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Case study

The metallography and corrosion of an ancient chinese bimetallic

bronze sword
Huang Wei a,∗ , Winfried Kockelmann b , Evelyne Godfrey b,c , David A Scott d
a
China Numismatic Museum, Beijing, China
b
Rutherford Appleton Laboratory, ISIS Facility, Chilton, UK
c
Uffington Heritage Watch, Faringdon, Oxfordshire, UK
d
UCLA/Getty Conservation Program, Cotsen Institute of Archaeology, University of California, Los Angeles, USA

a r t i c l e i n f o a b s t r a c t

Article history: A bimetal bronze sword, unearthed from Hunan Province China, dating to the Warring States period
Received 26 April 2018 (476–221BC) was examined analytically by optical metallography, neutron diffraction and X-ray diffrac-
Accepted 10 October 2018 tion. The results indicate that the tin content of the blade is 16%, not higher as previously reported. The
Available online xxx
bimetallic bronze sword possesses a typical cast structure with annealing on the edge of spine. Distinct
corrosion compounds pyromorphite was identified, with pseudomorphic malachite having replaced the
Keywords: original alpha phase. Redeposited copper and unusual phosphorus-containing corrosion products were
bimetal sword
analysed to investigate the mechanism of formation.
Chinese bronze
© 2018 Elsevier Masson SAS. All rights reserved.
Corrosion

1. Introduction
The earliest bimetallic artifacts found in Hebei province and
Beijing are bronze Yues with meteoritic iron blades dating to the
Middle Shang Period (14th century BC). Various bimetallic objects
such as a bronze dagger with an iron blade, an iron Ben with a
bronze hilt, an iron sword with a bronze hilt and an iron knife with
a bronze hilt dated from Western Zhou Dynasty (11–8th century
BC) to early Spring and Autumn period (770–476 BC) were found
in Henan and Shaanxi province [1], from the central plain and sur-
rounding area. Iron as a precious material was often used together
with bronze tools and weapons before the advent of its mass pro-
duction in the Late Bronze Age of ancient China. Recently two
typical iron-bronze bimetallic artifacts, iron-blade bronze chipping
knife and iron-blade bronze dagger axe (Ge in Chinese), were found
in Liangdaicun village, Han cheng city, Shanxi province, which are
examined technically by metallography [2], the two bimetallic arti-
facts are dated to early Spring and Autumn period (770–476 BC).
There are two kinds of bimetallic artifact in Chinese archaeo-
logical finds, iron-bronze combined mechanically, and bronze with
different tin contents on corresponding parts of a sword. During the
Warring States Period, (476–221BC), iron-bronze bimetallic arti-
facts were replaced by bimetallic bronze swords. These swords
were cast together in two different alloys for the back and the blade.
∗ Corresponding author.
This kind of bimetallic bronze sword was only found in South China,
within the area of the Chu culture and its southward neighbours.
Some bimetallic bronze swords excavated at Jiangxi, Zhejiang,
Hunan and Guangdong were subjected to preliminarily alloy com-
positional analyses [3,4,5] showing higher tin contents for the blade
as compared with the back. Four bimetallic bronze sword fragments
collected by the Shanghai Museum were examined using X-ray flu-
orescence; the tin content in the blade was found to be 22–24 wt%,
while the back had 8–15 wt% tin [6,7]. Simulation experiments
designed by the author were used to reconstruct the casting pro-
cesses: the back of the blade is cast first followed by annealing the
tenon slightly, and then the piece-mould of the blade with finished
back inset is prepared for pouring. The back and blade would be
integrated into a completed sword after the liquid metal solidifi-
cation and shrinkage (see Fig. 1, the middle part is finished firstly
and then inserting to the piece-mould with the blade hollow). Two
bronze bimetallic swords dating to early Warring States Period
(476–221BC) unearthed from Xintai city, Shandong province, were
analyzed by X-ray, CT, XRF and metallography, which show the low
and high tin bronze alloy are used respectively on spine and blade
for every sword [8].
However, little attention has been paid to the corrosion phe-
nomena of bimetallic swords, which provides a good opportunity
to investigate the mechanism of deterioration of different bronze
alloys with variable tin content under the same environmental con-
ditions. More case studies are needed to increase the technological
information on these swords from outside the central plain area in
ancient China.

https://doi.org/10.1016/j.culher.2018.10.004
1296-2074/© 2018 Elsevier Masson SAS. All rights reserved.

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Journal of Cultural Heritage (2018), https://doi.org/10.1016/j.culher.2018.10.004
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Fig. 1. The casting method for bimetal sword (after Haiping, 2002).

Fig. 2. Bimetal bronze sword excavated in Hunan Province.

Fig. 3. The colorful surface of the blade (yellow corrosion at the seam, left above).

Fig. 5. Redeposited copper in the crevice between the back and the blade (the
corroded alpha + delta eutectoid and lead particles can be seen). Magnification 20X.

content than the other sections. Fig. 5 It is worth noting that some
unusual yellowish green corrosion products are found in the seam
between the back and blade. On the other side of the sword, lay-
ered corrosion products are clearly visible, the cuprite is possibly
surrounded or covered by blue and green corrosion from loose to
compact green layers outwards. Soil minerals and corrosion prod-
ucts formed on the back section illustrate a light green color on the
outmost layer.

Fig. 4. The cross section for sampling.

2. Experimental details

Sampling on the sword was carried out, and samples were

Figs. 2–4 shows a remnant of the bimetallic bronze sword stud-
ied here dating to Warring States period, excavated in the Hunan
Province by Chinese archaeologists. Distinct colors of the corrosion
phases are observed on all parts of the sword: green, yellowish
green and blue, with some soil inclusions in different areas. Higher
magnification illustrates that the glazed green corrosion shiny layer
appeared only on the surface of the blade, which contains more tin
embedded in resin, followed by grinding, polishing and etching
(by using FeCl3 ·6H2 O in C2 H5 OH with HCl, Na2 S2 O3 and Na2 S2 O5
miscible liquids for colorful metallography) to investigate the
microstructure. The colorful metallography can show the distinct
phases clearly, such as in Figs. 6 and 7.The back and blade sam-
ples show a typical casting structure with ␣ phase, (␣ + ␦) eutectoid
and some dispersed lead particles. The re-crystallized grains on the

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Fig. 6. The corroded alpha phase in the middle area of the image. Magnification 20X.

edge of the tenon section indicate slight re-heating treatment after
casting.
A blade piece was sampled to be examined by time-of-flight
neutron diffraction, which provides a large volume and high
penetration measurement of the bulk phase compositions non-
destructively [9,10,11]. The phases in the alloy substrate and
corrosion products on the surface can be tested simultaneously,
and tin contents of the alloy are calculated in terms of chemi-
cal formula [12]. Neutron diffraction analysis was performed on
the General Materials Diffractometer (GEM) of the ISIS neutron

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Fig. 7. Layered corrosion products on the blade surface (Magnification 20X Polarized
Light).
source at the Rutherford Appleton Laboratory, UK. Neutrons are
produced by stopping 800 MeV protons in a tungsten target. ISIS is a
pulsed source operating at 40 Hz, thus delivering 40 polychromatic
pulses of neutrons per seconds to the sample. The pulsed operation
allows determining the wavelength of each diffracted and detected
neutron in the polychromatic pulse via a time-of-flight (TOF) mea-
surement. A neutron detector at a scattering angle 2 measures
the neutron TOF, i.e. the time that passes from the generation of
the neutron until its capture in the detector. GEM has about 7000
individual scintillation detector elements viewing the sample from
different angles.
3. Metallography and bulk composition
The neutron diffraction data given in Table 1 demonstrate that
two types of alpha phases with 14% and 10% tin contents, respec-
tively, are present in the sampled bronze substrate, indicating
coring during cooling to room temperature during solidification.
The coring means a process of the non-average elemental dis-
tribution in alloy. The delta phase of the (␣ + ␦) eutectoid is a
common phase in cast bronze. It is noted that a small amount of
epsilon phase, often found in tinned surfaces of ancient copper-
based alloys, is present in the blade sample of the bimetal sword,
which is seldom seen in bronze alloy analysis. Usually, attention is
given to copper, tin and lead contents. Hence the appearance of the
epsilon phase may be relevant with regards to pure tin being added
into the copper during the fabrication of the bronze alloy. Possibly,
the ␦ phase transforms to (␣ + ␧) at room temperature with abnor-
mal cooling conditions (Michelle, 2007), but this is seldom if ever
observed.
Table 1
Phase composition and tin contents from neutron diffraction data of the blade.
Identified phases: weight fraction (%) Calculated tin content: weight fraction (%)
Alpha-Cu/Sn (1) 57
Alpha-Cu/Sn (2) 13 Alpha-Cu/Sn(1)
Delta phase 20 Alpha-Cu/Sn(2)
Epsilon phase 0.5 Delta
Lead 7 Epsilon
Cuprite 2.5
Malachite < 0.2 Total tin
Total lead
(TOF-ND: GEM diffractometer; data analysis: GSAS program for Rietveld analysis).
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The total 16% tin content in the blade sample is different from the
composition reported by Haiping [6,7], which exhibits an average
23% tin content in the blade by XRF and a high result of 17–19% tin
content of the blade was also reported by Shifan [5]. Arguably, the
23% tin content, obtained by X-ray fluorescence energy dispersive
spectrometry, was due to the limited penetration depth of the X-
ray method, i.e. the composition is from the tin-rich layer on the
corroded surface of the blade that originates from copper depletion
to the environment. The phases and elements distributed in the
sword substrate are very unevenly distributed based on the neutron
diffraction data and metallographic examination.
XRF or SEM-EDS have the same short penetration depths of a
few␮m in a small area on the corroded surface of the bronze alloy.
The compositional data from the surface methods are less represen-
tative in revealing the alloy constituents reliably. More practical
case studies are needed to explore the compositions of bimetal
alloy quantitatively, for example by using non-destructive neutron
diffraction.
Furthermore, a 23% tin content of blade is not good for the
mechanical properties of sword as a weapon [13]. Although high
tin contents can improve the hardness of bronze alloys, 23% or
more tin generates brittleness for weapons while decreasing the
tensile strength. Ancient Chinese mirrors often contain tin con-
tents of more than 20%, which enhances light reflection by the shiny
silver-coloured surface. However such high tin bronze mirrors are
fragile. So the tin content of 16–18% for the blade of the Hunan
sword should be reasonable.
The lead content of the blade is 7%. Lead can only improve the
fluidity of the melt, and has no other purpose with regards to the
mechanical properties of the sword, since lead is generally not
added to bronze if it is hammered or worked to shape. For ancient
Chinese bronze, lead is usually added for the facility of alloy flowing
during casting.
4. Corrosion phenomena
Cuprite was observed as main corrosion product. Malachite was
not identified by neutron diffraction but it was found that the
amount of malachite is smaller than 0.2%.
As shown in Fig. 3 and Fig. 7, three kinds of patina were found on
the surface of the sword: glazed and compact green, yellowish with
soil minerals and powdery blue corrosion products. These prod-
ucts were analyzed by X-ray diffraction, the results being shown
in Table 2, which indicates that malachite, cuprite, cassiterite and
quartz are the major constituents in the corrosion. However, the
yellowish green corrosion products sampled between the seam of
the back and the blade found iron, lead and phosphorus-containing
compounds in addition to malachite, cuprite, quartz, and romar-
chite.
Diverse selective corrosion and redeposited copper were
observed in the microstructure of the sword sample. The
14.1 % Sn calculated
10.2 % Sn calculated
33 % Sn on phase diagram
38% Sn on phase diagram
16 wt% Sn
7 wt% Pb
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Table 2
Corrosion products of the bimetal sword examined by X-ray diffraction.
Sampling zone Corrosion products identified by XRD
Spine surface Malachite, cassiterite, quartz
Blade surface Malachite, cuprite, cassiterite, quartz
Seam between Pyromorphite, libethenite, malachite,
spine and quartz, goethite, phosphogartrellite,
blade(green- cuprite, romarchite, lanarkite,
yellow lepidocrocite
corrosion)
(Rigaku R-axis Spider machine at UCLA).
Fig. 8. XRD pattern for green and yellow corrosion from different parts.
phosphorus-contained corrosion products are rarely reported from
Chinese contexts.
5. Selective corrosion: type I structures
Ancient Chinese bronze corrosion features were suggested by
Chase [14] to show type I corrosion, namely the removal of the
tin-rich phase to form tin oxide or mixed tin oxide and cuprite cor-
rosion products on the surface [15]. In type II, the alpha phase of the
alloy is dissolved and the delta remains in an uncorroded state. As
Robbiola [16] pointed out, in an oxygenated corrosive medium, the
main phenomenon involved in bronze corrosion is selective disso-
lution of copper from the copper solid solution (␣phase) in type I,
while a coarse structure with a three-layer morphology is assumed
to be controlled by mass transportation of negative species from
the soil (mainly oxygen and chloride ions) characterizes type II.
In the bimetallic sword we have a typical type I corrosion struc-
ture, cuprite mixed with cassiterite and copper carbonates such as
malachite, shown in Fig. 2, Fig. 8, Fig. 7. The pseudomorphic den-
dritic structure shown in Fig. 6, Fig. 9 indicates that the preservation
of structure within the corrosion may originate from an epitax-
ial relation between substrate and product, with a corresponding
retention of shape [17]. The malachite crust in Fig. 7 shows a
well preserved pseudomorphic dendrites pattern. Few examples
of such structures have been published. One exception is a Han
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5
Fig. 9. Pseudomorphic structure on the surface of sword blade surface. Magnifica-
tion 20X.
dynasty (206BC–220BC) buckle reported by Scott [17], page 84,
plate 11). The dendritic malachite on the higher tin zone in the
metal corrosion could indicate the stable environment. In South
China, excavated bronzes with thick greenish malachite covered is
common, where the underground water is plentiful that has advan-
tages for the formation of copper carbonates. In this example, the
dense malachite corrosion not only protects the original cast struc-
ture itself in a good burial condition, but also hinders the massive
oxidation of cuprite in the inner layer with the low tin content.
In the meanwhile, it is noted here that the corroded (␣ + ␦)
eutectoid appeared in the alloy substrate, but in the outer layer,
corroded ␣solid solution is the main corrosion observed on the
surface exposed to the environment overlaying a totally mineral-
ized corrosion layer. A Chinese bronze vessel fragment dating to
the first millennium BC studied by Gettens [18], exhibited a simi-
lar corrosion structure to the bimetallic sword: in the intermediate
penetration zone the eutectic has been corroded leaving dendrites
of the alpha phase unattacked, while on the outer edge of the inter-
mediate penetration zone the alpha dendrites are attacked, and
from here outward only mineral corrosion products are found.
This corrosion phenomenon suggests that a passivating layer
formed in type I corrosion which controlled the oxygen and soil ions
migration into the inner alloy substrate. Between the seam of the
blade and back, corroded (␣ + ␦) eutectoid has created much rede-
posited copper, which will be discussed below. As distinguished
from type II corrosion structure and Getten’s research, no copper
chloride and lead carbonate compounds were found in the X-ray
and neutron diffraction analysis, yet the unusual corrosion product
pyromorphite was found here.
6. Redeposited copper: mechanism and optimum forming
condition
Redeposited copper is found in many archaeological copper-
based artifacts from all over the world, studied and reviewed by
many scholars. Scott [9] reviewed the mechanisms for the forma-
tion of redeposited copper, from decomposition of the delta phase,
the dissolution of cuprite inclusions within the bronze or corrosion
from the dissolution of cuprite crusts formed during burial, or voids
occupied by inclusions and lead globules which become replaced
by copper.
Jin bronze (West Zhou Dynasty, 1027 BC–771BC) fragments
excavated from southwest Shanxi were studied by Wang [19],
which showed that redeposited copper is very common both in the
bronze core and in external corrosion layers, displayed as fine par-
ticles within the cuprite, in filled cracks and surface bands. These
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phenomena are explained by the author as follows: preferential
removal of tin seems to have been the first stage followed by the
formation of cuprite, metallic copper was deposited from solution
when cupric or/and cuprous ion solutions were saturated under
reducing conditions. Bosi [20] provides a review and some case
studies on Chinese and Italian artifacts, which determined that in
most cases unalloyed copper was located in the core of the objects
far from the outer corrosion products layer. Three types were pro-
pose
• irregularly shaped forms, that pseudomorphically replaces other
phases, which is closely related to long-term corrosion processes;
• globular, that are surrounded by a layer of copper sulphide
formed during roasting of the copper ore; or;
• large, irregularly shaped masses, that display a twinned
microstructure, which is due to incomplete mixing of copper and
tin during the casting of the alloy.
From the metallography of the bimetallic sword, large rede-
posited copper illustrates type (a) structure described by Bosi [20].
The metallic copper attributed to type (a) is considered a result
of destannification by Wang and Merkel [21]. In the sword, cop-
per has also formed in pre-existing cracks or voids. A great deal of
redeposited copper assembled in the seam between blade and back,
this narrow gap was formed by the incomplete combination dur-
ing casting. In fact, destannification is just a step in the formation of
metallic copper. Copper or secondary copper reduced from cuprite
would replace the original alpha phase and eutectoid structure in
situ if there was not enough space to escape. The movable rede-
posited copper will selectively dwell into the cracks or voids which
provides a relatively large volume to accommodate, as exhibited
in the case of the bimetallic sword, which indicates that the void
could be one of the key conditions for the formation of redeposited
copper.
The redeposited copper and its various morphologies found in
archaeological metal objects contribute to the authentication of
works of art. Ying [22] suggested that redeposited copper is formed
in a long natural corrosion process which cannot be simulated in a
laboratory. But in recent years, Wang [23] claimed that the depo-
sition of regenerated copper on simulated archaeological bronzes
was simulated under experimental conditions. Copper (1) chloride
could be reduced to pure copper if reduction times were sufficiently
prolonged. However, the metallographic images of regenerated
copper shown by the author did not exhibit the morphology that
has been found in archaeological objects, such as the replacement
of the eutectoid, the alpha phase, or voids by free copper. This sim-
ulation experiment has yet to be verified by further case studies.
7. Unusual corrosion products: phosphorus-containing
compounds
Cuprite, quartz, tin oxide as either cassiterite or romarchite,
basic copper carbonates such as malachite are usual corrosion prod-
ucts found in archaeological bronze objects. The yellowish-green
corrosion (Fig. 3 left above, Fig. 4 left) found in the junction of
the back and blade was examined by X-ray diffraction; the domi-
nant species are pyromorphite with some libethenite. Libethenite
Cu2 (PO4 )(OH), is the most common copper phosphate found as
a corrosion product of bronzes excavated from cremation sites,
associated with decomposing bone and some other source of phos-
phorus [9].
Pyromorphite Pb5 (PO4 )3 Cl, a yellowish-green corrosion prod-
uct was found in a Han Dynasty (c. 175BC) bronze An [24], in lead
beads of the Early Bronze Age in Scotland [25], and a Roman coin
[26]. Pyromorphite is uncommon in archaeological materials. The
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Journal of Cultural Heritage (2018), https://doi.org/10.1016/j.culher.2018.10.004
mineral pyromorphite has been found in the oxidation zone of a
polymetallic vein in Argentina [27], the appropriate formula could
be Pb5 (PO4 , AsO4 )3 (Cl,OH)·xH2 O suggested by recent research [28].
Pyromorphite corrosion may be related to phosphate-
containing soil ascribed to degrading bones. Pyromorphite
could be formed in the soil as a weathering product of lead-bearing
minerals or inclusions. Phosphate amendments to the soil could
induce further formation of pyromorphite [29], which is effective
at immobilizing lead and reducing the associated bioaccessibility
[21]. It is speculated that the bimetallic sword was buried in a tomb
where the bone deteriorated to produce phosphates in a complex
burial context. The phosphate and lead in the soil with chloride
ions, for example, react to generate pyromorphite under environ-
mental conditions distinct from that of lead carbonate produced
in some Chinese bronzes. The lead dominantly transformed into
pyromorphite and lanarkite Pb2 O(SO4 ) in the bimetallic sword
case, whereas no cerussite was found.
8. Conclusions
We studied the bulk composition, microstructure and corrosion
phases of a bimetal bronze sword from Hunan Province, dating to
the Warring States period (476–221 BC). The 16% tin content of the
blade is not as high as that examined in a previous study which
found 23% tin for the blade of the sword. It is necessary to exam-
ine a larger volume of core metal using preferably non-invasive
analytical techniques such as neutron diffraction. The corrosion
phenomena illustrated in the examination of the bimetallic sword
suggest an unusual burial environment over a long period, with
decomposed bone in the tomb generating insoluble pyromorphite.
In this context, selective corrosion – both alpha phase and eutec-
toid had been corroded with the pseudomorphic original structure
having clearly being replaced by malachite. Voids or cracks pro-
vided the optimum condition for the migration and redeposition
of metallic copper in this sword. No bronze disease was found, so
chemical treatment is not necessary in this case. In conclusion, the
sword is stable, without active corrosion in terms of the analysis, so
keeping the bimetallic sword in a dry and clean atmosphere would
be appropriate for preserving the beautiful glazed green corrosion
layers.
Acknowledgments
Thanks are due the conservation laboratory at the Cotsen Insti-
tute of Archaeology at University of California, Los Angeles (UCLA),
The Getty Conservation Institute and Research Institute for provid-
ing the laboratory facilities and documental resources. The author
would like to thank the China Scholarship Council and Peking
University for financial support for his research at UCLA from
2007–2008. The samples were provided by Professor Zhou Weirong
from the China Numismatic Museum, which is gratefully acknowl-
edged.
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