Journal of the American Institute for Conservation

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Sublimable layers for protection of painted pottery

during desalination. A comparative study

Hamada Sadek, Barbara H. Berrie & Richard G. Weiss

To cite this article: Hamada Sadek, Barbara H. Berrie & Richard G. Weiss (2018) Sublimable
layers for protection of painted pottery during desalination. A comparative study, Journal of the
American Institute for Conservation, 57:4, 189-202, DOI: 10.1080/01971360.2018.1537414

To link to this article: https://doi.org/10.1080/01971360.2018.1537414

Published online: 08 Nov 2018.

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JOURNAL OF THE AMERICAN INSTITUTE FOR CONSERVATION
2018, VOL. 57, NO. 4, 189–202
https://doi.org/10.1080/01971360.2018.1537414

Sublimable layers for protection of painted pottery during desalination.

A comparative study
Hamada Sadeka, Barbara H. Berrieb and Richard G. Weissc
a
Faculty of Archaeology, Conservation Department, Fayoum University, Al Fayoum, Egypt; bConservation Division, National Gallery of Art,
Washington, DC, USA; cDepartment of Chemistry, Institute for Soft Matter Synthesis and Metrology, Georgetown University, Washington,
DC, USA

ABSTRACT KEYWORDS
Cyclododecane (CDD) has been used for several years as a temporary consolidant for organic and Desalination; temporary
inorganic materials of interest in cultural heritage. In this work, a comparative study has been consolidation; sublimation;
conducted with CDD and three other sublimable compounds – menthol, camphene, and elemental surface analysis;
cyclododecanone – as protectants of water-sensitive paint during the desalination of painted soluble salts
pottery. The experiments include salination, consolidation, and desalination, and were conducted
on samples newly prepared in the laboratory. Optical microscopy, SEM-EDS, elemental mapping,
and FTIR data have been used to evaluate the relative efficiencies of the four consolidants. In
addition, the relative rates of sublimation of the consolidants from a glass surface have been
measured. Although all of the consolidants are able to protect the painted layers, there are
distinct differences in efficacy and rates of sublimation that should make some better than
others depending on the specific nature of the objects being treated.

RÉSUMÉ
Le cyclododécane (CDD) est utilisé depuis de nombreuses années pour la consolidation temporaire
des matériaux organiques et inorganiques du patrimoine culturel. Dans cette étude comparative, le
CDD et trois autres composés sublimables, le menthol, le camphène et le cyclododécanone ont été
évalués pour la protection des enduits sensibles à l’eau lors des traitements de dessalement des
poteries peintes. Des échantillons ont été fabriqués en laboratoire et ont été préparés à l’aide de
solutions salines; par la suite, des consolidants ont été appliqués sur les échantillons et un
traitement de dessalement a été effectué. L’efficacité relative des quatre consolidants a été
évaluée par microscopie optique, par microscopie électronique à balayage, par cartographie
chimique et par spectroscopie infrarouge à transformée de Fourier. De plus, des mesures des
taux de sublimation des consolidants déposés sur une surface de verre ont été effectuées. Même
si tous les produits testés permettent une protection des enduits, des différences existent dans
leur efficacité et leurs taux de sublimation, ce qui implique une meilleure performance de
certains selon la nature des objets traités. Traduit par André Bergeron.

RESUMO
O ciclododecano (CDD) é utilizado há vários anos como consolidante temporário de materiais
orgânicos e inorgânicos de interesse para o patrimônio cultural. Neste trabalho, um estudo
comparativo foi conduzido com CDD e três outros compostos sublimados - mentol, canfeno e
ciclododecanona - como protetores da tinta sensível à água durante a dessalinização de
cerâmica pintada. As experiências incluem salinização, consolidação, dessalinização e foram
realizadas em amostras recém preparadas no laboratório. Microscopia óptica, SEM-EDS,
mapeamento elementar e dados de FTIR foram usados para avaliar as eficiências relativas dos
quatro consolidantes. Além disso, as taxas relativas de sublimação dos consolidantes de uma
superfície de vidro foram medidas. Embora todos os consolidantes sejam capazes de proteger as
camadas pintadas, há diferenças distintas na eficácia e nas taxas de sublimação que tornam
alguns consolidantes mais apropriados que outros, dependendo da natureza específica dos
objetos a serem tratados. Traduzido por Tereza Lança, e revisado pelo Beatriz Haspo.

RESUMEN
El Ciclododecano (CDD por sus siglas en inglés) ha sido utilizado por varios años como consolidante
temporal para los materiales orgánicos e inorgánicos que son importantes para el patrimonio
cultural. En este proyecto se llevó a cabo un estudio comparativo con CDD y otros tres
compuestos sublimables — mentol, canfeno y ciclododecano — como protectores de pintura
soluble en agua durante la desalinización de la cerámica policromada. Se realizaron
experimentos de salinización, consolidación y desalinización en muestras nuevas preparadas en

CONTACT Hamada Sadek hsr00@fayoum.edu.eg Faculty of Archaeology, Conservation Department, Fayoum University, Al Fayoum, Egypt
© American Institute for Conservation of Historic and Artistic Works 2018
190 H. SADEK ET AL.

el laboratorio. Se utilizó la información obtenida de microscopia óptica, SEM-EDS, mapeo elemental

y FTIR para evaluar la eficacia relativa de los cuatro consolidantes. Además, se midió el índice
relativo de sublimación de los consolidantes desde una superficie vítrea. Aunque todos los
consolidantes protegen a las capas de pintura, hay diferencias en la eficacia y en el índice de
sublimación que hacen que unos sean mejores que otros, dependiendo de la naturaleza del
objeto que va a ser intervenido. Traducido por Mirasol Estrada; revisado por Amparo Rueda.

1. Introduction may indicate that crystallization is occurring below the

Archaeological objects comprised of painted porous
materials often contain significant amounts of soluble
salts that may originate from production techniques or
as a result of environmental exposure over time (Zehn-
der 1987, 2007). In that regard, the salts may be present
within objects such as masonry, ceramics, and pottery
because the initial raw materials used in their construc-
tion contain salts or because soluble salts in the soil
have accumulated over time in buried objects (Charola
and Bläuer 2015). For example, the Tethys Sea, which
covered Egypt 40 million years ago, left salt deposits in
the sands that were used by many artisans to make cer-
amic objects (Sampsell 2014).
Salts also can be from indoor sources, including out-
gassing materials used for housing and displaying the
artifacts (Skipper and Rubinstein 2018). Several factors
affect the location of salt crystallization, including the
solubility of the salt, water evaporation rate, pore size
and structure within the materials, the water content
and its transport rate, temperature, humidity and
airflow (Charola 2000). The presence of salts in the por-
ous materials made from impure sand or other raw
materials can cause deterioration, especially when the
salts crystallize and cause cracks to form. Salts that crys-
tallize on the surface (i.e. efflorescence) hide paint layers
or decorative patterns, as shown in Figure 1, and finally
lead to paint spalling. The presence of salts on the surface
Figure 1. Salt crystallization on a piece of Egyptian painted
pottery in Cairo, Egypt, from the Greco-Roman period.
surface (i.e. sub- or crypto-efflorescence). This is a threat
to the stability and integrity of archaeological objects
because it causes separation and spalling of outer layers
and can result in damage to the entire structure (Bena-
vente et al. 2004; Espinosa-Marzal and Scherer 2010;
Scherer 2000).
The fluctuation between crystallization, dissolution,
and recrystallisation of soluble salts, such as halite, causes
deterioration to porous materials such as pottery,
especially in uncontrolled environments. The deterio-
ration results from the changes in phase transformations
inside the porous materials. The formation of crystals
leading to growth of salt crystals creates pressure on the
pores walls. Even inside museums or storage areas for arti-
facts, daily, seasonal, and annual variations of humidity
and temperature can cause repeated cycles of crystalliza-
tion and recrystallization. Thus, controlling indoor
environmental conditions minimizes the damage caused
by crystallization cycles or during removal of salts from
the artifacts. Crystallization by efflorescence causes
deterioration phenomena by flaking, powdering of the
object components, and honeycomb weathering (Delgado
et al. 2016). Furthermore, the damage caused by NaCl
(halite) is irreversible because of salt dilation in pores
(Desarnaud, Bertrand, and Shahidzadeh-Bonn 2011).
Sodium chloride is one of the most common water-
soluble salts found in porous materials. It can cause
serious damage to materials because its high solubility
enables ions to move throughout an object as long as
moisture is present. Also, the hydrophilicity of materials
associated with pottery, stone objects, and even edifices
aids water absorption that can lead to cycles of re-crystal-
lization of halite and other minerals with which it can
interact. The re-crystallization of halite (and other sol-
uble salts) can lead to the development and propagation
of cracks, spalling of surface layers, and changes in the
appearance of a pottery substrate and painted surfaces.
The long-term preservation and reduction of poten-
tial damage of some objects from the presence of salts
requires that they be desalinated. The method used for
desalination depends on the components of an artifact
and its sensitivity to the desalination method, as well
as its initial condition. Various methods for desalination
have been employed in cultural heritage preservation,
including poultices, water baths, and electromigration

(Skibsted et al. 2015). Poulticing involves the removal of
soluble salts by application of damp materials on the arti-
fact surfaces (Paterakis 1999). The effectiveness of the
poultice materials depends on their adhesion to the sur-
face of interest, shrinkage, and workability (Kamran et al.
2012). Traditional poultices are prepared using materials
such as bentonite, attapulgite, and paper pulp. They can
be effective also for removal of surface stains or paint
(Sawdy et al. 2010).
Objects with painted surfaces present a special chal-
lenge to be desalinated without causing significant ancil-
lary damage because paint films on pottery and other
porous substrates are very sensitive to water (Koob and
Ng 2000). However, the paint can be protected by conso-
lidation processes in which the cohesive strength
between the paint and the object is enhanced using
organic or inorganic compounds (Bromblet et al. 2011;
Pinto and Rodrigues 2008). In that regard, various
types of organic and inorganic compounds can be
employed. They include polymers and polymerizable
materials (such as polyacrylates, polyacetates, polysilox-
anes, ethyl silicate, and epoxy resins) and inorganic
salts (such as calcium hydroxide, barium hydroxide,
sodium and potassium silicates, fluorosilicates, and alu-
minates) (Torraca 2009). Obviously, the effectiveness of
a consolidant depends on the properties of the consoli-
dant and the surface of the object being treated.
Light, chemical, and mechanical factors can also affect
the stability of a consolidant while it is applied to a sur-
face. Therefore, the balance between beneficial mechan-
ical effects and possible adverse chemical and optical
effects must be weighed in each case. For example,
some consolidants cannot be removed completely from
an object after treatment without irreversible changes
to the surface being treated. To address the issue of
“reversibility” (i.e. optimization of the degree of remova-
bility of the consolidant and minimization of the chemi-
cal and aesthetic changes that permanent consolidants
can cause), temporary consolidants (i.e. those that can
be completely removed) have been used during desalina-
tion without mechanical or chemical methods.
The development of less invasive and less altering
materials for the treatment of water-sensitive paint sur-
faces are needed badly. Such materials and methods
are emerging as a result of unrelated research in areas
of chemistry, nano-science, and materials. The challenge
today is as much to learn how to apply these materials to
conservation as it is to discover their specific interactions
on different surfaces (Watters 2007). Examples of inter-
est are sublimable materials, such as menthol and cyclo-
dodecane (CDD). Sublimable compounds have been
used in the field of art and archaeological conservation
since the 1990s. They have been applied as temporary
JOURNAL OF THE AMERICAN INSTITUTE FOR CONSERVATION 191
consolidants, fixatives, masking materials, and barrier
layers in different areas of conservation. The most attrac-
tive characteristic of these reversible consolidants is their
ability to be removed without additional treatment by
slow sublimation at room temperature (Anselmi et al.
2015).
In this way, they can stabilize an object during the
treatment and be removed at a later date of the conserva-
tor’s choosing; no chemical or additional physical treat-
ment steps are needed for their removal (Han, Huang,
and Zhang 2016; Rowe and Rozeik 2009; Rozeik 2009).
Thus, menthol and CDD are considered reversible bar-
riers and consolidants and they have been used for protec-
tion of fragile materials such as stone and ceramic objects,
paintings, manuscripts, and textiles. They can be applied
as a melt, in solution, or as a spray (Keynan and Eyb-
Green 2000; Stein et al. 2000). CDD has been employed
as a temporary consolidant on marble, a porous substrate,
and its behavior and characteristics of sublimation and
penetration were investigated (Anselmi et al. 2011). Pre-
liminary examination of the ability of CDD to protect
water-sensitive ink on a ceramic during desalination has
been undertaken (Muros and Hirx 2004).
Removing or re-solubilizing traditional consolidants
requires either mechanical action or solvents, both of
which can lead to secondary changes in artifacts. How-
ever, the use of subliming materials comes with some
potential disadvantages that include a lack of data
about the long-term effects of these materials on an
object, concerns regarding their toxicity (Han et al.
2014; Horie 2010), and, as noted previously, compli-
cations associated with different modes of application
for different compounds.
Although cyclododecane and menthol had been used
previously in consolidation of artifacts at excavation sites
(Han 2014; Presciutti et al. 2015), our studies expand the
study of the use of sublimable compounds to other con-
solidants. In this work, we have used a number of
analytical techniques to evaluate and compare the
degrees to which four sublimable compounds, applied
as melts, are able to protect water-sensitive painted sur-
faces on pottery during its desalination (Chickos and
Acree 2003; Shahidzadeh-Bonn et al. 2010b; Trefil et al.
2005). They are cyclododecane (CDD; C12H24), menthol
(C10H20O), cyclododecanone (C12H22O) which has simi-
lar properties to CDD but sublimes more slowly, making
it preferable when longer consolidation times are
required, and camphene (C10H16) which has a consolida-
tion function and sublimes quickly comparing to other
consolidants in this study. Their structures and some
pertinent properties are included in Table 1. Safety and
health concerns about the consolidants in this study
are included in an appendix.
192 H. SADEK ET AL.
Table 1. Materials used in this study.
Cyclododecane (CDD), C12H24 Cyclododecanone C12H22O
Structure
Melting point (°C) 58–61
Boiling point (°C) 243
Flash point (°C) 114
Purity (%) 98
Vapor pressure at 20°C 0.0098
(kPa)
Source Kremer Pigments Acros Organics
2. Materials and methods
2.1. Materials
The pottery was made using Nile silt and sand added to
clay and kneaded, then shaped into 2 × 2 × 0.8 cm blocks
before firing at 800°C. The paint was prepared by mixing
10 grams of green earth pigment, a fine-grained siliceous
earth (i.e. a complex of SiO2, Al2O3, Fe2O3, MgO and,
CaO3, Na2O, MnO, and K2O) and binder consisting of
10 mL of 10% (wt/vol) animal skin glue in water. Both
materials were obtained from the Conservation Labora-
tories, Faculty of Archaeology, Fayoum University.
2.1.1. Preparation of test samples
Test samples consisting of painted pottery that simulates
archaeological objects were prepared by painting the sur-
face of the pottery using a tempera technique in which
the paint was brushed onto the surface. The painted
samples were dried at room temperature for 30 days in
air. The thickness of the final paint layer, 200–300 µm,
was measured using optical microscopy, observing the
focal plane of the top of the pottery and the top of
paint and scaling for the distance the stage moved for a
given objective. Also, glass slides were coated with
equal weights of melts of the sublimable compounds
and then allowed to cool to room temperature in order
to track their rates of sublimation.
2.1.2. Artificial salt weathering
The painted test samples were subjected to artificial salt
weathering using 10 wet/dry cycles. In each cycle, the
samples were submerged in 250 mL of an aqueous sol-
ution of 20% (wt/vol) NaCl for 16 hours, and then
removed and kept in air for 8 hours at ∼ 25°C. During
the weathering cycles, the samples suffered the growth
Menthol C10H20O Camphene C10H16
59–69 43–45 40–50
277 212 159–160
118 101 34
99 99 80
0.00075 0.11 0.33
Aldrich Aldrich
of halite crystals and dissolution of the organic paint bin-
der as indicated by a loss of adhesion between the pig-
ment and the pottery. A separate group of samples, as
a control, was not weathered.
2.1.3. Application of sublimable consolidants
Before desalination, one of the four sublimable com-
pounds was applied in melt form using a spatula to
form a layer ∼0.5 mm thick to the painted side of the
pottery samples. The melting temperatures of the conso-
lidants are listed in Table 1. The melts cooled and
became solid very quickly after their application. The
entire experimental protocol was conducted in a fume
hood because of the high vapor pressures of the tempor-
ary consolidants.
2.1.4. Desalination procedure
To remove salt, the artificially weathered samples were
weighed and immersed in a 50 fold (wt:vol) excess of deio-
nized water. The sample weights were recorded in a for-
mat developed at the Arizona State Museum (White,
Pool, and Carroll 2010). The time-dependent changes in
the conductivity of the water were measured with an
Amber model 604 conductivity meter periodically over
three days or until a time-invariant value was reached.
The data were treated according to Equation (1). Knorm,
the normalized conductivity change per day, is the desali-
nation rate; it is usually reported without units. ΔK is the
change in conductivity per unit of time in units of micro-
Siemens (µS/cm), L is the water volume in liters, t is the
time in days, and g is the sample weight in grams.
D KL
Knorm (1)
D tg

2.2. Methods
2.2.1. Optical microscopy
Optical microscopy, using a Leica DMRX microscope,
with 10x and 20x nPL objectives in bright and dark
field reflected light illumination, was used to evaluate
visually the condition of the salt-weathered pottery and
to compare the morphology of painted samples before
and after applying the sublimable consolidants. Images
were captured using a Canon EOS 5D Mark III camera.
Because the samples were not flat, the collected images
were stack focused using ImageJ software (Schneider,
Rasband, and Eliceiri 2012).
2.2.2. Scanning electron microscopy (SEM)
SEM was performed using a Hitachi S-3400N variable
pressure electron microscope (20 kV, 50 Pa) equipped
with a Hitachi backscattered electron detector. SEM-
EDS (SEM-energy-dispersive X-ray spectroscopy) was
very useful in determining the elements and their distri-
bution in the painted layer compositions. The SEM-EDS
analyses were performed at 20 kV to obtain element
maps and qualitative point analyses using an Oxford
X-Max 80 mm2 SDD detector and an Oxford Aztec
300 spectrometer. The working distance was 10 mm.
2.2.3. Attenuated total reflectance-Fourier
transformed infrared spectroscopy (ATR-FTIR)
ATR-FTIR measurements were carried out on a Perkin
Elmer 100 spectrometer in the ATR mode in the wave-
length range of 400–4000 cm−1 with a spectral resolution
of 8 cm−1, using a diamond cell sample holder. Thirty-
two scans were averaged and the spectra were normal-
ized with respect to the background of the clean diamond
cell for each analysis. In order to determine whether a
Figure 2. Stack–focused photomicrograph (using the plug-in of ImageJ) of the bright-field image of the painted surfaces of a pottery
sample: (a) before salination, showing the intact paint layer; (b) after salination in the absence of prior treatment with consolidant
where the green paint has been displaced by the formation of cubic halite crystals, revealing the orange-red color of the fired pottery.
JOURNAL OF THE AMERICAN INSTITUTE FOR CONSERVATION 193
detectable level of residue was present, spectra were
obtained from six positions on each sample.
3. Results
As indicated by the results provided below, the salt
weathering cycles damaged the paint layer as well as
the pottery substrate of the consolidated and unconsoli-
dated samples.
3.1. Weathered samples before desalination
3.1.1. Optical microscopy
Before being subjected to the salination procedure, the
film of paint on the surface of the pottery was homo-
geneous and continuous (Figure 2(a)). After salination,
damage from formation of halite crystals on the surface
of the pottery and the paint layers is visible (as manifested
by cracking of the pottery and disruption of the film of the
paint layer). Cubic crystals of halite formed between paint
grains as the samples were dried (Al-Jibbouri and Ulrich
2002). The concentration and grain size of the crystals
are known to influence the microstructure and degree of
damage (Desarnaud, Bertrand, and Shahidzadeh-Bonn
2013). A significant portion of the green paint was lost
as a result of salt crystal formation, leaving the matrix of
fired pottery visible at the surface (Figure 2(b)).
3.1.2. SEM-EDS
Back-scattered electron (BSE) and secondary electron (SE)
imaging in the SEM showed that cracks had developed in
the pottery from the crystallization of sodium chloride in
the ceramic body during the drying step in the salinization
procedure. Formation of crystals in porous materials cre-
ates pressure on the pore walls, and stress leads to crack
194 H. SADEK ET AL.
Figure 3. BSE image of microcracks in the pottery resulting from
halite crystal formation after salination.
formation (Shahidzadeh-Bonn et al. 2010a). Usually, such
micro-cracks are invisible initially; they become observa-
ble when the salt crystals grow and cause networks of
micro-cracks around the crystals (Figure 3). In that
regard, the SEM micrographs show the presence of
sodium chloride in both cubic and needle-like whisker
form, at and near the surface of the pottery (Figure 4).
The whisker-like crystals are known to grow one-dimen-
sionally on substrates in low humidity conditions or from
thin films (Lopez-Acevedo et al. 1997). A correlation
between elements in the maps shown in Figure 5 for the
whisker needles shows that sodium and chlorine are dis-
tributed in the same way throughout them.
3.2. Desalination process
Pottery samples were treated with one of the four conso-
lidants before desalination using the procedure described
Figure 4. SE image showing the presence of needle-shaped
whisker crystals on the surface of a painted pottery sample
after salination.
in section 2.1.4. The progress of the desalination was
monitored over three days and the samples were
removed when no more salt loss from the pottery
could be measured using Knorm (Unruh 2001).
The rate of desalination in water is dependent on the
NaCl concentration gradient within the pottery and
advection, which is influenced by pottery pore sizes. In
general, salts move from coarse pores into smaller
pores (Voronina et al. 2013; Voronina, Pel, and Kopinga
2014). Due to the presence of the very hydrophobic con-
solidants, the salts move primarily from the pottery into
the water through the surfaces that are not covered with
sublimable materials. The movement of the ions depends
on a number of factors, including the porosity of the pot-
tery, P = 26–27%, which can be calculated as
W −D
P= × 100 %, where, D is the weight of dry
W −S
sample, W is the weight of the sample when it is satu-
rated with deionized water (i.e. after being removed
from the water and wiped lightly with a tissue), and S
is the sample weight when it is saturated by and sus-
pended in deionized water (Lubelli and De Rooij 2009).
The extraction of salt is rapid over the short initial time
interval because the salt crystals on and near the surface of
the pottery dissolve almost immediately. Subsequently,
salt inside the pores of the pottery dissolves more slowly
and is transported to the surface of the sample. The
change in the conductivity of water in which the pottery
was immersed shows a rapid initial increase followed by
a slower continuous one (Figure 6). This behavior is con-
sistent with the model advanced for salt removal. The
rates of desalination (i.e. loss of halite), using each sublim-
able compound as a covering layer, follow a similar quali-
tative temporal course for desalination. Note also that the
rates of salt flow in samples with menthol and cyclodode-
canone layers are higher than those with camphene and
cyclododecane layers. Additional research will be needed
to determine whether specific interactions between the
consolidant and the pottery surface are able to influence
the rate of flow of salt crystals from the pottery matrix.
Following the desalination process, the pottery
samples were washed with distilled water in order to
remove any remaining salts that may have remained
on the surfaces. Visually and with additional magnifi-
cation by optical microscopy at magnification 10x and
20x, it is clear that the rate of sublimation depends on
the consolidant used. At one atmosphere of pressure
and at room temperature, camphene appears to have
sublimed totally after 4–6 hours, whereas cyclododecane,
cyclododecanone and menthol require much longer
periods (∼20 days) before visual inspection suggests
they are completely removed. We assume that little or
no consolidant was lost during the desalinization

Figure 5. EDS element maps of an area of the pottery surface that includes whisker crystals formed after accelerated salination. The two
maps focus on halite whisker forms: (a) sodium and (b) chlorine.
procedures because the samples were completely sub-
merged in water and the consolidants are insoluble in it.
3.3. The sublimation rates of consolidants on
glass slides
Sublimation rate here is the speed at which a consolidant
is lost from a surface in contact with the air at room temp-
erature. It is an important factor in the selection of a con-
solidant for a particular application. We monitored the
weight changes of the consolidants on glass slides as a
function of time to calculate these rates. Measurements
were continued until the weights returned to those of
the uncoated glass slides. Based on the data in Figure 7,
and consistent with the fact that the areas of the films in
contact with the air remained constant throughout the
sublimation, the rates remain constant. Because the film
Figure 6. Plot of Knorm (conductivity change) versus time, showing the loss of salt from the pottery samples that were coated with the
different consolidants.
JOURNAL OF THE AMERICAN INSTITUTE FOR CONSERVATION 195
thicknesses were nearly the same, it is possible to compare
the rates of loss of the 4 consolidants. Camphene had the
highest rate of sublimation; it was lost completely within
24 hours. Menthol and cyclododecane required ∼237
and ∼261 hours to sublime completely. The rate of subli-
mation of cyclododecanone was the slowest; it required
∼1300 hours to be removed completely. As expected,
this trend is qualitatively consistent with the vapor press-
ures reported in Table 1.
3.4. Analysis after desalination
The samples were analyzed after desalination using OM,
FTIR, and SEM-EDS to assess the efficacy of the four
materials for consolidating and protecting the paint
film, and to determine whether residue could be detected
on the pottery surfaces.
196 H. SADEK ET AL.

Figure 7. Degree of sublimation of the temporary consolidants on a glass slide versus time.

3.4.1. Visual investigations analyses performed, we conclude qualitatively that the

As noted, the accelerated saline weathering caused the
painted layers to be dissolved and damage to the pottery
(Figure 7(B)). The post-desalination stage is most impor-
tant in the evaluation of the protection afforded by the
consolidants to the paint layer in water. Based on the
consolidants did afford some protection to the paint
layers. However, although camphene protected the pig-
ments on the surface, some of the paint did suffer damage
in the water bath (Figure 8(D1)). Menthol, cyclododecane,
and cyclododecanone appeared to afford better protection

Figure 8. Pottery samples (A) before salination, (B) after salt weathering, (C) after salt weathering followed by consolidation, and (D)
after desalination and sublimation of the consolidant. Samples that were not exposed to salt and dried (i.e. controls) are shown in
column 6. In (C), pottery tiles in column 1 were consolidated with camphene, in column 2 with menthol, in 3 with cyclododecane,
and in 4 with cyclododecanone. Note that the unconsolidated samples (shown in column 5) experienced almost complete loss of
their paint layer during desalination.
 JOURNAL OF THE AMERICAN INSTITUTE FOR CONSERVATION 197

(Figure 8(D2–4)). Regardless, the samples not coated with
a consolidant lost most of their paint layers (Figure 8
(D5)). No residue from any of the consolidants was visible
by optical microscopy on the painted surfaces after the
desalination and sublimation procedures. Due to the sali-
nation and desalination steps, a small portion of the paint
might have been lost, and the paint surface roughened.
This creates a color change that can be detected when
comparing samples before and after treatment.
3.4.2. FTIR
Evaluation of the degree of final sublimation of the con-
solidants was assessed using ATR-FTIR spectra. The
spectra of the samples treated with camphene show no

Figure 9. ATR-FTIR spectra of the surfaces of accelerated-weathered painted pottery after consolidation and desalination, indicating the
absence of camphene, menthol, and cyclododecane residues and the presence of some residue from cyclododecanone.
198 H. SADEK ET AL.

Figure 10. EDS maps of the painted side of a pottery sample after completion of the desalinization and sublimation procedures: (a) Cl;
(b) Ca. The arrows point to sites where concentrations of these elements are highest.

evidence for bands characteristic of camphene at
3066 cm−1 (for = C–H), and saturated C–H stretches
and bending modes. FTIR spectra of samples treated
with menthol did not show bands at 3240, 2855–2924,
1448, or 1025 cm−1 that are characteristic of O–H,
CH3, −C–H, and C–O groups, respectively. Similarly,
the FTIR spectra of samples treated with cyclododecane
did not show bands at 2955–2870 cm−1 that are charac-
teristic of saturated C–H bond stretches. Thus, we con-
clude that the levels of residues with these consolidants
are very low. However, bands at 2850–2950 cm−1, due
to aliphatic C–H stretching modes, were detected on
the surface of pottery consolidated with cyclododeca-
none even after 10 days of sublimation (Figure 8).
The organic binder used in the paints for the samples
is animal glue that consists of polymerized amino acids
through amide linkages. FTIR bands from amide bonds
are found at three regions: amide I at 1600–1700 cm−1
includes C = O stretching, C–N and N-H bending;
amide II at 1500–1600 cm−1 from C–N stretching
with N-H bending; and amide III at 1200–1350 cm−1
from N-H bending, C–N stretching, and specific C–H
modes (Singh et al. 1993). The decrease in intensity
of the amide I, II, and III bands indicate that the
weathering process used for the pottery samples did
cause the loss of some of the paint, probably due to
the dissolution of the organic paint binder in the halite
solution.

Figure 11. SEM-EDS: (a) micrograph of SEM on painted pottery treated with cyclododecanone; (b) spectrum of a quartz grain in (a)
showing the presence of carbon; (c) element map of carbon by SEM-EDS showing the presence of carbon, presumably due to the pres-
ence of cyclododecanone residue.

3.4.3. SEM-EDS
The success of the desalination procedures and protection
of the sensitive paints from dissolution and spalling are
shown clearly by the absence of sodium in the SEM-
EDS maps in Figure 9. However, the EDS elemental
maps (Figure 10) do indicate the presence of a new cal-
cium species that correlates with the position of chloride.
We suspect that CaCl2 is produced in the pottery samples;
the clay contains some calcium. Although CaCl2 is not a
hygroscopic and water-soluble salt (Winkler 2013), pre-
caution should be taken to limit any alteration or chemical
reaction by it during conservation treatment.
Although elemental mapping of samples treated with
cyclododecanone is consistent with the disappearance of
the consolidant from most of the surface (as indicated by
the absence of carbon in the sum spectrum (Figure 11)),
some carbon is located on the surface of the quartz par-
ticles in the pottery as residue of the cyclododecanone on
the pottery samples.
4. Conclusions
The ability of four commercially available, sublimable
and relatively unreactive molecules, which are exten-
sively available commercially and inexpensive (i.e. cyclo-
dodecane, menthol, cyclododecanone and camphene), to
protect paint on pottery surfaces during their aqueous
desalination has been demonstrated and compared. We
have performed dynamic analyses of their behavior on
experimental test samples and have compared the
efficiency of their consolidation during desalination.
The results demonstrate that cyclododecanone and cam-
phene afford good protection to a water-sensitive paint
on pottery during desalination. Although menthol,
cyclododecane, and cyclododecanone protected the
painted samples better than camphene, all afforded
some degree of protection compared to not using a
consolidant.
Removal of salt from the samples occurs in two stages:
the more rapid one is the dissolution of salts at or near
the surface; the slower step is removal of salts located in
interior pores. Some of the results indicate that the molecu-
lar structure and bulk properties of the consolidants influ-
ence the desalination rate despite there being little, if any,
sublimation while the samples are submerged in water to
remove the salt; visually, the consolidants remained on
the surfaces throughout the desalination process. Also,
the desalination rates of samples treated with menthol or
cyclododecanone were found to be higher than those trea-
ted with camphene or cyclododecane.
Residues left as a result of the application of a protec-
tive treatment on a work of art are highly undesirable
and an important concern. In that regard, FTIR spectral
JOURNAL OF THE AMERICAN INSTITUTE FOR CONSERVATION 199
analyses indicate the absence of discernible camphene,
menthol, or cyclododecane on the surface of the treated
samples after leaving them for several days at room
temperature in the air (i.e. conditions under which the
consolidants sublime); however, traces of cyclododeca-
none did appear on the surface for a very long period.
In conclusion, the four sublimable consolidants pro-
tected the paint layer. Cyclododecane, cyclododecanone
and menthol afforded similar degrees of protection to
the paint layer while camphene was less efficient, perhaps
due to its more rapid rate of sublimation. Additional
studies and research on mixtures of cylododecanone
and camphene will be necessary to optimize the
efficiency of their temporary consolidation of pottery
and painted surfaces during desalination.
Future studies will include additional tests of these
and other sublimable consolidants to protect different
types of painted surfaces on different types of materials.
Those studies will include additional analytical investi-
gations of the properties of the object surfaces before
and after treatment, and measurements of sublimation
rates under different atmospheric conditions. Further
work includes measurements to determine the pen-
etration depth of the consolidants into samples and cul-
tural heritage objects.
Acknowledgments
HS and RGW thank the US National Science Foundation
(Grant CHE-1502856) for its support of the portion of this
research conducted at Georgetown University. HS is grateful
to the Fulbright Scholars Program, administered by the Coun-
cil of the International Exchange of Scholars, for a fellowship.
Disclosure statement
No potential conflict of interest was reported by the authors.
Funding
This work was supported by National Science Foundation
[grant number CHE-1502856]; Binational Fulbright Commis-
sion in Egypt (AY 2015/2016).
Notes on contributors
Hamada Sadek holds a M.Sc. and Ph.D. in Archaeological Con-
servation from Cairo University, Egypt. He is a staff member of
the Conservation Department, Faculty of Archaeology, Fayoum
University, Egypt. He was a Fulbright postdoctoral fellow at
Georgetown University and at the National Gallery of Art,
Washington, DC. Sadek was Samuel H. Kress Fellow for
Advanced Studies in Art Conservation 2010-2011, Arizona
State Museum – the University of Arizona. He has been fellow
at universities and institutes in France, Germany, Poland, Roma-
nia and USA. He is a Professional Associate and Sustainability
200 H. SADEK ET AL.
Committee member of the American Institute for Conservation
of Historic and Artistic Works. Since 2016 he has been a mem-
ber of the conservation team of the University of Michigan
Abydos Middle Cemetery (AMC) project. Mailing address:
Conservation Department, Faculty of Archaeology, Fayoum
University, Po Box 63511, Al Fayoum, Egypt. Email:
hsr00@fayoum.edu.eg.
Barbara H. Berrie holds a doctorate in chemistry from George-
town University in Washington, DC. Before joining the National
Gallery of Art in Washington, DC, she was an NRC postdoctoral
fellow at the US Naval Research Laboratory. Berrie has published
widely in conservation science on topics as diverse as new
materials for treatment of works, analytical methods for pigment
identication, and history of artists’ use of materials. She is editor
of volume 4 of the series Artists’ Pigments: A Handbook of Their
History and Characteristics. Berrie was awarded a Samuel
H. Kress Paired Fellowship (with Louisa C. Matthew) at the Cen-
ter for Advanced Study on the Visual Arts (2002) and in 2018
was awarded the John D. and Susan P. Diekman Fellowship at
the Djerassi Resident Artists Program. She is head of the Scien-
tific Research Department at the National Gallery of Art. Mailing
address: 2000B South Club Drive, Landover, MD, 20785, USA.
Email: b-berrie@nga.gov.
Richard G. Weiss received an ScB degree from Brown Univer-
sity and MS and PhD degrees from the University of Connecti-
cut. He was an NIH Postdoctoral Fellow at California Institute
of Technology and a Visiting Assistant Professor and National
Academy of Sciences Overseas Fellow at the Instituto de Qui-
mica of the Universidade de São Paulo in Brazil before coming
to Georgetown University in 1974, where he is a member of the
Chemistry Department and the Institute for Soft Matter Syn-
thesis and Metrology at Georgetown. He has been a visiting
professor at universities and institutes in Brazil, China, Costa
Rica, Germany, France, Italy, Japan, Slovakia, and Spain. He
is a Fellow of IUPAC, a member of the Brazilian Academy
of Sciences, and received a doctorate honoris causa from Uni-
versité de Bordeaux 1. He was a senior editor of the ACS jour-
nal Langmuir for 10 years, is currently a member of the
editorial advisory boards of the Journal of the Brazilian Chemi-
cal Society and Gels, and is an Associate Editor for Polimeros
and a member of the Scientific Committee of Substantia. His
research interests include investigations of photochemical,
photophysical and thermal reactions of molecules in anisotro-
pic environments, and the development and application of
ionic liquids, ionic liquid crystals, and new molecular and
polymer gels for various purposes, including chemical spill
remediation and the conservation of objects of cultural heri-
tage. Mailing address: 240 Reiss Science Building, Georgetown
University, Washington, DC 20057-1227, USA. Email:
weissr@georgetown.edu.
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Appendix
Health and safety issues concerning the
sublimable consolidants
Health and safety information about the use of the sublimable
consolidants is very limited. For that reason, storage containers
should be well sealed and marked with appropriate warnings.
Until adequate studies on the effects of the consolidants have
been performed on humans, conservators should avoid inhala-
tion and skin contact. The section below offers information
found in the safety data sheets for the materials.
Cyclododecane: low level of toxicity; direct contact can
cause eye and skin irritation (i.e. tearing discomfort and vision
obscuring), and may cause long lasting harmful effects to
202 H. SADEK ET AL.
aquatic life (Nichols and Mustalish 2002). There are no
available data about ventilation system and air sampling tests
(Pool 2006).
Cyclododecanone: no known effect on the eyes and mucous
membranes, but it may be slightly irritating. The oral LD50 is
2.5 g/kg (Schiffer and Oenbrink 2000). It may cause long-last-
ing harmful effects to aquatic life.
Menthol: exposure may cause irritation to skin, eyes, mucous
membranes, and upper respiratory tract. It may cause lesions to
biological membranes (Bernson and Pettersson 1983).
Camphene: inhalation causes irritation of the nose and
throat and direct contact with eyes or skin causes irritation.
It is toxic to aquatic life.
Precautions for applying sublimable compounds: Based on
the information above, conservators should avoid direct con-
tact with and breathing vapors of the compounds by applying
them in a fume hood or under an exhaust ventilator. In
addition, the usual precautions with the use of any chemical
should be followed: wearing safety glasses, chemical resistant
gloves, and lab coats.
The authors recommend these procedures, noting that
most of them are followed normally by conservators when
they are applying other materials. The water washes contain
virtually none of the consolidants (because they are not soluble
in aqueous media) and small amounts of salts; as such, they are
not considered to impose an environmental hazard.