Journal of Cultural Heritage 15 (2014) 165–172

Available online at

www.sciencedirect.com

Original article

Use of ZnO nanoparticles for protecting oil paintings on paper support against
dirt, fungal attack, and UV aging
Osama M. El-Feky a , Enas A. Hassan b , Shaimaa M. Fadel b , Mohammad L. Hassan b,c,∗
a
Restoration and Conservation Department, Faculty of Archaeology, Cairo University, 12622 Giza, Egypt
b
Cellulose and Paper Department, National Research Centre, Dokki, 12622 Giza, Egypt
c
Advanced Materials and Nanotechnology Group, Centre of Excellence for Advanced Sciences, National Research Center, Dokki, 12622 Giza, Egypt

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

Article history: Zinc oxide nanoparticles were prepared and used for surface treatment of oil paintings painted on paper
Received 2 October 2012 supports. The prepared coating mixture containing 2% of ZnO nanoparticles showed excellent trans-
Accepted 29 January 2013 parency. The effect of coating on protecting the paper support and paintings against microbial attack by
Available online 27 March 2013
Trichoderma reesei and Aspergillus niger, dirt accumulation, and UV aging was studied. Coatings contain-
ing ZnO nanoparticles enhanced the durability of linseed oil-based paintings toward UV aging regarding
Keywords: the change in color. Coatings containing ZnO nanoparticles improved resistance to microbial attack when
Aging
subjected to inoculums containing T. reesei or A. niger fungi. In addition, coatings containing ZnO nanopar-
Paper
ZnO nanoparticles
ticles reduced accumulation of dirt on oil paintings when left in open air for 6 months; cleaning of
Color paintings was quite easy compared to the non-coated paintings or those coated with the varnish without
Trichoderma reesei ZnO nanoparticles.
Aspergillus niger © 2013 Elsevier Masson SAS. All rights reserved.

1. Aim of the research
The aim of the current work is to investigate the use of ZnO
nanoparticles as a coating for oil paintings on paper supports to pro-
tect the paper support and oil paintings against UV aging, dirt, and
microbial attack by cellulose- and oil-degrading microorganisms,
namely Trichoderma reesei and Aspergillus niger fungi.
2. Introduction
Oil paintings on paper supports are deteriorated by time. Paper
has been praised and used by writers and artists such as Albrecht
Durer, Michelangelo, Giambattista Bodoni, Francisco Goya, and
Picasso [1]. There are archaeological oil paintings on paper supports
painted by Rembrandt, Delacroix, Hans Thoma, E. von Gebhardt,
and others [2]. There are many forms for deterioration of oil paint-
ings on paper supports such as darkening of the final varnish layer,
cracks in the varnish, paint and ground layer, and aging of paper
support. Moreover, parts of the ground layer and paint layer may
fall apart. So, restoration and conservation of these oil paintings is
an important target [3].
∗ Corresponding author. Cellulose and Paper Department, Centre of Excellence for
Advanced Sciences, National Research Centre, Dokki, 12622 Giza, Egypt.
Tel.: +202 33335926; fax: +202 33370931.
E-mail addresses: mlhassan2012@yahoo.com,
mlhassan2013@yahoo.com (M.L. Hassan).
Many natural and synthetic materials are used for restoration
of oil paintings. There are no ideal materials and there are short-
comings for each of them. The responsibility for choosing the
correct materials and methods of application lies on the conser-
vator who carries out the treatment. The conservator must have
sufficient understating of the processes involved to enable eval-
uation of the possible irreversible effects on a particular object
[4]. Therefore, preparation of durable and efficient materials for
use in the area of conserving oil paintings on paper supports is of
significant importance.
Paper supports and paintings are subject to biodegradation by
different microorganisms. Since paper consists mainly of cellulose
and hemicelluloses, it could be attacked by different microorgan-
isms that secret cellulases and hemicelluloases enzymes [5]. In
addition, the use of oils, such as linseed oil, in paintings makes them
subject to attack by microorganisms that can degrade oils [6].
Some metal oxide nanoparticles have antimicrobial activity.
Nanoparticles are much more active than larger size particles
because of their much higher surface area and ability to display
unique physical and chemical properties. The use of nanoparticles
as antimicrobial agents for archeological objects has been already
proposed and tested, but mainly on stone substrates [7,8].
Zinc oxide nanoparticles exhibit excellent antibacterial activ-
ity [9]. Although the exact mechanism for antimicrobial effect of
ZnO has not yet been clearly elucidated, the suggested mechanisms
include the role of reactive oxygen species (ROS) generated on the
surface of the particles [10], zinc ion release [11], and nanoparticles
internalization [12].

1296-2074/$ – see front matter © 2013 Elsevier Masson SAS. All rights reserved.
http://dx.doi.org/10.1016/j.culher.2013.01.012
166 O.M. El-Feky et al. / Journal of Cultural Heritage 15 (2014) 165–172

Regarding the antifungal activity, ZnO nanoparticles showed

significant antifungal activity against some fungal strains such as
Aspergillus flavus, A. niger and Candida albicans [13], postharvest
pathogenic fungi Botrytis cinerea and Penicillium expansum [14],
Saccharomyces cerevisiae, C. albicans, A. niger, and Rhizopus stolonifer
[15,16], plant pathogenic fungi Pythium debarynum and Sclerotium
rolfsii [17].
Being a semiconducting material, the band gap between con-
duction and valence electrons plays a vital role in the generation of
reactive oxygen species (ROS), which cause deterioration of micro-
bial cell membrane [18]. Moreover, for the production of ROS and
rupture of the microbial cell membrane, the surface contact of
nanoparticles with the biological membrane is necessary, which
assists in the damage of microbial enzyme bodies, thereby killing
the pathogenic microbes.
The use of ZnO nanoparticles with cellulosic materials to impart
them antimicrobial properties has been investigated. For example,
zinc oxide nanoparticles have been used on cotton fabrics or paper
sheets to impart them antimicrobial properties [19–26].
Another important property of zinc oxide nanoparticles is their
self cleaning effect on the surfaces they are applied onto in the
presence of UV light [27]. This phenomenon was explained by the
photocatalytic activity of ZnO nanoparticles. Under UV irradiation,
ZnO nanopaticles are able to decompose and to mineralize bio-
recalcitrant organic pollutants in the form of CO2 and H2 O [28].
In addition, ZnO nanoparticles prevent dust or dirt accumulation
on the surface of different materials by what is known as “lotus
effect” [29].

3. Experimental

3.1. Materials

Zinc chloride, sodium sulfide, and polyethylene imine were
reagent grade chemicals and used as-received. Commercially avail-
able Fabriano paper was used for painting. The following color
pigments were used [30]: titanium dioxide was used for the white
color; vermilion (mercuric sulfide) was used for red color; yel-
low ochre (iron oxide) was used for yellow color; and ultramarine
blue was used for the blue color. Commercial linseed oil was used
for preparation of the colors. Paraloid B66 (commercial acrylic-
based resin) was used for preparation the TiO2 white color. A
non-yellowing commercial varnish mixture (Satin) was used as-
received; its dry content was 24%. The varnish was containing
acrylic and ketone resin, linseed oil, matting agent (silica), an UV
stabilizer, and quick drying petroleum.
Scheme 1. Sketches for the different painting series used.
were used for comparison. The second series was Fabriano paper
sheets painted with linseed oil-based red, blue, and yellow col-
ors. Samples from this series were coated with the varnish with or
without the ZnO nanoparticles. The third series was Fabriano paper
sheets painted with linseed oil-based white color (titanium diox-
ide). Samples from this series were coated with the varnish with
or without the ZnO nanoparticles. The fourth series was Fabriano
paper sheets painted with acrylic-based white color (titanium diox-
ide). Samples from this series were coated with the varnish with or
without the ZnO nanoparticles.

3.2. Preparation of ZnO nanoparticles 3.4. Coating with varnish/ZnO nanoparticles mixture

The method used for ZnO nanoparticles was based on the previ-
ously used method for preparation of ZnS nanoparticles using Zinc
chloride and sodium sulfide in the presence of polyethyleneimine
[31]. After separation of ZnS, it was treated thermally in an
oven at 600 ◦ C for 120 minutes to obtain ZnO [32]. The pre-
pared ZnO nanoparticles were characterized using X-ray diffraction
(XRD) using Diano X-ray diffractometer with Co K␣ irradiation
at ␭ = 1.79026A◦ . Transmission electron microscopy (TEM) was
carried out using a JEOL 1230 transmission electron microscope
(Japan) with acceleration voltage 100 KV.
3.3. Preparation of oil paintings
Fabriano paper sheets (15 × 20 cm) were used for oil painting.
Four series of samples were prepared (Scheme 1). The first series
was Fabriano paper sheets coated with the varnish with or without
ZnO nanoparticles (2% wt. percent). Blank Fabriano paper sheets
ZnO nanoparticles were suspended in the commercial varnish
solution at concentration of 2%. To ensure homogeneity of the
nanoparticles in the coating mixture, the mixture was subjected to
ultrasonic treatment for 5 minutes under cooling using 750-watt
ultrasonic processor (Sonix, USA). The samples of different series
were coated with the ZnO nanoparticles suspension using a paint-
ing brush according to the common practice.
3.5. UV aging of oil paintings
For UV aging, a Fade-O-Meter instrument (Perkin-Elmer, Nor-
walk, CT) was used at room temperature for 150 h, and the
temperature and humidity were at about 30 ◦ C and 50%, respec-
tively. The UV light is generated by carbon arc light source and
wavelength range of emitted light was 350–430 nm. After the
experiments, the paper supports were conditioned at 65% relative
humidity and 25 ◦ C for 48 h before testing.
 O.M. El-Feky et al. / Journal of Cultural Heritage 15 (2014) 165–172 167

Table 1
Average temperature (◦ C) during the dirt accumulation test in open air.

Temperature Month

July August September October November December

Maximum 36 35 33 28 25 20
Minimum 24 24 22 18 14 12

3.6. Testing of oil paintings

Tensile strength was carried out according to TAPPI T494

standard method using a Lloyd universal testing machine at a con-
stant crosshead speed of 6.25 cm/min.
The changes in the color parameters L, a, and b were measured
with a Hunterlab colorimeter; L index of color represents black-
to-white color, a index represents green-to-red color, and b index
represents blue-to-yellow color. The overall change in color indices
due to aging was expressed as E according to the following for-
mula [33]:
 2
  2
  2
1⁄2
E = L + a + b
where L, a, and b are the differences between the values of
the color indices before and after aging.
3.7. Dirt accumulation test
The paintings were left in open air for 6 months from July to
December. Table 1 shows the average temperature during every
month.
3.8. Inoculation with T. reesei and A. niger fungi
T. reesei and A. niger used in this study were chosen because of
their ability to degrade cellulose and oils, respectively. They were
obtained from the culture collection of Northern Regional Research
Laboratory, Department of Agriculture, Peoria, IL. Fungi were main-
tained in peptone yeast extract agar slants in a 4 ◦ C refrigerator.
Each fungal strain was cultivated on peptone yeast extract agar
plates at 30 ◦ C for 7days. Pieces of samples (total area 70 cm2 ) were
placed inside the plates on a 1% agar agar suspension in water. This
suspension contained 1 g/L KH2 PO4 and 0.5 g/L MgSO4 [34]. Agar
agar by itself did not have any nutrients and was used only to keep
constant humidity.
Series 1 (Fabriano paper coated with the varnish with or without
ZnO nanoparticles) were inoculated with T. reesei culture. Series 2
(oil-painted Fabriano paper coated with the varnish with or with-
out ZnO nanoparticles) were inoculated with A. niger culture. All
samples were incubated at 30 ◦ C for 4 weeks.
Fig. 1. TEM of the prepared ZnO nanoparticles.
of ZnS nanoparticles; the diameter was in the range from 122 to
286 nm.
ZnO nanoparticles showed the known XRD pattern of hexagonal
phase of wurtzite structure (Fig. 2), which was in good agreement
with literature reports [32]. The XRD pattern showed peaks at 2␪
value of 31.7 (100), 34.4 (002), 36.2 (101), 47.5 (102), 56.6 (110),
62.8 (103), 66.4 (200), 67.9 (112) and 69.1 (201).
4.2. Coating of color-painted Fabriano paper with ZnO
nanoparticles
Fabriano paper sheets were painted with linseed oil-based col-
ors (blue, red, and yellow) and with linseed oil-based white color
(titanium dioxide). The coloring materials used are among the most
famous and most popular colors used in the past in different eras.
Vermilion (mercuric sulfide) was used for red color; it had been
used in ancient time. Yellow ochre (Iron oxide) was used for yel-
low color; it had been used during the Prehistoric age. Ultramarine
blue is a historical pigment found in Egyptian tomb paintings. In
addition, Raphael, Leonardo da Vinci and Michelangelo Buonarotti
used that pigment in their paintings.
Oil paintings that are usually not going to be framed under glass
are usually varnished to protect them from dirt, dust, and pollution.
The varnish also homogenizes the final appearance of a painting and
adds depth to the color paintings.
The oil-painted samples were varnished using the acrylic-
based varnish solution with or without ZnO nanoparticles. Due
to the nano-size nature of the ZnO used, the coating had high

3.9. SEM of oil painting samples

Scanning electron microscopy was performed using a Jeol 6310

(Jeol Instruments, Tokyo, Japan) system running at 5–10 keV. Before
scanning, samples were coated with gold using sputter coater sys-
tem (Edwards Sputter Coater, UK).

4. Results and discussion

4.1. Preparation and characterization of ZnO nanoparticles

In a previous work, ZnS nanoparticles with diameter of 9–17 nm

were successfully prepared using sodium sulfide and zinc chloride
in the presence of polyethylene imine at 8 ◦ C [31]. Fig. 1 shows
the TEM images of the prepared ZnO nanoparticles by heat-treated Fig. 2. XRD pattern of the prepared ZnO nanoparticles.
168 O.M. El-Feky et al. / Journal of Cultural Heritage 15 (2014) 165–172
Fig. 3. Paintings coated with (a) acrylic varnish containing ZnO nanoparticles and (b) varnish containing the commercial micro-size ZnO.
transparency compared to coating obtained on the same samples
with commercially available micro-size ZnO dispersed in the same
varnish (Fig. 3). As it is obvious from the images, a white layer is
clearly seen at the surface of the sample after drying in case of using
the micro-size ZnO while samples coated with ZnO nanoparticles
exhibited no color alteration.
4.3. Effect of ZnO nanoparticles coating on dirt accumulation
The effect of coating white-, red-, yellow-, and blue-color lin-
seed oil-based paintings samples (series 2 and 3) with the varnish
(with or without the ZnO nanoparticles) on accumulation of dirt
and dust was investigated. Fig. 4 shows pictures of oil-painted col-
ored samples left in the open air for 6 months; the samples were
hanged vertically on a wooden stand. The samples were divided
into three areas as sketched in Scheme 1: on the first area, only the
color was applied onto the paper, on the second area, the varnish
was applied above the color, and on the third area, the varnish con-
taining ZnO nanoparticles was applied. As it can be clearly seen, the
accumulation of dirt was very high in the areas where ZnO nanopar-
ticles were absent. Even the presence of the varnish layer resulted
in accumulation of dirt. The same results were obtained in case of
samples painted using the oil-based white color.
Cleaning of the areas coated with the varnish containing ZnO
nanoparticles was very easy using a soft brush compared to the
other areas where the dirt particles strongly adhered to the painted
layer or the varnish (Fig. 4).
4.4. Effect of ZnO nanoparticles coating on microbial growth
The ability of ZnO nanoparticles to affect the viability of the two
fungus strains T. reesei and A. niger on paper-supported oil paintings
samples was studied. An ascomycete, T. reesei is a mesophilic fungus
which is one of the most efficient xylanase and cellulase produc-
ers. T. reesei produces a suite of cellulolytic enzymes with distinctly
different activities, including endocellulases, exocellulases, and ␤-
glucosidases which synergistically depolymerize cellulose [35]. On
Fig. 4. Picture of colored paintings after being left in open air for 6 months (left)
and after cleaning with a brush and a dry piece of cotton (right). Area A: painted
with color + varnish + ZnO nanoparticles; area B: painted with color + varnish; area
C: painted with color.
the other hand, an ascomycete, A. niger is among the most well
known lipase producers; it can attack oils in paintings [36–38].
SEM of different oil paintings samples inoculated with T. reesei
and A. niger, and incubated for 4 weeks are shown in Figs. 5 and 6.
In Fig. 5 where Fabriano paper were coated with the varnish with
and without ZnO nanoparticles, SEM images clearly show that the
varnish containing ZnO nanoparticles inhibited the fungus growth
(Fig. 5c). On the other hand, in case of blank Fabriano paper sheets
growth of T. reesei was clear from spreading the spores of the fungus
(Fig. 5a). Even in case of applying the varnish on the paper sheets
(Fig. 5b) some spores of the fungus were seen.
Fig. 6 shows SEM images of linseed oil-painted Fabriano paper
samples inoculated with A. niger. Presence of linseed oil on the sur-
face of Fabriano paper sheets resulted in remarkable growth of the
A. niger fungus; the spores and hyphens of the fungus were clearly
seen (Fig. 6a). Coating of the linseed oil-treated paper sheet with the
varnish, which is acrylic-based varnish, could not completely pre-
vent the growth of the fungus and still the spores and hyphens could
be seen (Fig. 6b). Previous studies showed that acrylic coatings can
hinder the accessibility of the A. niger enzymes to the degradable
material [39]. Growth of the hyphens of A. niger on the acrylic var-
nish in this study could be due to the fact that the commercial
varnish used contains linseed oil. It could be also due to defects of
the varnish coating and thus the fungus hyphens can reach the oil
layer. On the other hand, in case of coating the oil-painted layer with
the varnish containing ZnO nanoparticles, there was no growth of
the inoculums of the fungus (Fig. 6c).
4.5. Effect of UV aging on Fabriano paper and oil paintings
The effect of UV aging for 150 hours on the properties of ZnO
nanoparticles-coated and non-coated Fabriano paper sheets and
paintings was studied. The effect on the change in color parameters
(L, a, and b) and tensile strength of paper supports was studied.
Tables 2 and 3 show the change in color (E) of the different
series as a result of UV aging at room temperature for 150 hours. In
case of series 1 (paper sheet coated with varnish layer with or with-
out ZnO nanoparticles), slight differences between the E of blank
paper sheet, the sheet coated with the varnish only, or the varnish
containing the ZnO nanoparticles was found. The decrease in E
of samples as a result of adding ZnO nanoparticles to the varnish
was ∼7%. This could be due to the fact that Fabriano paper sheet
is made of pure cellulose, which is known to be durable under UV
light. Cellulose unit has no groups absorbing UV radiation. Thus, its
photo-degradation is induced by internal, external chromophoric
impurities, or additives [40,41]. The photo-degradation processes
involved in cellulose are main chain scission, dehydroxylation,
Table 2
The change of color (E) of series 1 samples (Fabriano paper sheets coated with
acrylic varnish) as a result of UV aging for 150 hours.
E
Blank paper Blank paper Blank paper sheet +
sheet sheet + varnish varnish + ZnO nanoparticles
Series 1 8.86 8.13 7.54
 O.M. El-Feky et al. / Journal of Cultural Heritage 15 (2014) 165–172 169

Fig. 5. SEM of samples inoculated with Trichoderma reesei for 4 weeks: a: blank Fabriano paper sheets; b: Fabriano paper sheets + varnish; c: Fabriano paper
sheets + varnish + ZnO nanoparticles.

dehydromethylation and dehydrogenation, which lead to forma-
tion of several free radicals that cause degradation and yellowing
of cellulose [41]. In addition, zinc oxide is known to filter out
the shorter, i.e., higher energy, wavelengths of UV light. Due to
the nano-size nature of the ZnO used in the coating varnish, the
property of filtering out the shorter UV light is expected to be
much higher due to higher surface area of the nanoparticles [42].
Furthermore, the varnish used was containing an UV stabilizer to
enhance its durability to color change, as stated by the manu-
facturer. Therefore, a slight effect for the ZnO nanoparticles was
observed.
In case of series 2, where Fabriano paper was painted with the
linseed oil-based yellow, blue, and red colors followed by applying
a varnish with or without ZnO nanoparticles, UV light did not cause

Fig. 6. SEM of samples inoculated with Aspergillus niger for 4 weeks: a: linseed oil-painted Fabriano paper sheets; b: linseed oil-painted Fabriano paper sheets + varnish; c:
linseed oil-painted Fabriano paper sheets + varnish.
170 O.M. El-Feky et al. / Journal of Cultural Heritage 15 (2014) 165–172

Fig. 7. Effect of UV aging on the properties of the different oil-painted samples.

changes in color indices of paintings made using the yellow and red
colors inorganic pigments. Both of vermilion (mercuric sulfide) and
yellow ochre (iron oxide) had excellent fastness in UV light [43,44].
But in case of the ultramarine blue color, a drastic change in color
took place as a result of UV aging. The weak UV light fastness of
that pigment was reported before [45,46]. Coating of the blue paint
with the acrylic varnish significantly reduced the change of the blue
color as a result of UV aging. The presence of ZnO nanoparticles in
the varnish layer further reduced the change in the blue color. The
decrease in E as a result of addition of ZnO nanoparticles to the
varnish was 8, 15, and 23% in case of yellow, red, and blue colors,
respectively. The change in the color of the linseed oil used as a
matrix is also expected but it may not be obvious in the colored
samples.
In case of series 3 (TiO2 -linseed oil-based paintings), significant
change in E values took place in case of the painted sample and
the painted sample coated with the varnish (without ZnO nanopar-
ticles). The change in the color could be attributed to the oxidation
of the linseed oil under the effect of UV light [47]. In addition, tita-
nium dioxide pigment, upon e xposure to ultraviolet, induces the
 O.M. El-Feky et al. / Journal of Cultural Heritage 15 (2014) 165–172
Table 3
The change of color (E) of series 2, 3, 4 samples as a result of UV aging for 150 hours.
Samples E
Color painting Color painting Color painting layer +
layer layer + varnish varnish + ZnO nanoparticles
Series 2a
Red 2.67 2.36 1.81
Yellow 2.92 2.91 2.69
Blue 32.9 19.2 16.3
Series 3b 10.94 10.81 3.37
Series 4c 7.71 7.32 7.25
a
Series 2: Fabriano paper sheets painted with linseed oil-based colored (red,
yellow, and blue) paint.
b oxides of zinc and titanium to oxygen gas, J. Electrochem. Soc. 147 (2000)
Series 3: Fabriano paper sheets painted with linseed oil-based white colored
paint.
c
Series 4: Fabriano paper sheets painted with acrylic-based white colored paint.
formation of free radicals in vehicles (binders) leading to a destruc-
tion of the vehicle and chalking of the paint [48]. Presence of ZnO
nanoparticles in the varnish layer significantly reduced the color
change of the linseed oil by about 69% as compared to the varnish
without the ZnO nanoparticles.
In case of series 4 (TiO2 -acrylic-based paintings), no significant
difference in E values was found between the paintings coated
with varnish with or without ZnO nanoparticles (∼1% less in case of
the varnish containing ZnO nanoparticles). This may be attributed
to the fact that UV stabilizer is usually added to the commercial
acrylic resin-based varnish used in coating.
The effect of UV aging for 150 hours on tensile properties (ten-
sile strength and elongation at break) of the different samples was
studied and the results are presented in Fig. 7.
Generally, aging of painted paper samples resulted in a slight
to moderate increase in tensile strength. This could be due to fur-
ther drying and possible cross-linking of the painting matrix by
the action of UV light. No significant effect on tensile strength due
to the presence of ZnO nanoparticles in the coating mixture was
noticed. The same trend was found for the elongation at break of
aged samples.
5. Conclusions
ZnO nanoparticles were prepared and used in an acrylic-
based varnish to produce coatings with high transparency. The
coating mixture could be used to reduce the color change of lin-
seed oil-based paintings resulted from exposure to UV light. ZnO
nanoparticles in the varnish mixture could also reduce growth
of T. reesei and A. niger cellulose- and oil-degrading fungi, respec-
tively. The varnish containing ZnO nanoparticles could significantly
reduce accumulation of dirt and dust on the oil painting when left
in open air. In addition, cleaning of paper or paintings coated with
ZnO nanoparticles could be done with ease as compared to those
coated with varnish without the nanoparticles. The durability of
ZnO nanoparticles efficacy will be investigated in a further work.
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