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, ]] []]] 14 (2008)
DOI: 10.1111/j.1551-2916.2008.02383.x
r 2008 The American Ceramic Society
Journal
Mass-Produced Mullite Crucibles in Medieval Europe: Manufacture and
Material Properties
Marcos Martinon-Torres,w,z Ian C. Freestone,y Alice Hunt,z and Thilo Rehrenz
z
are ceramic vessels used for dry, i.e. high temperature, reactions. Since the late Middle Ages, the crucibles
manufactured in the German villages of Epterode and Almerode
(current GroXalmerode, in the Hesse region) have been
renowned among assayers, alchemists, chemists, metallurgists,
jewellers, and coin minters.1,2 The crucible-making recipe was a
closely guarded secret, and several potters failed at attempting to
replicate them3which led some to speak of the mystery of
Hessian wares.4 Crucibles were mass produced in Hesse since
the 12th century,2 and recent archeological and analytical work
has identied Hessian crucibles in a wide geographic region,
reaching Norway, Britain, Portugal, and even Jamestown in the
American colony of Virginia, and ranging from the 15th to the
19th century.57
In a previous paper we suggested that the main secret behind
the superior quality of these vessels was the development of
mullite during ceramic manufacture.8 Here we report further
work on the technology, microstructure, and material properties
of these crucibles.
RUCIBLES
Manuscript No. 24118. Received December 18, 2007; approved February 7, 2008.
Financial support for M. Martinon-Torres was provided by the Arts and Humanities
Research Council (UK) and Caixanova (Spain).
w
Author to whom correspondence should be addressed. e-mail: m.martinon-torres@
ucl.ac.uk
Mean (n 5 5)
Standard deviation
Maximum
Minimum
0.1
0.05
0.2
0.1
MgO
Al2O3
SiO2
P2O5
K2O
CaO
TiO2
FeO
0.5
0.09
0.7
0.5
36.9
0.39
37.5
36.5
56.8
0.22
57.1
56.5
0.2
0.11
0.4
0.1
1.3
0.13
1.5
1.2
0.3
0.05
0.3
0.2
1.9
0.08
2
1.8
2.0
0.18
2.2
1.7
Fig. 2. Secondary electron image of an unetched, unused Hessian crucible, showing ne vitrication porosity in a matrix of primary mullite.
2008
and chemical stresses. This may explain why the recipe was kept
secret and uniform for centuries, even if crucible makers would
not be aware of mullite as such. The exceptionality of Hessian
crucibles is better understood with reference to earlier and contemporary ceramics. Before the 16th century, most crucibles
manufactured across the world were made of clays with lower
Al2O3 concentrations than the Hessian ones and red to lower
temperatures.21 From the Renaissance, developments in alchemy and re assay led to the systematic conduction of chemical
reactions under increasingly high temperatures, using new acids
and uxes. Only standardized, mass-produced mullite crucibles
were capable of withstanding these conditions, hence allowing
for experimental replication. Thus, the changing demand may
have encouraged the changes in ceramic technology that led
Hessian potters to produce this earliest industrial exploitation of
mullite ceramics in Europe. Their only competitors would be the
graphite crucibles manufactured in Bavaria.57
Previously, mullite has been identied in postmedieval crucibles used for melting glass22 and manufacturing wootz steel.23
However, in both cases, mullite developed during the high-temperature utilization of the vessels, rather than the rst ring in
the potters kiln. The prering temperature documented in the
Hessian crucibles is exceptional for European premodern
ceramics. The only other ware produced in Europe at temperatures above 11501C was German salt-glazed stoneware,24 and
the possible link between both technologies deserves further
research. Another aspect warranting investigation is the possible
relationship between the manufacture of Hessian crucibles and
the discovery of porcelain in Europe: although the earliest Eu-
Fig. 6. Secondary electron image showing the needles of acicular mullite growing out of a matrix of primary mullite.
ropean porcelain was based on the use of a lime ux, rather than
feldspar, and the developments in porcelain ring were based on
experiments with burning lenses, it is interesting to note that
J. F. Bottger, the discoverer of porcelain, worked as an assistant
to an alchemist25 who could have utilized Hessian crucibles.
V. Conclusions
Potters in the Hesse region were mass producing mullite crucibles several centuries before mullite was identied as a mineral
phase. Mullite was synthesized by ring quartz-tempered kaolinite to temperatures above 13001C, with primary mullite developing in most of the glass and highly acicular secondary mullite
growing in regions uxed by feldspars. The resulting crucibles
showed superior material properties, including high-temperature strength, creep and thermal shock resistance, and thermal
and chemical refractoriness. This explains their outstanding success in the international market from at least 1500.
Acknowledgments
We are very grateful to H.-G. Stephan, who provided the reference samples of
Hessian crucibles, and to many other archeologists who facilitated our access to
further samples from across the world. We are also indebted to Kevin Reeves and
Philip Connolly for technical assistance.
References
1