A New Method For Conserving Waterlogged Archaeological Materials

Supercritical Drying: A New Method for Conserving Waterlogged Archaeological Materials
Author(s): Barry Kaye, David J. Cole-Hamilton and Kathryn Morphet

Source: Studies in Conservation, Vol. 45, No. 4 (2000), pp. 233-252
Published by: Taylor & Francis, Ltd. on behalf of the International Institute for
Conservation of Historic and Artistic Works
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SUPERCRITICAL DRYING: A NEW METHOD FOR
CONSERVING WATERLOGGED ARCHAEOLOGICAL
MATERIALS
Barry Kaye, David J. Cole-Hamilton and Kathryn Morphet
Summary-Supercritical drying is one physical option for drying delicate materials, includin
ological origin. The technique is applicable to conserving waterlogged wood in all stages
cork and bone, and to composite materials including wood, metals and other materials. N
required when using the technique. This paper describes the theory behind the technique, a
to archaeological finds. The results obtained by the technique compare favourably to those
drying. Preliminary studies on the environmental stability of wood conserved by this tech
As part of the supercritical drying technique involves the use of organic solvents, results fr
extractives from wood are also reported.
Introduction
Wetland and marine environments can preserve waterlogged wood has several disadvantages.
wood and other organic materials, greatly contribut-Amongst these are the very slow diffusion times for
ing to the archaeological value of these sites. Thelarge consolidant molecules into the wood, and the
materials themselves, however, have proved difficultaddition of large amounts of foreign material to the
to conserve. The reason for the difficulty encoun-wood. These disadvantages are reduced, but not
tered is that the wood becomes saturated (or nearly eliminated, by the freeze-drying technique. Analysis
so) with water, and undergoes a variable degree of of the problems associated with conventional conser-
deterioration due to microbial action prior to vation treatments led us to realize that an alternative
becoming stabilized towards further decay within antechnique, supercritical drying, had not been applied
anoxic environment. Generally, conservation pro-to this problem [2].
grammes are designed to stabilize the wood in a dry The supercritical drying technique eliminates dis-
environment, when lack of moisture becomes the tortion to ultra-structure caused by drying effects or
limiting factor preventing further decay from occur- the presence of consolidants. It has been the stan-
ring. Normally, exclusion of oxygen from the mater-dard method for preparing samples for electron
ial after excavation is not possible if the artifact is tomicroscopy for many years [3-5]. The technique does
be displayed or available for historical research. not require the use of consolidants and should, in
In its weakened state, wood is unable to resist dry-principle, satisfy the conservation ideal of minimal
ing stresses and will shrink excessively, crack, andintervention. The size of most archaeological mater-
may disintegrate completely. Whilst drying stresses ial, however, presents a problem for a technique that
are not the only source of conservation problems forhas been optimized to dry samples of only a few mil-
this material, the extensive programme of work ligrams weight.
required to prevent damage during drying is the Over the past six years we have extended the scale
main factor contributing to the cost of the conserva- of the method to allow it to cope with archaeologi-
tion programme. Further, many techniques that havecal objects, and evaluated it on a range of wood and
been developed to protect the drying wood rely oncomposite artifact types. Our aim here is to docu-
infusion of chemicals that can damage metal compo- ment the method and to present some of the results
nents, making the conservation of composite arti-we have obtained from the technique in full, together
facts problematical. with a statistical analysis of all wood samples treated
Our original goal had been to develop new materi-to date. We also present experimental results demon-
als to replace poly(ethylene glycol) (PEG) and sugarsstrating the reversibility of the technique and the
commonly used in these conventional treatments;environmental stability of wood conserved.
see, for example, the review by Grattan and Clarke
[1]. The use of consolidants for the treatment of
Theory
Received June 1999 Wood is subject to two distinct processes during
Studies in Conservation 45 (2000) 233-252 233
B. Kaye, D.J. Cole-Hamilton and K. Morphet
the pores of the cell wall pits, by capillary action.

Air dried As the water evaporates, its volume within the cell
is reduced. Surface tension forces compress the cell
until the energy required to further distort the cell
walls is greater than that required to overcome the
surface tension forces in the pits. When this occurs,
air is drawn into the cell and the cell walls may
rebound to their original shape. If the cell walls are
?- ?
weakened, however, then at no point is enough
elastic energy stored within them to overcome the
II~Inj-uI
surface tension forces in the pit pores, and the cell
Supercritically dried
collapses. The magnitude of the surface tension
force is inversely related to the diameter of the
pore. As a result, drying stresses are greatest in the
smallest voids.
Techniques for overcoming drying stresses

There are three physical techniques by which a liq-
Figure 1 Mediaeval elm (Ulmus sp.) sample. The uid can be removed from a porous solid. These can
sample to the right has been air-dried, resulting in be understood by consideration of the idealized
total structural collapse. The sample to the left was phase diagram shown in Figure 2. Brief notes are
supercritically dried and retained its original dimen- provided below for those unfamiliar with this type
sions. Both samples were originally the same size. of description, and further detail may be found in
Kaye [2].
Evaporation or air-drying (process 1-2 in Figure 2)
drying, namely shrinkage and collapse. Shrinkage is
The vapour pressure of water in the atmosphere
the less serious problem, being caused by loss of about the wood is reduced below the saturation
water between cellulose fibres within the cell walls
point. As a result the water evaporates from the
of the wood. Collapse occurs when drying stresses
wood, which is subjected to drying stresses caused
(see below) crush cells in the wood. Any acceptable
by the presence of a liquid/vapour interface within
conservation treatment for waterlogged wood must
reliably overcome the problems of shrinkage and
collapse caused by drying stresses. Even modern
wood that still possesses all of its strength will
crack during seasoning, as a result of drying Liquid Supercritical fluid
stresses. If it is intended to conserve wood that was
used in an unseasoned (wet) state then, even if the
wood has undergone no deterioration, it may crack
and distort unacceptably as it dries. Normally, -D Gas
wood from wetland sites will be very much weak- B

U
ened by microbial attack, and drying stresses will
result in total structural collapse, as shown in Solid Liquid Gas
Figure 1.
The nature of drying stresses

The origin of drying stresses can be understood by
Vapour
reference to two simple models. The more general
physical model is applicable to any porous solid. It
considers the consequences of taking a block of this
material saturated with water or some other liquid,
then reducing the volume of liquid within the block S3 , 2 1 , 4
and evaluating the changes in forces that would Critical temperature
occur as a result [6]. A simpler model that looks at Temperature
the microscopic structure of wood is based on that
reported by Grattan [7]. In this, the water is held at Figure 2 Stylized phase diagram. Detail inset shows
fine pores between cells in the wood structure, in how the critical point occurs (see text).
234 Studies in Conservation 45 (2000) 233-252
Supercritical drying
its structure. This process may be controlled by recover the liquid/vapour equilibrium at this higher
slowly reducing the relative humidity (RH) about temperature, the pressure must be increased to
the wood, so that it dries evenly. Occasionally, liq- point C (Figure 2, inset). The important point to be
uids with a low surface tension-such as aware of is that the density of the liquid and
vapour phases
di(ethyl)ether-are used to reduce drying at point C will not be the same as at
stresses
point A,
but, in order to avoid collapse, the water for two the
within reasons:
structure usually has to be replaced1 with a non-
The increase in temperature will have a small
volatile consolidant such as PEG. The amount of
effect in reducing the density of the liquid (due
consolidant required depends upon the degree to ofthe greater kinetic energy of its component
deterioration of the wood, and the type of wood,molecules).
but generally more than 50% of the water in the
2 The
wood must be replaced with consolidant to avoid increase in pressure will increase the den-
excessive damage during the drying process. sity of the vapour phase, but not the liquid
phase, as liquids are almost incompressible.
Lyophilization or freeze-drying (1-3 in Figure 2)
If the liquid/vapour phase boundary is followed
Drying stresses occur at the liquid surface, and
by repeatedly increasing the temperature and pres-
these may be avoided by eliminating this surface.
sure (following C-D-E, etc.), the densities of the
The classic technique for doing this is freeze-drying,
two phases will converge. Eventually both phases
when the liquid within the wood is frozen, then
will have the same density and will not, therefore,
removed by sublimation, usually at reduced pres-
separate under the action of gravity. As both
sure. As water expands as it freezes, the develop-
phases are disordered, they become physically iden-
ment of ice crystals within the wood can cause
tical, and increasing the pressure cannot create a
considerable structural damage. In practice, vari-
new liquid phase. The temperature and pressure at
able amounts of cryoprotectant must be introduced
which the liquid and vapour phases become identi-
into the wood before freeze-drying can be carried
cal are referred to as the 'critical point', defined by
out. PEG is the normal cryoprotectant used with
a critical pressure and temperature (and molar vol-
freeze-drying and, although much lower concentra-
ume). Tabulations of these values for a wide variety
tions are employed than would be necessary of for air-
substances can be found in most chemical refer-
drying, it does offer some physical support to the
ence books [9]. Any fluid above the critical temper-
wood after drying. The computer program PEG-
ature is referred to as a 'gas'. As fluids do not
CON has been developed by Cook and Grattan [8]
possess long-range order, no physical boundary
to allow the determination of the requisite amounts
exists between 'liquid' and 'gas' phases. Close to the
of PEG for use in freeze-drying operations.
critical temperature and pressure, the gas contains
Supercritical drying (process 1-4 in Figure 2)relatively long-lived clusters of molecules which
This is an elegant technique that avoids the behave
prob-in a liquid-like manner. Under these condi-
lems associated with the phase changes encountered tions, the gas is often referred to as a 'supercritical
in the other methods. Above a certain critical tem- fluid'. Supercritical fluids can dissolve some solids
perature, fluids cannot be liquefied by compression.and compatible liquids by clusters of supercritical
In the simplest case, the temperature and pressure fluid molecules collecting about solute molecules
and
are changed so that the liquid in the material is forming a solvation shell about them.
Supercritical fluids (including supercritical water)
above its critical temperature. This must be carried
out without crossing the liquid/vapour phase cannot form hydrogen bonds, and are almost inca-
pable of dissolving ionic solutes.
boundary. Above the critical temperature the fluid
can be removed by decompression without any pos- Small changes in the temperature and pressure
sibility of a liquid phase being formed, as longresult
as in large changes in the ability of the super-
critical fluid to solvate other molecules. A decrease
the temperature is not allowed to fall. As no phase
boundaries are crossed, no drying stresses are in pressure, for example, will greatly reduce the sta-
encountered. bility of a solvating cluster. As a consequence, the
Some understanding of supercritical fluids can solvent
be is physically 'tuneable', a fact that has
gained by considering the changes that occur as resulted
the in supercritical fluids gaining considerable
fluid follows the liquid/vapour phase boundarycommercial
in importance. Common industrial
the phase diagram shown in Figure 2. Starting processes
at employing supercritical fluids include the
any point on this boundary line and increasing polymerization
the of ethylene and the decaffeination
temperature will result in an equilibrium state,of tea and coffee; many of these processes are
under which both liquid and vapour co-exist, described by McHugh and Krukonis [10].
becoming unstable, and all of the fluid evaporates
Supercritical fluids are in many ways ideal solvents:
(step A-B in the inset to Figure 2). In order tolacking interfacial tensions, they readily penetrate a
into an enclosed atmosphere as it can act as an

Single phase - In. Incr~asing asphyxiant at high partial pressures, otherwise it
100 /
/ . temperature presents no toxic hazard.
Supercritical carbon dioxide has solvation prop-
95- .Reducing
.....m
erties similar to hexane, and is not miscible with
water. Placing a wet artifact into supercritical car-
bon dioxide results in the formation of a fluid/water
interface which results in surface tension forces
being exerted on the artifact as the water is
removed. These forces can cause considerable dam-
age to the artifact. In consequence, water within the
S50 Liquid and gas artifact must be replaced with a solvent that is solu-
ble in supercritical carbon dioxide.
Methanol is completely miscible in carbon diox-
ide above 500C and 95 bar pressure. It is also cheap
and readily recycled by distillation, so eliminating
disposal problems. Methanol used in the pre-treat-
0
ment stage of supercritical drying sterilizes the
wood and treatment solutions, so there is no need
0 10.5 1 to employ a biocide. Drawbacks to the use of
Mole fraction carbon dioxide methanol are that it is flammable, and toxic by
inhalation and skin contact. Care must be taken to
Figure 3 Phase diagram for methanol/carbon diox-design and implement safe handling procedures.
ide mixtures at 500C. The dashed line must be fol-The solvent exchange process must be carried out
in sealed fireproof treatment tanks.
lowed during the supercritical drying process to avoid
the possibility of forming a two-phase system. The process can be speeded up by using four or
five changes of solvent, which reduces the volume
of methanol in use at any one time and ensures
wide range of materials, whilst the ability to tunethat as large a concentration gradient is retained as
their properties provides considerably greater versa-possible throughout the process.t The concentra-
tility than is available with conventional solvents.tion of water in the artifact should be reduced
An important criterion in industry is that they are below 1% before supercritical drying can be carried
clean, and can be used to replace solvents that poseout successfully. The small size of the methanol
health and environmental problems. In this papermolecule means that diffusion is very rapid. The
we concentrate on one useful property-the absencediffusion kinetics for methanol are compared with
of interfacial tension-but recent industrial and those for PEG 200 and PEG 2000 in Table 1, using
academic studies have shown these fluids to have diffusion models for wood developed by Jensen et
far broader potential for use in conservation [11]. al. [12]. This shows that this technique is potentially
very much quicker than methods employing PEG.
The end-point of the exchange process can be
The supercritical drying technique determined by monitoring the density of the
methanol solution. As small changes in the concen-
tration of water are being measured, great care
The critical point for water occurs at 647K (3740C)
must
and 220-5 bar*; as a result, supercritical water isbe taken to ensure that all tests are carried
out at the same temperature. An alternative tech-
difficult to handle. The high temperature required
nique is to test the solution directly for its ability to
introduces the probability of thermal damage
occurring to an artifact during any process dryusingsuitable test samples. As gels are more prone to
shrinkage during drying than waterlogged wood,
supercritical water. Carbon dioxide is the most
commonly used supercritical fluid, with a lowthese
criti-make ideal sacrificial test samples. Test gels
cal temperature and pressure (304K (310C) and are prepared by dissolving 5g of agar in 95ml of
73.8
boiling water, and casting into moulds. As large or
bar). Carbon dioxide is produced as a by-product
of fermentation; as a result, it is cheap, environ-
mentally compatible, and presents no disposal tWe have never encountered problems with osmotic col-
problems. Carbon dioxide should not be vented lapse in wood, and always immerse directly into a 100%
methanol bath. We have encountered problems with
methanol exchange in jet and shale; however, we do not
believe that these are related to osmotic pressure.
*One bar is equivalent to 14-5psi or 0-1MPa pressure.
Table 1 Approximate exchange times are calculated for a 5cm-thick board of wood (transverse, other
dimensions greater than 50cm) with a dry density of 0-5gcm-3 (fairly well preserved) *
Substance Diffusion Time for 90%O Time for 99%

coefficient exchange (days) exchange (days)
(cm2s-1)
Methanol 1.26 x 10-5 9 20

PEG 200 0.65 x 10-5 16 33
PEG 2000 0-21 x 10-5 40 85
*The diffusion coefficient of methano

Most PEG-based treatments would re
ing should be four times faster than t
impermeable wood a cylinder made of samples

316 stainless steel, which is may
they may not sealed be at one in end andequilibrium
enclosed in a thermostatically
solution in thecontrolled bath heating jacket.being The other end tested of the
diffusion models chamber isdeveloped fitted with a door secured by bolts by to J
estimate the equilibration the autoclave body. The maximum design time.
operating U
the equilibration conditions time are 1000C and can200 bar pressure. result The i
age or cracking, solution ofas methanoldiscussed
in carbon dioxide is taken out in
results' section,of below. the autoclave into a low-pressure methanol col-
Once the water lector, where has the pressurebeen is reduced replac to 35 bar. The
can be replaced temperaturein of turnthe collector is with kept above 400C by sup
dioxide. The diagram in Figure 3 describes the a heater, preventing the carbon dioxide from con-
phase behaviour of methanol and carbon dioxide densing. In consequence, the pressure drop reduces
mixtures at 500C, the temperature we have deter-
mined to be optimal for this process. As carbon Test cables and thermocouples
dioxide is being introduced into the drying cham- Burstingdisc Flowof methanol in
ber, there is a possibility of forming a two-phase Pressure gauge , carbon dioxide

system. To avoid this, the carbon dioxide is blown S Pressure gauge
Carbon dioxide flow
through pure methanol in the bottom of the cham- Pressureressure
ber to pre-saturate it and the artifacts are wrapped

SCoolervalve
in methanol-soaked non-woven polyester protective Low
bags. This ensures that the artifacts have no ten- pressure
methatnol
dency to loose methanol to evaporative processes
Door
before a single-phase system is established at higher
pressures. The fluid in the wood therefore adopts Pump Pressure
the ideal process line, shown as a dashed line in Preheater olease
Figure 3. Heat / valve
The only problem remaining is to remove Exchanger ! - Carbon dioxide
methanol from the solution so that subsequent slow Carbon dioxide flow
Carbon dioxide Valve
decompression will not result in the formation of a inlet hose
separate liquid phase. Simple techniques employing

chemical desiccants have been described in earlier
papers [13-15]. These methods yield excellent Figure 4 Schematic of a supercritical dryer using a
physical separation technique to remove excess
results but are inefficient, as most of the drying
chamber is occupied by desiccant. The desiccantmethanol. Liquid carbon dioxide at 43 bar is intro-
duced under pressure and the autoclave is heated to
used is difficult to recycle after use, increasing
the operating temperature, which generates the
wastage and making it hard to scale the technique
up. We are, however, able to make use of the process
phys- pressure of 120 bar. The solution of methanol
ical and chemical properties of supercritical fluids
in carbon dioxide is decompressed into a low-pressure
to effect a physical separation of the methanol in collector, where the methanol drops out of
methanol
solution, and this method is described below. solution. The carbon dioxide is then heated and
The supercritical drying equipment is shown in
recompressed prior to injection back into the drying
schematic form in Figure 4. The drying chamber chamber.
is
B. Kaye, D.J. Cole-Hamilton and K Morphet
the density of the carbon dioxide so that it is no served using the technique include cork, bone,
longer able to dissolve the entrained methanol. The antler, rope and composite artifacts. Examples of
methanol collects in the bottom of the collector treatments for each type of material are given
under gravity and can be removed at intervals below.by
opening a valve. Carbon dioxide is taken from the
top of the collector, recompressed, heated and wooden artifacts and test samples
Simple
injected back into the autoclave where it can dis-
solve more methanol. In this manner a continuous Two samples, including a broken spear shaft (ash,
Fraxinus sp.), 23mm in diameter, from Nydam
extraction process can be operated, and the comple-
Mose in Denmark, were conserved over a period of
tion of the drying process is clearly indicated when
no further methanol is collected. Once the methanol 15 days from their arrival in the laboratory. The
samples had a wet weight of 113g in total and were
has been removed, the samples can be slowly
immersed in a sealed tank containing one litre of
decompressed at a rate not exceeding 20 bar per
methanol. The methanol was changed every two
hour. Being carried out in two stages facilitates the
days (six exchanges in total) prior to testing the
decompression process, from the drying chamber
solution for trace presence of water and supercriti-
pressure (initially 120 bar) to 35 bar in the exhaust
cal drying. The drying process took 24 hours. The
stack, and then to ambient pressure. This two-stage
rapidity of this process was aided by the fact that
decompression process eliminates problems with
the wood had a moisture content of 760%, and was
valves icing up, and the possibility of explosive
highly permeable. The results were good, with sam-
decompression of the sample.
ples showing between 2.5 and 5% transverse and c.
The design of the equipment allows carbon diox-
1% longitudinal shrinkage. No distortion was
ide to be recompressed to the cylinder, which wouldobserved.
ensure that all chemicals are recycled. As we were
using rental cylinders, however, this option was notCork and bark
available.
Operating conditions: main autoclave (dryingTwo cork artifacts have been conserved by super-
chamber) volume = 20 litres (20cm diameter bycritical drying. Jenssen [17] has reported that cork
65cm in length)*. Main autoclave pressure = is
120often difficult to conserve, as it is impermeable to
bar, temperature = 50'C. Exhaust stack (methanol PEG and other consolidants. Techniques for getting
recovery) pressure = 35 bar, temperature = 30'C. round this can involve freeze/thawing the sample to
Flow rate = 1 litre per hour as liquid carbon diox-break up cell walls and so increase their perme-
ide at O0C and 45 bar pressure. ability.
At this point, the supercritical drying process hasSupercritical drying offers a clear advantage for
been completed but the wood in the autoclave is conserving this material. For example, a large bung
very dry, and at 500C. In order to prevent thermal had been treated with PEG as a prelude to air-
stress it is important to allow the chamber and drying, but started to collapse as it was dried
wood enclosed to cool to room temperature before because no PEG had penetrated the structure.
opening the chamber. In principle this technique Upon re-hydration the item recovered its original
dimensions, and we then carried out supercritical
can be scaled up to cope with artifacts of any size.
drying as normal. As methanol is a very much
smaller molecule than PEG, it penetrated the cork
Example treatments without difficulty, allowing the item to be conserved
rapidly (within one month) and very successfully
We have used supercritical drying to conserve more (shrinkage 0.5%, no distortion or other damage, the
than 150 samples of wood. Other materials con- cork had a moisture content of 973%). A second,
smaller bottle cork has also been conserved success-
fully
*This represents the maximum dimensions of artifacts that by this technique. This cork had a moisture
can be conserved in the chamber we currently use, content of 760% and dried with 2.4% shrinkage but
although a cylindrical artifact of these dimensions
nocould
other damage or distortion.
not be conserved because there would be no room for the
Six samples (each of about 20g wet weight) of
scCO2. However, commercial units for the supercritical
birch bark have been conserved by supercritical
extraction of caffeine from coffee are available with vol-
drying. These were treated in four methanol baths
umes up to 44,000 litres [16], so there is no theoretical
over a period of one month; five samples showed
limit on size. The capital costs of installing a unit would
nobut
not be greatly different from those for a freeze-dryer, deterioration after drying but one was cracked.
These
the fast turn-around time and the ability to reuse both the samples were all quite dense, with moisture
methanol and the CO2 for supercritical drying offers contents
some between 50 and 100%, and showed quite a
economic advantages. high shrinkage after drying of about 6%. After
treatment these samples were quite hard and inflexi- 2

ble. Seven other samples of archaeological wood in 110 20 30 40 50 60 71 8"' -u ;t
the round with adhering bark have also been
treated by the technique. Of these samples only one ... . . .. . .. ~ ~ Xa EF~.-.?.??, ??r ???
. ... .. ...
. .. . .. .. . ..... ... ....... . .. . .
~,itKV MA
lost its bark during the treatment, the others
..............ri~ii iu ~ l ?
retained their bark without cracking. The loss of W~
bark was expected in the one instance where it =1 z? Eql.
occurred, as the cambium had decayed completely. .........

::;i.! . ..~~~n
. .. . .
These results indicate that bark treated by this I UD
technique shows very little distortion during drying. ft~?Ii6 a~ar
To date, the shrinkage observed for many bark

items has been larger than that observed for wood
dried using the same technique. This is probably
due to incomplete exchange owing to the dense and
rather impermeable nature of this material. The
results are, however, very encouraging, and further Figure 5 Conifer cones from the Mary Rose, con-
studies are required to evaluate whether or not an served by supercritical drying and subsequently con-
increased treatment time would reduce the shrink- solidated by application of Paraloid B72 in p-xylene.
age observed for dense bark objects.
good adhesion and the best possible consolidation
Very degraded wood samples effect were required, wax was not added to the
Paraloid solution to reduce the gloss finish. Despite
During the course of this study we have occasion- this, removing excess Paraloid with a brush soaked
ally been asked to attempt conservation of material in acetone attained a reasonable surface appear-
that it had not been possible to conserve by other ance, as shown in Figure 5.
methods. One such sample of Mesolithic wood was In this instance, the cause of the problem was not
supplied by English Heritage. This sample was so drying stress but a lack of sufficient mechanical
heavily degraded that it was difficult to identify as strength at the points of attachment to support the
wood. Some attack had apparently occurred due to needles of the cone in its dried (open) configura-
white rot, judging by the fact that the individual tion. Whilst extremely time-consuming, the conser-
wood fibres separated easily, indicating a loss of the vation procedure was reasonably successful.
lignin that normally occupies a location between
cell walls and binds them together (see [18 (1)]). As Composite artifacts
the sample was so weak, it could not be handled
wet and so was floated into a perforated box that Composite artifacts, usually of wood or bone and
ferrous metals, are common from marine and wet-
provided support throughout the process. Five
methanol exchanges were carried out over a period land sites and, because the component materials
of 10 days, the complete process taking 20 days. decompose or corrode at different rates and by dif-
The sample shrank by 3.9% but suffered no other ferent routes, their conservation requirements can
damage. Once dry, the sample was strong enough be very different. Frequently it is difficult to deter-
to support its own weight in air and could be han- mine a conservation strategy that is compatible
dled with care. with all of the components present and some sort
of compromise must be worked out. When wood is
Samples requiring consolidation present as part of the composite, this can be very
problematic as conventional treatments for wood
Two conifer cones from the Mary Rose (possibly onrequire prolonged treatment in aqueous solution,
board as tinder) have proved the most difficultnormally in the presence of consolidants which are
material to conserve. No alternative technique wasnot compatible with metal components [19]. By
available, however, so supercritical drying wascontrast to other techniques, supercritical drying is
attempted. These cones were too weak to clean in relatively quick, does not require the use of consoli-
their wet state, and collapsed into separate needlesdants, and water in the artifact is rapidly replaced
during the drying process as the cones opened. Thewith methanol. Ferrous metals must be kept at low
cones were photographed and drawn at each signifi-RH to prevent further corrosion after conservation
cant step of the reconstruction process. Each needleand, whilst supercritically dried wood does become
was consolidated individually with Paraloid B72 inbrittle at low relative humidity, small items can be
p-xylene solution (20% by weight) before beingstored at zero RH without damage. Larger items
stuck together with Paraloid B72 in acetone may require insulation to reduce the rate of temper-
(propanone) solution, again 20% by weight. As
ature changes that would cause stress and might
crack the dry wood. It may be possible to treat until it no longer tested positive for chloride ions
composite artifacts with a suitable consolidant to (using silver nitrate solution), a process which took
improve the strength or plasticity of the wood. one month. Subsequently the handle was moved
Such a study would, however, require an under- into a methanol bath and treated with six changes
standing of the environmental response of uncon- of methanol (each one litre volume) over a period
solidated wood, work that is as yet incomplete (see of 20 days. After drying, the handle showed a
the section on 'Environmental stability', below). transverse shrinkage of 2-8% and longitudinal
We have conserved 14 composite artifacts by shrinkage of 0-1%; no cracks were observed in the
supercritical drying with considerable success, with- visible wood. We have conserved 11 other handles
out the requirement to disassemble the artifact or of similar composition without problem [21].
the need to make modifications to the basic tech- A more complex problem was faced with the
nique. Here we shall discuss one sword handle, conservation of a compass base from the Duart
from the Duart Point site in West Scotland, that wePoint excavation. This composite item included a
have conserved for the National Museum of lead righting weight. Tests prior to starting the con-
Scotland, and summarize the important changes servation inprocess indicated that lead coupons were
technique that were required to conserveattacked another both in dry methanol solution and in car-
composite artifact made of lead and wood bon dioxide.
from theThe reason for this is that whilst lead
same site. is frequently well preserved in marine environments
The simplest procedure involves only drying the due to the formation of a pacifying film of lead sul-
artifact, and relying on subsequent maintenance phate,
at and in air by the presence of a surface layer
very low RH to prevent further deterioration of of oxide, it is actually a very reactive metal.
metal components. This was the method adoptedMethanol complexes and dissolves the oxide coat-
for the sword handle from the Duart Point site, ing, allowing the lead to oxidize without hindrance.
shown after successful conservation in Figure 6.Supercritical carbon dioxide may react with lead
This was a high status item, comprising an alder oxide directly to form lead carbonate, but bulk cor-
(Alnus glutinosa (L.) Gaertner) core which enclosed rosion relies on the presence of water. The possibil-
the remnants of an iron tang, padded on the out- ity of dismantling this piece was considered but the
wooden plate base was very degraded and the lead
side with vegetable fibre, and finally wrapped in fine
silver wire bound with two heavier gold alloy wires.nails holding the righting weight in place had been
Due to the possible presence of copper in theclenched over. In consequence, the nails could not
alloys, this artifact was pre-treated with 1% benzo-be extracted without ripping out lumps of wood
triazole in distilled water. Benzotriazole is com-
with them, and possibly cracking the item into
monly used as a corrosion inhibitor on copper
numerous fragments. Despite its degraded condi-
alloys [20]. Following this treatment the artifact
tion, turning marks were still clearly visible on the
was moved into distilled water, which was replaced
wood, and it was thought desirable to conserve the
artifact as a single unit if at all possible.
Further experimental work indicated that the use
of aluminium sacrificial anodes in electrical contact
and close proximity to test sheets of lead foil could
prevent the deterioration of this metal throughout
the process. In the case of the compass base, the
ideal point of attachment of the sacrificial anode
was the copper alloy pin bearing projecting from
the righting weight. After checking that this was in
good electrical contact with the lead, a small anode
was clamped to the pin. To prevent damage or
scratching, a soft copper foil sheet was placed
between the pin and the clamp. Five methanol
changes over a period of one month were sufficient
to allow supercritical drying to proceed. The tech-
nique was entirely satisfactory; the item showed no
Figure 6 Decorated sword handle from the Duart cracking or distortion during the process and all
Point site (Scotland). The handle is formed on an detail, including the turning marks, was
surface
alder core (Alnus glutinosa), which retained retained,
frag- as seen in Figure 7. Note that the shrink-
age
ments of iron tang. About the core is a layer of of this item could not be measured, through
fibre
padding, wrapped in fine silver wire and boundfear
with of damaging the very degraded wood with the
heavier gold wires. calliper gauge required for precision measurements.
Antler
Only one sample of antler, which had a moisture
content of 58%, has been dried by this technique.
No problems were encountered.
.i.,..
NP::
NIi Rope
We have conserved one short length of heavily
degraded vegetable-fibre rope. In order to prevent
the rope being damaged during the process, it was
wrapped in a linen bandage. We employed four
. IM
-4
changes of methanol and completed the process in

10 days. The rope retained its shape and dimen-
sions through the process, but was very fragile and
N
N..N
could only be handled with great care. In conse-
quence, the sample was sealed into a polyethene
.:i...
N..
.::.,=
... ..
. tube, which provided some protection whilst not
totally obscuring the item from view. As this was
the only specimen of its kind, it was not possible to
?%... optimize a consolidation process.
:I.lijilllll ?ii! i?lllllillliili.4l! ?i i 4 44??I ?
Jet and shale
.... "*" 1: 4' 5 6
t.I
We50were supplied
2Q60
with several
70 30
experimental
80 40
test9 0
samples in a condition similar to that of problem-
atic artifacts made from these materials. They did
not respond well to supercritical drying, undergoing
Figure 7 A compass base
extensive delamination during methanol exchange.
composed of a hardwood
Best results were obtained by using carefully
righting weight. The need
degassed (boiled) solvents and changing the concen-
card is made of a copper a
tration of the treatment solution in two steps: treat-
centre of the lead weight
ing first with 50% methanol solution before moving
by supercritical drying.
to 100% methanol. The fragility of the samples
required that they were held in clamps with rubber-
padded jaws to reduce vibration. The final
In this instance the treatment with methanol and exchange of methanol for carbon dioxide proceeded
supercritical carbon dioxide ensures that all of the
without further damage. We believe that the prob-
volatile organic components in the wood have been lem originates from the loss of cementing material,
extracted, and so the composite will be stable after
possibly organic or calcium carbonate, from
treatment.
between the layers of partially graphitized carbon
that form the bulk of this material. Therefore this is
Non-wooden materials not a drying problem but one of consolidation, and
so not amenable to treatment by this technique.
As the supercritical drying process is a physical
technique which avoids stress to the sample during
drying, the technique used on the following materi-
als was not modified from that employed for wood Analysis of results
in the preceding examples.
Bone Samples
Traditionally, bone has been conserved by air-dry-More than 150 samples of wood (including bark
ing, solvent drying or drying in the presence of con-and cork) have been conserved in our laboratory by
solidants [17]. We have conserved 11 bone samples,supercritical drying. All of these samples were from
including a number of disarticulated human hardwood species and approximately two-thirds of
remains from the Duart Point site. The moisture the samples came from freshwater environments,
content ranged between 17 and 137%. None of the balance from marine sites. The sample sizes var-
these samples suffered cracking during the process.ied between 1 and 2780g wet weight, with an aver-
The dimensional change ranged between 2-2%age wet weight of 170g (approximately equivalent
expansion and 4-4% shrinkage. No correlation wasto a cube of 5cm side).
apparent between moisture content and dimensional Most of the samples were archaeological mater-
change. ial, rather than clear-cut experimental samples.
Evaluation of dimensional changes due to the dry- and waterlogged states. When this solvation shell is
ing process relied on measuring the dimensions of removed, the dry cellulose molecules relax to elimi-
the sample before and after drying. As most sam- nate spaces between them and so generate an ener-
ples did not have simple geometric shapes, it was getically stable structure, resulting in the shrinkage
necessary to record them and take measurements at observed for samples dried by this technique. This
points that could be relocated from the record. process occurs as methanol is being replaced by
Consequently it was not normally possible to deter- supercritical carbon dioxide, and no further shrink-
mine shrinkage exactly along the principal trans- age is observed over a period of several years after
verse mechanical axes of the wood (radial and drying (see section on 'Environmental stability').
tangential). Transverse shrinkage, the primary vari- Rehydration studies confirm this statement: when
able examined here, is therefore determined as thedried samples are saturated with water they recover
average of several measurements carried out attheir original wet dimensions, showing that the
right-angles to the longitudinal axis of the wood.shrinkage process is completely reversible (see the
Longitudinal shrinkage was determined for all sam-section on 'Reversibility', below).
ples but was generally very small, equivalent to 1% As the sample size is quite large, it may conceal
or less of the wet dimension, and is not further con-groups or types of timber that do not respond well
sidered here. to the method. Inter-species comparison is difficult,
The genus of 100 of the conserved samples has for the reasons stated earlier. We can, however,
been identified: 63 oak (Quercus), 18 alder (Alnus), break down the shrinkage data into comparative
eight ash (Fraxinus), seven birch (Betulus), two wil-groups depending upon their moisture contents.
low (Salix), one elm (Ulmus) and one hazel
(Corylus). Oak samples were generally quite well
preserved, most having moisture contents of 35.00
between 150 and 300%. Other identified wood sam-
ples were more decayed, generally having moisture
contents in excess of 300%. Under these circum-
30.00
stances, no correlation can be made between genus
and treatment effectiveness, as the extent of decay
biases the results in favour of oak. We used
25.00
Schweingruber [22] to identify wood samples, and
this text allowed a smaller number of samples to be
E
identified to the species level.
Other material conserved included 15 bark items a 20.00-
0
and 14 composite artifacts (15 composite artifacts
Q,
have, in fact, been conserved, but it was possible to

dismantle one of these and conserve the separate
components). Of the bark items, seven had wood
attached to the bark. In only one of these did the10.00-
bark separate from the underlying wood during
conservation by supercritical drying. The conserva-
tion of two cork items by the technique was 5.00-
extremely successful.
Statistics 0.00
1000
The average (mean) shrinkage observed for 140 0 0 0 0 0 0 0o
samples conserved by the technique was 3.6%, the S h r2 k a 2r (

median value being 3-3%, indicating a slight skew
to larger shrinkage values. The calculated standard
deviation, assuming a normal distribution in shrink- Shrinkage range (%)
age results, is 2, indicating that the technique is
reproducible. A histogram of the shrinkage
observed for all samples is shown in Figure 8. The Figure 8 The transverse shrinkage observed for 140
shrinkage observed during supercritical dryingsamples is conserved by the technique. This was con-
'normal shrinkage', that is, cellulose molecules structed by rounding the shrinkage observed to the
within the cell wall structure are associated with a nearest tenth percent and counting the number of
solvation shell of liquid molecules in both living samples present in each range.
Table 2 The average shrinkage observed for samples in given moisture content ranges*
Moisture content Mean Median Equivalent

range shrinkage shrinkage class
0-185% 3.1% 2.8 Class 3

>185-400% 3.4% 2.9 Class 2
>400-800% 3-5% 3-2 Class 1
>800% 4-4% 3.1
*The mean shrinkage for all samples, irr
Moisture content is defined as: The median shrinkage observed is very similar for
all samples, and significantly smaller than the mean
moisture content (%) =
value for samples with moisture contents greater
weight of water in the wood (x 100%) than 800%. This indicates a considerable skew in
dry weight of wood the distribution for these samples, with some sam-
The moisture content is a measure of the amountples showing an abnormally large shrinkage. This
skew is visible in Figure 9, which shows the shrink-
of solid material in the sample, and a rough indica-
age histogram of samples with moisture contents
tion of its residual strength. Most unseasoned hard-
woods have a moisture content of between 100 and greater than 800%. The most plausible explanation
200%, whilst the most degraded wood we have con-
served (a sample of alder from a Bronze Age site) 30.00
has a moisture content of 1290%. By contrast, the
best-preserved piece of wood we have dried using
the technique had a moisture content of only 17%;
25.00
this was an unusually dense hardwood and we were
not able to identify the wood beyond the fact that
it was not native to Europe. The weight of water in
? 20.00
the wood was determined by weighing the wet sam-
ple and subtracting the weight of the supercriticallyE
dried sample, before allowing the sample to equili-

brate with ambient humidity. 15.00
As samples are not consolidated before supercrit-

ical drying, the weakest samples are most likely a,to
be damaged during the process. The weakest sam- a 10.00
a.
ples are also likely to have the greatest moisture
content. In consequence we have chosen four
ranges of moisture content: between 0 and 185% 5.00-
(25 samples), 185-400% (20 samples), 400-800% (57
samples), and greater than 800% moisture content
(28 samples). The first two categories correspond to
0.00
the definition of class by De Jong [23] (class 3 and
class 2, respectively). We have divided the third
ow a
class (class 1, defined as samples having a moisture
content greater than 400%) into two categories,
C` 9 9 9 9 9 9 9 9 0
introducing a separate 'very heavily degraded' class
with moisture contents in excess of 800%. The aver-
age shrinkage of the samples in each of the cate-
gories is shown in Table 2.
It is apparent that very much less shrinkage is Shrinkage range (%)
observed in all classes than would be expected dur-
ing the seasoning of modern wood. As expected, Figure 9 Shrinkage histogram for samples with
the most heavily degraded samples, with moisturemoisture contents greater than 800%. Note that this
contents greater than 800%, tend to show a greater
is not normally distributed, showing a considerable
mean shrinkage than the least degraded samples. skew to higher shrinkage values.
is that not all of the water in the samples has been after decompression and before opening the auto-
replaced with methanol before supercritical drying. clave. After eliminating this problem, however, a
This will result in additional drying stresses that small number of samples were still seen to crack
may result in collapse. This problem is probably during the process. In one set of experiments, simi-
present in all sample classes, but only the heavily lar samples were treated in methanol for either one
degraded samples show increased shrinkage as a month (the minimum time indicated by estimating
result. the diffusion rate of methanol through the samples,
Whilst shrinkage is an important factor in deter- based on a high permeability) or three months.
mining the suitability of a technique for conserving Many of the samples treated for one month were
material of this type, the appearance of other struc- badly cracked, whereas none of the samples treated
tural damage, such as warping and cracking, is vital over the longer period of time suffered any damage.
to the display quality of the material. We have Our conclusion is that cracking is again due to a
observed slight warping in one sample, and collapse failure to replace all of the water in the sample with
in one other (an experimental piece on which we methanol prior to supercritical drying.
were attempting to effect an accelerated treatment). Analysis of the data we have obtained shows that
Generally, distortion was not a problem, as evi- the technique is reproducible and gives very good
denced by the fact that fragmented samples dried as results. It is expected that these results will improve
separate fragments were readily re-united after the as more familiarity is gained with the technique,
process, the halves normally making a perfect and as we come to understand and are able to mea-
match [14]. sure diffusion coefficients in the samples being con-
Cracking is by far the most common problem; served. Until we have gained this understanding,
21% of all samples conserved showed longitudinal significant improvements on current results can still
or transverse cracks, or both. Normally this was be expected by introducing a safety margin to the
confined to hairline fractures, or to the opening up time taken to effect exchange of water in the wood
of pre-existing cracks in the sample (evidenced by for methanol.
the presence of dirt from the burial site within the
crack). Occasionally, however, these cracks were
severe, and greatly reduced the display value of the Environmental stability
sample. Over the course of the work, 22 samples
(15%) were categorized as being unacceptable by The environmental stability of wood conserved by
the definition developed by Hoffmann and Fortuin supercritical drying appears very good. A study of
[24] (samples showing transverse cracks, or shrink- eight ash (Fraxinus sp.) artifacts from the Nydam
age in excess of 1% with longitudinal cracks, or Mose site in Denmark showed no sign of damage
both longitudinal and transverse cracks with or or change in dimensions some three years after dry-
without shrinkage in the same sample). ing. The ash samples had a range of moisture con-
Cracking is caused by differential dimensional tents from 747 to 1036%. In a further study, six
changes within a sample, and crack formation oak (Quercus sp.) samples with moisture contents
releases the stress built up by these dimensional between 124 and 274% were re-measured five years
changes. In practice, a sample that cracks under- after supercritical drying; again, these showed no
goes complex structural modification, and the sim- sign of damage or change in dimension. All of these
ple shrinkage measurements we have carried out samples had been supercritically dried and subse-
cannot document this. One cause of crack forma- quently stored without environmental control in an
tion during supercritical drying is thermal stress openoncabinet. We have also carried out dynamic
the dried timber. In its dried state, wood ismonitoringvery studies to follow the dimensional
brittle and a poor thermal conductor. Changes in of clean-sawn, supercritically dried wood
response
temperature of the environment will therefore samples to changes in RH. These indicate that
establish stress between the core and the surface of wood conserved by supercritical drying has good
the sample. Large timbers do crack when rapidly environmental stability, and responds smoothly to
cooled to room temperature from 50'C, the temper- humidity step changes of 30% (40 to 70% RH)
ature at which the supercritical dryer is run. As(Figure
the 10). These studies, whilst some way from
wood absorbs water from the atmosphere it completion, indicate a safe 'window' in which
becomes more pliable and less susceptible to brittle humidity can be allowed to fluctuate freely between
fracture due to temperature changes. The problem 40 and 70% RH.
with thermal cracking was severe in the first trialsA high RH environment is not suitable for the
on large samples using the recycling autoclave but long-term storage of iron, or of wood containing
has now been overcome by allowing the autoclave large amounts of iron salts [25]. In consequence,
and its contents to cool slowly to room temperature composite artifacts containing iron must be stored
with small water droplets. If, however, any part

0.16
the sample were to become saturated with water
the drying process would have to be repeated to
prevent shrinkage or collapse during drying.
0.14
Reversibility
E 0.12
It is desirable for all conservation treatments to be
S0.1 reversible; this is to allow the use of improved

I
treatments in the future, or reversal of a treatment
that has proved deleterious, perhaps some time
after its application. The ability to reverse a treat-
" 0.08 ,
ment also ensures that the original material can be
reclaimed for analysis, possibly by techniques that
did not exist when the conservation work was car-
? 0.06
0
ried out. The advantages offered by supercritical
00 drying in this respect are considerable. Most mater-
( 0.04 ial dried by the technique did not require consolida-
a.
tion, which might make reversal problematic.
Supercritical drying is as close to the ideal of mini-
. 0.02 mal intervention as has been achieved to date.
For the sake of completeness, we have re-satu-
0 rated a small number of dried wood samples with
water. To do this, we carefully applied a vacuum to
10 00 the submerged sample to draw the air out, and left
-0.02
the sample at reduced pressure under water for two
months. This process resulted in the wood regaining
Time (min) between 93 and 97% of its original moisture con-
tent. We were not able to recover 100% of the orig-
Figure 10 The radial expansion of supercritically inal moisture content, due to air pockets becoming
dried, unconsolidated oak samples with dry densities
trapped within the wood structure. Although we
of 0-58gcm-3 (diamonds) and 0-26gcm-3 (squares). were not able to achieve complete saturation, the
These were equilibrated at 30% RH prior to chang- samples did recover their original wet dimensions
whilst suffering no apparent damage.
ing the relative humidity to 70%0 over a period of 10 We have carried out these tests on six wood sam-
seconds. The more decayed sample shows a smaller
percentage increase in dimension with increased RH.
ples (one alder, two oak and three birch samples)
Neither sample shows gross discontinuities in the with original moisture contents between 400 and
response curve, which would indicate cracks occur- 1100%. The samples used in this study all shrank
by less than 4% in the original supercritical drying
ring. The slight ripple in response prior to equilibra-
process. It is possible that samples that shrank by
tion at 70%0 RH is due to fluctuations in the
environmental chamber conditions. more than 4% during the original drying process
would not recover their original dimensions, but we
believe that the principle of reversibility for this
under controlled conditions. At very low RH (lesstechnique has been demonstrated.
than 20%), supercritically dried archaeological
wood is brittle and can crack in response to rapid
temperature changes. Our advice to date has been Consolidation of supercritically dried wood
to avoid direct lighting, or storage close to radiant
heaters, and this appears to have been adequate To date, we have preferred to avoid the use of con-
over a period of five years from the completion of solidants whenever possible. The use of a consoli-
the conservation of the first artifacts of this type. dant makes the process irreversible, as the
All of the evidence we have assembled to date consolidant can never be completely removed after
indicates that wood that has been supercritically application. Whilst many modern plastics have
dried is stable to ambient (uncontrolled) environ- excellent stability, they complicate both the mechan-
ments of between 30 and 70% RH. Tests have ical and the chemical responses of wood to changes
shown that samples are not damaged by in its environment. Whilst wood is known to be
contact
fairly stable, deterioration of a consolidant over has been dried by this process can be readily consol-
time may introduce breakdown products that might idated after treatment. We have successfully applied
harm the wood. A tough consolidant will increase consolidants by brushing and spraying them in solu-
the mechanical strength of the composite but pre- tion onto the artifact after supercritical drying. Only
vent wood from breathing in response to changes in the weakest wood requires consolidation, and this
RH. In consequence, wood fibres may be broken by can be severely distorted by any change in dimen-
straining against the consolidant matrix as they sion of the consolidant as it sets. Therefore the con-
expand or contracting as the temperature or RH solidant-solvent system must be chosen with care.
changes. The best results we have achieved were with
Despite these misgivings, it was apparent early on Paraloid B72 dissolved in p-xylene (dimethylbe
in our studies that some samples required consolida- zene), a combination recommended as showing v
tion (for example, the pine cones discussed earlier). little shrinkage during drying [28]. Conservati
In addition, many curators prefer robust samples grade epoxy cements might also be used to goo
that can withstand a degree of physical abuse. (Note effect to obtain very tough conserved items, a
that many artifacts conserved by supercritical drying might radiation-cured polymers [29], but these tr
are quite stable enough to survive being dropped, ments would be irreversible.
and being passed around audiences of 100 people
without suffering damage.) We have therefore car-
ried out a number of experimental studies to evalu- Extractives from archaeological timber
ate different consolidation strategies for wood
conserved by supercritical drying. These include sev- Any technique that employs organic solvents is
eral attempts to consolidate wood either before or going to remove some of the smaller organic mole-
after supercritical drying. Supercritical fluids have cules present in the wood, such as terpenes, steroids
been used by other workers to introduce poly(ethyl- and sugars. Initially our belief was that these were
ene glycol) into water-saturated wood [26]. The unlikely to be present in large amounts in archaeo-
technique allows very rapid penetration of PEG into logical material. In fact, we found that considerable
a wood. In consequence, high loading levels were amounts of methanol-soluble organic material were
achieved in a fraction of the time required for con- present in almost all of the samples we analysed-
ventional bath or spray systems. frequently in quantities that would be expected from
We have attempted to introduce PEG and other modern wood samples. For example, oak from the
potential consolidants directly into dry wood from warship Dartmouth (which sank in 1690 in the
supercritical solution. As supercritical carbon diox- Sound of Mull, west coast of Scotland) yielded 2.6%
ide is a poor solvent, however, very low loading lev- extractives (based on dry weight), in comparison
els were achieved. Pre-treatment of wood with PEG with 1.7% obtained by a soxhlet extraction with
dissolved in methanol, prior to supercritical drying, methanol of modern oak (Quercus petraea
results in the PEG being extracted in the continuous (Mattuschka) Lieblein).
flow apparatus we have developed, again leaving When practical, we have recovered and analysed
very little PEG in place at the end of the treatment. the materials extracted mainly by gas chromatogra-
In summary, our efforts to date to introduce con- phy-mass spectroscopy (GC-MS), using derivatiza-
solidants from supercritical fluids have not proved tion [30] for less volatile components. Generally,
very successful, but the experiments have demon- individual compounds are present in the extractives
in trace quantities and considerable effort has to be
strated the ability to reverse unsatisfactory conserva-
tion attempts or remove excessive amounts of made to avoid sample contamination, which can
consolidant from conserved artifacts. Another possi- make their detection difficult.
ble use for supercritical fluids in rectifying failed Our preliminary studies demonstrated conclu-
treatments is the reversal of collapse. It has been sively the presence of vanillin and syringaldehyde in
shown that collapsed waterlogged wood can be oak from the Roman London waterfront. As both
treated with PEG solution in water under an atmos-
components are quite volatile, we had expected
phere of supercritical carbon dioxide. When the them to have been lost over 1500 years of burial.
Wood steroids such as beta-sitosterol have also been
sample is subject to rapid pressure drops by venting
the carbon dioxide, the shrunken wood can be detected,
re- demonstrating that waterlogged wood rep-
inflated to close to its pre-collapse dimensions resents
[27]. a very stable chemical environment with
Such a procedure involves considerable risk toconsiderable
the ability to preserve all component com-
material and has only been carried out on experi-pounds, not just the structurally important long-
mental samples to date. chain polymers such as cellulose and lignin. Other
commonly detected compounds include long-chain
In contrast to our attempts to introduce consoli-
fatty acids (chain lengths of up to 18 carbon atoms
dants directly from supercritical solution, wood that
have been found in all analysed samples).

Qualitative comparison
During the studies to date we have only suc-
ceeded in conclusively identifying one 'fingerprint'
80.00 -
compound, the terpene dehydro-abietic acid. This is
present in high concentrations in softwood extrac-
tives but not found in hardwoods [18 (2)]. In conse- 70.00
quence, when this was detected in oak from the
Dartmouth, it demonstrated that this wood had been
60.00
treated with a softwood product, probably pitch, of
which no surface traces remained. Whilst the finding
is not surprising (ships' timbers are normally treated S50.00
with pitch to increase their durability and help caulk
gaps between timbers), the ability to demonstrate
the presence of a surface treatment from a bulk
"0
40.00
0
Freeze-dried
SCD
extraction is clearly of great potential value to
archaeologists. S30.00
To date we have analysed the extractives from six
0.
different wood samples, and a collection of human 20.00
bone from the Duart Point site in the Sound of
Mull (Scotland).
10.00
Comparisons between supercritically dried and 0.0oo

freeze-dried wood
Some advantages of the supercritical drying tech-

nique are immediately apparent. Physically the
process is very well understood, and it can be
applied to wood in all states of deterioration. The Sample quality
same method can be applied to composite artifacts
and a variety of other materials. The technique is a Figure 11 A crude com
lot faster than freeze-drying, which translates to a (light grey bars) and
greater efficiency and potential conservation cost bars) can be obtained
savings. Very little modification occurs to the wood faults observed in e
being treated, and reversal of the process is compar- instance the physical
atively simple. Prolonged treatments in aqueous rable but the freeze-d
solution are avoided, as are the attendant problemswood species. As softwoods respond better to
with the growth of microorganisms and algalfreeze-drying than hardwood species, this fact does
blooms. These organisms may use the wood as not a bias the results in favour of supercritical drying.
foodstuff, as a substrate for growth, or simply settleThe freeze-dried data set contained more examples of
on the artifact from suspension in the treatmentwell-preserved wood than our own, providing a fur-
tank. As they result in a surface slime or discol- ther slight bias in favour of freeze-drying. The rank-
oration, which must be mechanically cleaned off ing criteria used were: very good = no shrinkage or
after drying, it is normal to employ biocides, which cracks observed, good = shrinkage or longitudinal
may incur disposal costs and be retained in the cracks only, acceptable = shrinkage and longitudinal
wood after treatment. cracks or transverse cracks only, not acceptable =
Disadvantages are that the process is relatively shrinkage and transverse cracks, longitudinal and
new, and capital costs for equipment are signifi- transverse cracks, or all three. Sample sizes were 625
cantly greater. Some familiarity with high-pressure(freeze-drying) and 147 (supercritical drying).
systems and handling chemicals in bulk would
clearly be an advantage to anyone wishing to adopt
the method. drying. The largest reported statistical sample for
Perhaps the most important factor, however, is freeze-drying (625 samples) is that by Hoffmann
how reliable the method is in comparison with and Fortuin [24]; this provides a ranking procedure
freeze-drying. Comparisons of statistical results pub- that allows crude comparisons to be made, as
lished for the freeze-drying technique and those shown in Figure 11. A larger proportion of wood
reported here are very favourable to supercritical samples cracked during freeze-drying (40%) than we
have observed with supercritical drying (21%). In favour of freeze-drying, long-term studies of
Whilst this appears to be a significant advantage for PEG-treated wood indicate that the process appears
the supercritical drying process, there were consider- satisfactory over periods of up to 27 years [31, 32].
able differences between different freeze-drying labo- In contrast, our own studies on supercritically dried
ratories and some laboratories return very much material only go back to our first application of the
better results than the overall averages suggest. technique six years ago, but these show that there
Fifteen percent of the samples we have treated by has been no deterioration in the absence of environ-
supercritical drying are unacceptable according to mental control over this period. The comparative
the ranking technique developed by Hoffmann and simplicity of the conserved material, with no possible
Fortuin, in comparison to 18.9% of freeze-dried incompatibility between the wood and a consolidant,
samples [24]. Of these samples, we considered three suggests that supercritically dried samples will
(2%) to have no display value and very limited remain stable over the medium to long term.
research value after supercritical drying. Freeze-dried wood is very much denser than
It is commonly assumed that no shrinkage should supercritically dried wood, due to the presence of
be observed with wood that has been freeze-dried. PEG. The impact strength of heavily degraded birch
samples (moisture content of 900%) was estimated
In contrast, shrinkage is expected for supercritically
dried wood, as cellulose is not completely swollen from the penetration depth of a cone of known mass
by adsorbed water in air. We have rated all samplesdropped from a known height into the sample. The
showing greater than 1% transverse shrinkage supercritically
as dried samples had impact strengths of
having shrunk; on this basis, as expected, the results
between 1 and 4MPa, dependent upon the grain ori-
obtained for supercritical drying are significantlyentation in the face being tested. The matching
worse than those reported for freeze-drying [24]. freeze-dried
In sample was badly damaged during the
our studies, 7.8% of samples showed less than 1% drying process (Figure 12), but tests on the best-pre-
transverse shrinkage (5.7% of samples showed served surfaces gave an impact strength of 11MPa,
dimensional changes less than +1% of their originalindependent of impact orientation. These data show
wet dimensions), in comparison with 39.2% that
of freeze-dried material is tougher than supercriti-
freeze-dried samples. cally dried material. If either sample were dropped,
Ideally, comparisons should be made between however, the relative densities of the samples would
matched samples that are either freeze-dried or contribute to the energy of the impact. In this
supercritically dried. Regrettably, our attempts to instance the dry densities are 0.11gcm-3 for the
freeze-dry material, with the amounts and types of supercritically dried sample and 0.37gcm-3 for the
consolidant determined using PEGCON [8], simply freeze-dried material, almost cancelling out the
highlighted problems with this technique. For exam- strengthening effect of the consolidant. The data also
ple, Figure 12 shows two matched experimental sam- show that the mechanical properties of the freeze-
ples of heavily degraded birch (c. 800% moisture dried material are dominated by the presence of the
content), treated in PEG or methanol for the same
length of time (36 days) prior to freeze-drying or
supercritical drying. Whilst the freeze-dried sample is
externally robust and has a good appearance, insuffi-
cient time has been allowed to get the higher molec-
ular weight PEG into the core and this has collapsed
in consequence, as shown in Figure 12.
In a further series of experiments, matched oak
blocks were either freeze-dried (six samples), in this
instance after a considerably greater period had been
allowed for PEG to penetrate, or supercritically
dried (14 samples). This experiment demonstrated
that freeze-drying can result in no shrinkage being 1 2 3 41
observed; at 60% RH, in fact, these samples showed ,0 20 30 40 50 60 70 80 90 100 110
a slight expansion of between 0 and 1.2%. In com-
parison, the 14 supercritically dried samples showed
a transverse shrinkage of between 3-0 and 4.6%. The Figure 12 Matched birch samples treated for the
freeze-dried samples, however, showed surface dis- same length of time before freeze-drying (left) or
tortion, and fine cracks had developed between the supercritical drying (right). The freeze-dried sample
rays and the ground tissue of the wood. No prob- was not left long enough to allow the heavy molecu-
lems were evident in the samples conserved by super- lar weight PEG to penetrate before freeze-drying,
critical drying. and its core collapsed in consequence.
PEG. This suggestion is confirmed by general obser- Supercritical drying is a biologically sterile
vations; supercritically dried samples are fibrous, process, which arrests microbial decay of the mater-
whilst the freeze-dried samples are waxy and can be ial. The treatment solutions do not support biologi-
cut cleanly with a knife. The fibrous nature of many cal activity, preventing the development of surface
supercritically dried samples makes them hard to cut bio-films, which must be carefully cleaned off mater-
cleanly, as the cutting edge tends to rip fibres from ial after drying by conventional treatments.
the ground tissue matrix. It is normally necessary to In principle and practice, supercritical drying is
either freeze-fracture or embed these samples before very much faster than freeze-drying. The limiting
they can be sectioned for microscopy. In short, factor for both processes is diffusion during the
supercritically dried wood behaves like wood, and sample preparation phase. PEG or sugars must be
not like a waxy polymer. introduced prior to freeze-drying, whilst the smaller
Both techniques suffer problems with material methanol molecule is used in supercritical drying. In
being extracted from the wood during the course of practice, a non-destructive test for water within
the treatment, evident from the dark colour imparted wood samples to be supercritically dried must be
to PEG treatment solutions. The analysis of extrac- developed before full advantage can be taken of the
tives in the presence of PEG is likely to be extremely difference in diffusion rates. Supercritical drying can
difficult; indeed, we are not aware of any attempts to conserve materials impermeable to PEG, such as
characterize the material being lost during this cork, as the smaller methanol molecule is able to
process. The ease with which material extracted dur- penetrate into their structure.
ing the supercritical procedure can be analysed may Due to the increase in importance of supercritical
prove to be a significant advantage of this method.fluid processes to industry and academia over the
last five years, supercritical dryers can now be
obtained from specialist engineering firms such as
Conclusions NWA (see section on 'Suppliers' below). This devel-
opment makes the technique more readily available.
A wide range of organic materials can be preserved Whilst the equipment is complex, it performs a
in waterlogged environments. When these materials physically simple drying process within the material,
are exposed by excavation, they experience a dra- one which does not involve any phase changes in
matic change in environment, from burial in wet the fluid being removed. In consequence, the success
of the technique is independent of the substrate
anoxic sediment to dry, oxygenated air. Supercritical
drying allows many of these materials to be stabi- being dried, as long as that substrate is able to sup-
lized to ambient conditions without gross chemical port its own dry weight in air. In principle, any
or physical modification. We have accumulated waterlogged
a material can be dried by the method, as
considerable body of evidence demonstrating that long as it does not react with methanol or carbon
the method is applicable to wood in all states dioxide.
of
deterioration. Changes that do occur during the
treatment of wood, such as shrinkage and the
extraction of small organic molecules, can be docu-Acknowledgements
mented. The ability to analyse small molecules
extracted from wood as part of the conservation We gratefully acknowledge the help of the following
process has the potential for increasing its archaeo-people and institutions, for encouragement, provi-
logical value. It has further been demonstrated thatsion of experimental material, artifacts and financial
supercritical drying offers the ability to routinelysupport: Colin Martin, University of St Andrews;
conserve complex composite artifacts. Theo Skinner, National Museum of Scotland; Mark
A duty of care is placed upon the museum or Jones, Mary Rose Trust; Jim Spriggs and Ian
other holding institution to maintain artifacts for Panter, York Archaeological Trust; Poul Jensen,
long periods of time. Consequently it is important National Museum of Denmark; English Heritage;
that the artifact is stable within its display environ- Natural Environment Research Council (UK).
ment, as only limited environmental control can be
maintained indefinitely. Short-term studies over a
period of five years indicate that the environmentalHealth and safety
stability of wood dried by the supercritical drying
technique is good in the absence of environmentalAll pressure equipment must be professionally
control. As no consolidants are present, the con- inspected and tested regularly. Untested equipment,
served artifact is comparatively simple, and we areor the use of equipment at pressures or temperatures
confident that these short-term studies will be borne greater than its design rating, may result in explo-
out by longer-term experience. sion, damage to property, injury and loss of life.
Compressors and high-pressure pumps are noisy, Proceedings of the 4th ICOM Group on Wet
and suitable ear protection must be worn. Consult Organic Archaeological Materials Conference,
your suppliers' health and safety data sheets for the ed. P. HOFFMANN, ICOM, Bremerhaven
safe use and disposal of all chemicals. (1991) 239-251.
9 LIDE, D.R., editor in chief, Handbook of
Chemistry and Physics, CRC Press, Boston
Suppliers (1991).
10 McHUGH, M., and KRUKONIS, V., Supercritical
The autoclave body was constructed by Baskerville Fluid Extraction, Butterworth Heinemann,
(Reactors and Autoclaves) Ltd, 324c Barlow Moor Boston (1994).
Road, Chorlton, Manchester, UK. The circulation 11 KAYE, B., and COLE-HAMILTON, D.J.,
equipment was built to our specifications by NWA 'Supercritical fluids in conservation' in
Analytische Messgerate GmbH, Postfach 2026, Proceedings of the 6th Meeting on Supercritical
79510 Lorrach, Germany. Carbon dioxide in liquid Fluids Chemistry and Materials, Nottingham
withdrawal cylinders was supplied by BOC Ltd, 10 (1999) 107-113.
Priestly Road, Guildford, Surrey, UK. The chemi- 12 JENSEN, P., BOJESEN-KOEFOED, I., and
cals used are commonly available from fine chemical STRAETKVERN, K., 'Freeze-drying from water'
suppliers. in Proceedings of the 5th ICOM Group on Wet
Organic Archaeological Materials Conference,
ed. P. HOFFMANN, T. DALEY and T. GRANT,
References ICOM, Bremerhaven (1994) 253-286.
13 KAYE, B., and COLE-HAMILTON, D., 'Novel
1 GRATTAN, D.W., and CLARKE, R.W., approaches to the conservation of wet wood'
'Conservation of waterlogged wood' in in A Celebration of Wood, ed. J. SPRIGGS,
Conservation of Marine Archaeological York Archaeological Trust, York (1994)
Objects, ed. C. PEARSON, Butterworths, 35-48.
London (1987) 164-206. 14 KAYE, B., and COLE-HAMILTON, D.J.,
2 KAYE, B., 'Conservation of waterlogged archae- 'Supercritical drying of waterlogged archaeo-
ological wood', Chemical Society Reviews 24 logical wood' in Hidden Dimensions, The
(1995) 35-43. Cultural Significance of Wetland Archaeology,
3 SVITKINA, T.M., VERKHOVSKY, A.B., and ed. K. BERNICK, Pacific Rim Archaeology,
BORISY, G.G., 'Improved procedures for elec- UBC Press, Vancouver (1998) 329-339.
tron microscopic visualisation of the 15 COLE-HAMILTON, D.J., and KAYE, B.,
cytoskeleton of cultured cells', Journal of 'Supercritical drying of archaeological wooden
Structural Biology 115 (1995) 290-303. artefacts' in Proceedings of the 5th Meeting on
4 CARR, J.H., ANDERSON, R.L., and FAVERO, Supercritical Fluids. Vol. 1. Materials, Nice
M.S., 'Comparison of chemical dehydration (1998) 63-68.
and supercritical drying for the stabilisation16 GEHRIG, M., 'Extraction of foodstuff with car-
and visualisation of ageing biofilm present on bon dioxide: present status and potential' in
interior surfaces of PVC distribution pipe', Proceedings of the 5th Meeting on Supercritical
Journal of Applied Bacteriology 80 (1996) Fluids. Vol. 2. Natural Products, Nice (1998)
225-232. 495-500.
5 REVILLE, W.J., HEAPES, M.M., and 17 JENSSEN, V., 'Conservation of wet organic arte-
O'SULLIVAN, V.R., 'A survey to assess the facts excluding wood' in Conservation of
Marine Archaeological Objects, ed. C.
ultrastructural preservation of fixed biological
samples after air-drying from tetramethyl- PEARSON, Butterworths, London (1987)
silane', Journal of Electron Microscopy122-163.43
(1994) 111-115. 18 FENGEL, D., and WEGENER, G., Wood,
6 SCHERER, G.W., 'Theory of drying', Journal Chemistry,
of Ultrastructure, Reactions, de
the American Ceramic Society 73 (1990) 3-14. Gruyter, Berlin (1989) (1) 384-393, (2)
7 GRATTAN, D.W., 'Waterlogged wood' in 184-190.
Conservation of Marine Archaeological 19 SELWYN, L.S., RENNIE-BISAILLION, D.A., and
Objects, ed. C. PEARSON, Butterworths, BINNIE, N.E., 'Metal corrosion rates in aque-
London (1987) 55-67. ous treatments for waterlogged wood metal
8 COOK, C., and GRATTAN, D.W., 'A method for composites', Studies in Conservation 38 (1993)
calculating the concentration of PEG for 180-197.
freeze-drying waterlogged wood' in 20 WALKER, R., 'The role of benzotriazole in the
preservation of antiquities' in The development of a commercial reagent for silyl-

Conservation and Restoration of Metals, ed. ating aqueous solutions of hydroxy and poly-
E.A. SLATER and N.H. TENNENT, Scottish hydroxy compounds' in Recent Advances in
Society for Conservation and Restoration, Gas Chromatography, ed. I.I. DOMSKY and
Edinburgh (1979) 38-47. J.A. PERRY, Marcel Dekker Inc., New York
21 KAYE, B., and COLE-HAMILTON, D.J., (1971) 223-229.
'Conservation of knife handles from the 31 CHAMBON, M., COLARDELLE, M., HIRON, X.,
Elizabethan warship Makeshift', International and VERDEL, E., 'Bilan critique de 27 ans de
Journal of Nautical Archaeology 24 (1995) traitement des bois immerges de Chavarines
147-158. (Isbre)' in Proceedings of the 7th ICOM Group
22 SCHWEINGRUBER F.H., Anatomy of European on Wet Organic Archaeological Materials
Woods, Haupt, Bern & Stuttgart (1990). Conference, ed. P. HOFFMANN, C. BONNOT-
23 DE JONG, J., 'The deterioration of waterlogged DICONNE and X. HIRON, Grenoble (1999)
wood and its protection in the soil' in 25-31.
Conservation of Waterlogged Wood, ed. L.H. 32 HIRON, X., JANNET, M., and SIRAN, C., 'Les
DE VRIES-ZUIDERBAAN, Netherlands National sculptures sur bois des ex-voto gallo romains
Commission for UNESCO, The Hague (1979) des sources de la Seine: un cas de conserva-
31-40. tion preventive' in Proceedings of the 7th
24 HOFFMANN, P., and FORTUIN, G., 'An evalua- ICOM Group on Wet Organic Archaeological
tion study on the freeze-drying of waterlogged Materials Conference, ed. P. HOFFMANN, C.
wood' in Proceedings of the 4th ICOM Group BONNOT-DICONNE and X. HIRON, Grenoble
on Wet Organic Archaeological Materials (1999) 32-39.
Conference, ed. P. HOFFMANN, ICOM,
Bremerhaven (1991) 331-347.
25 MACLEOD, I.D., BROOKE, P., and RICHARDS, Authors
V., 'Iron corrosion products and their interac-
tion with waterlogged wood and PEG' in BARRY KAYE obtained his PhD in material science
Proceedings of the 4th ICOM Group on Wetfrom the University of Wales in 1987, before study-
Organic Archaeological Materials Conference, ing static charge uptake by polymer composites
ed. P. HOFFMANN, ICOM, Bremerhaven at the University of Exeter for Gestetner
(1991) 119-132. Manufacturing Ltd. He then moved to St Andrews
26 COEURt, P., CHAUMAT, G., TRAN, Q.K., and to work with Professor David Cole-Hamilton devel-
PERRE, C., 'Die Konservierung von NaBholz: oping new polymers for conserving waterlogged
Versuche mit Polethyleneglykol in Super- wood. Address. School of Chemistry, The University,
kritischer Kohlendioxid "Fltissigkeit"', St Andrews, Fife KY16 9ST, UK.
Arbeitsbldtter Heft 1 (1998) Gruppe 8-Holz,
262-265. DAVID COLE-HAMILTON obtained his BSc and PhD
27 CHAUMAT, G., TRAN, K., PERRE, C., and degrees in chemistry from Edinburgh University
LUMIA, G., 'Tentatives de restauration de before a period of postdoctoral work at Imperial
forme sur bois gorges d'eau affaisses par College, London. He was a lecturer and senior lecturer
traitement au CO2 supercritique' in at the University of Liverpool and moved to St
Proceedings of the 7th ICOM Group on Wet Andrews as Irvine Professor of Chemistry in 1985. His
Organic Archaeological Materials Conference, interest in conservation arose through discussions with
ed. P. HOFFMANN, C. BONNOT-DICONNE and his wife, Dr Liz le Bon, who was at the time working
X. HIRON, Grenoble (1999) 137-142. as a PhD student in maritime studies. The work on
28 HORIE, C.V., Materials for Conservation, supercritical drying was runner-up in the Museums
Butterworth-Heinmann, Oxford (1987). and Galleries Commission Award for Innovation in
29 TRAN, Q.K., RAMIERE, R., and GINIER-GILLET, Conservation in 1995. Address: as for Kaye.
A., 'Impregnation with radiation-curing
monomers and resins' in Archaeological KATHERINE MORPHET graduated from the University
Wood, Properties, Chemistry and Preservation,of St Andrews in 1996; she studied the mechanical
ed. R.M. ROWELL and R.J. BARBOUR, properties of supercritically dried archaeological
Advances in Chemistry Series No. 225, wood, and carried out early consolidation work. She
American Chemical Society, Washington DC is now completing her masters degree at the
(1990) 217-233. University of Bradford in scientific methods in
30 BRITTAIN, G.D., SULLIVAN, J.E., and SCHEWE,archaeology. Address. University of Bradford,
L.R., 'Silylation in the presence of water, the Bradford BD7 1DP, UK.
Resum&--Le sechage supercritique est une des possibilites pour secher les matiriaux dMlicats, incluant les
matiriaux archdologiques. La technique est applicable pour conserver les bois gorges d'eau a' tous les etats de
dkcomposition, a' la corne et a l'os, ainsi qu'aux objets composites comprenant du bois, des metaux et d'autres
matiriaux. Il n 'est pas ndcessaire de recourir aux consolidants lorsqu'on utilise cette technique. L'article dkcrit
la thdorie sur laquelle repose la technique en question, et les modalites de son application aux objets provenant
de fouilles archdologiques. Les resultats obtenus se comparent avantageusement a ceux obtenus par sechage
par cryogenation. Des etudes prnliminaires concernant la stabilite environnementale du bois traite avec cette
technique sont rapporties. Puisque certaines etapes du sechage supercritique necessitent l'emploi de solvants
organiques, les resultats de l'analyse des composantes extraites du bois sont egalement rapportes.
Zusammenfassung- Uberkritische Trocknung ist eine Mdglichkeit, empfindliche Materialien, insbesondere aus
archdologischen Zusammenhdngen, zu trocknen. Die Technik ist fiir die Konservierung von durchndj3tem Holz
in allen Stufen des Abbaus, Kork und Knochen, aber auch fiir Verbundmaterialien aus Holz, Metall und
anderen Werkstoffen anwendbar. Bei dieser Technik werden keine Festigungsmittel bendtigt. In der vorliegen-
den Arbeit wird die Theorie der Technik und die Methode der Anwendung auf archdologische Materialien
beschrieben. Die durch die Methode erreichbaren Ergebnisse stellen sich vorteilhaft gegeniiber den durch
Gefriertrocknung erreichbaren dar. Erste Ergebnisse zur Langzeitstabilitdt von mit dieser Technik kon-
serviertem Holz werden prdsentiert. Bei der aberkritischen Trocknung werden organischen Ldsungsmittel ver-
wendet. Ergebnisse deren Analyse bei der Extraktion von behandeltem Holz werden prdsentiert.
Resumen-El secado de tipo supercritico es una de las opciones fisicas para el secado de materiales delicados,
incluyendo los de origen arqueol6gico. La ticnica es aplicable a la conservacidn de maderas saturadas de
humedad en todos los niveles de descomposicidn, corcho y hueso, y a objetos complejos como madera, metales
y otros materiales. No se requieren consolidantes cuando se usa esta ticnica. Este articulo describe la teoria
tras de la pradctica, y como aplicarla a los hallazgos arqueol6gicos. Los resultados obtenidos por esta tecnica
se comparan favorablemente a aquellos obtenidos por medio del secado por congelacidn. Se describen los estu-
dios preliminares sobre la estabilidad ambiental de la madera conservada por esta tecnica. Ya que en la tic-
nica del secado supercritico es fundamental el uso de disolventes orgdnicos, se describen, por tanto, los
resultados analiticos de las extracciones realizadas de la madera.
Authors' note. Colour pictures of all the artifacts described in this paper, and many others, are available o
http://ch-www.st-and.ac.uk/wood/

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A New Method For Conserving Waterlogged Archaeological Materials

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Supercritical Drying: A New Method for Conserving Waterlogged Archaeological Materials

Author(s): Barry Kaye, David J. Cole-Hamilton and Kathryn Morphet

Barry Kaye, David J. Cole-Hamilton and Kathryn Morphet

Received June 1999 Wood is subject to two distinct processes during

Studies in Conservation 45 (2000) 233-252 233

the pores of the cell wall pits, by capillary action.

Techniques for overcoming drying stresses

wood from wetland sites will be very much weak- B

The nature of drying stresses

234 Studies in Conservation 45 (2000) 233-252

Studies in Conservation 45 (2000) 233-252 235

into an enclosed atmosphere as it can act as an

236 Studies in Conservation 45 (2000) 233-252

Substance Diffusion Time for 90%O Time for 99%

Methanol 1.26 x 10-5 9 20

*The diffusion coefficient of methano

impermeable wood a cylinder made of samples

ber, there is a possibility of forming a two-phase Pressure gauge , carbon dioxide

ber to pre-saturate it and the artifacts are wrapped

bags. This ensures that the artifacts have no ten- pressure

separate liquid phase. Simple techniques employing

Studies in Conservation 45 (2000) 233-252 237

238 Studies in Conservation 45 (2000) 233-252

treatment these samples were quite hard and inflexi- 2

. .. . .. .. . ..... ... ....... . .. . .

occurred, as the cambium had decayed completely. .........

These results indicate that bark treated by this I UD

technique shows very little distortion during drying. ft~?Ii6 a~ar

To date, the shrinkage observed for many bark

Studies in Conservation 45 (2000) 233-252 239

240 Studies in Conservation 45 (2000) 233-252

changes of methanol and completed the process in

Studies in Conservation 45 (2000) 233-252 241

have, in fact, been conserved, but it was possible to

The average (mean) shrinkage observed for 140 0 0 0 0 0 0 0o

samples conserved by the technique was 3.6%, the S h r2 k a 2r (

242 Studies in Conservation 45 (2000) 233-252

Moisture content Mean Median Equivalent

0-185% 3.1% 2.8 Class 3

*The mean shrinkage for all samples, irr

dried sample, before allowing the sample to equili-

As samples are not consolidated before supercrit-

Studies in Conservation 45 (2000) 233-252 243

244 Studies in Conservation 45 (2000) 233-252

with small water droplets. If, however, any part

S0.1 reversible; this is to allow the use of improved

Studies in Conservation 45 (2000) 233-252 245

246 Studies in Conservation 45 (2000) 233-252

have been found in all analysed samples).

Comparisons between supercritically dried and 0.0oo

Some advantages of the supercritical drying tech-

Studies in Conservation 45 (2000) 233-252 247

248 Studies in Conservation 45 (2000) 233-252

Studies in Conservation 45 (2000) 233-252 249

250 Studies in Conservation 45 (2000) 233-252

preservation of antiquities' in The development of a commercial reagent for silyl-

Studies in Conservation 45 (2000) 233-252 251

252 Studies in Conservation 45 (2000) 233-252

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