O. Hunt, S. Mclaren. An Imperial Legacy? An Exploration of the
Environmental Impact of Ancient Metal Mining and Smelting in Southern Jordan. Journal of Archaeological
Science, 27, 2000, 771-778.

M. Ponting and I. Segal, Inductively coupled plasma-atomic emission spectroscopy analyses

of Roman military copper-alloy artefacts from the excavations at Masada, Israel. Archaeometry 40.1 (1998), pp.
109–122.

Nanoindentation in archaeology
Felix Riede, Jeffrey M. Wheeler. “Testing the „Laacher See hypothesis‟: tephra as dental abrasive.” Journal of
Archaeological Science, 36, (2009) 2384–2391.
Gordon D. Sanson, Stuart A. Kerr, Karlis A. Gross. “Do silica phytoliths really wear mammalian teeth?” Journal of
Archaeological Science, 34, (2007) 526-531.
Harry Lerner, Xiangdong Du, Andre Costopoulos, Martin Ostoja-Starzewski . “Lithic raw material physical
properties and use-wear accrual.” Journal of Archaeological Science, 34, (2007) 711-722.

Modern copper product nanoindentation

Jin-Yuan Hsieh, Chuan Chen, Jun-Liang Chen, Chien-I Chen, Chi-Chuan Hwang. The nanoindentation of a copper
substrate by single-walled carbon nanocone tips: a molecular dynamics study. Nanotechnology (2009), 20, (9), no
page numbers.
Chung-Ming Tan, Yeau-Ren Jeng. Computer simulations of nanoindentation on Cu (111) with a void. International
Journal of Solids and Structures (2009), 46, (9), 1884-1889.
Eralp Demir, Dierk Raabe, Franz Roters. The mechanical size effect as a mean-field breakdown phenomenon:
Example of microscale single crystal beam bending. Acta Materialia (2010), 58, (5), 1876-1886.
Neng-Kai Chang, Yong-Siang Lin, Chi-Yao Chen, Shuo-Hung Chang. Size effect of indenter on determining
modulus of nanowires using nanoindentation technique. Thin Solid Films (2009), 517, (13), 3695-3697.
T.B. Britton, D. Randman, A.J. Wilkinson. Nanoindentation study of slip transfer phenomenon at grain boundaries.
Journal of Materials Research (2009), 24, (3), 607-615.
B.X. Xu, Z.F. Yue, X. Chen. Numerical investigation of indentation fatigue on polycrystalline copper. Journal of
Materials Research (2009), 24, (3), 1007-1015.
Z H Cao, P Y Li, H M Lu, Y L Huang and X K Meng. Thickness and grain size dependent mechanical properties of
Cu films studied by nanoindentation tests. Journal of Physics D: Applied Physics (2009), 42, (6), 065405/1-
065405/6.

Site studies and artifact descriptions

Archaeological survey of the southern temple at Petra. Martha Sharp Joukowsky. Syria, T. 72, Fasc. 1/2 (1995):
133-142.
Martha Sharp Joukowsky. Petra Great Temple Volume 1: Brown University Excavations 1993-1997. Providence, RI:
Petra Exploration Fund (1998).
Hauptmann, Andreas. The archaeometallurgy of copper: evidence from Faynan, Jordan. Springer (2007).
Blanchard, Ian. Mining, Metallurgy and Minting in the Middle Ages: Asiatic supremacy, 425-1125. Franz Steiner
Verlag (2001).
Forbes, R.J. Metallurgy in Antiquity. The British Journal for the Philosophy of Science, Vol. 4, No. 14 (Aug., 1953),
pp. 165-168.
G. Artioli, Crystallographic texture analysis of archaeological metals: interpretation of manufacturing techniques,
App.Phys.A. 89, (2007), 899-908.
Serneels, V. and S. Perret. 2003. Archaeometallurgy in Europe. Proceedings of the International Conference (Milano,
24-26 septembre 2003). Milano: Associazione Italiana di Metallurgia, Vol. 1, 469-478.
Also of interest (all Cu-related items found at Petra's Great Temple, perhaps for reference/comparison...?):

http://opencontext.org/sets/Jordan?q=copper

Grattan: The heavy metal content of skeletons from an ancient metalliferous polluted area in southern Jordan with
particular reference to bioaccumulation and human health.

g.m. ingo et al. Large scale investigation of chemical composition, structure and corrosion mechanism of bronze
archeological artefacts from Mediterranean basin. Appl. Phys. A 83, 513–520 (2006)

Mike R. Notis and Aaron N. Shugar. ROMAN SHEARS: METALLOGRAPHY, COMPOSITION AND A
HISTORICAL APPROACH TO INVESTIGATION. Proceedings of: ARCHAEOMETALLURGY IN EUROPE,
24th – 26th September 2003.

Thilo Rehren. The archaeometallurgy of copper and lead and their related alloys.

F. Cattin & B. Guénette-Beck & M. Besse & V. Serneels. Lead isotopes and archaeometallurgy. Archaeol Anthropol
Sci (2009) 1:137–148.
(This just has a ton of sources on copper in it; it is just a compendium of everything ever written on LIA)

Alessandra Giumlia-Mair. Chemical Analyses And Archaeometallurgy: Problems and Possibilities. Proceedings of
the 10th International Conference on Particle Induced X-ray Emission and its Analytical Applications.

M. Pernot. Lecture technologique, chaîne opératoire, expérimentation et fouille d‟ateliers : des outils pour
comprendre les artisans du métal.
(French, but has a few English sources)

A. Bernard Knapp. ARCHAEOLOGY, SCIENCE-BASED ARCHAEOLOGY AND THE MEDITERRANEAN

BRONZE AGE METALS TRADE. EUROPEAN JOURNAL OF ARCHAEOLOGY 3(1): 31-56.

Web sources
http://www.dartmouth.edu/~toxmetal/metals/stories/copper.html

Awesome:
http://cat.inist.fr/?aModele=afficheN&cpsidt=2463203

****
http://www.revue-
metallurgie.org/index.php?option=article&access=standard&Itemid=129&url=/articles/metal/abs/2002/02/P97/P97.
html
http://www.sciencedirect.com/science?_ob=ArticleURL&_udi=B6TJN-4P5NWYD-
1&_user=489286&_coverDate=10%2F31%2F2007&_rdoc=1&_fmt=high&_orig=search&_sort=d&_docanchor=&
view=c&_searchStrId=1240614030&_rerunOrigin=scholar.google&_acct=C000022678&_version=1&_urlVersion=
0&_userid=489286&md5=fc1fbfd879b1229c47601156327bf794

This is totally relevant:

http://www.jstor.org/stable/504330

http://books.google.com/books?hl=en&lr=&id=U64OAAAAQAAJ&oi=fnd&pg=PA317&dq=related:9_gUsk-
Ef4sJ:scholar.google.com/&ots=7EIjHF9lF5&sig=3_P1P5wWnroZHWTA4mJ6k67goKY

http://www3.interscience.wiley.com/journal/119387787/abstract

http://pubs.acs.org/doi/abs/10.1021/ba-1988-0220.ch009

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http://books.google.com/books?id=k0SfRS8fQFoC&pg=PA51&lpg=PA51&dq=archaeometallurgy+bronze+petra&
source=bl&ots=9UX251_34s&sig=KoPJYrh0SFiHLpJqlgS1KUm4YMM&hl=fr&ei=2FCWS-
3fGZS0tgesvPjsDQ&sa=X&oi=book_result&ct=result&resnum=1&ved=0CAYQ6AEwAA#v=onepage&q=archaeo
metallurgy%20bronze%20petra&f=false

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