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Conservation of a composite cannon Batavia (1629)

Article  in  International Journal of Nautical Archaeology · February 2007

DOI: 10.1111/j.1095-9270.1982.tb00081.x

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 The international Journal ofNautical Archaeology and Underwater Exploration (1982), 11.3: 213-219
Conservation of a composite cannon Batavia (1629)
Ian D. MacLeod and Neil A. North
Department of Material Conservation and Restoration, Western Australian Museum, Cliff Street,
Fremantle, WA 6160
Over the past two decades there has been a
steady improvement in treatment methods for
material recovered from shipwreck sites.
Although a number of problems still remain it
is, at this stage, generally possible to stabilize
any marine archaeological artefact provided it is
composed of only one material. A significant
number of artefacts, however, are composed of
more than one material and treatment of these
artefacts is often difficult, or impossible, with
our present knowledge. Usually the treatments
for one component material of the artefact will
either destroy the other components or leave
them in an unstable condition. Typical examples
of such material combinations are wood and
iron (e.g. pulley blocks), leather and rope
(e.g. leather wrapped rigging ropes) and dis­
similar metals (e.g. bronze handles on swords).
If the object can be dismantled, it is possible
then to treat each of the components separately
but damage can be caused during the dis­
mantling. Dimensional changes during treatment
often make it very difficult to put the artefact
back together. In other cases the construction
of the artefact makes dismantling impossible
and in these cases the conservator is faced with
a different treatment problem. One such
problem we have recently treated was an iron,
lead, copper composite cannon from Bat(ll'ia
(1629) and the methods used may be useful to
others faced with similar problems.
The raising, examination and sectioning of
this cannon have been described by Green
(I 980). During this examination the cannon
was sectioned lengthways to form two pieces.
The major slice consisted of approximately
three-quarters of the original cannon and in­
cluded both trunnions. The minor slice had the
same overall composition and construction as
0305-7445/82/030213 + 07 $03.00/0
the main section but, being judged Jess impor­
tant, it was treated first to ensure the proposed
method worked satisfactorily. The construction
of this cannon is shown in Fig. I with details
of its walls in Figs 2 and 3. A careful exami­
nation of the cannon prior to treatment showed
the presence of three major and two minor
components. These were analysed and found
to be:
I. wrought iron rings;
2. wrought copper sheeting;
3. lead-tin filler;
4. yellow brass brazing;
S. leaded bronze cascable.
For chemical analyses of some of the materials
see Table 1.
There are treatments available for each of
these components when considered separately
but in all cases the normal treatments for one
component would cause damage to other com­
ponents. For example, the treatments commonly
used for marine iron are either reduction in
°
hydrogen at 400 C or electrolysis in O·S M
sodium hydroxide solution. Both these would
cause damage if used on this cannon. The
hydrogen reduction would produce metal­
lurgical changes in the copper alloys and
°
melting of the lead filler (m.p. l 90 C). The
electrolysis in sodium hydroxide would cause
corrosion of the lead filler, particularly in
crevices. However, the cannon could not be left
untreated as chlorides present in the corrosion
products were producing active corrosion,
particularly of the iron rings. Consequently
if was decided to examine all conservation
techniques previously used on the individual
component materials to determine if any of
these could be adapted for treating the corn-
© 1982 The Nautical Archaeology Trust Ltd.
 NAUTICAL ARCHAEOLOGY, 11.3

posite cannon. Before any treatment was

undertaken the cannon and its attached con­
cretions were thoroughly examined, analysed
and identified to extract all possible information
and in particular that which could be lost
during the conservation treatment.

Examination and preliminary treatment

The cannon when recovered had a thin layer of
dense calcareous concretion adjacent to the
metal surface and an outer layer of corals,

••••
molluscs and other sedentary epifauna. Such
growth is unusual on copper alloys as their
biological toxicity usually prevents significant

�,,...=
marine growth on their surfaces. Examination
of this concretion under a scanning electron
microscope showed that the layer adjacent to
the metal was predominantly inorganic calcium
carbonate. As the composite cannon contained
iron and, on the seabed, was in contact with

·..• cast iron cannon this inorganic calcium car­

Figure I. Major section of the composite cannon
with cascable attached, after treatment.
Scale in centimetres.
bonate probably formed as a result of galvanic
coupling. The iron cannon formed the anode
and the composite cannon the cathode; the
resulting increase in alkalinity (pH) at the
copper surface caused precipitation of CaC03
from the seawater. Once the copper was covered
with a layer of calcium carbonate the marine
organisms grew on the surface in the same
fashion as they do with any biologically inert
substrate on the Batavia wreck site (North,
1976). The biological marine growth was readily
removed by chipping as it was only weakly
attached to the substrate. The inorganic CaC03
layer, by contrast, was very strongly adherent.
Normally such concretion would be removed
by placing the artefact in citric acid (with
thiourea inhibitor). As this procedure would
cause corrosion of the iron and lead com­
ponents an alternative procedure of physically
deconcreting using a flat hammer and a vibrating
pen was used. This gave good results but was
very slow, taking several man weeks work.
Beneath the concretion layer the copper was
covered with the usual marine copper patina,
consisting mainly of Cu2 0 (cuprite) with areas
of active corrosion characterized by the presence
of blue-green Cu2 {0H)3 Cl (atacamite and
paratacamite).
After sectioning, the calcareous concretions
were mechanically removed from the bore of

214
l. D. MACLEOD AND N. A. NORTH: CONSERVATION OF COMPOSITE CANNON

Figure 2. Detail of cannon walls near trunnion.

Figure 3. Detail of cannon walls near muzzle.

215
NAUTICAL ARCHAEOLOGY, 11.3
Table 1. Composition of major alloys used in the construction of the composite cannon
Copper Lead Zinc
Filler metal 0-26 72-8 0·006
Copper sheathing 98-85 0•275 0·01
Bronze cascable 66-9 22-6 0·28
"' These unusually high levels of arsenic and antimony may be due to errors inherent in sampling such inhomo­
geneous materials.
the cannon. These consisted of an inner layer of
inorganic CaC03 and an outer layer of seabed
debris. Beneath the inorganic CaC03 the sur­
face of the copper was patinated primarily with
CuO (tenorite). The presence of CuO on marine
copper is most unusual as this oxide is generally
associated with high temperature oxidation of
copper (Mellor, 1967). It is probable that the
CuO was formed prior to the shipwreck. High
temperatures may have been attained during
firing of the cannon or during manufacture; in
the latter case the CuO on the outer cannon
surface could have been removed by sub­
sequent polishing. Longitudinal scoring on parts
of the barrel was found and this is consistent
with the firing of shrapnel and grape shot.
Active corrosion was indicated by the
presence of large patches of Cu 2 (OH)3 Cl as
well as active bronze disease on the copper
surfaces, particularly the copper barrel lining.
On the cut surfaces exposed by sectioning the
iron was weeping yellow droplets of iron
chloride solution.
Examination of the cannon section near the
muzzle end showed flow-lines in the filler metal
which were °
consistent with the lead-tin alloy
(m.p. 190 C) having been poured into the 'cold'
cannon which was positioned vertically, muzzle
down. Copper sheet used in the fabrication of
the breech had been joined with copper rivets
and subsequent corrosion had etched the
copper to reveal longitudinal lines associated
with stress developed during construction.
Similarly corrosion on the seaward surface of
the copper sheet in the bore showed up large
(approx. 0·007 m) metal crystals which indicates
that the metal had cooled over a long period.
The bronze cascable was found to have
traces of the original iron screw thread left
behind in the form of corrosion products.
Excavation of the breech revealed part of the
original iron thread, which was left-handed over
216
Tin Iron Arsenic Antimony
26·5 0-101
0·25 0-05 n.d. n.d.
2-84 0·13 4·0 "' 3.5•
the cannon length and right-handed in the cas­
cable. This thread combination ensured that the
seal between the iron bar and the cannon would
not be damaged during periodic removal of the
cascable. The high leaded bronze of the cascable
had suffered minimal corrosion, approx.
0·2 mm, after 350 years in the sea.
Treatment
From the detailed examination of the com­
posite cannon it was seen that major degradation
was occurring in the iron and copper com­
ponents and was being caused by the presence
of chlorides in the iron and copper corrosion
products. Therefore the aim of the first con­
servation stage was to safely remove the
chlorides from the artefact. Extraction into
aqueous solutions appeared the most promising
method of treatment.
Chlorides can be washed out of marine iron
by soaking the iron artefacts in solutions of
high pH (usually 2% by weight NaOH), although
this method is not widely used as the extraction
rates. are frequently far too slow (North &
Pearson, 1978). Similarly, chlorides can be
removed from marine copper alloys by soaking
in distilled water or in a solution containing
equal weights of NaHC03 and Na2 C03. With
both iron and copper alloys the chloride
extraction rate can be considerably improved
by electrolysis, with the artefact as cathode
(negative). This behaviour suggests that, if
copper and iron only were present, satisfactory
treatment could be achieved by soaking or
electrolysing in an alkaline solution, such as
Na2 C0 3 or NaOH. The presence of lead com­
plicates the treatment procedure as lead, being
amphoteric, is corroded by both high and low
pH solutions. Even in neutral solutions lead can
corrode at a significant rate.
In conservation there are two common means
for overcoming the problem of lead corrosion
 l. D. MACLEOD AND N. A. NORTH: CONSERVATION OF COMPOSITE CANNON
during treatment. The first is to add S04 '.l- ions
to the wash solution; these form a precipitate
of PbS04 on the lead surface and thus stifle
corrosion. However, so/- ions accelerate the
atmospheric corrosion of iron and any S04 2 -
remaining on the iron after treatment could
cause subsequent corrosion problems. A second
method of controlling lead corrosion is electro­
lysis, in which the potential of the lead is made
more negative and the corrosion rate is thus
reduced [ this is a form of cathodic protection­
for further details see Schrier (1979) or other
standard corrosion control texts]. This method
works well provided there are no deep cracks or
crevices in the artefact. If these are present
there is a risk that strongly alkaline solutions
can form in these crevices due to a combination
of poor exchange with the bulk solution and
generation of OH- ions in the electrolysis
reactions. If this situation arises then corrosion
of the lead can occur. This alkaline corrosion of
lead cannot be suppressed by addition of
S04 2 -, as PbS04 is soluble in strong alkaline
conditions and thus cannot form a protective
film. Under alkaline conditions brass is also
corroded with selective removal of the zinc
component (dezincification).
After due consideration of these factors it
was decided that treatment would be tried on
the minor and Jess important cannon section
first. The experience gained would then produce
a better and safer treatment of the main section.
Initially it was decided to treat the minor
section by washing in a solution containing 2%
by weight NaHC0 3 and 2% by weight Na2 C03
(or 4% by weight Na2 C0 3 /NaHC0 3 ). During
BOO�-- - ---------------------
700
i 600
� 500
!.. 400
-- ...
-g 300
0
6 200
.............
...
100 .....�..• """"
0 10
Figure 4. Chloride release rate versus the square root of wash time for the smaller section of the composite
cannon. For details sec text.
this initial washing the Cl- content of the wash
solution was regularly measured to determine
the Cl- release rate and the Pb and Cu content
of the wash solution was regularly measured,
together with the electrochemical potential (E
corr) of the cannon to determine if corrosion
was occurring. The washing was carried out in a
fibreglass tank, for corrosion prevention, using
a wash solution of approximately 300 1.
The chloride release rate is shown in Figure
4. Note that the horizontal axis is the square
root of time (in hours ½ ). The linearity of this
graph for O < t½ < 18 shows that the chloride
release rate is diffusion controlled (North &
Pearson, 1978) and is also relatively slow. After
324 h (t ½ = 18) it was clear that the Cl- release
rates would have to be increased if treatment
was to be completed within a reasonable time.
At this stage the analyses of the wash solution,
inspection of the cannon section and measure­
ment of its electrochemical potential (E corr)
all indicated that corrosion of the cannon section
was occurring. After the initial 140 h of washing
the lead content of the solution had increased
to 47 parts/106 and the copper content to
6·6 parts/I 06 • The exposed iron sections of the
cannon were coated with a layer of red-brown
material composed of 63% lead and 37%
copper. This material is presumably formed by
the cementation reactions:
Fe + Cu 2+ --- Fe2+ + Cu
and Fe + Pb 2+ --- Fe2+ + Pb.
The E corr potential of the cannon section was
measured at -0·750 V versus NHE and Lhe pH
of the solution was 9·95. Inspection of the
Pourbaix diagrams for iron, lead and copper
-
-,
.... , .,. ....... -·---·--�
i"
........---··_...............
�
20 30 40 1 50 60 70 80
T,me ( h2J
217
NAUTICAL ARCHAEOLOGY, I 1.3
show that at this pH and potential the copper
should be immune but both the lead and iron
actively corroding.
To improve the chloride release rate and to
suppress the iron and lead corrosion, electro­
lysis (artefact negative) was commenced on the
cannon section after 3 58 h using sheets of mild
steel as the anodes. The applied voltage was
2·25 V; this voltage produced a smaH but
steady evolution of hydrogen from the cannon
section. Measurement of the cannon section
voltage against a standard reference electrode
showed it now had a potential of - l ·018 V
versus NHE. From the Pourbaix diagrams at
pH 9·9 lead, copper and iron should be immune
at this potential and pH.
Regular chloride analysis of the wash solution
after commencement of electrolysis showed
that the c1- extraction rate had increased from
2·80 ± 0·08 to 13·3 ± 0·5 g Ci-/h\ which
indicates that the diffusion coefficient for Cl­
ions in the corrosion product had increased by
a factor of 22 (North & Pearson, 1980). The
reduction in the Cl- extraction rate after approx.
1OOO h (/h = 3 I ) is typical of diffusion con­
trolled c1- extraction treatments and indicates
that a- extraction is nearing completion. The
solution was chan�ed at 2450 h (r'i2 = 49·4) and
again at 3000 h (l2 = 54·5). Very little chloride
was extracted in the last wash and treatment
was terminated at 5500 h (t¼ = 74). Electro­
lysis was continued throughout treatment
and the cannon section was rotated at 1500 h
to ensure that areas in contact with supports
were treated-as is standard practice in electro­
lysis (Pearson, 1972). In all 205 g of chloride
were released from this section of the cannon.
The current density was approximately
0·8 mA/cm2 and total electricity consumption
29 kWh. After electrolysis the cannon was
cleaned of surface deposits by brushing with a
soft wire brush, washed briefly in deionized
water and protective clear paints applied (see
surface coating section) before going on display.
Although this procedure had successfully
stabilized the cannon section, it was soon found
that residual Na,. C03 /NaHC03 was a problem.
On standing these salts gradually effloresce as
NaHC03 and appear on the cannon section
surface as white fluffy deposits. Although these
did not appear detrimental to the cannon they
did spoil its appearance. To minimize this
218
problem it was decided to treat the main
cannon section at a lower concentration of
Na2 C03 /NaHC0 3 • Using a lower concentration
had two added advantages. Firstly it reduced
the initial chlorides present in the wash solution,
these arise mainly from Cl impurities in the
commercial Na2 C03 and NaHC03 , and
secondly, the treatment cost is reduced.
The main section of the cannon was treated
by electrolysis in a tank containing 1500 l of
Na,. C03 /NaHC03 solution with an applied
voltage of 2·25 V and a current density of
0·2 mA/cm2 • The lower current density, cf. the
minor cannon section, is solely a factor of the
larger surface area of the main cannon section
(approx. 3·6 m2 compared to 0·4 m 2 ). Chloride
content of the wash solution was measured and
graphed as described earlier for the minor
section and the solution changed when neces­
sary. Initially the electrolysis solution contained
3 weight % of Na,. C0 3 /NaHC0 3 but after the
first change this was reduced to l ·8 weight %.
Both these solutions gave good results and after
the second wash the concentration was further
reduced to 0·7 weight %. This level proved
unsuitable as it resulted in pronounced corrosion
of the mild steel anodes and the solution became
full of suspended iron corrosion products.
This problem was solved by increasing the
Na2 C0 3 /NaHC03 to 1· 1% by weight. Treat­
ment continued for 6900 h (290 days) at
which stage 832 g of chloride had been released
and n o further significant release was occurring.
The cannon was then brush-cleaned with a fibre
bristle brush and washed with flowing deionized
water during cleaning.
Protective coatings
After the chloride extraction treatment the
main cannon section was held, uncoated and
inside, for several weeks to allow any efflores­
cence of NaHC03 to take place before coating.
Some efflorescence did occur but the deposits
were easily wiped and washed off the surface.
When efflorescence ceased, protective surface
coatings were applied to the cannon section.
The cut faces of the cannon section were
polished with fine abrasive paper before coating
so as to highlight the different metal surfaces.
The copper areas were initially coated with a
3% by weight solution of benzotriazole (BTA)
in alcohol, BT A being a good corrosion inhibitor
I . D. MACLEOD AND N. A. NORTH: CONSERVATION OF COMPOSITE CANNON

particularly for bronze disease. These were then
coated with INCRALAC which is a clear
acrylic paint containing BTA. The iron and
lead surfaces were coated with a high durability
clear epoxy which incorporates a phosphate
inhibitor (KEPHOS 253 Dulux Paints). All
painting was done with brushes. This system
has proved satisfactory to date with the only
problem being one isolated spot of NaHC03
efflorescence.
The bronze cascable was washed in deionized
water for six months then dried in air and
coated with INCRALAC. The section of iron
screw thread from the breech was impregnated
°
with microcrystalline wax (m.p. 82 C) after
drying in acetone.
NaHC0 3 solution might be successful in
removing the chloride salts from the cannon
without damaging any of the metals. Prelimi­
nary tests on the smaller section of the cannon
showed that washing was unsatisfactory due to
metal corrosion and slow chloride release rate.
Electrolysis gave good results and this method
was subsequently applied to the main cannon
section. The concentration of electrolyte
initially used was 4% Na2 C03 /NaHC0 3 but
this was later reduced to 1·2% which gave
fewer problems with subsequent efflorescence
of NaHC0 3 from the cannon. The method
described here should be generally applicable to
marine artefacts containing wrought iron-lead,
wrought iron-copper, copper-lead or all three
materials.

Summary
Recovery of an iron, lead, copper composite
cannon from the Batavia (1 629) presented a
conservation problem due to the different
metals present. A study of the properties of
each of the component metals and the treat­
ments normally used on them suggested that
either washing or electrolysis in a Na 2 C03 /
Acknowledgements
We would like to thank the Australian Research
Grants Committee for providing financial
assistance for this work. We also acknowledge
the assistance of the CSIRO Division of
mineralogy for their help with electron micro­
probe, electron microscopic and X-ray
diffraction analyses.

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219
NAUTICAL ARCHAEOLOGY, 1 l . 3
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continued u,r p, 232