J. Am. Ceram. Soc.

, ]] []]] 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

Institute of Archaeology, University College London, London WC1H 0PY, UK

School of History and Archaeology, Cardiff University, Cardiff CF10 3EU, UK

microscope (Wetzlar, Germany) and subsequently carbon coated

for analyses on a scanning electron microscope with an energydispersive spectrometer (SEM-EDS). A few specimens were etched
by dipping for 1025 min in 5%12% HF solutions, then neutralized in acetone, and washed in industrial methylated spirit. These
were subsequently gold coated to optimize electron imaging.
Carbon-coated specimens were analyzed using a Philips
XL30 SEM-EDS (FEI, Eindhoven, the Netherlands) with an
INCA Oxford spectrometer package (Oxford, UK), operating at
20 kV and a working distance of 10 mm. Compositional analyses of ceramic matrices were obtained through EDS measurements of areas of B70100 by 100150 mm, with 510 analyses
per crucible section. These were performed with spot sizes of
4.75.3 (INCA conventional units) and process time 5, corresponding to a detector dead time of 25%40%, and an acquisition time of 75 s. Results are reported as normalized weight
percentages. Etched and gold-coated specimens were examined
using a eld emission SEM JEOL JSM-6301F (Akishima,
Japan) operating at 6 kV and 15 mm.
For XRD analysis, a small portion of sample was crushed in
an agate pestle and mortar until fragments passed a 72-mesh
British Standard sieve. The powder was put into an aluminum
sample holder using the back-packing method to avoid sample
orientation. Data were obtained using a Philips 1720 diffractometer (FEI, Eindhoven, the Netherlands) tted with a curved
graphite crystal monochromator using CuKa radiation, 40 kV,
30 mA, a 0.5 mm divergent slit, a 0.2 mm receiving and 0.5 mm
scatter slit, ratemeter 5
102 cps at time constant 5. Scan range
was from 21 to 601 2y at 0.51 2y per minute. The data were
processed and interpreted using the Philips PC-APD software
version 1.6.

Crucibles from the German region of Hesse have been famous

since the Middle Ages due to their exceptional quality, regarded
by many as a mystery. We analyzed 50 Hessian and non-Hessian archeological crucibles using SEM-EDS, FESEM, and
XRD to investigate their technology and material properties. It
was revealed that Hessian crucibles were systematically made of
kaolinitic clay with a low ux content, mixed with quartz sand,
and red to temperatures in excess of 13001C. Primary mullite
developed in most of the glass matrix, with secondary mullite in
some regions of clayfeldspar relict mixtures. Consequently, the
vessels showed superior creep and thermal shock resistance,
high-temperature strength, and thermal and chemical refractoriness. These crucibles represent the earliest industrial exploitation of mullite in Europe, which explains their historical success.
I. Introduction

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

III. Results and Discussion

All the unused Hessian crucibles analyzed have very similar
characteristics, which indicates that raw materials and manufacturing techniques were kept standardized for centuries. The
ceramic matrices are composed of a relatively pure kaolinitic
clay, with a mean Al2O3 content of 39.6% and very low levels of
alkali and earth alkali oxides, their sum being just about 2%
(Table I).
The most typical nonplastic addition consists of 2040 vol%
subrounded or spheroidal quartz sand grains, moderately well
sorted in the medium to coarse sand range (+0.251 mm)
(Fig. 1). These grains appear internally cracked and show dissolution interfaces with the surrounding ceramic, even in unused
vessels, which indicates a ring temperature above 12001C.9 A
few (o5 vol%) smaller inclusions were identied, namely
monazite, humboldtine, rutile, and some concentric ferruginous
concretionsall of which are known to occur in Hesse. Some
relict structures of molten potassium feldspars were also noted.
Overall, the scarcity of mineral inclusions other than the quartz
sand suggests that the clays were levigated, i.e. size sorted by
settling in owing water.

II. Experimental Procedure

We analyzed ca. 50 Hessian and non-Hessian crucibles from 10
archeological sites, both used and unused, prepared as cross sections in epoxy resin and polished to a 1 mm nish with diamond
pastes after initial grinding with SiC and water. Most specimens
were rst examined under a Leica DM LM reected light optical
W. Leecontributing editor

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

Vol. ]], No. ]]

Communications of the American Ceramic Society

Table I. Chemical Composition (wt%) of Unused Hessian Crucible Matrices
Na2O

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

Porosity is about 20 vol% and manifest in three forms: (a)

subrounded pores around quartz grains; (b) long, subangular
pores parallel to the wall surfaces; and (c) ne vitrication
porosity (Figs. 12). The rst type is because clay platelets
tend to be aligned with their plane faces tangential to the surface of the nonplastic particles, and the cavities are then enlarged due to the high expansion/contraction coefcient of
quartz grains during lattice inversion upon ring and cooling.10
The long pores are due to the shrinkage of the ceramic matrix
during ring, and their alignment is a reection of the overall
clay orientation during the manufacture of the crucibles on a
rotating potters wheel. The closed microporosity in the ceramic
matrix results from the development of glass during ring, with
the subsequent lling of small pores and gas diffusion into
growing, larger ones.1011
XRD of a powdered sample from an unused crucible showed
the presence of mullite, cristobalite,z quartz, and hematite. The
presence of hematite is consistent with the generally reddish color of these fabrics, in spite of the relatively low FeO concentrations (B2%), and suggests that the crucibles were red in an
oxidizing atmosphere. It should be noted, however, that a recent
study3 has identied metallic iron within the vitried matrix of a
Hessian crucible.
Most important here is the presence of a mullite phase, most
likely crystallized following the decomposition of kaolinite under high temperatures, and which we interpret as the main secret
behind the superior material properties of the vessels. The XRD
results are consistent with the SEM observations on etched
specimens of unused crucibles. The vitried groundmass
appears composed of cuboid, primary mullite. In areas of higher ux content caused by molten feldspars, a network of interlocking needles (r120 mm) of secondary mullite is present (Figs.
35). As noted by Iqbal and Lee12,13 and Lee and Iqbal14 in their
study of porcelains, primary mullite crystals formed in the pure

clay agglomerates have the lowest aspect ratio because of the

high viscosity of the matrix. Conversely, secondary mullite crystals can grow unhindered in the low-viscosity clayfeldspar relict
mixtures. The needles of secondary mullite can be clearly seen to
originate from the surface of the clay and grow into the less
viscous feldspar relict (Fig. 6), in agreement with previous
observations of the possible transformation of primary into secondary mullite.1214 In addition, the substantial growth of these
crystals is consistent with its ring in an oxidizing atmosphere.15
The presence of well-developed mullite indicates ring temperatures in excess of 12001C, while the limited presence of bubbles
and the lack of mullite dissolution suggest that a temperature of
14001C was not exceeded during ring.12 Thus we estimate that
the ring of Hessian crucibles involved sustained temperatures
in the 1300114001C range, in agreement with a recent, independent estimate.3

IV. Material Properties and Performance

The characterization of these crucibles allows inferences about
their material properties and performance. The use of levigated
clays would minimize the risks of crucible failure during ring or
use due to the presence of mineral inclusions of unpredictable
thermal behavior. The abundant and relatively coarse quartz
grains would be benecial in two ways: rstly, the presence of
this refractory ller would prevent the body from shrinking or
distorting excessively during ring; secondly, it would increase
the toughness and thermal shock resistance of the red vessels. It
has been suggested that the cracks and pores induced by the
presence of quartz grains in vitried stonewares may be their
main structural aw.16 However, experimental studies of coarsetempered ceramics have demonstrated that this network of
microcracks and hard inclusions help arrest and dissipate fracture lines caused by mechanical or thermal stresses, requiring
more energy for them to propagate catastrophically through the
ceramic body.17,18 High toughness would be an asset for handling and long-distance transportation of the crucibles. Thermal

Fig. 1. Backscattered electron image of the fabric of an unused Hessian

crucible, showing cracked quartz grains with dissolution interfaces in a
vitried matrix. Note presence of porosity (black) around the quartz
grains and as elongated voids in the glass.
z
The identication of cristobalite is based on a reassessment of a previously published
XRD spectrum.8

Fig. 2. Secondary electron image of an unetched, unused Hessian crucible, showing ne vitrication porosity in a matrix of primary mullite.

2008

Communications of the American Ceramic Society

Fig. 3. Secondary electron images of etched specimens, showing an

area of highly acicular secondary mullite formed in a clayfeldspar relict
mixture. The surrounding matrix is composed of primary mullite.

shock resistance would be of utmost importance, as these vessels

were repeatedly moved in and out of furnaces operating at
10001C and above.
We believe that the main factor leading to superior material
properties was the development of mullite through high-temperature ring. Mullite is deliberately developed in a wide range
of modern ceramics, including building materials, refractories,
optical materials, and ceramic matrix composites.19 All of these
applications exploit relevant properties of mullite such as low
thermal expansionand the associated excellent thermal shock
resistancehigh creep resistance, high-temperature strength,
and an outstanding stability under aggressive chemical environments.19,20
Because of the scarcity of feldspar grains in the crucible fabrics, high aspect ratio secondary mullite is only present in certain
areas, whereas the bulk of the matrix is dominated by primary
mullite. A larger concentration of interlocking secondary mullite
crystals might have conferred these vessels with even higher
strength and toughness. However, more ux would have been
necessary for this, for example through the addition of ground
feldspars as in porcelain technology.14 This would have resulted
in a lower bulk Al2O3 concentration in the matrix, with the
subsequent decrease in thermal refractorinessand thus a limitation for the performance of the crucibles. Overall, it appears
that the raw materials and manufacturing techniques employed
were optimum for the required material properties of the crucibles, which would be used under extreme mechanical, thermal,

Fig. 4. Secondary electron image of another etched specimen, showing

well-developed secondary mullite in a clay-feldspar relict area, surrounded by a matrix of primary mullite.

Fig. 5. Detail of the highly acicular prismatic needles of secondary

mullite in a ux-rich area.

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.

Communications of the American Ceramic Society

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.

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